摘要:

JASPE2 8(8j 61 N-66N 1053-1 122 337R-405R 9 9 ) Typeset by Burgess Thames View Abingdon Oxfordshire December 1993 Printed in Great Britain by Journal of Analytical Atomic Spectrometry Including Atomic Spectrometry Updates CONTENTS NEWS AND VIEWS 61 N Obituary-David A Hickman 61 N Reconstruction of Boris L'vov's Electrothermal Atomizer-Judith Egan-Shuttler 61 N Gordon Kirkbright Bursary 62N Book Review-Adam McMahon 63N Diary of Conferences and Courses 65N Future Issues PAPERS 1053 1059 1067 1075 1085 1091 1097 1103 1109 1113 1117 1121 Determination of Ultratrace Levels of Heavy Metals in Arctic Snow by Electro- thermal Vaporization Inductively Coupled Plasma Mass Spectrometry-Ralph E Sturgeon Scott N Willie James Zheng Akira Kudo D Conrad Gregoire Determination of Palladium and Platinum in Fresh Waters by Inductively Coupled Plasma Mass Spectrometry and Activated Charcoal Preconcentration-Gwendy E M Hall J C.Pelchat Determination of Selenium in Marine Certified Reference Materials by Hydride Generation Inductively Coupled Plasma Mass Spectrometry-Hiroaki Tao Joseph W H Lam James W McLaren Arsenic Speciation in Seafood Samples With Emphasis on Minor Constituents an tnvestigation Using High-performance Liquid Chromatography With Detection by Inductively Coupled Plasma Mass Spectrometry-Erik H Larsen Gunnar Pritzl Steen Honore Hansen Speciation of Arsenic by Ion Chromatography and Off -line Hydride Generation Electrothermal Atomic Absorption Spectrometry-Han Heng-bin Liu Yan-bing Mou Shi-fen Ni Zhe-mmg Electrothermal Vaporization for Sample Introduction in Microwave-induced Plasma Atomic Absorption Spectrometry-Ytxiang Duan Xingyou Li Qinhan Jin Improvement in Mercury Cold Vapour Atomic Techniques by Resorting to Organized Assemblies and On-line Membrane Drying of Vapour-B Aizpun Fernandez M R Fernandez de la Campa Alfred0 Sanz-Medel Improvement in Detection Limits in Graphite Furnace Diode Laser Atomic Absorption Spectrometry by Wavelength Modulation Technique.Plenary Lecture-Christoph Schnurer-Patschan Aleksandr Zybin Henning Groll Kay Niemax Preliminary Study on the Use of Palladium as a Chemical Modifier for the Determination of Silicon by Electrothermal Atomic Absorption Spectrometry-Zhixra Zhuang Pengyuan Yang Xiaoru Wang Zhiwei Deng Benli Huang Effect of Aqueous Organic Solvents on the Determination of Trace Elements by Flame Atomic Absorption Spectrometry and Inductively Coupled Plasma Atomic Emission Spectrometry-M Todorovic S Vidovic.Z IIIC Indirect Flame Atomic Absorption Spectrometric Determination of Papaverine Strychnine and Cocaine by Continuous Precipitation With Dragendorff's Reagent-Marceltna Eisman Mercedes Gallego Miguel Valcarcel CUMULATIVE AUTVOR INDEX ATOMIC SPECTROMETRY 337R Industrial Analysis Metals Chemicals and Advanced Materials-John Marshall UPDATE John Carroll James S. Crighton Charles L. R. Barnard 377R References continued on inside back cover 0267-9477C199318:l-YJASPE2 8(8j 61 N-66N 1053-1 122 337R-405R 9 9 ) Typeset by Burgess Thames View Abingdon Oxfordshire December 1993 Printed in Great Britain by Journal of Analytical Atomic Spectrometry Including Atomic Spectrometry Updates CONTENTS NEWS AND VIEWS 61 N Obituary-David A Hickman 61 N Reconstruction of Boris L'vov's Electrothermal Atomizer-Judith Egan-Shuttler 61 N Gordon Kirkbright Bursary 62N Book Review-Adam McMahon 63N Diary of Conferences and Courses 65N Future Issues PAPERS 1053 1059 1067 1075 1085 1091 1097 1103 1109 1113 1117 1121 Determination of Ultratrace Levels of Heavy Metals in Arctic Snow by Electro- thermal Vaporization Inductively Coupled Plasma Mass Spectrometry-Ralph E Sturgeon Scott N Willie James Zheng Akira Kudo D Conrad Gregoire Determination of Palladium and Platinum in Fresh Waters by Inductively Coupled Plasma Mass Spectrometry and Activated Charcoal Preconcentration-Gwendy E M Hall J C.Pelchat Determination of Selenium in Marine Certified Reference Materials by Hydride Generation Inductively Coupled Plasma Mass Spectrometry-Hiroaki Tao Joseph W H Lam James W McLaren Arsenic Speciation in Seafood Samples With Emphasis on Minor Constituents an tnvestigation Using High-performance Liquid Chromatography With Detection by Inductively Coupled Plasma Mass Spectrometry-Erik H Larsen Gunnar Pritzl Steen Honore Hansen Speciation of Arsenic by Ion Chromatography and Off -line Hydride Generation Electrothermal Atomic Absorption Spectrometry-Han Heng-bin Liu Yan-bing Mou Shi-fen Ni Zhe-mmg Electrothermal Vaporization for Sample Introduction in Microwave-induced Plasma Atomic Absorption Spectrometry-Ytxiang Duan Xingyou Li Qinhan Jin Improvement in Mercury Cold Vapour Atomic Techniques by Resorting to Organized Assemblies and On-line Membrane Drying of Vapour-B Aizpun Fernandez M R Fernandez de la Campa Alfred0 Sanz-Medel Improvement in Detection Limits in Graphite Furnace Diode Laser Atomic Absorption Spectrometry by Wavelength Modulation Technique.Plenary Lecture-Christoph Schnurer-Patschan Aleksandr Zybin Henning Groll Kay Niemax Preliminary Study on the Use of Palladium as a Chemical Modifier for the Determination of Silicon by Electrothermal Atomic Absorption Spectrometry-Zhixra Zhuang Pengyuan Yang Xiaoru Wang Zhiwei Deng Benli Huang Effect of Aqueous Organic Solvents on the Determination of Trace Elements by Flame Atomic Absorption Spectrometry and Inductively Coupled Plasma Atomic Emission Spectrometry-M Todorovic S Vidovic. Z IIIC Indirect Flame Atomic Absorption Spectrometric Determination of Papaverine Strychnine and Cocaine by Continuous Precipitation With Dragendorff's Reagent-Marceltna Eisman Mercedes Gallego Miguel Valcarcel CUMULATIVE AUTVOR INDEX ATOMIC SPECTROMETRY 337R Industrial Analysis Metals Chemicals and Advanced Materials-John Marshall UPDATE John Carroll James S. Crighton Charles L. R. Barnard 377R References continued on inside back cover 0267-9477C199318:l-Y

ISSN:0267-9477    

DOI:10.1039/JA99308FX029

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

J.A!3"€2 847) 53N-60N 935-1 052 261 R7336R ( 1 983) Journal of Analytical Atomic I n c I u d I n g Atom I c S pec t ro m et ry CONTENTS October 1993 Spectrometry Updates NEWS AND VIEWS 53N Conference Reports-Damon Green Mark Rummeli 56N Book Reviews-Phil Riby J F van Staden E Hywel Evans 58N Diary of Conferences and Courses 66" Future Issues PAPERS 935 945 955 961 965 969 979 983 989 995 999 1005 101 1 1015 1023 1029 Operation Principles and Design Considerations for Radiofrequency Powered Glow Discharge Devices. A Review-R Kenneth Marcus Characterization of a Helium Discharge for Hollow Anode Furnace Atomization Non-thermal Excitation Spectrometry-Philip G Riby James M Harnly Furnace Atomization Plasma Excitation Spectrometry Effects of Sodium Chloride and Sodium Nitrate on Lead and Silver Emission-T D Hettipathirana M W Blades Use of the Hildebrand Grid Nebulizer as a Sample Introduction System for Microwave- induced Plasma Spectrometry- H e n ry k Mat u s i ewicz Determination of Lead by Electrothermal Vaporization Microwave-induced Plasma Atomic Emission Spectrometry After Flow-through Electrolytic Deposition in a Graphite Tube Packed With Reticulated Vitreous Carbon-Ernest Beinrohr Ewa Bulska Peter Tschopel Gunther Tolg Diagnostic Investigations of Aerosols with Varying Water Content in Inductively Coupled Plasma Mass Spectrometry-Norbert Jakubowski lngo Feldmann Dietmar Stuewer Determination of Trace Metals in Concentrated Brines Using Inductively Coupled Plasma Mass Spectrometry On-line Preconcentration and Matrix Elimination With Flow Injection-Les Ebdon Andrew Fisher Howard Handley Philip Jones Isotope Ratios of Calcium Determined in Calcium-46 Enriched Samples From Infants by Automated Multiple-collector Thermal Ionization Mass Spectrometry- Judith R Turnlund William R Keyes Karen C Scott Richard A Ehrenkranz Evaluation of Linear Photodiode Array Detection for Continuum Source Atomic Absorption Spectrometry With Electrothermal Atomization-Clare M M Smith Robbin Nichol David Littlejohn In Situ Concentration of Selenium and Tellurium Hydrides in a Silver-coated Graphite Atomizer-Ni Zhe-ming He Bin Han Heng-bin Comparison of Chemical Modifiers for Simultaneous Determination of Different Selenium Compounds in Serum and Urine by Zeeman-effect Electrothermal Atomic Absorption Spectrometry-Jane K Johannessen Bente Gammelgaard Ole Jalns Steen H Hansen Mineralization of Biological Materials Prior to Determination of Total Mercury by Cold Vapour Atomic Absorption Spectrometry-Jorge E Tahan Victor A Granadillo Jose M Sanchez Hernan S Cubillan Romer A Romero Immobilized Cysteine as a Reagent for Preconcentration of Trace Metals Prior to Determination by Atomic Absorption Spectrometry-Hayat A M Elmahadi Gillian M Greenway Determination of Gold by Slurry Electrothermal Atomic Absorption Spectrometry After Preconcentration 'by Escherichia Coli and Pseudomonas Putida-L Carlos Robles Concepcion Garcia-Olalla A Javier Aller Study of X-ray Fluorescence Spectrometry and Spark Ablation Inductively Coupled Plasma Atomic Emission Spectrometry for Chromium Determination in Ferrochromium From Bulk Metal Samples-Aurora G Coedo Teresa Dorado Carlos J Rivero Isabel G Cob0 Determination of Traces$ of Lutetium in Geological Samples by Resonance lbnization Spectroscopy-Theodor Borislavov Krustev Svetlana Trifonova Mincheva ;Dimitar Angelov Angelov Elena Petkova Vidolova-Angelova 4 continued on msde back cover1033 1037 1043 1049 1051 COMMUNICATIONS Rapid Sample Preconcentration by Aerosol Deposition for the Determination of Trace Elements by Inductively Coupled Plasma Spectrometry-Robin Rattray Jorge Mifioso Eric D Salin Isotope Ratio Measurement by Inductively Coupled Plasma Multiple Collector Mass Spectrometry Incorporating a High Efficiency Nebulization System- Andrew J Walder Dagmar Koller Nicola M Reed Robert C Hutton Philip A Freedman Complementary Radiofrequency Glow Discharge Source for a Commercial Quadrupole Mass Spectrometer System-Charles R Shick Jr Angelika Raith R Kenneth Marcus ERRATUM CUMULATIVE AUTHOR INDEX ATOMIC SPECTROMETRY 199R Atomic Mass Spectrometry and X-ray Fluorescence Spectrometry-Jeffrey R UPDATE Bacon Andrew T Ellis Adam W McMahon Philip J Potts John G Williams 31 3R References WHY PAY A FORTUNE GBC Scientific Equipment U.K Ltd.13 Frederick Sanger Road The Surrey Research Park Guildford Surrey GU2 5YD Tel 0483 304988 Fax 0483 303071 Circle 002 for further information

ISSN:0267-9477    

DOI:10.1039/JA99308BX031

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

The Second International Symposium on Speciation of Elements in Toxicology and in Environmental and Biological Sciences June 15-18,1994 Loen Norway. AIMS The Symposium will focus on recent speciation research related to the chemical physical and morphological states of elements as they appear in various compartments in environmental and biological systems. The aims of the symposium are to provide a forum at which recent progress in analytical methodology of element speciation can be discussed and to provide an opportunity for an interchange of ideas between analytical and other scientists investigating fundamental aspects of environmental and human toxicology nutrition or metal containing drugs. THEMES The main themes for the Symposium are A. Sampling Characterization Detection and Determination of Chemical or Particulate Species * InAir * In Water * In Soil * In Biological Systems B.Thermodynamic and Kinetic Aspects C.Importance of Speciation in Environmental and Human Toxicology Nutrition and Medicine. * Speciation of the elements will be considered in the context of pathways to humans exposure routes uptake distribution metabolism toxicological mechanisms and excretion.SUBMZSSZON OF ABSTRACTS All contributions (oral or poster) presented will be eligible for publication in a Special Symposium Issue of the journal The Analyst. Prospective authors should submit an abstract (A4 format) of one-page length including tables and figures by February 15 1994(deadline). ORGANIZING COMMZTTEE Yngvar Thomassen (Symposium Chairman) Rita Cornelis (Gent Belgium) Brit Salbu (Am Norway) Evert Nieboer (Programme Chairman) J ytte Molin Christensen ( Copen hagen Denmark) Wolfgang Frech (Umea Sweden) Jan Aaseth (Elverum Norway) FOR FURTHER INFORMATION CONTACT The Second International Symposium on Speciation of Elements in Toxicology and in Environmental and Biological Sciences Yngvar Thomassen National Institute of Occupational Health P.O.Box 8149 DEP N-0033 Oslo 1 Norway. TEL 47 22466850; FAX 47 22603276 This Symposium has been organized by The Institute of Environment and Health (University of Toronto and McMaster University Canada) ; and The National Institute of Occupational Health (Oslo Norway) . Lr The 5th Nordic Symposium on Trace Elements in Human Health and Disease June 19-21,1994 Loen Norway AIMS The Symposium will focus on recent research related to trace elements and their relevance in human physiology and toxicology.The programme will emphasize cross-disciplinary issues and promote participant interaction. The conference is intended both for scientists in academia with expertise in toxicology clinical and analytical chemistry pathology metabolic disorders occupational and environmental health and nutrition as well as environmental and health professionals. THEMES The main themes for the Symposium are * Environmental and Occupational Exposure * Analytical and Clinical Chemistry * Trace Element Imbalances Related to Human Diseases (e.g. Cancer; Cardiovascular Liver and Neurological Diseases) * Dietary Levels and Critical Requirements (Essentiality versus Toxicity; Geomedicine) * Reference Concentrations as Drugs Chemotherapeutics Diagnostic Agents and Chelation Therapy * Reproductive and Development Effects SUBMZSSZON OF ABSTRACTS The Organizing Committee cordially invites you to submit an abstract of original research related to the themes of the Symposium.Prospective authors should submit an abstract (A4 format) of one-page length including tables and figures by February 15 1994(deadline). All contributions (oral or poster) presented will be eligible for publication in a Special Symposium issue of The Analyst ORGANIZING COMMZTTEE Jan Aaseth (Symposium Chairman) Hedmark Central Hospital Norway Jan Alexander Institute of Public Health Oslo Norway Evert Nieboer McMaster University Hamilton Canada Jetmund Ringstad Ulleval Hospital Oslo Norway Brit Salbu Agricultural University As Norway Yngvar Thomassen (Symposium Secretary) Oslo Norway FOR FURTHER INFORMATION CONTACT Trace Elements in Human Health and Disease Yngvar Thomassen National Institute of Occupational Health P.O.Box 8149 DEP N-0033 Oslo Norway. TEL 47 22466850; FAX 47 22603276I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I 1 I I I 1 I I I I I I I I I I I I I I I I I I I I 1 I I I I I I I I I I I I I I 1 I I I I I I I 1 I I I I I I I I I I I I I I I I I I I I I I 1 I 1 I I I I I I I I I I I I I I I I I I I I I I I 1 I I I I I I I I I I I I I n 1 6 I I I I I I I I I I I I I I I I I I I I I I 1 I I I I I I I I I I I I I I I I I I I I I I I I I I I -- JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER '93 READER ENQUIRY SERVICE For further information about any of the products featured in the advertisements in this issue please write the appropriate number in one of the boxes below.Postage paid if posted in the British Isles but overseas readers must affix a stam. r Valid 12 mon rhs PLEASE US€ BLOCK CAPITALS LEAVING A SPACE BETWEEN WORDS 1 NAME I l l 1 1 I I I 1 I I I I I I i 1 1 I 1 1 1 I I I i 1 I u ' -1 1 I l l I l i l l I l l 1 1 I 1 I I H I I 1 I H I l 1 I l [ I I I I I I I ~ I I I I ~ I I i I I I I I I i I ~ I i l i i I 1 H I l I I l l 1 I I I 1 1 1 I 1 1 1 I I I I 1 1 1 1 1 ( ! I 1 I I I I I I I I I I I I I I i I I I i I I I I I I I 1 7 I I I I I I 1 I I I I I 1 I I I I 1-l.I I 1 1 i Ll _ - 1 . 1 i I I i 1 1 I I I I I I I I I I I I i I I I I I I I I I i I I I I ! I TT7 POSITION I l l l l l l l l l l l l l l l l l l l l i l l l i l l i l l - I I I I I I I I I I OFFICE USE ONLY I t [ ( U 11111 PHO( I) 2 COMPANV I r PLEASE GIVE YOUR BUSINESS ADDRESS IF POSSIBLE.IF NOT PLEASE TICK HERE 13 3 STREET 4 TOWN 5 COUNTY r I POST LODE 6 COUNTRY 7 DEPARTMENT DIVISION 8 YOUR JOB TITLE 9 TELEPHONE NO I I I I I I I I I I I I I I I I I I I I I 1 I I I I I I I I I I I I I I I I I I I I I I I I I I I Postage I paid by I Licensee will be ! Do not affix Postage Stamps if posted in Gt. Britain Channel Islands N. Ireland or the Isle of Man BUSINESS REPLY SERVICE Licence No. WD 106 Reader Enquiry Service Journal of Analytical Atomic Spectrometry The Royal Society of Chemistry Burlington House Piccadilly LONDON W1E 6WF England 2A"' ' ' "'"""SSI STANDARD TYPE S.&. J. JUNl 7 Potter Street Hark Circle 001 for further information JAASbase A unique database of atomic spectrometry reference information for the practising analyst JAASbase is a new PC-based product from the The database consists of listings of published Royal Society of Chemistry designed to meet every atomic spectrometry papers and conference atomic spectroscopist's need for a cmprehensive papers and includes tabulated information relating yet inexpensive source of current analytical atomic to the application of relevant techniques. The spectrometry information. It contains over 20,000 references are easily searched with the database regularly updated references compiled from the manager Idealist which also enables the addition of atomic spectrometry literature. personal data to the database. I 1 1 Subscription Details JAASbase 1993 Updates f99.00/$218.00 JAASbase Backfile (1987-1992) &230.00/$506.00 Idealist Software f2 10.OO/$462.00 Six updates will be issued at regular intervals through 1993. Special Introductory Offer Take out a subscription to JAASbase Updates buy the JAASbase Backfile and receive Idealist 1 absolutely free! Offer available only until July 1993. I I I ROYAL CHEMISTRY SOCIETY OF JAASbase is an invaluable tool for all practising analysts - order your copy today! @- To order JAASbase and for further information please contact Sales and Promotion Department Royal Society of Chemistry Thomas Graham House Tel +44 (0)223 420066. Fax +44 (0)223 423623. Telex 818293 ROYAL. Science Park Milton Road Cambridge CB4 4WF United Kingdom. && lnformat ion Services

ISSN:0267-9477    

DOI:10.1039/JA99308BP047

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 53N Conference Reports 5th Surrey Conference on Plasma Source Mass Spectrometry July 4-6 1993 Lumley Castle Hotel Chester-le-Street County Durham UK Lumley Castle Hotel The 5th Surrey Conference on Plasma Source Mass Spectrometry was at- tended this year by over 90 delegates from more than 20 countries. The setting was the resplendent XIV cen- tury Lumley Castle Hotel in County Durham where many of the delegates were accommodated. As its name sug- gests this is a castle purposefully reno- vated for hotel use with many castle features retained such as four-poster beds a dungeon bar and the obligatory resident ghost. Other delegates stayed at one of Trust House Forte’s finest in nearby Chester-le-Street. The opening reception on Sunday evening provided the first opportunity for civilized con- versation over a glass or two of wine courtesy of Fisons Instruments fol- lowed by dinner in the State Room where the evening was to amble its inevitable course away from sobriety.On Monday morning the confer- ence was officially opened by Dr Kym Jarvis (Royal Holloway College UK) with Dr Cameron McLeod (Sheffield Hallam University UK) chairing the first session introducing Dr Sam Houk as the ‘knight in shining armour’ of ICP-MS. Dr Houk (Ames Laboratory 10 USA) described the capabilities of and recent improvements in instru- mentation for ICP-MS. Particular emphasis was placed on a cryogenic desolvation technique that provides a reduction in polyatomic interferences and allows multi-element analysis of relatively volatile solvents such as acetonitrile methanol ethanol and acetone.Cryogenic desolvation is ex- tremely effective for reducing the amount of oxygen introduced into the plasma resulting in almost two orders of magnitude reduction in species such as La0 and polyatomic species of C1. The effectiveness of the procedure was demonstrated with the determination of ultra-trace amounts of As and V in sea-water. The talk was concluded with a description of a new micro- concentric direct insertion nebulizer which removes the need for a conven- tional spray chamber and therefore reduces greatly any memory effects of problem elements such as Fe and Hg. Dr Phil Shaw (Varian UK) then gave a comprehensive talk on the origin and control of continuum back- ground in ICP-MS concluding that over 40% of the background is due to colliding ions and a better vacuum within the instrument would give better detection limits.Mick Ford (Plymouth University UK) described the beneficial effects of adding 0.2-0.5% of ethene into the Ar flow. He presented data showing how a range of polyatomic interferences may be either greatly reduced or completely removed using this approach. Dr Ahmet Ince (Royal Holloway College) was the last to speak before the coffee break and showed how the implemen- tation of a ‘bonnet’ device can stabilize a plasma and reduce ‘white noise’ within the system. Following the break Dr Fadi Abou- Shakra (Surrey University UK) de- scribed a method of reducing mass bias and space-charge effects by vary- ing the potential across the accelerator cone.Isotope ratio determination was the theme of the last two talks of the morning with Dr Nishikawa (Sheffield Hallam University) determining lead isotopes from atmospheric aerosol col- lected in Sheffield city centre and Dr Ros Cox (Harwell Laboratory UK) describing how a high resolution ICP- MS instrument allows the direct mea- surement of Ca isotopes without the need to correct for the associated polyatornic ion interferences. Following a splendid buffet lunch industrial and biological applications were addressed. Dr Andrew Walder (FI Elemental UK) described how replacing a conventional pneumatic nebulization system on a new high resolution multi-collector instrument can significantly reduce sample con- sumption while maintaining high levels of analytical precision simplify sample preparation and extend the range of potential applications.Dr Ingemar Gustavsson (Swedish Insti- tute for Metals Research) then dis- cussed the analytical problems associ- ated with the analysis of steel and metals showing how the use of matrix- matched standards together with one or more internal standards allows the accurate determination of a large num- ber of trace elements in these ma- terials. Dr Paul Paulsen (NIST MD USA) presented data on two new standard reference materials (auto- catalysts) with an emphasis on the financially important precious metals Pt Pd and Rh and the environmen- tally significant Pb. The analytical method used gave precisions of better than 1% RSD and this was compared to the 10% precision of other workers.Dr Beat Wernli (Paul Scherrer Insti- tute Switzerland) gave an informed talk on the importance of understand- ing the behaviour of LiOH in pressur- ized water reactors and the role of ICP- MS in determining the concentrations of Li incorporated in corrosion layers on fuel rods from within these reactors. After the tea break Dr Ian Jarvis (Kingston University UK) described the latest advances in the determina- tion of platinum group metals high- lighting the problems of high total dissolved solids content and suggesting a cation-exchange method for reducing this to allow ICP analysis of the low concentrations found in natural samples. An alternative method of sample introduction involving slurry nebulization was also briefly discussed.The academic session finished with a poster session of 20 presentations on subjects ranging from instrumentation and environmental applications to the analysis of rat tissue. All delegates were balloted for what in their view was the best poster and the prize was duly awarded to Miss Bridget Gibson of the NERC ICP-MS Facility Royal Holloway College for her presentation on matrix effects associated with an enhanced sensitivity interface. (This was slightly embarrassing as she had personally wrapped the award herself earlier that day!) Socially the day was rounded off with the conference din-54N JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Delegates enjo-ving the Conference Dinner in the Barons Hall of Lumley Castle ner.Being a castle this took the form of a candlelit banquet in the Main Hall with excellent food and seemingly end- less supplies of wine and port provided by Perkin-Elmer UK. I believe I would be justified in saying that the event was thoroughly enjoyed by all who at- tended particularly the subsequent trek around the dark passageways try- ing to find the bar! Tuesday morning began bright and early much to the dismay of those who had maybe spent too much of the previous evening quenching their thirst! Dr Joe Brenner (Geological Survey of Israel) chaired the morning session and introduced Dr Conrad Gregoire (Geological Survey of Canada) who described the applica- tion of electrothermal vaporization (ETV) using chemical modifiers as a means of sample introduction.It was demonstrated that adding microgram quantities of sodium chloride im- proved the linearity of the calibration curves and increased the sensitivity of certain elements by as much as an order of magnitude. The steady state and transient background spectra were also discussed with respect to a com- mercially available system. Dr Eva Bertaan (Hungarian Geo- logical Survey) then described a method of analysing a NiS fire assay button by laser ablation ICP-MS suc- cessfully addressing a conference in English for the first time. The proce- dure described allows the rapid deter- mination (30 s) of platinum group elements directly from an NiS bead by avoiding the usual loss of analytes during the dissolution stages. Laser ablation was also the theme of a talk by Dr Simon Chenery [British Geologi- cal Survey (BGS)].He described how a thin section of a rock (30 pm) mounted on a slide can be analysed by ‘tickling’ the sample with a laser at low power. The problem of calibration and valida- tion of the results was discussed with reference to two recent projects under- taken by the BGS. A dual gas flow calibration method was cross-vali- dated by comparison with electron probe microanalysis and bulk data and showed an accuracy of within a factor of two. The following two talks were also concerned with laser abla- tion. Dr Rui Feng (University of Mon- treal Canada) presented data from a study on Pb U and Th and the implications for optimizing trace ana- lysis in zircon. Dr Robert Hutton (F1 Elemental) showed how detection lim- its using small spot sizes can be im- proved by optimizing and improving the spectrometer laser ICP and mode of data acquisition 1,eaving us with the conclusion that ‘it’s not the size that’s important but they way you use it!’ Dr John Watling (Chemistry Centre Western Australia) gave an eye-open- ing talk on the various methods used by criminals to steal and smuggle gold with particular reference to the work his laboratory had undertaken finger- printing gold and other precious metals.Gold samples from the 53 Australian and international mining operations investigated so far all have unique trace-element associations (quantification of elemental compo- sition is unnecessary) and the results of this work have been successfully used by the Australian Police Gold Stealing and Detection Branch as court evidence to prosecute gold thieves and receivers.In the final half hour before lunch Dr Andreas Stroh (Perkin-Elmer Germany) discussed the development of solid and slurry sampling by electrothermal vaporiza- tion with a wide ranging talk covering software optimization of hardware method development and selected ap- plications finishing with the benefits of this approach. After another excellent buffet lunch Dr Cameron McLeod (Sheffield Hal- lam University) talked on the subject of flow injection pointing out that this form of sample introduction is emerging as the preferred method for the analysis of complex matrices. The benefits are numerous improved sensitivity; reduced interferences; im- proved long-term stability; high sample throughput; and cost-effective operation.Micro-column field samp- ling was also discussed. He was fol- lowed by Dr Dadfarnia (Sheffield Hallam University) who gave a well- presented talk concerning on-line trace enrichment and the determination of uranium in waters using flow injection. Dr Conrad Gregoire then kindly filled the only gap in the programme with a presentation on the application of ETV-ICP-MS to the analysis of environmental and geological ma- terials. He reported on the background spectral features ofthis form of analysis and on the impact of carbon-bearing polyatomic ions on the determination of some elements. The ultra-trace ana- lysis of arctic snow was given as an example of the application of ETV- ICP-MS whilst an example of direct analysis of solids was given with data from ovine tissue analysis (including a dubious slide of sheep in ‘a defensive pose’).The final talk of the meeting was presented by Dr Hans Vanhoe (Univer- sity of Ghent Belgium) who discussed the characterization of reference serum by ICP-MS concluding that ICP-MS provides a good alternative to and/or complements other techiques such as in st rumental neutron activation anal y- sis and ETAAS. The meeting was then closed by Dr Sam Houk who thanked the organizing committee from Royal Holloway College University of Lon- don for their hard work and excellent choice of venue. The meeting was undoubtedly a success with a truly international mix of academic and industrial delegates presenting evidence of improved sen- sitivity and precision with an ever expanding element list and even more uses for ICP-MS.Damon Green School of Geological Sciences Kingston University Kingston upon Thames Surrey CIK KTI 2E‘EJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 55N XXVlll Colloquium Spectroscopicurn lnternationale Post Symposium Analytical Applications of Glow Discharges in Optical and Mass Spectrometry July 4-7 1993 University of York UK American Independence Day brought a gathering of different sorts in York England. Delegates of an international origin were invited to exchange ideas about the analytical applications of glow discharge sources (GDS) in opti- cal and mass spectrometry. Thankfully (and surprisingly) we were at least able to offer our foreign colleagues fine weather for the CSI Post-symposium. Those delegates who were lucky enough to have basked in the sun from the previous weeks conference were now only on factor 2 sunblock! Fine weather aside York was a good choice of venue for any who had a few hours to spare and wished to spend it explor- ing a historic city.After the Roman invasion in AD 71 York became the centre from which the North of England was governed for I600 years. It therefore boasts many important archaeological finds-a Viking dig in 1976 on the River Foss uncovered tenth century houses and workshops still containing shoes tools jewellery and cooking utensils. These artifacts had been preserved in a 6 feet layer of water-logged soil. A reconstruction of the Viking street could be seen in the new Coppergate shopping complex.Not to be forgotten of course was York Minster (the largest Gothic Cathedral in Europe north of the Alps built between 1220 and 1480). Return- ing to the job in hand the Post- symposium which was held at York University and organized by Dr E. B. M. Steers (University of North London UK) proved to be a thor- oughly enjoyable affair. The customary format was followed where each day was split into two sessions. A different area of GD work was covered in each session which commenced with a keynote lecture. After a little confusion in the issuing of delegate name tags early Monday morning the post-symposium swung into action. The first session on GD optical emission spectrometry was in- troduced by Ed Steers giving an up-to- date summary of GDS in this field.Presentations were followed by discus- sion which grew more lively as the day wore on. In particular D. G. Jones’ (BHP Steel New South Wales Australia) presentation covering quan- titative depth analysis on non-metallic samples by the combination of d.c. and r.f. sources provoked much dis- cussion particularly among the French representatives. The afternoon lectures finished early and were followed by demon- strations of equipment and software by the attending firms. The well pre- sented demonstrations covered both traditional and novel areas including up and coming r.f. GDS where there is presently much interest in both indus- try and academia. Running parallel with the demonstrations was the poster session. The well attended and disparate posters provoked much in- terest.By the end of the demon- strations and poster presentations it was clear that all were looking forward to the evenings conference dinner; we were not to be let down. The meal took place at the Merchant Adventurer’s Hall in York. The hall was founded in AD 1357 as a religious institution and subsequently became the home of the Merchant Adventurer’s Company. A superb meal was served in the great hall which was thoroughly enjoyed by all including the catering staff. Bon- homie filled the air and wine flowed copiously. The second day began with a quiet breakfast in the college halls of resi- L. to R. W. Schelles University ofAntwerp Belgium; C. Jonkers University of Antwerp Belgium; M. Rummeli University of North London UK; and W. Mecarthy Atomic Weapons Establishment UK who attended the meeting dence apparently the previous night had taken its toll on many.Soon after breakfast it was discovered that the posters were under attack. The univer- sities zest for efficiency led to posters being removed ahead of time (they were to remain up for the remainder of the day). Fortunately this mistake was spotted early and after giving the Post-symposium organizers a brief fright the matter was quickly resolved and the morning session began. Sur- face analysis was the topic and began with Dr. A. Bengtson’s (Institutet for Metallforsking Stockholm Sweden) keynote lecture-his vast knowledge in this area shone through. The after- noon session began with an uninvited interruption by the slide projector which the previous day had developed a taste for slides.Once again it de- Delegates enjqving the Conference Dinner at the Merchant Venturers ’ Arms56N voured a slide and was very reluctant to give up its catch this led to its replacement with a more sociable pro- jector. Despite the interruption Profes- sor K. Marcus (University of Ken- tucky IL USA) gave an enjoyable and ‘athletic’ slide show indicating the acceptance of GDS in mass spectro- scopy as well as the growth of r.f. GDS in this technique. After supper a discussion session on the fundamental processes in GDS JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 took place this began rather slowly but ended with some heated debates. Most delegates then retired to the bar and exchanged addresses on this our last evening together. On the last day the second meeting of the European Working Group on Glow Discharge Spectrometry took place. Round robin tests organized a year previously were discussed and new ones set up. It was decided to expand some GDS topics such as GDS fundamentals within the Working Group. It was also agreed that the next Working Group meeting would take place at one of the next Colloquium Spectroscopicum Internationale sym- posia. In conclusion the Symposium was a great success. Mark Rummeli Universiiy of North London Holloway Road London UK N7 8DB

ISSN:0267-9477    

DOI:10.1039/JA993080053N

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

56N JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Book Reviews ~ Inductively Coupled Plasmas in Ana- lytical Atomic Spectrometry. Edited by Akbar Montaser and D. W. Golightly. Second edition. Pp. xxii + 10 17. VCH 1992. Price DM 296.00 El 11.00. ISBN 28339-0. 1-5608 1-5 14-0 ISBN 3-527- This book is an excellent review of the area of inductively coupled plasmas with a number of the world’s leading researchers contributing a series of chapters in the areas of their own expertise. The book starts with a chapter re- viewing plasmas in general and placing inductive coupling into context with other plasma generation techniques. Further chapters deal specifically with certain areas of ICP. Initially the book deals with atomic emission spectrome- try with a chapter on the background theory of emission and discussion of local thermal equilibrium (LTE) plas- mas.LTE is also discussed in two further chapters considering funda- mental properties such as electron number density and temperature mea- surements and ICP modelling. Chapter three deals with the principles and instrumentation required for the separ- ation and detection of emitted light and to compliment this work chapter six deals with spectral interferences and line selection. The individual instru- mental components required to gener- ate an ICP and to introduce a sample are dealt with in a chapter on radiofre- quency generators torches and sample introduction. Further in depth discus- sion of sample introduction is dealt with in chapters 15 16 and 17 where liquid solid and gaseous introduction are discussed respectively.To empha- sise development work in the area of torch design presented in chapter 4 an entire chapter (chapter 18) is used to discuss the effectiveness of low flow torches. For readers who are not aware of the wide applicability of ICP-AES there is an excellent examination ofthe area of its use in analysis of a variety of different sample matrices. A book on ICP would be incomplete without at least one section on the rapidly expanding area of ICP-MS. Many of the earlier chapters deal with subjects consistent with both ICP-AES and ICP-MS however the editors have fortunately included three chapters specific to ICP-MS. These deal with the fundamentals as well as two infor- mative chapters on applications which include disciission of instru- mentation interferences and semi- quantitative and quantitative analysis.For completeness the book also deals with the ICP as an atomization cell for fluorescence and looks at ICPs in gases other than argon. This book has tried to put together a study of ICPs in all their forms. The amount of literature reviewed is ex- tremely large considering the extensive bibliographies and references in each section. As with all books made up of contributed chapters from different authors there are a number of sections which overlap and organizing such information into separate chapters has proved difficult. In terms of use as a textbook the book contains a great deal of useful information but at El 1 1 I can only see it being available in libraries.Having said this the individual chap- ters have been extremely well written and I would recommend anyone who is interested in finding out all about ICPs to take a serious look at this book. Phil Riby Department of Biological and Chemical Sciences University of Greenwich London UK SE18 6PF Flow Injection Separation and Pre- concentration. Zhaolun Fang. Pp. xiv+ 259. VCH Weinheim ISBN 3-527-28308. VCH New York 1993. Price DM 148.00 E61.00. ISBN 1-5608 1 - 1 47- 1. The book consists of nine chapters divided into basic principles (Chapter 1 ) general instrumentation (Chapter 2) followed by five chapters on chemical aspects of separations liquid-liquid extraction (Chapter 3) sorption (Chapter 4) gas-liquid separ- ation (Chapter 5) dialysis (Chapter 6) and precipitation (Chapter 7). This is succeeded by two chapters on applica- tions one on environmental and agri- cultural (Chapter 8) and one on clini- cal and pharmaceutical (Chapter 9) applications.In the first chapter the author briefly outlines the historical perspectives and basic principles of F1 before concen- trating on and giving a well-described version of the general characteristics and fundamental aspects of FI separa- tion and preconcentration. He outlines some very important and valuable features necessary in designing and optimizing FI separation systems for good performance. Chapter 2 gives a general description of the basic com- ponents including pumps valves manifolds and detectors with valuable information on their proper usage in FI devices. The following five chapters are on various chemical aspects of separa- tions.The third chapter introduces the successive sequences required in FI extraction beautifully illustrating and explaining the different segmentors coils and separators the mechanism of phase transfer and dispersion phase separation modes and coupling of FI liquid-liquid extraction systems to various detectors. FI sorption is very well demonstrated in Chapter 4. This chapter considers characteristic fea- tures to be attended to for the proper design of FI column separation sys- tems classifies FI column techniques looks at dispersion in different parts of an FI system such as sample loading sorption and elution and eluate trans- port and post column reactions. A valuable aspect of this chapter is also the description of different columnJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 57N packings and examples of on-line col- umn separation and preconcentration systems. In Chapter 3 the well-written outlay of the previous chapters is followed with gas-liquid separation systems starting with classification examples of gas-liquid separators out- lining FI separation systems and coup- ling to various detectors and conclud- ing with an important concept of vapour-generat ion. Chapter 7 on dialysis covers features such as funda- mental aspects dialyser designs mem- branes on-line manifolds and coup- ling to various detectors. In the final chapter on chemical aspects of separa- tions (Chapter 7) the classical tedious and time-consuming manual tech- nique of gravimetric determination is brilliantly transformed into on-line precipitation-dissolution FI manipu- lations. Examples of precipitate collec- tors and on-line precipitation-dissolu- tion systems are given.The concepts in the preceding chap- ters are applied in Chapters 8 and 9 in well-illustrated examples in the en- vironmental agricultural clinical and pharmaceutical fields covering the re- cent literature very well. In conclusion this is a generally well-written and informative book. The author is a prominent scientist in this field and the qualities are shown in this book. The book gives workers in FI the opportunity to view relevant and outstanding contributions on a rapidly developing area in a single monograph. I am sure that this parti- cular book will find a place on the book shelves of many workers in FI analysis.J. F. (Koos) van Staden Department of Chemistry University of Pretoria Pretoria 0002 South Africa ~~ Advances in Atomic Spectrometry. Vol- ume 1. Edited by Joseph Sneddon. Pp. xii+238. JAI Press. 1992. Price €53.00. ISBN 1-55938-157-4 This book is a snapshot of five selected areas of atomic spectrometry com- prising five chapters with various ex- perts contributing essays on the state of the art in their respective areas. Chapter 1 is contributed by Kuang- Pang Li and James D. Winefordner and is a tutorial covering Analyte Excitation Mechanisms in the Induc- tively Coupled Plasma (ICP). The ICP is described from the perspective of the spatial distribution of electrons temperature and the analyte and the possible mechanisms for analyte exci- tation are explained.The equilibrium approach is explained with reference to the local thermodynamic equilib- rium (LTE) and partial LTE models Penning ionization charge transfer and recombining plasma models. The kinetic approach is explained in terms of the rate and steady state collisional- radiative and dynamic models. Mathe- matical equations and derivations are kept to an absolute minimum which will appeal to many atomic spectro- scopists especially at the post-graduate level. Chapter 2 authored by Robert B. Green and Michael D. Seltzer covers Laser Induced Ionization Spectro- metry and is a fairly comprehensive review of the field incorporating developments in instrumentation methodology figures of merit and fun- damental studies.It would be of use to new researchers investigating this area for the first time. Chapter 3 by Joseph Sneddon is a summary of Sample Introduction in Atomic Spectrometry covering pneu- matic (including high solids) ultra- sonic and thermospray solution nebu- lizat ion electrothermal vaporization laser ablation hydride generation hol- low cathode and glow discharges chro- matography archpark flow injection and direct sample introduction and is essentially a practical guide to the different alternatives available. Chapter 4 by Gerald Dulude is a tutorial on Background Correction Techniques in AAS including deuter- ium arc Zeeman Smith-Hieftje and wavelength modulation. Chapter 5 contributed by Julian Tyson is a comprehensive overview of the application of Flow Injection Techniques for Atomic Spectrometry which touches upon almost every conceivable application and should provide considerable material for re- searchers new in the field and for old hands looking for fresh ideas.In general because the book covers five very diverse areas of application there is a tendency for it to fall between two stools; i.e. by not being comprehensive enough for the purist while containing too much that is irrelevant to someone looking for a rundown of a particular area. Ad- ditionally because of its multi-author- ship and consequent uneveness in the treatment of subject matter certain chapters will appeal to some readers and not to others. For these reasons it is unlikely to appeal to the individual purchaser though it would be useful as a library reference text for researchers wishing to gain an insight into one of the subject areas described. E. Hywel Evans Department of Environmental Sciences University of Plymouth Drake Circus Plymouth UK PL4 8AA COPIES OF CITED ARTICLES The Royal Society of Chemistry Library can usually supply copies of cited articles. For further details contact The Library Royal Society of Chemistry Burlington House Piccadilly London WlV OBN UK. Tel +44 (0)71-437 8565; fax +44 (0)7 1-287 9798; Telecom Gold 84; BUR2 10; Electronic Mailbox (Internet) LIBRARY@RSC.ORG. If the material is not available from the Society’s Library the staff will be pleased to advise on its availability from other sources. Please note that copies are not available from the RSC at Thomas Graham House Cambridge.

ISSN:0267-9477    

DOI:10.1039/JA993080056N

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

58N JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Diary of Conferences and Courses 1993 Environmental Analysis and Assess- ment. A Series of Nine Short Courses Modules October 1993-March 1994 Details can be found in J. Anal. At. Spectrom. 1993 8 40N. For further information contact Im- perial College Continuing Education Centre Room 558 Sherfield Building South Kensington London UK SW7 2AZ. Telephone 071 225 8667; fax 071 225 8668. 3rd International Conference LASER M2P December 8-10,1993 Lyon France Details can be found in J. Anal. At. Spectrom. 1993 8 12N. For further information contact Centre Jacques Cartier Conference Laser M2P 86 rue Pasteur 69365 Lyon Cedex 07 France. Telephone (33) 78 69 72 21; fax (33) 78 61 07 71. 1994 WCFIA 94 1994 Winter Conference on Flow Injection Analysis January 5-7 1994 San Diego CA USA Details can be found in J.Anal. At. Spectrom. 1993 8 47N. For further information contact WCFIA 94 Gary Christian Depart- ment of Chemistry BG- 10 University of Washington Seattle WA 98195. Telephone (206) 543-1635; fax (206) 685-3478; e-mail christia@ chem.- washington.edu. 1994 Winter Conference on Plasma Spectrochemistry January 10-15 1994 San Diego CA USA Details can be found in J. Anal. At. Spectrom. 1992 7 49N. For further information contact Dr R. M. Barnes 1994 Winter Conference on Plasma Spectrochemistry c/o ICP In formation Newsletter Department of Chemistry GRC Towers Univer- sity of Massachusetts Amherst MA 0 1003-0035 USA. Telephone 4 13 545 2294; fax 4 13 545 4490. Sanibel Conference on Mass Spectro- metry in Polymer and Material Science January 22-25 1994 Sanibel Island FL USA For further information contact Judith A.Sjoberg ASMS 815 Don Gaspar Santa Fe NM 87501 USA. Telephone (505) 989-45 17; fax (505) 989-1073. 45th Pittsburgh Conference and Expo- sition on Analytical Chemistry and Applied Spectroscopy February 28-March 4 Chicago IL USA For further information contact Pittsburgh conference 300 Penn Center Boulevard Suite 332 Pitts- burgh PA 15235-9962 USA. ANATECH 94 4th International Sym- posium on Analytical Techniques for Industrial Process Control April 10-13 1994 Royal Hotel Casino Mandelieu La Napoule France Details can be found in J. Anal. At. Spectrom. 1993 8 48N. For further information contact ANATECH 94 Secretariat Elsevier Advanced Technology Mayfield House 256 Banbury Road Oxford UK OX2 7DH.Telephone +44 (0) 865 512242; fax +44 (0) 865 310981. 24th Annual Symposium on Environ- mental Analytical Chemistry May 16-19 1994 Ottawa Canada For further information contact M. Malaiyandi CAEC Chemistry De- partment Carleton University 1255 Colonel By Drive Ottawa Ontario Canada. International Symposium on Micro- chemical Techniques (ISM '94) May 16-20 Montreux Switzerland The International Symposium on Microchemical Techniques (ISM '94) will have its next meeting in a joint organization with th.e Deanville Con- ference 1994-Symposium on Analyt- ical Sciences (SAS '94) in Montreux Switzerland from May 16-20 1994. For further information contact Nicko & C.R.I. Associes 7 Rue d'Argout F-75002 Paris France.Telephone + 33- 1-42 334766; fax +33-1-40 41 92 41. ASMS Short Courses on Mass Spec- trometry May 22-29 1994 Hyatt Regency Hotel Chicago IL USA Introduction to Interpretation of Mass Spectra Advanced Interpretation of Mass Spectra LC-MS The Art and the Practice GC-MS for Environmental Analysis Practical MS-MS Analysis 42nd ASMS Conference on Mass Spectrometry and Allied Topics May 29-June 3 1994 Hyatt Regency Hotel Chicago IL USA For further information contact Judith A. Sjoberg ASMS 815 Don Gaspar Santa Fe NM 87501 USA. Telephone (505) 989-45 17; fax (505) 989- 1073. Scandinavian Symposium on Infrared and Raman Spectroscopy SSIR-94 May 30-June 1 1994 Department of Chemistry University of Bergen N-5007 Bergen Norway Details can be found in J. Anal.At. Spectrom. 1993 8 48N. For further information contact Dr. Alfred A. Christy Department of Chemistry University of Bergen. Tele- phone +47 5-2 13363 (after 09.09.93) +47-55-213363); fax +47-5-329058 (after 09.09.93) +47-55-329058). Laila Kyrkjebo Department of Chemistry University of Bergen telephone +47-5-2 13342 (after 09.09.93 +47-55-2 13342).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 59N Biosensors '94 The Third World Con- gress on Biosensors June 1-3 New Orleans LA USA Details can be found in J. Anal. At. Spectrom. 1993 8 42N. For further information contact Kay Russell Conference Department Elsevier Advanced Technology May- field House 256 Banbury Road Oxford UK OX2 7DH. Telephone +44 (0) 865 512242; fax +44 (0) 865 310981.6th International Conference on Flow Analysis June 8-11 Toledo Spain Details can be found in J. Anal. At. Spectrom. 1993 8 42N. For further information contact M. Valcarcel/M. D. Luque de Castro Flow Analysis VI Departamento de Quimica Analitica Facultad de Cien- cias E- 14004 Cordoba Spain. Tele- phone 34 57 218616; fax 34 57 2 18606. 7th International Symposium on Reso- nance Ionization Spectroscopy and Its Applications (RIS-94) Bernkastel-Kues Germany The Seventh International Symposium on Resonance Ionization Spectroscopy and Its Applications (RIS-94) is organ- ized by the International Advisory Committee and the Local Organising Committee from the University of Mainz and the GSI Darmstadt. The meeting will be held in a modern con- ference hotel complex (Hotel Mosel- park) in the medieval Moselle wine village of Bernkastel-Kues Germany from July 3-8 1994.On July 3 a one- day introductory course on RIS physics is planned for students in particular. The conference site is easily reached by rail road and by air via Frankfurt Luxembourg or Cologne airports. Symposium topics will include the theory of light matter interaction; pic0 and femtosecond spectroscopy; atomic ionization spectroscopy; molecular ionization spectroscopy; analytical and environmental applications; ultra-sen- sitive methods; nuclear applications; surface and bulk analysis; chemical applications; biological and medical applications; atomic molecular and ion sources; laser sources; and new techniques and exotic applications. For further information contact RIS-94 R.Chitty Institut fur Physik July 3-8 1994 Universitat Mainz Postfach 39 80 D-5 5092 Mainz Germany telephone 0049-6 13 1-393628; fax 0049-6 13 1- 393428; telex 418-7155 phmz d; email RIS94@VIPMZA.PHYSIK. UNI-MAINZ.DE. Spectroscopy Across the Spectrum IV Techniques and Applications of Analyt- ical Spectroscopy University of East Anglia Norwich UK Spectroscopy Across the Spectrum (SAS) is organized by the Royal So- ciety of Chemistry Analytical Division into three parts plenary sessions poster sessions and workshops. There will be an equipment exhibition and a social programme. July 11-14,1994 Venue The conference will be held on the campus of the University of East Anglia close to the historic city of Norwich and the Norfolk Broads. En suite accommodation will be available in new buildings designed to meet modern conference standards.Posters There will be a generous allocation of time to poster sessions covering all areas. Submission of a title and ab- stract should be made to the confer- ence secretary by March 3 1 1994. Workshops Any company group or person may submit a proposal to organize a work- shop which will be held in the late afternoon. For further information contact Dr. D. L. Andrews School of Chemical Sciences University of East Anglia Norwich UK NR47TJ. Fax 0603 25936. Seventh Biennial National Atomic Spectroscopy Symposium July 20-22 1994 University of Hull Hull UK Details can be found in J. Anal. At. Spectrom. 1992 7 49N. For further information contact Dr Steve Hill Department of Environ- mental Sciences University of Plymouth Drake Circus Plymouth Devon UK PL4 8AA.13th International Mass Spectrometry Conference August 29-September 2 Budapest Hungary For further information contact Hun- garian Chemical Society; FO u. 68 H- 1027 Budapest Hungary. Telephone 361 201 6883 fax 316 15 61215. EUCMOS XXII XXII European Con- gress on Molecular Spectroscopy September 11-16 1994 Essen Germany Details can be found in J. Anal. At. Spectrom. 1993 8 49N. For further details contact Gesell- schaft Deutscher Chemiker Abt. Tagungen P.O. Box 90 04 40 W-6000 Frankfurt 90 Germany. Telephone f 4 9 697917-366; fax 3-49 69 7917- 475; telex 4 170 497 gdch d. Geoanalysis 94 An International Sym- posium on the Analysis of Geological and Environmental Materials September 18-22,1994 Charlotte Mason Conference Centre A m bleside UK.Details can be found in J. Anal. At. Spectrom. 1993 8 49N. For further information contact Mr. D. L. Miles Analytical Geochemistry Group British Geological Survey Kingsley Dunham Centre Keyworth UK NG12 5GG. Telephone 0602 363100; fax 0602 363200. 7th International Symposium on Envi- ronmental Radiochemical Analysis September 2 1-23 Bournemouth UK Dates to Note Synopses of papers January 28 1994. Final date for registration July 15 1994. For further details contact Dr P. Warwick Department of Chemistry Loughborough University of Tech- nology Lough borough Leicest ers hi re UK LEll 3TU. Telephone 0509 222585 or 0509 222545; fax 0509 233 163. 6th International Colloquium on Solid Sampling With Atomic Spectroscopy October 11-13 1994 A msterdam The Net herlands This colloquium organized with the support of the Institute for Reference Material and Measurements Geel consists of papers and posters with discussion time for topics of particular importance covering AAS ICP-MS,60N JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 GDMS etc. With solid sampling; methodology and procedures; metal speciation; biological and medical applications; food applications; en- vironmental applications; product and quality control; and preparation and use of certified reference materials. For further information contact Dr. R. F. M. Herber Coronel Laboratory University of Amsterdam Meiberg- dreef 15 NL-1105 AZ Amsterdam The Netherlands. Analytica '94-Second National Sym- posium on Analytical Science December 1994 Western Cape South Africa The theme of Analytica '94 will be 'Toward the Welfare of Man and his Environment' and is organized by the Analytical Division of the South Afri- can Chemical Institute along with the SA Spectroscopic Society.Scientific sessions will be scheduled in the mornings and early evenings allow- ing afternoons free for technical visits and/or scenic tours. For further information contact Dr. I. M. Moodie c/o PO Box 1970 Tygerberg 7505 South Africa. Fax 02 1-932-4575. 1995 Colloquium Spectroscopicum Interna- tionale (CSI) XXIX August 27-September 1 1995 Leipzig Germany Details can be found in J. Anal. A t . Spectrom. 1993 8 50N. For further details contact Prof. Dr. K. Dittrich Universitat Leipzig FB Chemie FG Atomspektroskopie Lin- nestr.3 D-04 103 Leipzig Germany. Telephone and fax (49)-341-6858377. UFZ-Centre for Environmental Re- search Department of Analytical Chemistry Permoserstr. 15 D-043 18 Leipzig Germany. Telephone (49)- 341-235-2370; fax -2625.

ISSN:0267-9477    

DOI:10.1039/JA993080058N

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

60N JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Future Issues will Include Use of Palladium as a Chemical Modi- fier for the Determination of Silicon by Electrothermal Atomic Absorption Spectrometry-Zhi-xia Zhuang Peng- yuan Yang Xiaru Wang Zhiwei Deng and Benli Huang Determination of Palladium ad Plati- num in Freshwaters by Inductively Coupled Plasma Mass Spectrometry and Activated Charcoal Preconcentra- tion-Gwendy E. M. Hall and J. C. Pelchat Improvement in Mercury Cold Va- pour Atomic Techniques by Resorting to Organized Assemblies and On-line Membrane Drying of Vapour-B. Aizpun Fernandez M. R. Fernandez de la Campa and Alfredo Sanz-Medel Indirect Atomic Absorption Spectro- metric Determination of Papaverine Strychnine and Cocaine by Continu- ous Precipitation With Dragendorff's Reagent-Marcelina Eisman Mer- cedes Gallego and Miguel Valcarcel Determination of Ultratrace Levels of Heavy Metals in Polar Snow by Elec- trothermal Vaporization Inductively Coupled Plasma Mass Spectro- metry-Ralph E.Sturgeon S. N. Willie and D. Conrad Gregoire Speciation of Arsenic by Ion Chro- matography and Off-line Hydride Generation Electrothermal Atomic Absorption Spect romet ry-Heng-bin Han Yan-bing Liu Zhe-ming Ni and Shi-fen Mai Arsenic Speciation in Seafood Samples with Emphasis on Minor Constituents. An Investigation by High-performance Liquid Chromatography With Induc- tively Coupled Plasma Mass Spectro- metric Detection-Gunnar Pritzl and Steen H. Hansen Effect of Aqeuous-Organic Solvents on the Determination of Trace Elements by Atomic Absorption Spectrometry and Inductively Coupled Plasma Atomic Emission Spectrometry-M. Todorovic S. Vidovic and Z. Ilic Electrothermal Vaporization for Sample Introduction in Microwave- induced Plasma Atomic Absorption Spectrometry-Yi-xiang Duan Xing- you Li and Qin-han Jin Improvement in Detection Limits in Graphite Furnace Diode Laser Atomic Absorption Spectrometry by a Wave- length Modulation Technique-Chris- toph Schnurer-Patschan Aleksandr Zy- bin Henning Groll and Kay Niemax Determination of Selenium in Marine Certified Reference Materials by Hy- dride Generation Inductively Coupled Plasma Mass Spectrometry-Hiroaki Tao Joseph W. Lam J. W. McLaren Atomic Spectrometry Update The Update in the December issue is-Industrial Analysis Metals Chemicals and Advanced Materials- John Marshall John Carroll James S. Crighton and Charles L. R. Barnard

ISSN:0267-9477    

DOI:10.1039/JA993080060N

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 261R ATOMIC SPECTROMETRY UPDATE-ATOMIC MASS SPECTROMETRY AND X-RAY FLUORESCENCE SPECTROMETRY Jeffrey R. Bacon The Macaulay Land Use Research Institute Craigiebuckler Aberdeen UK AB9 2QJ Andrew T. Ellis* Oxford Instruments Industrial Analysis Group 19-20 Nuffield Way Abingdon Oxfordshire UK OX14 1 TX Adam W. McMahon Department of Chemistry Manchester Metropolitan University John Dalton Building Chester Street Manchester UK M I 5GD Philip J. Potts Department of Earth Science Walton Hall The Open University Milton Keynes Buckinghamshire UK MK7 6AA John G. Williams NERC ICP-MS Facility Royal Holloway and Bedford New College Department of Geology Egham Hill Egham Surrey UK TW20 OEX Summary of Contents 1. Atomic Mass Spectrometry 1.1.1.2. 1.3. 1.4. 1.5. 1.6. 1.7. 1.0. 1.9. Introduction Accelerator Mass Spectrometry (AMS) Glow Discharge Mass Spectrometry (GDMS) Inductively Coupled Plasma Mass Spectrometry (ICP-MS) 1.4.1. Reviews 1.4.2. Fundamental studies 1.4.2.1. Operating parameters and instrument development 1.4.2.2. Sample introduction 1.4.2.3. Interference effects 1.4.3.1. Geochemical 1.4.3.2. Environmental 1.4.3.3. Biological 1.4.3.4. Industrial 1.4.3. Applications Laser Ionization Mass Spectrometry (LIMS) Resonance Ionization Mass Spectrometry (RIMS) Secondary Ion Mass Spectrometry (SIMS) Spark Source Mass Spectrometry (SSMS) Sputtered Neutral Mass Spectrometry (SNMS) 1.1 0. Stable Isotope Ratio Mass Spectrometry (SIRMS) 1.1 1. Thermal Ionization Mass Spectrometry (TIMS) 1.12.Other Methods 2. X-ray Fluorescence Spectrometry 2.1. Reviews 2.2. Instrumentation 2.2.1. SRXRF microprobes and X-ray microfluorescence (XRMF) 2.2.2. Excitation 2.2.3. Detectors 2.3. Total Reflection X-ray Fluorescence (TXRF) 2.3.1. Chemical analysis 2.3.2. Surface analysis and depth profiling 2.4. Synchrotron Radiation X-ray Fluorescence (SRXRF) 2.5. Calibration and Data Processing 2.5.1. Fundamental parameter (FP) calculations 2.5.2. Matrix correction using scattered radiation 2.6. Applications 2.6.1. Specimen preparation 2.6.2. Chemical analysis 2.6.3. Thin films 2.6.4. Geological 2.6.5. Environmental 2.6.6. Archaeology and forensic 2.6.7. Industrial *Review Co-ordinator to whom correspondence should be addressed.26213 JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 2.6.8. Clinical and biological 2.6.9. Chemical effects ~ ~~ Strong development continues in most areas of atomic mass spectrometry. There is an ever increasing pressure to push back limits with the result that reported performances in terms of absolute detection limits sample requirement and isotopic abundance sensitivities are reaching levels that could only have been dreamed of a few years ago. This can have the drawback of extremely complex and expensive instrumentation which is only available to a few laboratories. There is an increasing tendency to decouple sample atomization and ionization with the result that various combinations are possible and the traditional definitions become less applicable. This is particularly true for techniques employing one or more lasers.It is however pleasing to report that attempts are being made to make instrumentation simpler and more practical for routine analyses. The combination of chromatography with atomic MS has received increasing attention with particular potential for metal speciation studies. Amongst the vast range of applications of atomic MS the detection of low levels of contaminants in environmental samples and high-purity materials continues to be of prime importance. The past year has seen a continuing high level of publication in the XRF field once more indicating the rude health of this long-established multi-element instrumental analytical technique. Of particular note is the great interest in total reflection XRF (TXRF) and its rapid acceptance in the semiconductor industry for its ability to determine extremely low levels of surface contamination on wafers and also to carry out depth profiling on the same devices.One particular benefit of the technique when used in the semiconductor industry is that it is non-destructive-a clear benefit in reducing costs yet maintaining high product quality. In addition to TXRF the topics of XRMF and SRXRF are given increased prominence in this Update in line with the level of interest evident from the literature during the review period. 1. ATOMIC MASS SPECTROMETRY 1.1. Introduction This year’s Update follows the format established in previous years with the exception that treatment has been rationalized for methods in which laser radiation is used to simultaneously atomize and ionize samples.Both bulk and microprobe analysis have been brought together under the heading Laser Ionization Mass Spectrometry. This does not include those methods in which laser ionization is used to ionize previously-atomized material-readers are referred to the sections on RIMS and SNMS for these techniques. This review article does not set out to be comprehensive in its coverage but is based on critical selection of develop- ments in instrumentation and methodology notable for their innovation originality or achievement of significant advances. The review of Koppenaal (9312158) is rec- ommended for a comprehensive coverage of developments in atomic MS over a two year period. Conference papers have only been considered for inclusion when they have been judged to include enough detail and information to give evidence that they meet the criteria. Routine applica- tions of atomic MS are not generally included in the Update and readers are referred to the Updates on Industrial Analysis Metals Chemicals and Advanced Materials (92/2626) Environmental Analysis (9213828) and Clinical and biological materials Foods and Beverages (9214562).The large number of papers in the current review year gives further evidence for the very healthy activity in most of the techniques covered. Most atomic MS techniques continue to receive close attention and advances have been considerable. There is an ever-growing requirement for all types of analysis (bulk microprobe isotope) in a wider range of matrices.The need to press limits (detection resolution spatial or depth resolution precision and accu- racy) continues to grow and advances are still being made in all these areas. It is notable that every year more MS techniques associated mainly with organic analysis are evaluated for application to atomic analysis. The versatility of MS in general is apparent and it is clear that many analyses can be performed through the use of one of a number of different MS techniques. 1.2. Accelerator Mass Spectrometry (AMS) The large number of reports in the current review year is evidence of the considerable activity in the development of AMS instrumentation and procedures. Readers are referred to a review with 59 refs. (9312517) for recent technical developments and trends.A notably comprehensive review with 78 refs. (9312442) covered the techniques of radionu- clide dating and trace element analysis for numerous areas of study and included a discussion of the design of the stable element AMS facility at the University of North Texas. Other reviews covered a number of new applica- tions such as biomedical clinical and geochemical studies and industrial applications (93/2557) and the use of AMS for radioisotope tracing in biomolecular studies (93/2662). The diverse nature of 36Cl studies and some of the difficulties encountered in application of ultra-sensitive measurements to environmental problems have been illus- trated (93/2560) by colloborative studies involving the authors’ own laboratories. Descriptions of new instruments have been more limited in number this year but it is clear that such developments continue in various establishments throughout the world.A new tandem accelerator system built at the AMS facility of Beijing University and some of its proposed applications have been described (9312665). The multi-functional data acquisition system for the Beijing instrument was designed for low cost and high reliability (93/2657). A description of the facility and a progress report have been presented (93/2541) for the commissioning of the Fragment Mass Analyser (FMA) currently being brought into operation at the Argonne Tandem Linear Accelerator System (ATLAS). The FMA is a recoil MS 8 m in length which will be used to separate nuclear reaction products from the primary beam and disperse them at the focal plane according to the mlz ratio.A wider range of nuclear studies was proposed. The design of a recoil MS at the Idaho National Engineering Laboratory has been described (9311138) and the proposed application to otherwise inaccessible exotic nuclei dis- cussed. The interest in new high-intensity Cs sputter-ion sources is emphasized by the appearance of descriptions of three new designs (9312637 9312638 9312639) in the same issue of one journal. In some respects the three designs are remarkably similar. They all have a multi-target sample magazine in a separate vacuum chamber isolated from the source chamber in order to facilitate changing of samples without interruption of operation and to minimize sample cross-contamination. Spherical ionizers were incorporated to achieve large negative ion currents and a small beam emittance.The geometry of the ionizer target region and electrostatic lenses of the ErlangenJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 263R instrument (93/2637) were optimized by extensive ion optical computer simulations. A specially designed shield in the Shanghai instrument (9312638) protected the metal-ceramic bonded ring which supported all parts at sputter potential from vapour depositions and possible breakdown of insulation. Beams of 10 pA BeO- 5 pA Al- 4.5 pA Fe- and 350 pA C- have been delivered. Difficulties addressed in the design of the Zurich instru- ment (9312639) included the high electric fields inside the vacuum chamber in an environment of high Cs vapour pressure large temperature gradients and reliability in the operation of all mechanical components.Developments at the CERN-ISOLDE facility included (9312546) a new control system based on personal com- puters with Intel 80386 microprocessors running under MS-DOS and Microsoft Windows. Network-wide distri- buted front-end computers which accessed the hardware for control and measurement were operated through PC consoles via a local area network with a PC file server used as a database. Variable magnetic or electric multipoles have been built into the ISOLDE-3 on-line mass separator (9312542). A resolving power of m1Am > 10000 allowed the isobaric separation of 37Ca from 37K using a tungsten surface ionization source. The molecular ion stability and population in tandem AMS was predicted initially by theoretical calculations and then measured experimentally (93125 1 8).The relative abun- dance dissociation cross-section in the stripper gas and the charge fraction branching ratios for the atomic fragments of B2 were reported in order to assess background levels likely to be encountered in AMS studies.A system has been set up (93/2536) for the detection of radionuclides. Ions were separated according to their nuclear charge by deflection in a gas-filled Q3D magnetic spectrograph with high dispersion. The resolution relative to the displacement of peaks of different isobars measured for the three isotopes studied (41Ca 59Ni and 90Sr) corre- sponded to Az of < l o Concentrations could be measured with sensitivities of 41Ca:40Ca < 2 x 10-l2 59Ni:58Ni 2 x 10-l' and 90Sr:88Sr 3 2~ lo-".Activities of t l Bq kg-l for 90Sr in the biosphere could be detected within a few hours of extraction. The masses of the short-lived nuclides 91Rb-97Rb have been measured (93/2543) precisely using a prism MS (resolution 3 x lo4) installed on-line with a mass separator and synchrocyclotron. Samples containing the stable refer- ence isotopes 95997M~ 93Nb or 91992994996Zr were introduced into the ionizer of the prism MS for calibration of the mass scale by simultaneous ionization with the Rb isotopes coming from the mass separator. Simultaneous measurement of two isotopes has been achieved (9312482) on the University of Tokyo tandem facility. Using a unique technique called the internal beam monitor method the isotope ratios 26Al:27Al and loBe:9Be were determined without accelerating each isotope sequen- tially.Negative ions of 26A1 and loBel6O were injected into the accelerator along with pilot beams of 9Be170- and 11Be160- respectively and converted into positive ions by passing the-accelerated ions through a thin Ar gas in the stripping canal at the high voltage terminal of the accelera- tor. The triply-charged ions 26A13+ and loge3+ were counted by a heavy ion detector while the pilot beam ions 9Be3+ and I6O2+ were monitored simultaneously with Faraday cups at the focal plane of the magnetic analyser. Sensitivities of 1 x and 5 x 10-14 were achieved for 26A1 and IOBe respectively. The most widely reported application of AMS continues to be to radiocarbon dating. New design ideas have been presented (93/2656) for a minicyclotron as a supersensitive MS for 14C dating.High count rates for Li ions in the measurement of 14C were traced (93126 17) to the Li content in the quartz tubes used in the graphitization of the samples and were almost completely eliminated through the use of borosilicate glass reaction tubes at lower reaction tempera- tures. The commonly-used acid1base-acid extraction tech- nique for the removal of contaminants before the 14C dating of soils was found (9312619) not to give acceptable results. Satisfactory alternative procedures involved sample pre- treatment with hot 70% HN03 solution or by a treatment sequence involving chlorate oxidation. Difficulties in the removal of organic carbon as a contaminant (especially as humic materials) were discussed.Some novel applications of 14C determination have been reported. The emission of 14C in the ventilation air from a nuclear power plant in Sweden was measured (9312535) by AMS of 0.050 m3 samples. On-line sampling by Q-spectro- metry would require samples of several m3 volume and would present difficulty in that other sources of activity are present in the air. The concentration of I4CO2 in clean air from the Southern Hemisphere was found (9312648) to be 40% lower than that in air from comparable latitudes in the Northern Hemisphere. The large differences were consi- dered surprising and were found to contradict predictions using photochemical models. The AMS method was included in a review of accelerator methods for the determination of Be (931253 1).A method for the preparation of Be0 targets (9312257) used laO- enriched water as an alternative to the expensive I7O- enriched water. Beryllium was extracted from the sample as Be(OH) using EDTA and various ions were precipitated sequentially at different pH values. The natural I60 in Be(OH)2 was replaced by l 8 0 by exchange and the Be(Ia0H) converted into Be180 at high temperature in vacuum. The exchange efficiency was 49.6%. Calibration on the Daresbury tandem Van de Graaff accelerator was linear over at least five orders of magnitude for the determination of 26AE used in human absorption experiments (9312537). The 26A1 detection limit was h~ 3.8 x g and the limiting 26Al:27Al ratio x 7.4 x 10-14.The potential for the systematic determination of 1291 in the hydrosphere using AMS has been explored (9214718). Pre- and post-bomb samples of marine organisms such as algae sponges and some forms of coral have been analysed. Precious metals in polished mineral samples have been determined in situ with nominal detection limits in the range of 0.1 (Au) to (600 (0s) ng g-l (9213860). Samples were analysed in the form of small polished cores derived from sulfide- and oxide-rich rocks and from Ni-S- domi- nated fire assay beads. The Cs probing beam (500 pm diameter) averaged out inhomogeneities but still had the spatial resolution to provide grain-by-grain analysis of coarse ore samples. Interest in the application of AMS to materials analysis continues. The use of a superconducting AMS minicyclo- tron for ion microbeam analysis (9312530) has been described with consideration of the design criteria and with particular reference to the determination of Be and C.The capabilities of the elastic recoil detection analyser (ERDA) method for depth profiling have been investi- gated (9312534) using high energy (260-420 MeV) very- heavy-ion (1271 and 129Xe) beams with energies close to the Coulomb barrier. The high velocities even of heavy recoil ions allowed their detection with unambiguous mass and adequate energy resolution for depth profiling up to depths of for example 3-4 pm in Si and 2 pm in GaAs. The concentration profiles of all target elements could be measured simultaneously because their isotopic masses were separated up to the Ga-As mass range at least.The group in Munich continues to test the Pauli exclu- sion principle for nucleons and atomic eiectrons (931 122 1 9312608). Searches were made for non-Paulian atoms and264R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 nuclei and the limits of for example 36Ar 5He 5Li and ,ONe presented. In addition the feasibility of radio- chemical /3/3 decay experiments with AMS were discussed (9311221). 1.3. Glow Discharge Mass Spectrometry (GDMS) Although not specifically on GDMS the review by Harrison (92/4598) gives an excellent description of the GD and its advantages and limitations as an analytical source. Investi- gations into instrumental developments continue to be numerous but many reports are still in the form of conference abstracts which can range from totally inade- quate in the detail presented to highly informative.Regret- tably most tend to be inadequate for assessment of their content. Assessment of the quadrupole-based instrument contin- ues. Accuracy and precision in the direct analysis of high- purity copper metal in the form of bars and pins were comparable to those for traditional archpark optical emis- sion spectrometric techniques but detection limits (sub- pg g-!) were superior (93/1006). A comparison of the analytical performance of the quadrupole-based system with the commercial magnetic sector instrument was based (93/2063) on polyatomic-ion abundances the stability of relative sensitivity factors (RSFs) and analytical results for several matrices. The fast scanning and low resolution properties of the quadrupole analyser offer advantages for applications to depth profling.The combination of variable sputter rate (0.1 to > 1 pm min-l) with fast scanning enabled (93/C341) quantitative surface analysis on a wide range of layer thicknesses including galvanized steel ( 1-30 pm) and multi- layer metal structures (< 1 mm). A depth resolution of 10 nm could be achieved (93/2064) for Cr-Ni multilayers using a low resolution instrument fitted with a Grimm-type obstructed discharge. Flat crater profiles were obtained by maintaining a material-dependent critical burning voltage. With a penetration rate of up to 0.1 prn s-l the technique is particularly suited for the analytical characterization of surface layers with a thickness in the pm range.A direct insertion probe has been designed (93/1020) explicitly for r.f. GDMS applications. The device was inserted through a type of ball valve assembly which acted as vacuum interlock so that sample change was accom- plished without breaking the source vacuum. Small sample sizes (t0.5 cm) could be analysed. Spatial variations of the various populations of ionic species were observed indicat- ing the need for careful positioning of the discharge in relation to the sampling orifice. A new discharge cell has been developed (93/2101 93/2226) that can accommodate frat samples such as silicon wafers which tend to be insulating at the cryo- temperatures associated with pin analysis. Instrument sensitivity was improved by varying plasma conditions to maximize silicon ion yields but reduce mass spectral interference from molecular species and contaminants.Detection limits of sub-ng g-l were attainable for most elements and an ultimate limit of detection of a few pg g-I was forecast. The properties of alternative discharge gases in particu- lar of mixtures of gases in Ar have been investigated. The after-peak observed in pulsed GDMS was found (93/C1502) to decrease in size when a gas mixture was used instead of a pure gas. After-peaks were formed or elimi- nated for certain species depending on the discharge gas and its concentration. In addition metal-gas dimer species were observed to form in the gas mixtures. The use of Ar-H discharge gas with 0.1-0.5% H2 resulted (93/2220) in ion intensity signals 1.5-15 times those obtained in Ar alone.This was attributed to an increase in the abundance of metastable Ar atoms. An increase of H2 content to 1% resulted in a significant decrease in ion intensity for Nb S Ti and Zr most probably due to reaction with H,. The method was proposed for the detection of ultra-trace elements (< 1 ng g- I ) in solid samples. The use of cryocooling resulted (93/C394) in the quick removal of gaseous contaminants from the discharge by the physical removal of water vapour. The use of getter reagents however yielded a higher ultimate M+:MO+ ratio in the analysis of metal oxides. The two methods were considered to be complementary rather than competitive. The processes involved were being investigated by intro- duction of water vapour or chemical reagents into the discharge.Although GDMS is considered to be generally free of matrix effects the relative ion yields were found to be over ten times higher for some elements than for others. Relative ion yields calculated theoretically using the electron affin- ity and first ionization potential of the elements plus two unknown parameters a temperature parameter and a chemical potential parameter could be made to match experimental values if a temperature of 16000 K was used. It should be noted that this approach closely mirrors that followed for SSMS two decades or more ago. For a given matrix relative sensitivities were found (93/C 1442) to correlate closely with applied power which leads to the possibility of predicting changes in relative sensitivities by measurement of Ar excitation and ionization temperatures.Isobaric polyatomic interferences from metal-dimer and metal argide ions have been demonstrated (93/C1445) by the use of tandem MS. The interferences could be removed by collision-induced dissociation. Although of value in a research context such sophisticated instrumentation is likely to remain out of reach of most users. The metal argide contribution to the discharge was predictable (93/C 1444) and correlated with discharge parameters operating pres- sure and power. This should permit reduction of interfering species through the judicious modulation of the GD plasma. Spectral interferences for Ti due to doubly-charged ionic species of matrix-argide or Mo were observed (93/1651) in the analysis of a Cr-Mo-steel sample. New values of RSFs were determined from calibration graphs based on NIST SRMs. Water vapour in the source exhibited a variety of reactions (93/C 1472) most of which were detrimental to analysis.The water vapour depopulated the metastable Ar atoms by an eficient transfer of energy from the metastable species to the water molecule. This affected greatly the ionization of sputtered species. At a water vapour content in the ion source as low as 2.5% the spectrum was dominated by ions at mlz 18 and 19 (H20+ and H,O+). A new sample preparation protocol for the analysis of high-purity titanium involved (93/2065) machining of the material using an A1203 cut-off wheel followed by a double etching process with a H2O2-based acid etchant.This method reduced the time of conventional preparation (machining into a pin using a diamond cut-off wheel surface cleaning using ultra-grade acid mixture and pre- sputtering) from 3 h to 20 min and pre-sputtering time from 1 h to 20 min. Trace amounts ((20 pug g- I ) of C N and 0 in high-purity steels could be determined (93/240 1 ) if certain procedures were followed. The background was improved by cooling the GD cell and the ion chamber was evacuated for 20 min after sample introduction to improve the determination of N. Surface contaminants a major source of interference in the determination of C were removed by pre-sputtering. The determination of 0 was improved by purification of Ar with a ZrO catalyst. Following these procedures trace amounts of t 2 0 pg g-l could be determined.Nigh temperature superconductors for exampleJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 265R YBa2Cu30x have been analysed (93/2360) using pins maintained at liquid nitrogen temperature by cell cryocool- ing. The claimed independence from matrix effects would mean that the lack of suitable standard samples is not a limitation. Three alternative sample introduction techniques have been investigated for the analysis of solutions (93/C393). In the first a coiled tungsten filament mounted on a probe allowed application of both current to dry and vaporize the sample and voltage to produce a negative glow around the coil. In the second introduction technique a filament probe was placed in the ion source perpendicular to a typical GD thus allowing separation of atomization and ionization.The third method employed a pulsed solenoid injection valve to allow direct introduction of the solution during short open times (as little as 200 p). 1.4. Inductively Coupled Plasma Mass Spectrometry 1.4.1. Reviews If the maturity of an analytical technique is to be judged by the number of reviews it receives then ICP-MS is rapidly settling into middle-age. A special issue of Atomic Spectros- copy included both a 27 reference review of current trends (93/1074) and a discussion of the future of the technique (93/457) which considered amongst others mixed-gas plasmas desolution (sic) techniques and software develop- ments. Both Lust (93/2205) and McLaren (93/2262) pre- sented bibliographies in later issues of the same journal.The former contained 400 citations and the latter 152 refs. on the applications organized into the four main subject areas of geological environmental clinical and health and industrial and miscellaneous. Horlick (93/2485) reviewed (68 refs.) current trends and developments Beauchemin (92/4528) with 30 refs. highlighted the possi- bilities for 'a multi-elemental analysis technique with almost unlimited potential' and Hieftje (93/2039) assessed the present state of the technique and suggested where attention should be directed to reduce the shortcomings (interferences suppression etc.). Baumann (9312096) presented a 52 reference review of solid sample introduction including ETV LA direct sam- ple insertion arc nebulization and slurry nebulization.Jarvis (92/3448) examined the role of slurry nebulization for the analysis of geological samples for both ICP-MS and ICP-AES. Hall (93/1925) Jarvis and Jarvis (9213845) and Perkins (93/998) all assessed the impact of ICP-MS on the earth sciences in particular the ability to determine precious metals REE and refractory elements such as Hf Ta and W at geologically natural levels. Approaches to preconcentration and separation based upon solvent extrac- tion ion exchange and chelation with immobilized func- tional groups were discussed by the Amherst group (92/47 15) in a 2 15 reference review. (ICP-MS) 1.4.2. Fundamental Studies 1.4.2.1. Operating parameters and instrument develop- ment. A 23 mm plasma torch was evaluated for use in ICP- MS (93/2124). The optimum plasma conditions were 1.5 kW forward power and 19.2 1 min-' total Ar flow.Compared with an 18 mm MAK torch detection limits were better for high mass but similar for low mass ions. Oxide ion ratios were lower in the larger torch but doubly charged ion ratios ArO+ and ArN+ interferences were higher. Gray (93/2093) used a flared torch extension to stabilize the ICP. An audiofrequency peak in noise power spectra of signals from emission and mass spectrometers has been associated with instability at the boundary of the plasma plume where it enters the surrounding atmosphere at the mouth of the torch The flared extension provided the necessary separation of the plasma and surrounding atmos- phere. Evidence of the improvement was provided in the form of colour photographs of the plasma interface.Using a custom-assembled instrument Ross et al. (9214704) compared a conventional inverted coil with a centre-tapped load coif. Under optimum conditions only minimal differences were found. Load coil geometry was found however to dictate the optimum nebulizer flow rates and sampling depth which was reported to create differ- ences due to differing solvent loads. The centre-tapped coil also showed a greater loss in sensitivity. Myers and Hieftje (92/C3749) reported on the develop- ment of a time-o$jlight (TOF) mass spectrometer for ICP- MS. The advantages of TOFs over quadrupole and sector systems are high transmission efficiency rapid spectral generation simultaneous extraction of all atomic species and low cost.Initial considerations indicated that a TOF tube placed orthogonal to the continuous ion beam would achieve better resolution and sensitivity than one in-line. The full paper on this subject is awaited with interest. Ketter (93/2084) described the determination of lead isotope ratios in environmental samples using a batch quality control protocol involving thallium as internal standard to correct for mass discrimination and two separate control samples. The statistical treatment indi- cated that 95% of the 43 sample batches had estimated overall relative uncertainties for the ratios 206Pb:204Pb 207Pb:204Pb and 208Pb:204Pb of less than 1.23 1.45 and 1.77% respectively. Walder and Freedman (9214579) reported on the cou- pling of a magnetic sector mass analyser equipped with seven Faraday detectors to an ICP source.An electrostatic filter located between the plasma source and the magnetic sector was used to create a double focusing system. Isotope ratio measurements of Pb Sr and U revealed levels of internal and external precision comparable to TIMS. External precision of 0.01 4% RSD was obtained for 235U:238U measurement of NIST SRM U-500 and 0.022% RSD obtained for 206Pb:204Pb ratio from the measurement of NBS SRM Pb-98 1. Measured ratios deviated from refer- ence values by approximately 0.9% per u. The analysis of NBS SRM Sr-987 gave an RSD of 0.008% for the 87Sr:86Sr ratio after normalization to the 86Sr:88Sr ratio. This devel- opment marks a significant step in the determination of high precision isotope ratios. Several workers have investigated the effects of adding nitrogen to the plasma gases.Craig and Beauchemin (93/2062) investigated the addition of 2-10% N2 to the plasma outer gas whilst keeping the r.f. power and nebuliza- tion efficiency constant. Determinand response decreased with N2 addition (consistent with a shift of the initial radiation zone away from the sampling cone) together with the S/N and S/B ratios except where determinands (Cr Fe and Se) suffered from interference by Ar polyatomic species. Here S/N and SIB ratios were improved. The matrix effect of 0.0 1 mol dm-3 potassium on determinands in the 51-1 14 m/z range was eliminated with 10% N,. Adjusting the amount of N2 could eliminate the effect of the potassium matrix on a given determinand but not for the whole m/z range.Caruso et al. (93/2061) reported that the addition of 1% N2 to the outer Ar gas flow could eliminate the ArCl+ interferences and dramatically reduce C10+ interferences without losing sensitivity for a representative determinand. Addition of 3% N2 to the carrier gas had the same effect but led to a loss of determinand sensitivity. No significant effects on oxides and doubly charged species were found. Addition of CH4 to the Ar gas flows had a similar effect but resulted in carbon deposition on the sampling cone and more complex spectra. Elsewhere 4.5%266R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 N2 addition was found to eliminate ArCl+ interference in the presence of 1 O/o chloride (93/ 1022 9214084). Addition of N2 to the outer gas had a similar effect however addition to the intermediate gas had little effect.Louie and So0 (9214576) reported that the addition of N2 or H2 to the outer gas enhanced signal intensities whilst doubly charged and oxide ions were maintained below 3% of their singly charged ions. Contrary to other reports the S/B ratio was increased for a wide range of elements investigated. Addition of H2 to the carrier gas in ETV-ICP-MS (9312 1 12) led to an increase in analyte sensitivity. The ion signals increased as the flow rate of hydrogen was increased and the signal enhancement rates were found to be dependent on the ionization potential of the analyte species. Palmer et al. (9214204) submitted a conference abstract notable for its informative content on methods of data correction.Points considered included a comparison of scanning and peak sampling data acquisition as well as internal standardization and external drift correction. These workers preferred a combination of single-element internal correction and non-matrix matched drift correc- tion standards run every 22 samples with the scanning method of data acquisition. 1.4.2.2. Sample introduction. There has been a sustained level in the number of non-conference laser ablation abstracts available for review this year covering a broad area of applications. The number of conference abstracts promises further useful developments in this field. Five zircon reference materials were prepared as fused glasses solutions and pressed powder pellets and Hf REE Th U and Y determined in each (93/1004 9311054).The results obtained for Bureau of Analysed Samples (BAS) CRM 388 were compared with an independent analysis using INAA. Results from LA were in good agreement with certified values and those independently determined. Provisional results indicated that pressed powders of zircon RMs could be used to calibrate the LA system. Pearce et af. (9311001 93/ 1048) produced standards for fully quantitative LA-ICP-MS by adding elemental standard solutions to a carbonate powder base. The standards gave internal preci- sions of < 5% on calibration graphs with correlation coefficients of >0.97. A multi-element semiquantitative application of the standards provided results of k 10% of accepted values for geological reference carbonate ma- terials.The same group (9213827) also reported the use of a modified Nd:YAG laser coupled to an ICP-MS for the direct analysis of carbonates zircon olivine and feldspars. The modification to the laser produces Q-switch ablation craters with a diameter between 20 and 30 pm compared with 150-200 pm in the unmodified version. Spatial resolution was approximately ten times poorer than that of an electron probe micro-analysis (2-5 pm) but was said to have the advantage of lower limits of detection and wider dynamic range. Crain and Gallimore (93/1003) semiquanti- tatively determined 23 impurity elements in a U308 RM. Accuracy for most elements was to within one standard deviation of certified values. Limits of detection for low mlz elements were about lpg g-l and approximately 200 times better for high mlz elements.Median short-term signal reproducibility was 8% RSD when 234U was used as the internal standard but poorer without the internal reference. Van Heuzen et al. described the analysis of fly ash and basalt RMs prepared as fused glass beads (93/2109) and leaves grasses coal fly ash and geological materials as pressed pellets (93121 10) by LA. Major problems for glass bead analysis were memory effects from deposits of particles in transfer tubes and significant interferences from polyatomic ions for mlz t80. Results were within a factor of 5 of the reference values for pressed pellets using Pd as an internal standard added to the pellets. Accuracy was not affected by laser mode elements studied or sample ma- terials. Limits of detection were at pg g-' levels for low m/z elements and 100 ng g-l for high m/z elements for both sample preparation methods.Yasuhara et al. (92/4092) reported that the fixed-Q mode of a Nd:YAG laser was the most suitable for the determination of trace metal elements in steel and the Q-switched mode most suitable for both non-metallic elements and elements with a high melting- point. The optimum conditions for LA were achieved when the ion yield was a maximum at the focus position in the fixed-Q mode and above the focus position in the Q-switch mode. Two plant-based SRMs Orchard Leaves (NIST SRM 1371) and Tomato Leaves (NIST SRM 1573) were analysed using a ruby LA-ICP-MS system (9312091). The same system was used in the analysis of NIES (Japan) tea leaves (No.7) and Pepperbush (No. I) IAEA milk powder (CRM A1 1) and sediments GSD2-GSD8 from the Chinese Institute of Geophysical and Geochemical Prospecting (93127 13). Accuracy was described as 'fairly good' although the use of a ruby laser cannot be considered to be representative of the LA systems currently in operation. High-voltage spark ablation can be applied to the direct determination of conductive samples (or materials con- verted to a conductive form) with little or no sample preparation. For such samples this technique could serve as an alternative to LA in cases where larger sampling sites ( X 1-2 mm) can be tolerated. The technique was applied to the analysis of a series of copper RMs (93/1946) using inexpensive and simple to operate prototype instrumenta- tion.Good accuracy and precision were obtained without any correction procedures such as internal standardization for trace elements in a concentration range of 0.75-125 pg g-l. Jakubowski et al. (9214605) used a commercial spark ablation system (LISA) originally developed for ICP-AES applications in the analysis of steels. Polyatomic interfer- ences were negligible limits of detection were < 100 ng g-l precision was about 3% and RSFs corresponded to those obtained by GDMS. Little information on accuracy was provided. The use of electrothermal vaporization as a sample introduction technique continues to arouse interest. Gre- goire and co-workers made several useful contributions. Interference from MgC12 in the atomization of Mn in ETAAS was investigated using ETV-ICP-MS (9214648 93/1045).Two different mechanisms were found in which Mn was lost at a charring temperature of > 700 "C. Ascorbic acid could be used as a modifier to eliminate interference from MgC12. Using an Mg-Pd chemical modifier (931 1642) a 5-fold enhancement in peak area sensitivity for Ag Pb and Sn was shown to be possible. In addition analytical precision was significantly improved. The linearity and slope of the analytical calibration curves were dependent on the presence of concomitant elements. The phenomena were attributed to a change in the mass transport efficiency of the sample from the ETV to the ICP caused by the presence of the matrix element. The importance of mass transport effects in ETV-ICP-MS was demonstrated (93/999) and was said to indicate that knowledge of the physical and chemical forms of the analyte and matrix components was important to the practical application of the technique.Modifications to a commercially available graphite furnace (9214705) was shown to improve analyte transport efficiency. The results obtained with the system also indicated a reduction in isobaric interferences on As and Fe with absolute detection limits of 1.5 and 0.2 pg respectively. Shibata et al. (93121 12) reported that the ion signals for Ag Bi In Pb Te and T1 increased with the addition of hydrogen to the argon carrier gas. Close correlation between rate of signal enhancement and the ionization potential of the species was observed. This was attributed to the elevated electron number density andJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 267R excitation temperature between the sampling and skimmer cones. An increase in background ion species such as Ar+ and ArH+ at the interface was also thought to promote signal enhancement through collisions or charge transfer. Ulrich et al. (93/1052) emphasized the need for com- promise operating conditions if ETV-ICP-MS is to be used as a multi-element technique. The influence of ramp time at the vaporization step temperature-time profiles recovery precision and reproducibility under mu1 ti-element and single element conditions were discussed together with the implications for the analysis of sandstone samples (9311 05 1). A method was developed for the determination of Cu Fe Mn Na and Ni impurities in photoresist for very large scale integrated circuits (VLSI) (93/568).Samples were diluted 10-fold with ethoxyethyl acetate and the standard additions calibration method was used. The ETV parameters were optimized for maximum analyte signal and results were in good agreement with those obtained by ETAAS. Detection limits for Fe and Na were 0.2 and 0.06 ng ml-l respectively. A simple modification in a Meinhard nebulizer and Scott spray chamber system provided an efficient continuous hydride generation gas-liquid separator (93/2204). The system was simple easy to construct and inexpensive. Recoveries for As Bi Sb Se and Te in natural waters were quantitative and detection limits were at the low ng g-' levels. The design of a hydride generator was important for the determination of Se in biological materials (93/2 154) in minimizing interferences from HC1 and maximizing sensi- tivity.Two digestion procedures were described with either 3.8 or 7.2 mol 1 - I HCl in the final solution and a method for the elimination of interference from Cu discussed. Sample-to-sample cross contamination was negligible and a detection limit of 6.4 pg was obtained under optimum conditions. Different inorganic and organic Ge species were determined (9211 235) in natural and waste waters following an off-line HG procedure. Generated hydrides were carried by the He flow through a series of traps to remove water and then trapped in a U-tube cooled in liquid nitrogen. Subsequent volatilization allowed the hydrides to be intro- duced into the ICP.Detection limits were 0.08-0.10 pg for the different Ge species. Stroh and Vollkopf (9311044) illustrated the use of a commercial flow injection system in the analysis of samples with dissolved solids >0.5%. Parameters such as tube diameters pump speed and sample loop volume were optimized for maximum signal without allowing a steady state to develop on the transient signals. Long-term stability (90 min) for signals from 5 ng ml-l of Rh in a 3% m/v NaCl solution were good. An FI method for introducing tri- methylgallium and methyllithium samples dissolved in volatile organic solvents has been described (92/4083 9312056). Small volumes of organic solvent were injected into a carrier stream of dilute HN03 (2%) using an FI valve. The uptake rates employed were typical of those used for aqueous solutions and the volume of sample used was such that the plasma was not disturbed.The optimum operating conditions were determined using a variable step-size simplex procedure. Detection limits were in the ng ml-' range but could be improved when a membrane dryer tube was used for desolvation. Determination of metallic im- purities present at levels of about 1 ng ml-I were reported. Eaton et al. (92/3847) discussed the advantages of the FI technique for the analysis of small volume samples such as fluid inclusions extracted by the crush-leach technique. Matrix suppression effects by high salt content solutions could be reduced by changing the sample dispersion. The analysis of RM PCC- 1 (peridotite) by FI-ICP-MS illustrated that detection limits for PGMs of 0.03-0.3 ng g-* could be obtained which are superior to those for conventional nebulization.The use of LC coupled to ICP-MS to obtain information about the chemical form of elements continues to attract a great deal of interest. Houk and Jiang (93/2425) reviewed the analytical capabilities of ICP-MS as an element selective detector for Chromatography. The 67 reference review also considered isotope ratio measurements for individual ele- ment species and removal of interfering matrix elements with LC and also GC. In their 7 1 reference review Olson et al. (93/23 15) presented a summary of both gas and liquid chromatographic methods combined with ICP-MS and MIP-MS detectors. Caruso et al. used ion pair reversed-phase gradient HPLC coupled to ICP-MS to separate and determine inorganic Pb and three alkyllead species (9214573).Detection limits were between 0.14 and 3.9 ng and the reproducibility of peak height was between 3.1 and 4.2% depending on the Pb species. Results from the analysis of an NIST SRM 2715 Lead in Fuel and an EPA Water Quality Control Sample compared favourably with reference values. Houk et al. (93/1943) also used ion pair reversed-phase HPLC to separate various cationic species of Hg and Pb in human urine. A direct injection nebulizer (DIN) minimized band broadening and yielded good sensitivity by injecting all the sample into the plasma. Lead was detected at about 0.2 pg and Hg at about 7 pg. The same technique was used to separate As and Sn species (92/4100). Detection limits were 0.2-0.6 pg for As species and 8-10 pg for those of Sn. The use of a DIN was reported to offer superior absolute detection limits and chromatographic resolution compared with conventional nebulizers and the dependence of analyte signal on solvent composition was less severe.Salou et al. (93/1942) reported an HPLC-ICP-MS for the deter- mination of six inorganic halogen ions. Absolute limits of detection for Br C1 and 1 species were 0.8 ng 36 ng and 25 pg respectively. In the application of the method to the analysis of human urine three unidentified halogen com- pounds were detected. In order to overcome many of the matrix effects associated with REE determination Braver- man (92/3825) used an HPLC system to separate the REEs prior to ICP-MS detection. Limits of detection were in the sub-ng ml-l range and the response was over four orders of magnitude.A preliminary comparison of isotope dilution and external calibration for the determination of REEs in NIST SRM 1633a Fly Ash was presented. Owen et al. (92/4 104) used size-exclusion reversed-phase chromato- graphy to separate Zn-containing species in chicken meat that had been intrinsically and extrinsically labelled with stable isotopes of Zn. The intrinsic label ratio agreed with that obtained by using TIMS. Although the use of time resolved analysis techniques permitted rapid data acquisi- tion data handling proved time consuming. Iron accumulating to excess in tissues of animals and humans occurs mainly as complexes of Fe. To determine the distribution of Fe between these molecules ICP-MS was used as an on-line isotope specijic detector for LC separation (9312322).Enriched 57Fe was used as a tracer to monitor the Fe content of eluent fractions. The Fe distribu- tions in healthy rat livers together with liver and heart tissues from Fe-loaded human subjects was reported. Results by this method correlated well with those obtained using Zeeman-corrected ETAAS detection. Sheppard et al. (93/409) separated and detected four As compounds by single column ion chromatography. Interference from ArCl+ was reduced by chromatographically resolving CI from the negatively charged As species. Detection limits of between 73 and 260 pg were obtained for the four species in wine. Sensitivity was improved using an He-Ar mixed gas ICP.Although this also increased the ArCl+ interference detection limits were improved by about 50%. Peters and Beauchemin (9 3/2066) described an interface that allowed the coupling of a gas chromatograph to an268R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 ICP-MS instrument whilst allowing aqueous solution nebulization with no instrumental re-configuration. The interface incorporated a switching T-valve with a stacking device for the addition of the make-up gas to the chromato- graph effluent. The performance of the system was evalu- ated and detection limits of 2.6 2.2 and 2.6 ng were reported for dichloromethane 1,1,4-trichloroethane and trichloroethylene respectively. The performance of the interface from direct solution nebulization was also as- sessed while aspirating a multi-element aqueous solution both with and without the interface in place.Limits of detection were reduced for all elements studied except Zn. Kim et al. (93/2092) described the interfacing of a GC to an ICP-MS which required only a simple modification to the ICP torch and the construction of a heated transfer line. The quantitative analysis of alkyloid compounds in a complex hydrocarbon mixture was reported with a 0.7 pg s-l LOD and t5% RSD. Caruso et al. described the use of supercritical fluid chromatography with plasma-MS detection for the determi- nation of organic compounds (93/2067) and halogenated hydrocarbons (93/2070). For organotin compound mix- tures the SFC parameters such as interface temperature oven temperature C02 pressure programme mobile phase composition and column length were evaluated and optim- ized. Detection limits of between 0.20 and 0.8 pg were found for the organotin compounds and the RSDs were in the range 1.3-3.4%.A helium MIP-MS system was used as a detector for halogenated hydrocarbons. The absolute mini- mum detectable amounts of Br and C1 were 25 and 100 pg with limits of detection of 0.75 and 15 pg respectively. The calibration lines were linear over three orders of magnitude and reproducibility for sample injections was about 5% RSD. A preliminary chromatogram for an RM pesticide was also presented. Houk et al. (92/1224) described an improved direct injection nebulizer. Precision was typically 0.5% for signals not limited by counting statistics.A wash time of 15 s was sufficient to reduce the analyte signal to 0.1 % of its steady state value even for elements such as Hg and I. Limits of detection were similar to those obtained with conventional nebulizers but absolute LODs were improved by an order of magnitude as the flow rate was only 120 pl min- l . Powell et al. (93/2 163) used a DIN in the analysis of drinking water for Hg. Memory problems were 'drastically' reduced and results were compared with those obtained by cold vapour AAS. Jakubowski et al. (93/528) described the optimization of a hydraulic high pressure nebulizer. A nozzel with a 10 pm diameter positioned in front of an impact bead leads to the production of a very fine aerosol and 30% nebulizer efficiency. However a desolvation system was necessary to reduce the high water loading of the aerosol.Compared with conventional nebulization an intensity gain by a factor of about 30 was obtained. The same group investi- gated the influence of desolvation on aerosols generated from pneumatic nebulizers (93/2583). About 80% solvent could be extracted which coupled with an increase in sample uptake from 1.2 to 2.5 pl min-' lead to a gain in sensitivity of between 2- and 5-fold. Chen et al. (93/2058) reported on the evaluation of a recycling nebulization system (RNS) which allowed 5 min for data acquisition from 0.5 g of sample solution. The sensitivity with the RNS was similar to that of a conven- tional system. Four internal standards (Bi Ge In and Re) were used to correct for matrix effects instrumental drift and enrichment of the sample solution by evaporation an inherent problem for recycling systems.Results from the analysis of four geological RMs were in good agreement with reported data. A system to help in the introduction of volatile organic solvents was described by Hill et al. (9213822). Peltier coolers were used to reduce the temperature of an interface placed between a heated spray chamber and the ICP. Detection limits were in the sub-ng ml-I range. Flow injection techniques were used to reduce the amount of volatile organic solvent entering the plasma. Smaller sam- ple loops (50 pl) enhanced plasma stability and facilitated faster flow rates leading to better transient peak shapes and reduced memory effects. Taylor et al. (93/2 16 1) used an ICP-MS to quantify trace elements in specific sub-micrometer size fraction particu- lates separated by sedimentation Jield-flow fractionation. The usefulness of the tool was demonstrated by elucidation of the surface water suspended matter collected from two Australian rivers.An on-line anodic stripping voltammetry (ASU) jlow system (93/2090) was used to deposit Cd and Cu from NIST SRM 2670 (Toxic Metals in Freeze-dried Urine) at a working electrode. Analyte was released for analysis by ICP-MS after the matrix was cleared from the cell. Recoveries were 92- 106% and sodium matrix removal was highly efficient for up to 1 x lo4 pg ml-*. Wiederin and Houk (93/2 1 19) used photography and laser scattering to show that a DIN produced a finer aerosol with a narrower drop-size distribution compared with a conventional concentric nebulizer.Hobbs and Olesik (9214685) investigated the fluctuation of ICP-MS signals due to analyte species solvent combinations of solvent and plasma or enhanced gases and the plasma gas. Signal fluctuations were found to be sometimes larger than one order of magnitude and on a tens of microseconds time scale. The nature of signal fluctuations at a fixed sampling point depended critically on the centre gas flow rate. 1.4.2.3. Interference eflects. The intensity of Mi M2+ and MO+ signals has been studied (9312387). The influence of several instrumental parameters associated with sample introduction and plasma operation on the ions as well as the MO+:M+ and M2+:M+ ratios was studied. Simple qualitative explanations were given to explain some of the observed results.No quantitative results were given for the MO+:M+ and M2+:M+ ratios as the experiments indicated that they were influenced by several instrument parameters. Houk and co-workers (9312 157) reduced the water load to the ICP by using multiple desolvation steps at - 80 "C for a continuous-flow ultrasonic nebulizer. Oxide ratios MO+:M+ for Ca La and Mo were as low as 0.02-0.05%. Polyatomic ion interferences were also reduced by several orders of magnitude. Isotope ratios for Cd Fe and Ni were in good agreement with accepted values and the detection limits for As Cd Fe Ni and U were 2-20 ng l-' in the presence of HCl Ca and Mo matrices which would normally cause polyatomic ion interferences. Wash-out times using this nebulizer were increased by only 8 s.Ketter and Biddle (93/2 1 60) applied multiple linear regression (MLR) and principal Components regression (PCR) to the determination of Cd in the presence of interfering MOO+ ions from a molybdenum matrix. The effect of changing instrumental conditions and sample matrix content on the MoO+:Mo+ ratio was also examined. Both MLR and PCR enabled the accurate determination of Cd in the presence of molybdenum even with large variations of MoO+:Mo+ ratios. Principal components analysis (PCA) was used by Templeton and Vaughan (9214709) to separate Fe and Ni spectra from interferences. The advantages of PCA are that no sample manipulation or instrument modification was required. The pressure and solvent loading in thejrst stage have been manipulated (93/24 16) in order to regulate the degree of analyte signal suppression in the presence of highJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 269R concentrations (1 0 mmol I-]) of concomitants. The first- stage pressure was found to have a significant affect on the oxide-ion and doubly-charged ion ratios. In addition for some interferent-analyte combinations the identity of the concomitant anion and subsequent pH of the solution determined whether the interference effects could be entirely eliminated. Evans and Caruso (931 1083) used simplex optimization to identify the best ion lens conditions for the reduction of non-spectroscopic interferences caused by a uranium matrix of 10 000 pg g-l. The extraction lens potential was found to have the greatest effect on the extent of analyte signal suppression. The use of a 0.4 mm sampling cone resulted in a large reduction in analyte suppression at all extraction voltages however the propensity for a secondary discharge to form was increased.In addition doubly-charged ions and the tendency of the cone orifice to rapidly block in the presence of the matrices increased. Reduction of the first stage pressure also decreased the degree of analyte suppres- sion although it was not always reproducible. Campbell et al. (9311005) reported that differences of about 50% were found in the Hg results determined by ICP- MS and cold vapour atomic fluorescence spectrometry for the analysis of CRM 422 Cod Muscle. Good agreement between the methods was obtained when standard addi- tions and isotope dilution techniques were used for ICP- MS. The authors suggested that the chemical species of the mercury present in the samples and standards influenced the ICP-MS results.Tanner (93/1049) in an extended abstract discussed the implications of space charge effects in ICP-MS as one of the main causes of matrix effects. It was proposed that accelerating the extracted ions as soon as possible down- stream of the skimmer would overcome space charge effects as the mass-dependent energy spread would become a small fraction of the total kinetic energy. However it was acknowledged that the ions would have to be decelerated prior to entry into a quadrupole mass analyser in order to achieve acceptable resolution and the space charge effects would return at that point.1.4.3. Applications Most reported applications of ICP-MS have little novel content which is a reflection of how established the technique has become. The reader is directed to the Atomic Spectrometry Updates concerned with analysis for a broad review of ICP-MS applications. This review will deal with those pieces of work with notable ICP-MS developments. 1.4.3.1. Geochemical. Many of the applications are con- cerned with the analysis of RMs . Rare earth minor and trace elements have been determined in iron-formation samples (93/19 19 93/2203); major minor and trace ele- ments in six USGS rock standards (93/1935); and 37 elements were determined in 32 international geostandards (9312339). The use of isotope dilution (ID)-ICP-MS allevi- ates the need for matrix-matched standards.In addition the technique is immune to signal drift and chemical effects. In a comparison with conventional ID-TIMS (93/2130) the major benefit of ICP-MS for the determina- tion of Th and U in silicate rocks was a large increase in sample throughput with no degradation of precision and accuracy. In the determination of 0 s abundance in molyb- denite mineral (9311 093) by ID-ICP-MS sample solutions were prepared by acid decomposition using microwave digestion techniques with addition of potassium dichro- mate as oxidizing agent. The analytical precision for the 0 s abundance was 1 %. The development of a dry-chlorination procedure for the determination of low concentrations of platinum group elements (PGEs) and Au in rock pulps has been reported (9312054).The procedure converted the elements into sodium salts which were then dissolved in weak HCl prior to analysis by ICP-MS. Reagent contamina- tion was extremely low (Pt < 1 ng g-l; other PGE and Au g0.2 ng g-l) PGE recoveries were >90% and the accuracy of the procedure was considered to be comparable to conventional fire assay techniques. 1.4.3.2. Environmental. A significant number of applica- tions have been directed to the determination of radionu- clides. Kim et al. (9312438) determined the distribution and behaviour of 241Am 237Np 239Pu 240Pu and 99Tc in the coastal and estuarine sediments of the Irish Sea. Only 99Tc was determined by high-resolution ICP-MS the remainder with a quadrupole system.The 241Am:239-240P~ and 237Np:239*240Pu ratios were reported to be almost constant with distance from the Sellafield source but the activities of the isotopes decreased exponentially. In a comparison of ICP-MS with NAA (9312440) for the determination of low levels of 237Np and other actinides as alternatives to alpha- spectrometry the former technique was found to be particularly suitable. Particular advantages of ICP-MS included the ability to determine other long-lived actinides simultaneously and to quantify 239Pu:240Pu ratios. Neutron activation analysis was found to be particularly prone to interferences especially from uranium oxide. Quadrupole ICP-MS was reported to be a very fast and sensitive method for the determination of 230Th in marine sediments (92/3859).A detection limit of 36 fmol was determined with a precision of <3% (In) comparable to alpha- spectrometry. However ICP-MS offered significantly shor- ter analysis times (5 min compared with two weeks) and simplified sample preparation. Cox et al. (931 1008) devel- oped a method capable of measuring 1291 at contamination levels in vegetable samples. To overcome the low transport efficiency of the ICP-MS nebulization system analyte was introduced in the form of I,. An LOD of 0.2 ng was reported equivalent to approximately 1.4 ng g-l of fresh mass of vegetable. A method precision of 12% RSD at 2.7 ng ml-l was achieved. A variety of preconcentration procedures have been used for the determination of trace elements in sea-water. Shabani et al.described a rapid preconcentration method to separate REEs by complexation onto a C18 cartridge (93/2 1 5 5 ) which provided 200- 1 000-fold enrichment fac- tors. This group also reported the determination of Re in sea-water (93/23 19) using on-line column preconcentration with enrichment factors of between 38 and 10 1. The LODs after preconcentration of 10 and 50 ml of sea-water were 0.27 and 0.1 pg ml-l respectively. In addition Shabani et al. (931 1040) developed a method for the determination of sub-parts per trillion ( lo',) levels of Bi in sea-water after preconcentration with solvent extraction and back-extrac- tion. The RSD after a 1000-fold enrichment was <2.2% and contamination was below 1% of the concentration of Bi in sea-water. Sample preparation took 30 min per aliquot.Platinum was preconcentrated under the same conditions as Bi and therefore used as an internal standard to check for analyte losses during the preparation procedures and correct for any matrix effects during the ICP-MS analysis. McLaren et al. (9312055) determined Fe and ten other trace elements in Open Ocean Seawater RM NASS-3 by ICP- MS after separation and concentration on silica-immobil- ized 8-hydroxyquinoline. Determination of Fe in the concentrates by ID with 56Fe as the reference isotope and 57Fe as the spike required the use of a nitrogen-argon mixed-gas plasma with partial aerosol desolvation. The LOD of the method based on a 90-fold preconcentration range from 0.04 ng 1-l for U to 6.3 ng 1-1 for Zn.270R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 1.4.3.3. Biological. It is encouraging to see more wide- spread use of the isotope capability of ICP-MS being made particularly for stable isotope tracer studies. Williams et al. (92/4603) assessed the feasibility of measuring Fe absorp- tion in humans by incorporation of stable Fe isotopes in red blood cells. Instrument parameters were optimized to reduce polyatomic interferences to such a level that both precision and accuracy of isotope ratios were approaching those theoretically determined. Correct use of dead-time correction procedures and standards ensured that analyte concentration and mass bias effects were negligible. Iron solutions of 10 ppm or greater routinely gave a precision of (0.4% for 57Fe:56Fe and (0.6% for 58Fe:56Fe. Blood samples from two human subjects showed that after incorporation of enriched isotopes 57Fe:56Fe and 58Fe:56Fe ratios were clearly distinguishable from the baseline.Willi- ams (92/408 1) also reviewed ETV-ICP-MS for the determi- nation of Fe and Zn isotope ratios in biological samples where only small volumes (< 1 ml) were available. A separation/preconcentration preparation method using CC14 with APDC was optimized for the determination of 70Zn:68Zn ratios by ICP-MS on samples of blood faeces and urine taken from pre-term babies after oral or intravenous administration of 70Zn (93/2059). Ratios were determined with ‘acceptable’ precision (< 1% RSD) for samples with > 200 ng ml-l of Zn in solution. This type of procedure was used elsewhere (93/2 132) but analytical precision was reported to be 0.3-0.8% RSD for natural Zn concentrations of about 200-600 pg g-l.A simple and sensitive procedure for the determination of total Hg in whole blood and urine has been described (93/2426). Specimens were prepared by precipitation/ extraction with 50% HCl containing EDTA and cysteine centrifuged and finally filtered through a frit ended screen- ing column prior to ICP-MS analysis. The calibration graph was linear between 2 and 200pg 1-l and recoveries of organic and inorganic Hg from blood samples were between 9 1.6 and 1 10.2%. Gold based drugs auranofin myohrysine and their meta- bolites have been determined in urine by ICP-MS after separation by reversed-phase ion-pair chromatography with tetrabutylammonium chloride as the ion-pairing agent (93/2437).The LOD for auranofin the last compound to be separated was 0.3 ng. The recovery for the process was >go%. Dicyanogold(1) anion Au(CN)~ was detected in the urine of several patients. After acid dissolution ICP-MS was used to determine 69 elements in cashmere fibre samples (93/1078). Of these elements only Ca and Mn were reported to meet the requirements for estimating cashmere yield in fleece. The most suitable indicator appeared to be Ca because it provided excellent correlation between the predicted and experimentally determined values. In a comparison of INAA with ICP-MS for the multi- elemental analyses of 50 digerent food types and mixed human diet RM (93/2439) it was reported that the former could not match the superior sensitivity of the latter technique.However although INAA was considered incon- venient and time consuming for many applications it was found not to suffer from ‘blank problems’ when low LOD were required for trace concentrations in solid samples. 1.4.3.4 Industrial. Some applications of ICP-MS to the determination of trace elements in nuclear materials have been reported. In the analysis of uranium oxide (93/4575) an on-line solvent extraction procedure was used. An aqueous solution containing 2% m/v uranium in 1 mol 1-’ nitric acid and an organic phase containing the uranium was removed on-line by allowing the solution to pass through a hydrophobic microporous PTFE tube. The technique was considered rapid sensitive and accurate with a LOD of between 1 and 45 ppb for most elements and recoveries of between 95 and 106%.An off-line solvent extraction procedure was used to extract 237Np from enriched uranium solutions (93/2060). Instrument quadru- pole parameters had to be optimized to prevent remaining 238U matrix overlap with 237Np. However uranium concen- trations had to be kept below 100 mg 1-l. Internal standards (not given) were used to correct for analyte suppression and the LOD for Np was found to be 0.005 pg g-l. The ICP-MS method was considered preferable to an alpha-spectrometry method because of its simplicity accuracy LODs and short analysis times. Park et al. (93/1009) developed a controlled electrodepo- sition method for the determination of trace impurities in pure copper SRMs [394 unalloyed copper(1) and 395 unalloyed copper(11)1. More than 99% of the matrix was removed with >90% recovery for trace elements. Isotope dilution was used for calibration with spikes being added prior to elect rodeposi t ion.A method for the determination of Th and U in high- purity tungsten metal has been developed (9312230). The metal was dissolved with HF and HNO mixed acids (3 l) evaporated to dryness and redissolved in mixed acids (1 mol 1-l HF-0.1 mol 1-l HNO,) prior to being passed through an anion-exchange column. The effluent was evaporated to dryness dissolved in 1% HNO and finally analysed by ICP-MS. Recovery for both analytes was > go% LODs were below 0.1 ppb and the analytical precision was t5% RSD at the 10 ppb level. 1.5. Laser Ionization Mass Spectrometry (LIMS) Reports on LIMS tend to fall into two categories-funda- mental studies mainly by researchers in the former Soviet Union into the use of laser ionization for the analysis of bulk materials and applications employing the laser micro- probe.The group in Julich Germany have produced two substantial but similar reviews-the first (93126 10) with 13 1 refs. on the characteristics and analytical features of LIMS for inorganic analysis and the second (9312290) on the more specific trace analysis of ceramics. The use of the laser microprobe in geochemistry has also been reviewed (93/2373) with emphasis on the determination of trace elements and noble gas isotopes in minerals and fluid inclusions. The time dependence of ionization and the initial kinetic energy of ions have been used (93/2365) to study the mechanism of laser ionization.With a high energy laser pulse secondary ionization took place for about 0.2 and 0.4 p s on A1 and Au respectively. The initial kinetic energy was about 1 keV for H but lower for C and 0 ions. It was considered that strict control of analytical conditions could lead to the possibility of microchemical analysis. A test stand built for fundamental studies of LIMS was composed of an electrostatic analyser with a resolving power > 106 for the energy analysis of charged particles and a laser source of ions (9312448). The electron tempera- ture mean degree of ionization charge composition and energy distribution of plasma ions could be determined. The resolution and magnitude of the analytical signal in LIMS was found (9312602) to increase 2- to 3-fold when the accelerating voltage applied to the target was increased from 1 to 4 kV.Appropriate shielding reduced (93126 13) the deviation of ion beams in the a-slit region caused by scattered magnetic field some 4-fold and suitable ion optical adjustment reduced by 20% the residual transmis- sion error in the 7 to 181 u range. The formation of clusters which were dependent on laser power density and target potential has been studied in a novel way (9312365). Cleaved surfaces of highly orientated pyrolytic graphite were positioned either 10 cm fromJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993. VOL. 8 271R materials ablated at 133.32 x Pa by 1-3 excimer laser (308 nm) pulses of 20 ns duration or 1 m from materials vaporized at 133.32 x Pa by ten Nd-glass laser pulses of 1 ms duration.The clusters intercepted by the graphite were analysed by scanning tunnelling microscopy and were composed of up to 30 units. Three different sample geometries (thin film spheres and shards) for microprobe analysis of a glass sample have been studied (9312505) and their effects on quantification deter- mined by measurement of RSFs. The best precision for all elements 16-29% was achieved for thin film samples using RSFs relative to Ba. The precision for analysis of particles was at best 20-40% with an accuracy of a factor of 2 if RSFs for elements with low ionization potential were measured relative to another element of low ionization potential. Non-planar geometries resulted in variations in laser focus power density and analysis volume and created difficulties.Single particles have been analysed (93/22 12) by passing the particles through a PTFE tube to the source of the MS through a differentially-pumped nozzle. Passage of single particles was detected by the scattering of a He-Ne laser beam which triggered an excimer laser for desorption and ionization of the particle. A TOF-MS was used to record the mass spectra. Both simple cations (K+ Na+ NH4+) and clusters (K2C1+ Na,Cl+ NaKCl,) were formed when particles from mixtures of KCl NaCl NH4C1 (NH4)2S04 and ZnS04 were analysed. The procedure was similar to conventional laser desorption in the types of ion observed the threshold laser irradiances needed for detection of ions the small spatial resolution over which ion formation occurs and the significant distribution of ion kinetic energies.It differed however in that the location in the ion source at which desorption occurred differed from sample to sample and this resulted in a significant time shift. Improvements in the stray-light rejection during the scatter detection step could lead to the analysis of sub-pm sized particles. Standardization of microprobe analysis has been ad- dressed. Standard reference materials were prepared (93/2609) by anodization of n-Si polycrystalline discs in 20-30% HF containing 10% alcohol washing with water impregnation with metal salt solution in an ultrasonic bath and thermal treatment at 400-700 "C. The calibration graph for the determination of Cu was linear over the range 1 0-4-0.50/o.Thin films of polymerized Spurr's tissue- embedding medium doped with or containing Hg In or Li have been investigated (93/2443) for use as laser power density internal standards in the analysis of human tissue for studies of trace element involvement in neurological diseases. Applications of microprobe analysis cover an ever-ex- panding range of study. Interesting examples include the localization of toxic ions in tissues at the cellular or sub- cellular level (92/44 19) the analysis of individual bacterial organisms and of isolated bacterial compounds in microbi- ological studies (9312434) and the determination of A1 and Pb in fine roots and their ectomycorrhizal mantles in Norway spruce (93/2660). 1.6 Resonance Ionization Mass Spectrometry (RIMS) A number of review papers have discussed the fundamental principles and some of the applications of RIMS.Becker (93/2370) discussed both resonant and non-resonant photo- ionization techniques in a review paper with 77 refs. Ledingham (931250 1) briefly reviewed the fundamentals of RIMS and focused on a number of applications in particular depth profiling in semiconductors. Pellin (93/2595) discussed the problems involved in the analysis of very small samples using SIMS and SNMS particularly in the analysis of semiconductor materials. The high useful yield (X 1%) attained by laser post-ionization is useful in such applications and can yield detection limits of a few pg kg-l. The choice of mass spectrometer is also discussed with attention paid to transmission efficiency.In the future advantages should be gained from the development of diode-pumped solid-state lasers and widely-tunable solid- state lasers. Falk (92/4629) discussed the concept of single- atom detection in the context of atomic spectroscopy and atomic MS. Surprisingly RIMS was not mentioned al- though laser confinement of atoms was addressed with fluorescence detection as a potential analytical develop- ment of this technique. Falk does refer to a technique whereby a continuous ion beam is interfaced with a TOF mass spectrometer via an ion trap which if applied to RIMS would allow the high throughput of TOF-MS to be used in conjunction with CW laser ionization of a continuous atom beam. The important task of cataloguing spectroscopic data for the multiple photon transitions in RIMS continues.Salo- man (9312585) has extended the RISIRIMS data service to cover Bi Na P Sb and Sn. This valuable series collates published information on the optimum ionization schemes and conditions required to effect resonance ionization. The reported errata should also be noted (93/2588). Smyth et al. (93/2588) have mapped 240 new 238U states in the range 38500-41 200 cm-I. Despite interest from both the analyti- cal and isotope enrichment communities the energy level data for uranium are still incomplete. The group noted the importance of high precision assignment for two colour resonance ionization schemes. The spectrum was recorded whilst simultaneously measuring the laser induced fluores- cence spectrum of I,.Johnson et al. (93/2589) reported a detailed study of autoionizing states of thorium and have found an ionization potential for thorium which differs significantly from previous literature values. Using differ- ent two-colour two-photon ionization schemes and by carefully controlling the electric field in their ion source they confirmed their reported value of 6.310+ 0.002 eV. The paper also documented autoionizing levels which fall within 2000 cm-I of the ionization threshold. These workers reported typical lifetimes of a few picoseconds and excitation cross-sections of = cm2 for these states which represented an enhancement by a factor of between 50 and 100 over excitation to continuum levels. A number of autoionizing states of Ru were reported by Ma et al.(93/1208) who achieved ionization efficiencies a factor of 20 better than by excitation to continuum levels. Bushaw et al. (93IC200) reported the use of CW isotope-selective ionization via Rydberg states for the measurement of the rare isotopes ,IoPb and 90Sr. The effects influencing isotopic selectivity in resonance ionization are still not fully understood. Wunderlich et al. (93I2510) have studied the influence of laser wavelength bandwidth power and polarization on isotopic selectivity with particular attention paid to 0 s and Ti isotopes because of their geochemical importance. A thermal atom source was used in combination with a one-colour ionization scheme. Small wavelength changes were found to cause significant changes in isotopic selectivity.The group uti- lized a method of wavelength stabilization based on observation of isotopic selectivity to achieve a precision of < 0.5%. England et al. (93/2164) examined Re isotope ratio variations. Satisfactory precision was obtained for a one colour ionization scheme but improvements were required if a more sensitive and selective two-colour scheme was used. Photoionization cross sections for 1 -k 1 ionization processes have been reported for Cr Fe Mg Ni and Ti (93/24 1 7). The cross-sections for the ionization step were determined on the assumption that the first excitation step was saturated. The results compared well with theoretical272R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 estimates giving cross-sections of the order of lo-'' cm2.These relatively large cross-sections were shown to allow the determination of Mg in aluminium or Ti in steel at low mg kg-l levels for a single shot. The atomization step used an Ar+ ion beam of 5 mm diameter which sputtered less than a monolayer in each case. Measurements by RIMS are potentially of great value in geochemical analysis because of the combination of a sensitive microanalytical capability with freedom from matrix effects and isobaric interferences. Spiegel et al. (9312 153) have used a three-colour ionization scheme to determine Ti isotope ratios in the presence of Ca. A rather disappointing selectivity of 500 was reported for the Ti ionization relative to Ca but this was shown to be of value to a range of geochemical applications including melilite the mineral with the lowest Ti:Ca ratio studied.Bottazzi et al. (9312469) have measured RSFs for REEs in various mineral phases as well as in glasses obtained by fusing silicate minerals which could be used as standards for quantitative analysis. The same potential advantages of freedom from matrix effects and isobaric interferences combined with high sensitivity is of value in the analysis of high-purity ma- terials. Downey et ul. (93/2465) have applied sputter- initiated resonance ionization spectroscopy (SIRIS) to the quantitative measurement of Be in GaAs/(Al,Ga)As ma- terials thereby avoiding many of the matrix effects observed in SIMS at interfaces. A number of matrix effects still observed in SIRIS measurements are discussed in the SIMS section of this review.Maeda et al. (9312221) have used laser ablation resonance ionization spectroscopy (LARIS) to determine Cr in high-purity iron and in silicon wafers they report an LOD below lo9 atoms cm-*. Ledingham et al. (9312590) have applied resonant laser ablation (RLA) to the detection of A1 in steels at mg kg-' levels. This technique used the same laser for resonant ionization and sample ablation thereby compromising the selectivity which can be obtained by separating the atomization and ionization processes for a degree of experimental simplicity and lower cost. The method was more selective and sensitive than LIMS but less so than LARIS. The same group (9312502) have measured Au in a copper matrix by LARIS demonstrating linearity of signal versus concentra- tion in the range 10-2000 mg kg-l and giving a detection limit of -200 pg kg-l.This was rather disappointing for such a sophisticated method but improvement by a factor of 10 was predicted if ionization could be saturated using the 266 nm Nd:YAG output and with the use of a new detector. Nogar et al. (9212152) have reported a 10 fg detection limit for Cr using laser desorption RIMS. The sample in solution was spin coated onto a poly(methy1 methacrylate) disc. The desorption occurred 3.2 cm from the ionization region and the group suggested that an improvement in source geometry could enhance the signal by up to four orders of magnitude. Their measurements indicate that the energy distribution of the desorbed plume has an equivalent temperature of 1000 K.Kato et al. (9311232) have used selective dissociative photoionization at 532 nm of nascent UF5 itself formed by 266 nm irradiation of UF6. Combined with TOF-MS the technique was used to measure 235U:238U isotope ratios and the method was suggested for real-time measure- ment of separation factors in molecular isotope separa- tion. Young et al. (931C254) reported further work using semiconductor lasers for one excitation step in resonance ionization schemes. The narrow bandwidth (25 MHz) of these CW lasers allowed them to achieve some degree of isotopic selectivity. Developments in this area could potentially lead to a much less expensive RIMS instru- ment. 1.7 Secondary Ion Mass Spectrometry (SIMS) There is a confusing proliferation of acronyms relating to surface-specific analytical methods.This has to some extent been addressed by the American Society for Testing and Materials (ASTM) (9312567) who have defined stan- dard terminology (reference E673-90) relating to surface analysis including SIMS. Some of the more esoteric techniques particularly those which involve post-ioniza- tion have not been addressed however. The ASTM (93/2568) have issued a set of recommenda- tions for sample handling in AES SIMS and X-ray photoelectron spectroscopy (XPS) analyses. The paper addressed problems with contamination from various sources electrical charging of samples ion and electron beam damage sample visualization and procedures for sample preparation storage and mounting. The recommen- dations were in brief note form (with 35 refs.) but gave a useful overview for newcomers to the field.There have been a number of reviews of the fundamental principles and recent progress in the development of SIMS. Stevie (9312571) reviewed the current status of SIMS in an attempt to dispel myths that the method cannot be used for quantitative analysis analysis of electrically insulating samples and for high spatial resolution analysis of metals. Electron beam neutralization and sample rotation tech- niques were discussed in this context. Depth profiling methods based on sputtering including AES SIMS and XPS have been reviewed by MacDonald and King (93/2489 93/2490) these techniques were also compared by Janssen and Weijers (9214394). Grasserbauer (9312564) discussed the contribution made by solid state MS to the development and production of new materials and Smith et al.(9312431) reviewed the role of Rutherford back- scattering (RBS) and SIMS in the development of metalization technology in microelectronics. A number of comparisons have been made between SIMS and other surface-specijic techniques. Hofmann (9214478) has reviewed methods of depth profiling by sputtering and Riviere (921409 1) has reviewed recent advances in surface analytical methods including static AES SIMS XPS and atom-probe field-ion microscopy. The relative merits of AES SIMS and XPS and electron-probe microanalysis (EPMA) for the analysis of composite matrices were reviewed by Mischler et al. (9312569) and the value of microfocused Ga ion-beam SIMS was also highlighted. Other comparative reviews included that by Cookson (9312 1 28) which covered particle-induced X-ray emission (PIXE) nuclear reaction analysis (NRA) elastic recoil detection analysis (ERDA) and RBS.Powell et al. (931237 1) compared ion scattering spectroscopy (ISS) AES RBS SIMS SNMS and XPS and Czanderma (921447 1) outlined the fundamentals of AES ISS RBS SIMS and XPS. Daolio et al. (9312362) have compared a variety of MS-based techniques including SIMS for the measurement of REEs in mineralogical biological and environmental matrices. A number of new instruments or modifications to existing instruments have been reported. Slodzian (9214299 9312291) described the capabilities of a new Mattau- ch-Herzog geometry instrument which allowed simulta- neous acquisition of four (negative) ion images and an ion- induced electron image. The primary Cs ion gun could be focused to a 30 nm diameter spot and the mass spectro- meter was capable of a mass resolving power of 6000 (at 20% valley). The current status of the sensitive high- resolution ion micro-probe (SHRIMP I) which was used in mineralogical studies has been outlined (9214698) and plans for its successor SHRIMP 2 which is under construc- tion were presented. An instrument with a secondary-ion and field desorption source for depth profile analysis has been described (9312497) and applications to steel super- conducting films and ceramics discussed.Hutter and Grasserbauer (931238 1) have modified a Cameca IMS-3F to allow extensive computer control of the instrument and image processing.The channel plate detector voltage wasJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 273R dynamically varied according to the most and least intense signal from the charge-coupled device (CCD) array. A dynamic range of secondary-ion intensities of lo8 was achieved. The fundamental mechanisms of sputtered-ion formation continue to receive attention. Petravic and Williams (9312528) have investigated the anomalously high ioniza- tion efficiencies of the atoms C1 F H N and 0 observed in some matrices which they attributed to an electron- mediated core hole creation mechanism. Using molecular dynamics simulations sputtering from single crystals of silicon at normal and oblique incidence has been investi- gated and predictions made of the angle of incidence which should give maximum analytical sensitivity (92/4688). The correlation between ion intensity and the bulk rather than surface thermodynamic properties provided evidence that secondary ions were emitted from sub-surface layers of liquid samples (92/4690).This is in agreement with theories which suggest the formation of a supercritical fluid phase prior to ion ejection. Blumenthal et al. (92/4693) have measured the angular distributions of sputtered ions from GaAs surfaces and have related these to bond directions in the underlying layers. The effects of disordering due to ion beam damage of these surface layers were also observed. The role of large cluster fragmentation in molecular ion formation was investigated by Reed and Vickerman (92/4696) who examined the fragmentation patterns of tin and vanadium cluster ions using collisionally-induced dis- sociation in a triple quadrupole instrument. It was consi- dered likely that the small cluster ions are formed by dissociation of larger clusters.Surface modijication by primary-ion beam bombardment has been investigated for a number of primary ions and sample matrices. Effects include ion-beam induced surface- topography changes ion-beam induced segregation and migration swelling oxidation and amorphous layer forma- tion. Some of these matrix effects are therefore of relevence both to SNMS and sputter initiated RIMS. A knowledge of these effects for the particular combination of primary ion analyte and sample matrix is essential if high spatial resolution and quantitative measurements are to be made.Altered layers produced in silicon by bombardment with Cs+ ions have been investigated by Valizadeh et al. (93/25 19). They note that knowledge of the charge state of Cs in the surface layer was critical in profile simulation as the densities of neutral Cs and Cs+ in silicon were very different. Stevie (93/2574) has specifically examined the use of sample rotation to overcome ion- beam induced surface- topography effects in the analysis of aluminium coatings on silicon. Aluminium surface layers are particularly prone to ion-beam induced surface roughening and a number of workers have addressed this problem. Hofmann (92/4478) in a comprehensive review of methods of depth profiling by sputtering discussed a number of methods for attaining high depth resolution in particular sample rotation and crater-edge profiling.Pamler and Wangemann (93/2570) have investigated various methods of enhancing depth resolution. In their examination of A1 metalization in microelectronics devices they have examined the angle of incidence of the primary-ion beam sample rotation and the use of both heavy and reactive primary ions. Bombardment with N2+ and 02+ was shown to generate an amorphous surface layer which sputters more uniformly than unmodi- fied polycrystalline aluminium. Heavy-ion bombardment at near-grazing incidence or 02+ bombardment at normal incidence gave improved depth resolution by an order of magnitude over normal analytical conditions (Ar+ at 55"). Todorov et al. (93/2499) have compared experimental and simulated measurements of target modification by oxygen in a study of 20 nm aluminium films on silicon substrates using O,+ as the primary-ion beam and the background reagent gas.Structures with sharp boundaries are generally used in studies of depth resolution. Kim et al. (93/2328) examined the influence of incident beam angle on depth resolution in the depth profile analysis of Cr-Ni multilayer structures. They reported an optimal resolution of 6 nm for normal incidence of their 02+ primary-ion beam down to crater depths of 500 nm. Zalm and Vriezema (93/2532) discussed the variation of ion-beam induced mixing as a function of energy and angle of incidence and related their findings to experimental data from low-energy depth profiling with Ar+ 02+ and Xe+ primary ions of delta-like antimony layers in silicon.Little dependence on projectile and dopant concentration was observed. The effect of ion beam mixing on depth resolution in SIMS was addressed by Likonen et al. (93/25 15) comparing theory with experiment using a 5 keV Ar+ primary-ion beam. The combined effects of the initial collisional cascade and the subsequent liquid-metal diffusion processes in the thermal spike were found to give an upper limit on the broadening found experimentally. Treichler et al. (93/247 1 ) have investigated primary-ion beam damage of GaAs InP and Si by Cs+ and 02+ primary beams. The craters have been examined by AES and TEM and evidence was found for re-crystallization in the dam- aged regions. In the GaAs samples damage was observed well beyond the penetration range of the Cs+ primary ions.Ion-induced migration effects were observed in the depth- profile analysis of Be implants (9214680). In InP-GaAs materials bombarded with 02+ primary ions a distortion of the Be profile was reported which is much larger than the expected width of the pre-equilibrium zone. The effect was found to depend upon the oxygen content of the surface and the angle of incidence and energy of the primary beam. The group also examined the sputter-induced surface topogra- phy by SEM and TEM. Quantification by SIMS requires the measurement of relative sensitivity factors (RSFs) in the matrix of interest; RSFs have been determined for Al As B C C1 Cu F Fe Ga In K Li N Na P Sb and Sn in zinc selenide (93/2572).Measurements were made on ion implanted samples and the quoted RSF accuracies (+50°/o) were limited by the uniformity of the implant and the error in the measurement of crater depth. The large number of cluster ions and their isotopomers from the matrix limited sensitiv- ity for certain elements. Satoh et al. (93/22 19) have assessed the use of RSFs for quantitative analyses in oxide glass samples using a focused Ga primary-ion beam. The method was demonstrated using coal fly ash and glass fibre samples and good agreement with bulk analytical methods obtained. The internal indicator method was used by Michiels et al. (93/2577) to correct for secondary-ion yield changes whilst profiling through a sample. Arsenic segregation in silicon samples was studied by correcting the As secondary-ion signal using the SiO+:Si2+ ion ratio as a measure of local oxygen content.An Ar+ primary-ion beam was used in this study and the authors suggested that further work should be carried out to investigate the applicability of the method for other primary-ion beams. Effects due to surface modification ionization enhance- ment or molecular ion formation can be used to advantage in SIMS ana€ysis in a variety of ways. Schroer (9312470) has demonstrated that the oxygen enhancement eflkct can be used to classify a region as being in either a low or high oxygen state. Classification is based on the relative yields of singly and doubly charged ion as a function of ionization energies. Adduct ions are less prone to the effect of matrix ion yield than atomic ions.It was reported (931C1462) that if CsM+ adduct ions were used in the measurement of M then274R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 matrix effects were reduced. Gauneau et al. (9312520) have measured the useful yields of M- InM- and P,M- ions for ion implants in indium phosphide. Particularly high useful yields were reported for the P,M- clusters (for M = Mg S and Zn). Clusters containing Al Be C Cd Cu Fe Ge Mg N 0 Pb S Sb Se Si Sn Te Ti and Zn were also investigated. The SIMS analysis of indium phosphide and related materials was reviewed by Geva (93/2500) and a number of workers discussed the SIMS analysis of mercury cadmium telluride (92/4494 93/2327 and 93/2467). Witt- maack (93/2521) has studied the formation of CsM+ ions in more detail noting the effect of the angle of incidence.The Cu and Ge adduct-ion signals showed no angular depen- dence whereas the A1 and Si adducts gave anomalously low signals at near normal incidence. Yields of AsCs+ and ZnCs+ which represented extreme cases differed by a factor of 30 (this was considered reasonable in the context of monatomic ion yield differences in SIMS for which ion yields can vary over several orders of magnitude). Matrix effects were attributed to differences in sputter yield and to variations in Cs mobility in the surface. Klein et al. (92/4422 9214692) have used adduct secondary ions such as C3- and C4- to determine the local chemical state of carbon in metallurgical samples. The ionization mechanism was not clear and the technique was used only for samples containing known phases.The signals were then compared with samples of the pure single phase. Dorozhkin et al. (93/2549) have examined the cationic carbon clusters formed in the SIMS analysis of hot-pressed carbon ribbons. They reported that C,+ clusters with n > 4 were formed in significantly higher yields in the films formed at higher pressures. Segregation of B P and S in steels has been studied by direct observation of the atomic ions by Jackman et a/. (93/2474). Vriezema and Zalm (93/864) discussed effects which gave rise to ion-beam induced migration. Effects included the formation of oxide during analyses which can cause segregation of impurities and swelling of the sample and charging which caused migration of those elements able to form mobile singly charged positive ions.These workers critically reviewed mechanisms proposed for ion-beam induced segregation (IBIS) in the light of their experimental results and concluded that electric field induced effects were the most significant. Darque-Ceretti et al. (93/2575) have investigated the effects of IBIS sputter yields and oxygen enhancement effects in measurements on silicon implanted with Cu and polycrystalline copper implanted with Zn. Samples were also analysed by AES and XPS. Kilner et al. (9312523) examined ion-beam induced migration of Cu in silicon as a function of primary-ion (02+) beam energy and angle of incidence. The decay length varied a little with energy (between 2.5 and 14 keV) whereas the effect of incidence angle was much more pronounced.Electrical charging of insulating samples can cause changes in secondary-ion energies image distortion and ion signal fluctuations. Reed et al. (9214697) reported that even with a neutral primary beam secondary-ion and electron emission led to sample charging effects and that electron beam compensation was desirable. Extreme sample biases have been used to compensate for charging effects in insulating samples. With 0- primary and positive secon- dary-ion analysis (93/2484) analytical sensitivity was re- duced but spectral interferences were suppressed al biases of approximately 90 V. A number of novel applications of SIMS have been reported. The application of mass spectrometric methods to in situ analysis of extraterrestrial solid samples has been reviewed by Kissel (9312561).The application of SIMS to lunar and asteroid surfaces continues with a study of the solar wind as a primary-ion beam. The solar wind is composed of 95% H+ and 5% He2+ with a flux at the lunar surface of between 10-104 ions cm-2 s-I. Elphic (9312344) and colleagues have mimicked this effect using 1.5 keV H+ ions and 4 keV He2+ ions in the analysis of Apollo soil simulants. The secondary-ion yield was lower by a factor of 400 than for a 5 keV Ar+ primary-ion beam. NonetheIess the solar wind primary-ion beam was shown to produce a useful secondary-ion signal. Micrometeorite sputtering was also a significant contributor to this secondary-ion yield (93/2345). Clear evidence that these types of sputtering occur is given by the amorphous surface layer observed on lunar grains.The imaging capabilities of SIMS are particularly impor- tant in biological applications but care must be taken as quantification is difficult owing to sample inhomogeneity and the large potential for interference from organic isobars. Spectroscopic techniques including SIMS suitable for the analysis of biological specimens have been re- viewed by Linton and Goldsmith (93/171 I) (185 refs.) and by Aller (93/2331). Jauneau et al. (9312289) have examined the distribution of Ca and Mg in histological sections of flax plantlets. They discussed approaches to sample fixation which limited migration and loss of soluble analyte ions. Marchal-Segault et al. (92/4282) have determined the distribution of Cu in the organs of fruit flies intoxicated with a copper sulfate based fungicide.Briancon et al. (9312292) discussed the use of SIMS to study 1251 and 1291 uptake in both animal (in vivo) and human (in vitro) thyroid glands. The application of SIMS for determining the subcellular distribution of B derived from drugs used in boron-neutron-capture therapy was reported by Bennett et al. (93/2293). The distribution of A1 in brain tissue sections from renal dialysis patients has been examined by Mountfort et al. (9312659). Background was reduced by sputter-coating metal foils with silver for use as sample substrates. Chassard-Bouchard et al. (93/2585 93/26 14) have stud- ied the distributions of stable and radioactive elements in biological tissues. Whilst a great deal of useful information is presented regarding elemental distributions the ability to image 241Am and 239Pu is alarming.These data implied local concentrations >> 1 mg kg-' (equivalent to = 127 kBq g-l for 241Am). The group did not demonstrate that the signals were free from isobaric interferences such as 197A~42Ca at mlz = 239 and 197A~44Ca at mlz = 24 1. The Au is available from the substrate on which the sample has been placed and the importance of the 197A~40Ca adduct signal in similar tissue samples has been reported by the same group. Such interferences could be eliminated by the use of silicon rather than gold substrates and by carbon-coating to reduce electrostatic charging. At low mass high resolution has been used to identify and quantify interferences in 27Al measure- ments. In another paper by the same group (93/2614) the distribution of Ag Al Ba Ca Cr Cs Fe Hg Ni Pb S Si Sn T1 and Zn was examined in a number of biological samples. In both studies electron microprobe imaging was used where possible to confirm mass spectral identifica- tion.The use of SIMS for the study of microscopicparticles has been addressed by a number of workers. Van Grieken and Xhoffer (92/4599 93/2223) have reviewed the use of microprobe techniques for the study of individual particles (citing 117 refs.). The use of laser microprobe mass spectrometry (LMMS) EPMA SEM and SIMS was dis- cussed including the application of SIMS to the analysis of coal fly ash particles and oil soot particles. The problems of surface topography and charging were not addressed.Hisashi et al. (93/2483) reduced charging in insulating particulate samples by embedding them in graphite. How- ever residual charging was seen to have an influence on ion energy and impurities in the graphite binder were ob- served. Goshnick et al. (93124 12) discussed the capabilitiesJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 275R of SIMS for depth profiling in particulates from pigments outdoor aerosols and welding fumes. Advances in the use of SIMS for high spatial resolution imaging in two and three dimensions and applications to ever smaller microelectronic devices have been reported. Nihei et al. (93/22 18) reported high spatial resolution three-dimensional (3-D) analysis of sub-micrometre struc- tures using Ga-focused ion-beam SIMS.Fleming (93/2376) discussed approaches for converting 2-D surface analyses into a 3-D analysis. Stevie et al. (93/2454) have developed test structures on silicon wafers as aids to the microanalysis of small regions of production wafers. Harris et al. (93/2455) discussed the use of such structures on the unused portions of product wafers. The test structures aided in the analysis of the very small regions which might be of interest in the failure analysis of production wafers. High spatial resolution using Ga liquid metal ion guns has also been reviewed (92145 3 1 ). Dupuy et a[. (93/2524) reported that depth resolution in the depth profiling analysis of an Fe-Ti multilayer structure with an 02+ primary-ion beam was improved by oxygen flooding at 133.32 x 1 0-5 Pa.Without oxygen flooding surface roughness developed. Zalm and Vriez- ema (93/2522) reported the advantages and disadvantages of oxygen flooding techniques. Reduction in the erosion rate was compensated for by the enhanced ionization efficiency the formation of an amorphous surface layer had advantages and sputter equilibrium was rapidly achieved but segregation effects were also observed. Sykes et al. (93/2595) reported that the useful yield of Cs sputtered from a silicon matrix was reduced by oxygen flooding. This was ascribed to the formation of CsO and changes in the kinetic energy distribution of secondary ions rather than collisions with gas molecules above the surface. Secondary ion mass spectrometry is one of the few surface techniques capable of the determination of H concentration Depth profile measurements of D and H ion implants in polished graphite were reported by Paynter et al.(93/2578) who compared their results with ERDA measurements. Good agreement was found between the peak position and integral of the implant as measured by the two techniques. The CH+ adduct ion was used for the measurement of H. Pavylak (93/2581) has examined the influence of vacuum conditions on H background signals using an Ar+ primary-ion beam and a background pressure of Pa. The purity of the primary-ion beam was also addressed. Instrumental variations presumably depend upon the pumping systems used for the sample chamber. Migeon et al. (92/4699) reported a 666.61 x Pa vacuum in the sample chamber of their Cameca IMS-4F instrument owing to the addition of a cryo-pump a bakeable source chamber and a new bakeable sample air- lock.This allowed H and 0 to be determined at 1 x 1016-2 x 10I6 and 3 x 1015-4 x 1015 atoms ~ m - ~ respec- tively. Gnaser and Oeschner (93/2525) have used the CsH+ adduct ion signal for quantitative determination of H at concentrations of lOI9 H atoms ~ m - ~ . Hayashi and Matsu- mot0 (93/2650) reported their use of the SOH+ ion to investigate surface silanol concentrations in silicate glasses. The method was calibrated against XPS measurements. The SIMS technique has been a valuable tool in the microanalysis of mineralogical specimens. Isotopic discrim- ination effects relevant to geochemical applications were discussed and examined by Deloule et al.(93/225 1). Isotope discrimination in D:H measurements were studied as this measurement showed the most pronounced effect. Discrim- ination effects were also reported in the measurement of I1B:loB 34S:32S and 87Sr:86Sr. The application of SIMS to the analysis of fluid inclusions in minerals was also reported (92/4429). 1.8. Spark Source Mass Spectrometry (SSMS) Although still used in a number of laboratories around the world and still capable of uniquely valuable analysis the further decline of this technique is underlined by the limited number of publications in this review year. Studies of fundamental processes can rarely be considered to be original and are either a repeat or a derivative of studies performed up to three decades ago. Instrumental modijications have included (93/C36 1 ) the re-design of the spark-excitation electrode geometry and alteration of the electrode connection to decrease the ion energy spread.This resulted in a more focussed beam of ions and a significant reduction in analysis time. The Tesla transformer was also re-designed to improve stability and hence reproducibility of the ion-beam composition. Relative sensitivity factors in particular for the volatile elements have been found (93/2607) to be dependent on the number and duration of prior periods of sparking. A linear correlation was observed between In(RSF) and boiling temperature for some trace elements but not for volatile elements and C. Elements with a large diffusion coefficient had a large RSF. Workers in Beijing used the isotope dilution method for the certification of eight trace elements in a U308 SRM with an average precision of -t 11% (93/2606) and for the determination of Ce Cu Dy and Pb in a Y203 SRM with a precision of <6% accuracy of < 5% and detection limits in the range 1-100 ng g-l (93/2626).Particular attention was given to spectral interferences optimum addition of spike and choice of conducting medium. The method was considered to have advantages of simple sample prepara- tion simultaneous determination with high sensitivity and absolute analysis with no need for calibration standards. The report on the analysis of solutions describing instrumentation and analytical procedures is now available in English (93/2094). Stable ion currents were achieved for HCl with concentrations in the range 20-32% by cooling at -70 "C and applying an r.f. voltage in the range 7-1 5 keV.Detection limits of 47 elements were in the range 1 0-7- 1 0-4 and good reproducibility was achieved. The application to the trace analysis of organometallic compounds used for epitaxy was unique (93/2364). In one procedure the compounds were hydrolysed in an organic solvent-mineral acid system to produce metal oxides and cations of the contaminants which were pelleted with graphite for analysis. In a second preferred procedure the compounds were pyrolysed directly in graphite used to form the SSMS electrode. The method was fast and avoided introduction of further contaminants. 1.9 Sputtered Neutral Mass Spectrometry (SNMS) Sputter initiated resonance ionization spectroscopy (SIRIS) is a form of SNMS and there is therefore some overlap between this section and the RIMS section of the review.Becker et a/. (93/2464) published a review paper discussing SNMS in particular photoionization of sputtered neutrals was compared with SIMS showing the advantages of the former for quantitative measurements at buried interfaces and of ultrashallow implants. Non-resonant photoionization allows sensitive multi- element analysis with less sensitivity than RIMS but greater sensitivity and less matrix dependent signals than SIMS. The method is known as surface analysis by laser ionization (SALI) Andersson and Rosen (92/4630) have assessed the quantitative capabilities of SALI in the analysis of steel samples. In their instrument which incorporates a reflec- tron TOF-MS material was sputtered using a 5 keV Ar+ ion beam and ionized with 193 nm ArF exiplex laser light.These workers reported accuracies in the range of 10-1 5%276R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 through the use of RSFs and claim that precision is limited by statistical effects rather than matrix influences. Careful sample cleaning allowed quantitative 'bulk' analysis to be performed for components present at the 10 mg kg-l level or higher. The authors also reported that doubly charged and molecular ions were generated in the ionization process. Rapid surface changes were noted owing to adsorption from the 3 x loe7 Pa residual gas pressure. Kikuta and Jenett (9312232) have noted instrumental effects on sensitivity factors in SNMS.Target potential was particularly influential in their plasma ionization instru- ment. Bickel(93K226) has analysed zirconium alloys using both resonant and non-resonant post-ionization of laser ablated neutrals. Whilst non-resonant ionization provided multi-element information resonant ionization of the analyte reduced the space charge due to ionization of the zirconium. A collaborative research project (93/2283) investigated the calibration and optimization of AES and SNMS for the analysis of scales and tarnishing layers on steels. A series of well-defined surface layers were prepared for the measurement of sputter rates and sensitivity factors. Matrix effects are in general similar to those found in SIMS with the notable exception that ion yields are not critically dependent on the matrix type.Inherent and sputter induced surface topography effects were discussed by Koch et al. (93/2384) for depth profile analysis of steel and silicon wafer samples using GD-OES and SNMS. Depth resolution was discussed in terms of surface rough- ness parameters. 1.10. Stable Isotope Ratio Mass Spectrometry (SIRMS) The most active area of technique development continues to be the use of GC-combustion-SIRMS for a wide range of applications. Sources of error in the determination of 13C:12C ratios in organic compounds were (9312249) mainly the quality of the furnace-tube packing and the perform- ance of the cryogenic trap. Precisions (la) of up to 0.23°/w were obtained for 70 ng samples using fine-grained (0.35-0.5 mm) CuO packing but were poorer ( ~ 0 .6 2 ~ 0 ) for coarser (0.35- 1 mm) grade packing. Poorer performance could also result from inefficient trapping. Efficient trapp- ing of water combined with improvements in furnace performance resulted in precisions of <0.4O/bo and accura- cies of <0.65°/bo for high-molecular-weight compounds (268-338 u) and precisions and accuracies of <0.2%0 for compounds of lower relative molecular mass ( 142- 1 73 u). The system description and technical requirements for multi-dimensional GC-SIRMS have been discussed (9312429) for applications in flavour analysis. A number of interesting applications of the GC-combus- tion-SIRMS technique have been evaluated. Routine rnea- surements of 13C:12C ratios could be made (93/2 156) with precisions of < 1 O/oo for < 10 ng of highly-enriched uni- formly-labelled fatty acid used as a metabolic tracer and < 1OOo/oo for (30 pg of fatty acid the latter corresponding to a 100 fmol sample.The procedure was considered superior to organic GC-MS and radiotracer methods in terms of required doses and analytical efficiency. A system for the on-line purification of expired breath C 0 2 and determination of its isotopic composition has been used (93/23 18) to analyse breath samples down to a volume of 50 p1 with high precision and within 150 s. The carbon isotope of bubble CH4 evolving from wetlands could be measured (93/2479) with an accuracy of kO.S%. Two commercial elemental analyser-SIRMS combina- tions have been compared (92/4687) for the simultaneous measurement of 13C12C ratios and total C content in organic samples.Performance characteristics discussed were overall accuracy of analysis memory effects minimal sample size requirement and liquid nitrogen consumption. The authors were surprisingly allowed to declare one system as superior to the other. Efforts are being made to make isotopic measurements on small volumes of water. Dissolved inorganic C 613C and 6l80 could all be measured (93/2247) in a water sample of <2 mi by injection through a septum into a temperature- controlled and evacuated chamber containing 0.3 ml of H3P04. Evolved C02 was drawn through two 90" traps to separate water vapour and was condensed in a liquid nitrogen trap before introduction into the MS.The method was fast (45 min per sample) reproducible (O.lo/oo) and accurate down to 1 mrnol l-I. The ultimate in small volume analysis was the determination of 6l80 in sub-pl volumes of water in geological fluid inclusions (92143 14). A key feature was a 30 mm length of glass capillary tubing (2 mm i.d.) used for C02-H20 oxygen isotope equilibrium exchange with subsequent analysis of the C02. An apparatus for the automated hypobromite oxidation of ammonium salts (the Rittenberg procedure) used in nitrogen isotope analysis has been modified (93124 19) to improve performance and to reduce analytical time. No memory effects were observed even following samples containing 40 at.-% 15N and the reproducibility at the natural abundance level (n= 10 50-1 50 pg of N) was <0.0001 at.-% 15N.Analyses in the range 0.2-1 at.-% 15N (50-150 pg of N) gave good agreement with manual Rittenberg analysis ( 1 mg of N) but in the range 2-20 at.-% I5N the automated analyses gave slightly lower results which were attributed to out-gasing of N2 from plastic microplates used to contain the samples. Laboratories continue to evaluate commercial elemental analyser- SIRMS against the traditional manual procedures for determination of 15N in plant and soil samples and have found yet again that the automated procedure is suitable for routine analysis (92/45 12) with the proviso that attention to sample homogeneity is necessary. Coupled 613C and 615N measurements are possible on a newly-developed instrument (9214686) in which samples were combusted in an elemental analyser to produce C02 and N2 for subsequent cryogenic purification and isotope analysis.Throughput was more than 30 samples per day and good agreement was achieved for SRMs. The relatively poor precision of conventional quadrupole MS has precluded its use for nitrogen isotope analysis. It has been demonstrated (9312378) however that satisfactory performance can be achieved for enhanced 15N abundances but not for natural lSN abundance. An improved inlet line resembling a double-beam spectrophotometer was pro- posed to improve performance. A sample preparation procedure for hydrogen isotope analysis was based (9311252) on the reduction of water by Pt-activated Mg at 400 "C for 1 h. Activation of the Mg involved annealing of Mg granules in vacuum for 2 h at 550 "C separation of the 0.5-1 mrn fraction reaction with H2PtCl6.6Hz0 and separation and drying of the solids.The prepared reagent was stored in the dark in air-tight containers and de-gassed at 400 "C for 1 h before use. Highly reproducible results were obtained for 5 pl samples Developments continue in noble gas isotope analysis. A commercial MS has been modified (9312330) with a fully automated inlet system for preparation and purification of natural water samples for the measurement of He isotopes and trace tritium concentrations. The 3He detection limit was close to cm3 STP corresponding to a tritium level of 0.003 TU for a 500 g water sample stored for 6 months for 3He re-growth. A new instrument called HIRU was designed and constructed (9214428) for the argon isotope analysis of minerals from young volcanic rocks as well as metamorphics and granitoids.The new system allows the dating of geological materials with high sensitivity (e.g. of H20.JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 277R mica of the Cretaceous age) high precision ( 1 Yo) reliability and ease of analysis. 1.1 1. Thermal Ionization Mass Spectrometry (TIMS) The continuing large number of reports on this high- precision technique confirms increased activity over the last few years. Readers are referred to two substantial review papers which give particular emphasis to the determination of relative atomic mass (93/2359) and the use of ID for the determination of trace elements (93/23 57) respectively. An instrument with tandem magnetic sectors has been used (9312508) to study ion transmission efficiencies both theoretically and experimentally.Transmission was found to be strongly dependent on the source filament geometry and a single V-filament ion source increased transmission from 75 to 100%. Ion transmission was also increased significantly without changing source geometry by location of a cylindrical einzel lens near the focus between the magnets thereby providing vertical focusing of the ion beam without perturbing focal properties on the plane of mass dispersion. An attempt has been made (93/2576) to improve under- standing of the fundamental ionization process on rhenium filaments by measuring the influence of metal overlayers on the polycrystalline rhenium filaments.Work function and near-surface electron density data for Ag-Re Cu-Re and Ir-Re were compared with earlier data for Au-Re Pd-Re and Pt-Re in order to aid understanding of the influence of surface additions to the work functions of ionization sources. Observed changes in work function were consistent with a simple initial-state understanding of X-ray photoe- lectron spectroscopy core-level data involving charge flow away from the surface. Faraday cup eficiencies in a multicollector instrument were established (93/462) by measurement of Nd isotope ratios using five different cup configurations. This led to improved analytical performance through correction for the different cup efficiencies and identification of damaged Faraday cups. It is not possible in the analysis of two-isotope elements to correct for instrumental massfractionation by normaliza- tion to a fixed ratio.A new procedure (93/2162) proposed to overcome this problem involved the analysis of monox- ide ions and normalization to the oxygen isotope ratios. Using La0 as an example it was shown that mass fractionation caused both the 139La180 138La160 and 138La:- 160:139La160 ratios to vary almost linearly with the 139La- 180:139La160 ratio. Normalization of the 139La180:139La160 to the l80:l6O ratio allowed measurement of the shift in the 138La:139La ratio using both the 139La180:138La160 and 138La160:139La160 ratios. It remains to be shown that this is a feasible procedure. Very high long-term reproducibility has been demon- strated (9312246) for the multicollector measurement of Nd and Sr ratios. Exponential fractionation correction for Sr data and an empirical correction for Nd data for which exponential correction was ineffective resulted in mean external reproducibilities ( 2 4 of f 0.0000 19 for 87Sr:86Sr and kO.000008 for 143Nd:144Nd over a four year period.The best 142Nd:144Nd data would only agree with previously published values however if an exponential correction were applied. High dynamic range has been exploited (93125 1 1) for the precise determination of the isotopic compositions of Ra Th and U. A dynamic routine employed a Daly detector whereas a static routine used both the Daly detector and off-axis Faraday cups. The Daly detector had a linear response up to ratios of at least 5 x lo4 and in the dynamic mode was used to measure ion beams in the range 5- 1 x 1 O5 counts s-l.In the static mode isotope ratios up to 5 x lo5 were measured successfully. Procedures have also been described (92147 17) for the measurement of isotope ratios in picogram size samples of Pu and U. The ability to measure very low 230Th:232Th ratios is being increasingly exploited. Ratios as low as 2.75 x were measured (93/2252) with an average precision of 0.5% in leucite-bearing lamproites from the Gaussberg volcano Antarctica. Concentrations of 232Th in both living and fossil specimens of the solitary coral Balanoppyllia elegans were (93/234 1) much higher than in reef-building corals (1 2-624 and 0.1-1.6 pmol g-l respectively). The results indicated that a significant amount of 232Th is incorporated in the aragonitic skeleton during growth or is attached to clay-size silicates trapped in the skeletal material. The calculated initial 234U activities in the fossil specimens of B.elegans were higher than the 234U activity in modern sea-water or in living specimens. Much attention continues to be paid to boron isotope analysis. The B isotopic composition in B4C was measured (92/4315) with a precision of <0.03% by reaction with CsOH in the MS to produce a strong and stable beam of Cs2B02+ cations. Boron has been extracted (9312342) from aqueous fluids and purified by ion-exchange methods and determined with a precision (20) of 0.025% by the caesium metaborate method. The isotopic composition of < 1 pg of B in silicate samples and in natural fluids was measured (9312248) with precisions of 0.1 and 0.02% respectively following sample dissolution in HF and HCl containing mannitol which suppresses boron volatilization and isoto- pic fractionation by formation of a boron-mannitol com- plex.The Cs2B02+-graphite method was employed for analysis. The use of negative ion TIMS (9312250) for the determination of B isotopic composition is a new approach. An increase in sensitivity of 100- to 1000-fold compared with the caesium metaborate method was achieved by addition of La(N03)2 as activator and by measurement of B02- ions formed on a single filament. Such high sensitivity allowed analysis of as little as 0.1 ng of B with a precision of 0.2%. Fractionation and memory effects and the effect of temperature have been studied systematically for the isotopic analysis of lithium (9312275).The best chemical forms for analysis were found to be LiCl and Li2B407. Fractionation of lithium isotopes was observed (93125 12) in the measurement of Li2B02+ ions but it was considered that it could be controlled so that the 6Li:7Li ratio could be determined without application of correction factors. Attempts have been made by a group in Tokyo to detect variations in molybdenum isotopic composition. A chemical procedure was developed (92/4585) for extraction of micro- gram amounts of Mo cleanly and rapidly from gram amounts of iron meteorites. Particular attention was paid to the complete separation of Mo from Ru and Zr. It was possible to separate Mo from Fe by solvent extraction over only a narrow range of HC1 concentrations.A special triple filament technique was used (931241 3) to obtain a stable Mo+ ion beam for the measurement of Mo isotope ratios in molybdenites. No differences in isotope ratios bigger than 0.004% could be detected. The negative-ion TIMS technique continues to be devel- oped in particular by Heumann and colleagues at Regens- burg. Sample amounts as low as 1 ng of 0 s were extracted (92/4682) from geological materials and loaded as hexa- chloroosmic acid (H20sC16). Analysis of picogram amounts was considered feasible using a Faraday cup detector. Introduction of O2 or Freon into the ion source enhanced the emission of Os03- ions by a factor of up to more than 10. Both compounds also stabilized the high voltage potentials of the optical ion lenses instability of which is a permanent problem in negative-ion TIMS.A microwave digestion system using K2Cr207 as oxidizing agent has been278R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 developed (9311033) for the isolation of 0 s from molybden- ite for Re-0s age determination. The determination of S Se and Te has been investigated (93/2509) using a double-filament ion source with BaO applied to the ionization filament in order to reduce the work function of the rhenium filament material. The most abundant ions were S- Se- and Te- although low intensities of SeO- Se02- TeO- and Te02- were also detected and high ion currents of SO2- were observed from BaSO samples. Silica gel added to the sample enhanced the Se- ion current by a factor of 40 and the Te- intensity by a factor of about 10 but did not enhance the S- ion current at all.A range of reference materials produced and character- ized by the group at Geel Belgium included 20 synthetic 239Pu:242Pu mixtures for isotopic measurement of Pu (93/2280); a highly-enriched 244Pu solution certified for 244Pu concentration (93/2282); an llB spike solution (93/2506); a 6Li spike solution (93/2507); and two samples of silicon certified for isotope abundances (93/2446). In addition two types of 235U:239Pu solid spikes for the assay of reprocessing plant input solutions were under study (93/2281). Three U solutions have been certified in Russia for isotopic composition (93/2277). Results for the determi- nation of sulfur content in five bauxite and two sediment NIST SRMs by ID-TIMS confirmed (93/1913) that the previously certified values had a positive bias of up to almost 100%.Isotope dilution analysis continues to be widely reported both for new procedures and relatively routine applications. Optimization of the ratio of the estimated but unknown amount of element in a sample solution to the known amount of element in the tracer solution has been examined (93/2279) in order to minimize the relative uncertainty in the determination of the unknown amount of element in the sample solution. An automated spike preparation and dispenser system has been developed (92/4440) for the analysis of dissolved irradiated nuclear materials at the Savannah River Site. The system maintained and updated all the records on the individual spike containers and their contents and carried out a statistical analysis of spiking accuracy.Isotope dilution is a particularly powerful technique for ultra-trace analysis and a number of new procedures have been reported in the current review year. A single bead of anion exchange resin (Dowex 1 or Wofatit SBW) holding preconcentrated U was fixed (92/4555 92/4556) to the rhenium filament for determination of U in spent nuclear fuels. Sub-pg amounts of Th and U have been measured (93/2538) in four different target materials used or pro- posed for electronic neutrino detectors. An improved method for the determination of Eu Gd and Sm at concentrations of 50 ng g-' in 1 g of UJOs involved (93/2605) ion-exchange extraction and separation from other REEs and analysis using a single filament.Precisions were in the range 1-3%. Detection limits of 0.008 and 0.006 ng g-' were achieved (9312379) for Th and U respectively in the refractory metals molybdenum and tungsten. The detection limits for Ca Cd Cr Cu Fe and Ni were in the range 0.12- 19 ng g-l. Selective cation exchange chromato- graphy extraction and electrolytic methods were combined with positive-ion TIMS. Comparison of results with those obtained by a number of other MS techniques (GDMS ICP-MS SIMS) revealed a wide spread over the different techniques. A similar procedure has been described (93/2100) for the determination of Ag Cd Cu Fe T1 U and Zn at very low concentrations (ng g-l levels but with Th and U at sub-ng g-l levels) in high-purity aluminium using a quadrupole TIMS.Traces of Si in water could be determined (93/2326) at the ng g-I level with an accuracy of better than 10% by analysing Si in the form of sodium silicate and with Ba(OH) as an ionization enhancer. Matrix elements can also be determined by IDMS. Ion- exchange procedures were used (93/2441) to separate Zr from Al Pu and U in U-Zr-A1 and Pu-Zr-A1 alloys for MS analysis. Care was taken to eliminate problems encountered in the chemical exchange between Zr isotopes in the spike and in the sample. A precision of better than 1% was achieved. Workers in China continue to calculate more accurate relative atomic masses. That of boron has now been measured (92/4368) as 10.809 k 0.003 (20). Measurement of the Il3In:lL5In ratio as 0.044804 with a precision of 0.05% (93/2266) has allowed the relative atomic mass of indium to be fixed as 1 14.8 185 in comparison to the previous value of 114.82.1.12. Other Methods In the atom probe specimens are analysed in the form of fine needles (end radius 50-200 nm) cooled ( ~ 5 0 K) and under high vacuum. Single atoms are removed either by very short (1 0 p ) high voltage ( 1.5-30 kV) pulses on top of a 10 kV d.c. voltage (field evaporation) or by nanosecond laser pulses. Ions are analysed by TOF-MS. The technique is one of several covered in a review (921409 1) on advances in surface analysis. A new class of atom probe instrument combined (93/2494) single-atom sensitivity MS with posi- tion sensing and had the potential of reconstructing nanometre-scale composition in three dimensions.Difficul- ties arose in the first instrument constructed when more than one ion was evaporated from the analysis area on a single field evaporation pulse. Improvements to be incor- porated in subsequent instruments were described. Another TOF atom probe field ion microscope had (9312496) the unique feature of low temperature (18 K) sample cooling to allow stable H ion images even of aluminium alloys and a switchable detector system with a channeltron electron multiplier and a channelplate electron multiplier. Applications of the atom probe to studies of alloys and semiconductor materials have been reviewed (9312625). Use of the ion trap for atomic analysis continues to show potential. A method for the LA sampling of solid metal samples directly into the ion trap (93K379) has received the acronym LAITMS (laser ablation ion trap MS).A pulsed Nd:YAG laser beam was used to ablate sample pins inserted radially through the ring electrode. Improved analytical performance was achieved through better va- cuum pumping a differentially-pumped sample probe new hyperbolic ion-trap electrodes with better mechanical toler- ances improved optics for the ablation laser and an optical path through the sample volume of the ion trap to allow optical studies of the stored ions. Laser desorption experi- ments on microparticles contained within an ion trap have been carried out (9312354) for silicon carbide particles coated with quaternary ammonium or phosphonium salts and uncoated particles of silicon carbide iron and niobium.The potential of the ion trap as mass analyser for ions generated in the GD has been investigated (93/2 159). Ions derived from the argon plasma gas were depleted in the ion trap by rapid electron and proton transfer reactions to background gases in the trap and the terminal ions were quickly ejected. Chemical noise owing to relatively high background pressures in the ion source precluded analysis of components at concentrations lower than a few tens of Pg g-'. The Penning trap has found increased use for the analysis of unstable isotopes. A compensated Penning trap for the measurement of the mass of an ion relative to some calibration ion has been described (93/2435) and applied toJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993.VOL. 8 279R the determination of the atomic masses of 3H and 3He. The masses of Fr and Ra isotopes at the ISOLDE on-line isotope separator were measured (9312436) on a tandem Penning trap MS with a resolving power of 5 x los and an accuracy of 1.8 x lo-'. The ion motion of unstable isotopes in a Penning trap was excited (93/2544) with time-separated oscillatory fields and the Ramsey fringes observed for dipole and quadrupole excitations. The mass of unstable Ba Cs Fr Rb and Sr isotopes have been measured (93/2647) for the first time with high accuracy. The high resolution of laser desorption Fourier transform ion cyclotron resonance MS (FTICR-MS) was considered in a review article (92/4451) to be an advantage in atomic analysis for the separation of interfering ions such as oxides from the atomic ions.The technique is however best suited for the analysis of polymers. The potential of coupling GD sources with FTICR-MS is being evaluated by a number of groups. Introduction of the ions from the externally- mounted ion source has been accomplished (9312245) without the use of ion optics and relying simply on the kinetic energy of the ion. Resolving powers of > 100000 are considered achievable and would be sufficient to overcome almost any isobaric interference. An alternative design used (93/24 1 5) a four-element electrostatic lens to accelerate and focus the externally-generated ions into the analyser cell. At the current stage of development the detection limits attainable are several orders of magnitude poorer than those achieved by commercial GDMS instruments but considerable improvements were foreseen.The combination of atomic absorption and MS is occa- sionally used to investigate atomization processes. The coupling of the atomization efficiency and microsampling capability of ETA with the simultaneous multi-element capability of MS offers the prospect of a powerful analytical technique. Aspects of a new technique called atomic beam TOF-MS (AB-TOF-MS) have been discussed (92/4629). In order to avoid losses while using continuous ETV in combination with the pulsed TOF-MS some sort of ion storage such as an ion trap must be used. Using estimates of the efficiencies of each stage in the instrument theoretical LODs of 300-1 x lo6 atoms were obtained. Another ETA- MS design (93K275) included a modified graphite furnace an atmosphere/vacuum interlock and MS with electron impact (EI) ionization.The atomized sample was trapped on a cooled tantalum second surface and after insertion into a quadrupole MS was released into the MS by heating. Many interferences were eliminated because much of the matrix and the decomposition products were not trapped on the second surface. The use of electron impact MS for the analysis of metals is rare and probably reflects the lack of access to alternative procedures. A method for the determination of REEs in geological samples involved (93/2352) deriva- tization as the acetylacetonates and selective ion monitor- ing to avoid interferences from the sample matrix. Detec- tion limits were in the pg g-' range with good reproduci- bility.Agganval and co-workers continue to develop methods for the determination of metals in clinical samples in particular urine by GC-MS. Three derivatizing reagents were investigated (931232 1 ) for the determination of Se. Although all three offered the same precision (1-7% at the 10 ng level) 4-trifluoromethyl-o-phenyldiamine was pre- ferred because it showed no measurable memory effect. Other workers have used (9214028) chelation with 4- trifluoromethyl-o-phenylenediamine and GC-MS to study the absorption of Se by lactating women. Whereas lactating women did not absorb or retain more Se than non-lactating or never-pregnant women when administered in the form of selenomethionine they did retain more when Se was administered in the form of selenite. This was seen as clear evidence of a speciation effect in human nutrition.The determination of Co involved (93/2423) the addition of a known amount (1 pg) of enriched-62Ni as internal standard chelation with lithium bis(trifluoroethy1)dithiocarbamate and detection by selective ion monitoring of the m/z 57 1:574 ratio (corresponding to the 59Co:62Ni ratio). The detection limit was as low as 1 pg I-' in urine and the dynamic range was about 100. The use of enriched-'j2Ni avoided problems of endogenous Ni in the urine and also allowed Ni to be determined in the same sample. In a separate development (93/2424) Pb was determined at the ng g-l level in water samples by addition of a 206Pb spike ethylation with sodium tetraethylborate extraction into heptane and detection by selective ion monitoring at mlz 293 (triethy1-*O6Pb) and m/z 295 (triethyl-208Pb). The calibration was linear over the range 0.5-1 50 ng g-' and the detection limit (30) 0.3 ng g-l in 2 ml samples.The use of fast atom bombardment (FAB) for the measurement of trace metal absorption in human nutrition studies continues to find application. Ions were formed (93/2504) from a dry residue on a high-purity silver probe tip in the measurement of Zn stable isotopes. Isotope ratio measurements had a precision of better than 2% ( l a ) for a sample size of 1-5 pg. The FAB-MS technique has also been used (93/2550) for the determination of 54Fe:56Fe ratios in red blood cells following administration of enriched s4Fe as stable tracer in studies of iron bioavailability.Another technique generally associated with organic analysis electrospray MS was considered (93/2242) to be a low-cost and simple source of ions for elemental analysis. Preliminary results showed that the M+ ion was the dominant species for the alkali metals and several transi- tion metals in both aq. and methanol solvents. Background molecular ions were also observed and it was possible to select conditions to make these dominant in the determina- tion of U and V. It was suggested that direct speciation of inorganic solution components was feasible. The US Bureau of Mines has developed (9214297) an MS method for the determination of helium in the I ppm to 10% range with an accuracy of k 1 %. The system incorpor- ated a chrornotographic gas sampling inlet valve an activated coconut charcoal trap with liquid nitrogen cooling and MS detection.2. X-RAY FLUORESCENCE SPECTROMETRY 2.1 Reviews Trends in all aspects of X-ray emission spectrometry were presented by Van Grieken and colleagues (93/1975) who reviewed papers published over the period 1969- 1989. The authors partitioned the relative contributions to the litera- ture of various excitation and detection modes different application areas and from different countries whilst giving special attention to the literature of XRF in environmental analysis. The principles and applications of XRF were reviewed by Ehrhart (9311678) and Stoeppler (9312400). Klaentschi (931 1728) and Bujdoso (931 1876) included XRF techniques in their wide-ranging reviews of instrumental methods for inorganic elemental analysis. Blau and co- workers (93/2708) reviewed the modern arrnoury of X-ray and neutron-ray techniques including XRF spectrometry,280R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 which can be applied to the bulk and surface investigation of metals. Advances in XRF spectrometry in China continue apace and have been reviewed in both English (92/4483) and Chinese (93/2703) by Yuan. Unfortunately the authorita- tive contribution by Ji Ang (92/3978) is in Chinese and less accessible to Western readers. It is pleasing to report the publication of the book entitled ‘Handbook of X-ray Spectrometry Methods and Tech- niques’ (Marcel Dekker New York 1992) edited by Van Grieken and Markowicz. Such comprehensive guides to the subject can only help to support the large and ever- increasing number of XRF practitioners who perhaps because of the academic notion that XRF is a long- established and rather dull technique have had little experience of the theoretical and practical aspects of this important industrial analytical technique.As is the case every year the proceedings of the most recent Denver X-ray Conference (Advances in X-ray Analy- sis 1992 Volumes 35A and 35B) are published but the abstracts cannot be registered by the ASU abstracting system until the year after. The most recent proceedings are Volumes 35A and 35B and whenever it is necessary to consult details of the latest work in the field ‘Advances in X- ray Analysis’ should be an early source in a search of the XRF literature.2.2 Instrumentation There are a number of X-ray techniques on the fringe of XRF spectrometry that could be combined with XRF measurements. Kato and Sugitani (93/ 1872) made simulta- neous XRF and X-ray photoacoustic measurements which allowed the determination of the absolute quantum yield of XRF. The authors also used the combined measurement to characterize more fully layered synthetic materials. The use and observation of circularly-polarized X-rays during XRF measurement was reported for probing metallic magnetism (92/4052) nuclear magnetic moments (92/4069) and site- specific magnetic moments in thin metal layer systems (92/3959). The high power available from synchrotron radiation (SR) sources was used in circularly-polarized X- ray excited optical luminescence (XEOL) measurements on chiral Eu3+ complexes (93/2768).The assertion that XRF spectrometry is well-established may be true in some respects but there continues to be a significant number of patent applications for a wide diversity of XRF instrumentation. Schuster (93/ 1908) filed a patent for a TXRF spectrometer using an LSM as the primary reflector unit which combined the benefits of high reflectivity with energy tunability. Detection limits of 10” atoms cm-* were claimed for silicon wafer surface analysis. Kawai (9311763) made a patent application for what appears to be a conventional WDXRF spectrometer to which was added additional electronics to compensate for energy shift in the proportional counter. The use of a detector filter to carry-out selective energy detection of X- rays for trace elements in the presence of strongly-excited major elements in an EDXRF system was claimed in an application by Guyon (93/2802) although the technique itself is hardly new.A new elliptically-curved crystal monochromator was claimed (92/4362) and Berdikov et al. (92/3996) described what appears to be a conical crystal holder. Watanabe (92/3997) claimed an XRF film thickness gauge incorporating the commonly used idea of a shutter with a calibration material arranged such that a spectro- meter drift check can be performed each time the shutter is closed. A thin-film analyser comprising two detectors was claimed (9311 909) for the determination of the thickness of a zinc layer on galvanized sheet and the composition of the zinc layer.Although the simultaneous WDXRF spectro- meter claimed by Medolazov and co-workers (93/ 1996) appears at first sight to be fairly conventional the descrip- tions of a coaxial X-ray tube-sample-monochromator geo- metry (93/1997) and a spectrometer in which the source and detector are placed on the sample holder walls (93/ 1762) seem to be much more innovative and interesting but are unfortunately only available with descriptions in Russian. In the wake of the recent RSC Instrumental Criteria reports on sequential and simultaneous XRF spectrometers (91/223 1 92/2590) Richardson and Riddle(93/1070) pre- sented some very practical guidelines for purchasers of high- value analytical instruments including XRF spectrometers.The few publications concerned with on-line XRF mea- surement do not fully reflect the real level of application and interest in this area. Kalnicky and Ramanujam (93/1803) Kannan (92/403 1) and Cooper (9311 864) briefly reviewed the current technology and applications and Newman (92/4684) reviewed the related subject of portable and mobile spectrometers. The on-belt measurement of Ca in limestone was described in detail (93/2009) and shown to be suitable for material classification despite the low emergence depth for Ca K X-rays and the unavoidable variations in sample distance. These distance variations could be compensated for by means of a simple spectrum background ratio correction and the standard error in the analysis of bulk material was shown to be about 10%.Rapid quantitative on-line XRF analysis of rolled metal was reported (93/1730) and a flue-mounted XRF spectrometer was successfully applied to the real-time monitoring of the chemical composition of process waste gases from pyrome- tallurgical processes (9312803). The practical difficulties of implementing on-line XRF measurements may be such that it is better in some applications to develop a fully automated sample prepara- tion and XRF analysis facility. Delaurie and colleagues (93/1737) devised just such a scheme to support a fully automated steel-making process. With the exception of the taking of the sample and placing it in the pneumatic transport system the complete analytical process was automated. Samples were surface ground under automatic control in a system which used a video camera to maintain the quality of the analytical surface.From ordering to acceptance the system took 12 months and over the eight month period since acceptance the bad-sample rate was only 0.3%. A dual-robot system was developed (93/18 I 8) for the fully automated preparation and analysis of fusion beads from 0.3 g samples of mixed-oxide nuclear fuel. This fully automated analysis procedure took 1.5 h for two sub- sample measurements on one sample and yielded accuracy of 0.3-0.7% relative and precision better than 0.5% relative. In view of their versatile capabilities it is surprising that more reports have not appeared in the current review period describing the use of portable XRF instruments. However a few applications have been published particu- larly in the areas of mineral environmental and industrial analysis.Zhou et al. (9312749 9311774) used a portable XRF instrument for prospecting for copper ores with particular reference to those from NE China interest being centred on the detection of the following elemental associa- tions ( i ) As Bi Co Cu Hg Ni Pb Sc W and Zn; (ii) Ag Ba Cd I In Sb Sn and Te; and (iii) Co Cu and Ni. Eterradossi et al. (92/4024) used a portable XRF instru- ment to determine in situ the ore grade and to study the distribution of sphalerite in quartz schist in a productive mine. Contaminated soil was analysed by field portable XRF by Raab et al. (9311716) as part of the clean-up requirements of hazardous waste sites particular considera- tion being given to lead contamination.Lead in groundwater at the ng g-l level associated with hazardous waste sites was also analysed in real time by portable XRFJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 281R using a radioisotope source and semiconductor detector by Driscoll et al. (92lC3697). To achieve satisfactory detection limits lead was preconcentrated from a 20 ml sample on to an ion-exchange membrane filter which after drying in air was analysed directly. Further work on lead this time in paint films was reviewed by McKnight (93/1842). A metallurgical application of portable XRF instrumentation was described by Huang and Tuo (9314364) in the analysis of white metal consideration being given to methods for overcoming the effect of segregation and to correct ions for matrix effects.Two applications of transportable XRF laboratories have been described. Ruhter et al. (92/4442) used a transportable system to analyse Pu and U in solution thus avoiding the difficulty and expense incurred by safeguards authorities in transporting hazardous samples from inspected facilities to the laboratory. Measurements were made inside a glove box using an instrument fitted with a germanium detector and a 57C0 source to excite the U and Pu K lines and a combined 57C0 and lS3Gd source for transmission measurements to correct detected intensities for sample self-attenuation matrix effects. And finally a mobile laboratory was described by Kirchnawy (93/2775) in which EDXRF was one of several techniques used to monitor the commercial transport of hazardous materials normally at Austrian customs border crossing points.The state of the art in modern WDXRF analysis was presented in concise readable reviews by Uhlig and Peter (93/2790) and Adamson (9213884). The former authors reviewed the achievable performance for Be and ably demonstrated the wide elemental coverage for Be to U which can be provided by WDXRF. In a second contribu- tion Adamson and colleagues (93/ 1989) presented the latest advances in the XRF measurement of B with particular reference to the all-important non-destructive analysis of borophosphosilicate glass coatings on silicon wafers. Price and colleagues (93/1904) reviewed the relative merits of the newer low-powered WDXRF and conven- tional EDXRF spectrometers and Bonvin et al.(93/1858) reported on the use of a modern high-sensitivity WDXRF spectrometer for environmental monitoring. Advances in XRF calculation and operating software were presented by Kuiperes and van den Bosch (92/C3685) and Adamson and colleagues (92/C3686). Both sets of authors described the benefits which accrue from increasing application of funda- mental parameter (FP) calculations and noted the increas- ing level of ‘expertise’ being incorporated into software systems to assist novice users. In something of a contrast it was concluded in a comparison of optical emission and XRF spectrometry (93/ 1856) that almost similar results were obtained by both techniques but this conclusion only applied to fairly straightforward qualitative analysis and failed to capitalize on the standardless semiquant itative and FP quantitative capability of XRF to provide high quality analytical data.Finally the characteristics and performance of a second-generation combined simulta- neous WDXRF-EDXRF spectrometer were described (931C946). There has been little activity in the development of improved analyser crystals during the review period. Su et af. (93/1757) compared a standard pentaerithritol (PET) PET002 crystal with one comprising trihydroxymethyl- aminomethane (TAM). The TAM (TAM020) crystal offered superior analytical performance including lower high-order diffraction intensities equivalent resolving power (based on partial resolution of the severe Ti I@-V Ka overlap) equivalent peak-to-background ratio superior mechanical properties and a significantly lower coefficient of thermal expansion.In addition the TAM crystal had improved stability in vacuum and a more consistent d- spacing. Providing there are no unforeseen production problems TAM crystals seem likely to supplant PET crystals in future WDXRF instruments. Problems caused by the refraction properties of LSMs that result in inconsis- tencies in the apparent 2d spacing and the occurrence of multiple order lines that are apparently shifted in 2-theta angle were reported by the soft X-ray spectroscopy group at QMC University of London (Luck et af. X-ray Spectrorn. 1992 21 77-8 1 ‘Caveat Emptor Gross Refraction Effects Pose Problems in the Use of Multilayers for Soft X-ray Spectroscopy’). A modified XRF spectrometer incorporat- ing an open-window gas-discharge tube operated typically at 5 kV and 3 mA was used to study first and higher order reflections from a molybdenum-carbon LSM with a nomi- nal 2d spacing of 20 nm.For B Ka the 2d spacing calculated on the basis of the 2-theta peaking angle agreed with the manufacturer’s value. However this value was not consis- tent over the wide range of wavelengths studied and the discrepancies were identified with the LSM exhibiting refraction as well as diffraction properties. The apparent 2d spacing increased with increasing order of diffraction converging to a limiting value of 2 1.05 nm. The refraction constant was found to vary by a factor of 25 over the wavelength range 2.35-1 3.5 nm and the authors’ advice of ‘Caveat emptor’ should be borne in mind when setting spectrometer angles on the basis of the manufacturer’s 2d values for LSM analyser crystals.A new method for manufacturing elastically bent crystals and LSM diffracting devices was described (93/ 1901). The resulting improve- ments in resolving power were presented in detail when the devices were installed in two different types of sequential WDXRF spectrometer. Although there is little to report on their use as analyser crystals there is much work published on LSMdevices used as optic elements. The theory and applications of LSM reflection gratings were presented by Neviere and Den Boggende (9213956). Their report included results for work on multilayers in which the layer thickness varied from the bottom to top of the structure. Smither and Fernandez (93/1968) described the way in which ‘variable-metric’ LSM devices in which the layer spacing varies with position can be produced and characterized.The variation can be controlled either by introducing temperature gradi- ents during crystal growth or by changing the relative proportions of the two elements during this process. A substantial gain in intensity per unit energy can be achieved when these devices are used in double-crystal monochroma- tors fitted to SR beam lines. Furthermore when fabricated as bent crystals these devices were shown to provide large magnification and de-magnification factors. Platonov et af. (92/3953) described the use of spherical multilayer X-ray mirrors for measurements in the 0.1-1.5 keV energy range. The development of new technology for the deposition and growth of multilayer structures from new material and with novel microstructure is an important research area.Kata- oka (93/ 17 19) reviewed the use of dual ion-beam and direct ion-beam deposition techniques and described new ultra- precision grinding and ultra-smooth machine polishing techniques for LSM devices. X-ray reflectivity of Ni/C LSM was reported (92/3958) to be improved by 40% through the use of optimized substrate temperatures (around 100 “C) and by a factor of 4 for surfaces etched by bombarding with 200 eV Ar+ ions. Seki and co-workers (93/1787) produced W/C LSMs using a laser-induced chemical vapour deposi- tion (CVD) process. The X-ray reflectivity at 5 nm was lower than expected and this was attributed to interfacial roughness and inter-diffusion. Further performance degra- dation occurred after storage at room temperature for two months and it was suggested that oxidation of the tungsten film was the cause.Interest in Ag-B Pd-B and Si-B multilayers was shown by Kearney and co-workers (92/3957) who favoured the use of Ag-B for a crystal superlattice X-ray mirror. Unfortunately the silver was282R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY7 OCTOBER 1993 VOL. 8 reported to have a tendency to form islands and failed to provide a working device although the high theoretical X- ray reflectivity of these multilayers was sufficient to encourage this group to continue with various fabrication techniques. Shao et al. (9213955) succeeded in producing Ag-Si LSMs but the useful 90" reflection was for 11.4 nm X-rays and this made them only useful at rather low X-ray energies.Other workers (92/4049) reported the potential benefits of smoother layering greater stability lower ab- sorption and improved reflectivity when using tungsten- boron carbide LSMs as opposed to the usual tungsten- carbon or tungsten-silicon devices. The latter authors also discussed the manufacture of these new devices. An LSM mirror made from Ni-B203 layers and suitable for use as a soft X-ray mirror was the subject of a patent application by Ito and Eto (93/1983) and Shing and Catura (93/1902) reported the fabrication and characterization of Mo-Si LSMs which yielded X-ray reflectivity of up to 42% at 17.1 nm. Yamashita (93/1782) reviewed the manufacture and characterization of LSM X-ray optic elements.X-ray reflectivity was investigated for amorphous silicon crystals grown by an annealed Czochralski process and found to be enhanced when compared to crystals of perfect flat zone-grown silicon. The performance was discussed with reference to the improved monochromatization of SR beams in the energy range ( 5 0 keV. A double-focusing crystal spectrometer in which 13 single silicon crystals were used to reflect the beam on to three CCDs was described (92/3873). A resolution of 4 eV FWHM was achieved at the Ar K lines. A very high resolution four crystal monochromator using a novel mechanical design was built by Tolent ino and colleagues (92/392 1). The monochromator was compact could be used in high vacuum and covered the energy range 0.8-10 keV with high stability.Positional repeatability was claimed to be 0.6 arc s in the region of the Cu K lines. The use of a technique which Yokhin (92K3815) described as preliminary energy selection for an EDXRF system is interesting. A high-luminosity Bragg reflector was placed between the sample and the Si(Li) detector and this acted as a high energy cut-off filter. Limits of detection ( 100 s) of 0.34 and 0.2 ppm for Pb and Se respectively in water were obtained when a 200 W X-ray tube was used. 2.2.1. SRXRF microprobes and X-ray microfluorescence (XRMF) A considerable growth in XRMF is once again evident during the review period. Much work is still carried out using highly-collimated SR beams but there is a noticeable and pleasing increase in the number of publications in which laboratory-scale instrumentation is being developed and applied.The developments in XRMF and how they extend the existing elemental imaging available from electron microscopes were reviewed by Pozsgai (92/2998). The use of synchrotron radiation (SR) sources continues to be important for XRMF and provision for XRMF (X-ray microprobe) facilities is being made at the third-generation European Synchrotron Radiation Facility (ESRF Greno- ble) and Advanced Photon Source (APS) in the USA. The Antwerp group have carried out calculations to predict the optical and analytical characteristics of the proposed X-ray microprobe at ESRF (93/2869). Typical beam spot sizes were predicted to be 2-7 1-6 and 0.8-3 pm for bending magnet wiggler and undulator sources respectively.Detec- tion limits were expected to be in the range 10 ppb- 1 ppm. Thompson et al. (93/2801) at Lawrence Berkeley Labora- tory (LBL) indicated that the APS X-ray microprobe will provide 1 x 1 pm spatial resolution combined with femto- gram sensitivity. To make progress in the development of optics for the proposed APS microprobe the authors carried out experiments with a hard X-ray undulator at the existing CHESS (Cornell USA) facility. Using a Fresnel zone plate beam spot sizes of 8.5 x 30 pm were obtained and when LSM mirrors were used in a Kirkpatrick-Baez configuration a spot size of 4 x 9 pm was achieved. As a result of these experiments at CHESS the authors were able to present the requirements for the optics in the APS X-ray microprobe.Erko and co-workers (93/2870) also used Kirkpatrick-Baez optics to produce a spot size of 2-3 pm using 10 keV SR X-rays at the LURE (Paris) facility. X-ray images with 5 pm resolution were obtained from test objects. Workers at the Photon Factory Japan (93/1836) used image reconstruction in conjunction with a novel SR beam de-magnifier which produced a narrow line-beam of a 'few microns' dimension. The authors claimed that XRF images also with resolution of a 'few microns' were obtained and they applied the technique to chemical state analysis using absorption edge shift measurements. Mura- matsu et al. (Rev. Sci. Instrum. 1992,63 5597) used an SR beam line at the Photon Factory fitted with a 26-period multipole wiggledundulator. The final beam of 8 x 0.1 mm was not designed as a microfluorescence experiment but was used for measurement of B using both direct XRF and also XANES for chemical state analysis in semiconductor materials.Rivers and co-workers (93/2843) described the design and performance of the XRF microprobe at Brook- haven and compared it with other SRXRF microprobes. Susuli and Yoshio (93/1966) obtained a spot size of 3.5 x 4.8 pm in a hard X-ray microprobe using a Kirkpa- trick-Baez optics configuration and Kurmaev et al. (9311789) described an XRF spectrometer for which they claimed a spatial resolution of 4 pm. Recent developments were described in the X-ray microprobe at NSLS Brookha- ven USA (9311679) and ELETTRA Italy (92/3879) and Xiao and co-workers (92/C4 17 1) presented details of the 20 x 20 pm beam produced at the Beijing Electron-Positron Collider facility. Further brief reviews on SR-XRMF were provided by Guttmann et al.(93 1847) Aoki (92/3244) and Hakayawa (9312856). Although not strictly XRMF the proceedings of a recent conference on X-ray Microscopy (93/1688) provide an insight into the use of X-rays directly for sub-structure imaging rather than for generation of fluorescence X-rays which are subsequently measured and used for elemental imaging. A group at the ESRF (Grenoble) has described the technique of X-ray fluorescence correlation spectroscopy (93/2751) which they propose to use in time-resolved studies of local concentrations of slowly diffusing macro- molecules carrying XRF labels. Small probe volumes (< 10-Io ml) and ultra-low concentrations were determined to be necessary prerequisites for the experiment. The small analytical volume is expected to be achieved by the use of grazing incidence X-ray excitation and detection will be by a specially designed CCD-type camera.The use of a direct X-ray microprobe was ruled out due to excessive heating of the sample by the intense SR beam. A zone plate with a primary focal length of 40 cm for 8 keV radiation was designed and tested by Lai et al. (92/3960). The usable energy range was 5-1 1 keV and the spatial resolution obtained was measured to be around 2 pm when using the third order focus and a monochroma- tized SR beam. Piestrup et a/. (93/2743) produced a 0.5 mm diameter focus spot from X-rays derived from a so-called transition radiator.The rather exotic source was a 93 MeV electron beam striking a stack of eight Mylar foils (each 3.5 pm thick) which produced an annular conical X-ray beam. This beam was collected by a quartz cylinder and provided the 500 pm spot at a distance of 1.35 m from the radiator. The useful X-ray energy range was 1-4 keV but the use ofJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 283R alternative less-exotic X-ray waveguide technology appears to offer better performance for XRMF with the clear benefit of the instrumentation being more accessible. Cross and Augenstine (93/2004) made a comparison of the detection limits obtainable with three types of instru- ment a conventional EDXRF spectrometer; a commer- cially available laboratory X-ray tube excited XRMF instru- ment using a collimator/aperture; and a conventional SEM-EDX instrument.The XRMF instrument used a 50 kV/l mA fine focus X-ray tube and provided a 100 pm beam spot produced by a pin-hole collimator. Detection limits (250 s) for single element measurements were in the range 5-8 pg for elements in the first transition series and 100-300 pg for A1 and Si. The detection limits for the elements in the 2 range 22 to 30 deteriorated by a factor of 25 to 50 in complex matrices owing to difficulties in modelling spectrum background and in resolving peak overlaps in the software package used. The same XRMF instrument was used for the limited-area analysis of thin films used in semiconductor device processing (92/2466). A beam spot better than 50 pm was claimed by the authors. A similar instrument was the subject of a patent application by Roessiger and Riedel (93/202 1).In order to maximize the detector collection efficiency Scholze and Buckley (9311722) designed a novel Si(Li) detector with a hole through it for a highly-collimated excitation beam. The authors intend to use this device in conjunction with a zone plate optic behind the detector such that the detector’s sensitive front surface can be as close as possible to the radiation produced in the specimen under study. The problem of retaining good spectral characteristics (background and tailing) with such a detec- tor will doubtless pose a challenge and we must await experimental results before the outcome of experiments with this interesting detector design is known.A new type of 2-0 imaging XRF detector was designed by Koile and co-workers (93/2 125). The device was claimed to offer count rates of 1 O5 counts s- with 20% counting losses and a positional resolution better than 400 pm. Interest in glass capillary X-ray waveguides relying on total external reflection of X-rays from the inner walls of the capillary has continued during the review period. This interest is particularly valuable as instrumentation using such devices offers the potential for laboratory scale X-ray microprobes which use conventional X-ray tube sources rather than the somewhat less accessible SR facilities. A group at Cornell University (USA) gave a complete descrip- tion of the fabrication and characteristics of tapered capillary waveguides (93/166 1) for the production of high intensity sub-micrometre hard X-ray beams.The same group reported a 1.6 m long flexible tapered capillary waveguide/concentrator made from a glass fibre (93/4 19). A beam intensity enhancement of 10 was observed and with an input spot size of 470 pm a 1 10 pm beam was produced at the end of the waveguide. The plastic coated flexible guide was used with a conventional copper anode X-ray tube and due to the promising reflectivity per bounce of 87% the authors hoped to produce capillary optics yielding a 2 pm beam spot and a beam intensification factor of lo4. Carpenter and Taylor (93/ 1869) described improvements to their previously-reported laboratory-scale XRMF instru- ment which uses a demountable anode microfocus X-ray tube designed for X-ray radiography and a tapered capillary optic.The X-ray tube and optics are of a novel design allowing for anode adjustment such that the primary beam spot can be placed very close to the entrance of the 10 pm capillary waveguide. An intensity improvement of 2-3-fold was obtained and the overall system sensitivity was in- creased by a further factor of 3.7 through the use of a larger area (50 mm2) Si(Li) detector whose crystal was located nearer to its beryllium entrance window. The system provided impressive XRMF images of ore and alloy samples in which 5 pm resolution was observed. Kobayashi and colleagues (92/4044) built an XRMF microprobe using a 12 x 0.4 mm line-focus conventional X-ray tube a 15 cm long 20 pm i.d.capillary waveguide and two 80 mm2 Si(Li) detectors. A spatial resolution of better than 20 pm was claimed and detection limits (60 s) ranged from 19 to 0.6 pg for elements in the 2 range 16 to 27. Workers in the former Soviet Union continue to develop X-ray waveguides and have recently being investigating multilayer waveguides. Dudchik et al. (9312032 93/2844) prepared a waveguide using a silicon substrate and 250 layers (each 30 pm thick) in which tantalum and aluminium were used as alternate layer metals. The device was intended for use with X-rays in the 30-100 keV energy range. A curved X-ray waveguide was investigated by Bushuev et al. (93/2798) and the theory of propagation of X-rays along a waveguide with a step-wise decreasing transverse cross-section rather than a continu- ous taper was developed by Glebov and co-workers (93/1785). Using a cobalt anode X-ray tube a 15-fold increase in X-ray flux and the multilbeam nature of the profile was observed at the waveguide outlet of a device based on this theory.As the brilliance of SR sources has risen there has been increasing interest in the use of wavelength dispersive detection systems to avoid the problems of peak overlap interferences observed in energy dispersive Si(Li) detectors which have hitherto enjoyed almost a monopoly in SRXRF work. A team at the Photon Factory (93/1873 91/C35078) used a flat crystal WD analyser and position-sensitive detector and Chevallier and co-workers (92/3877) at LURE France used a similar set-up in which slits could be used to reduce background and peak overlap.This latter system also included for comparison a highly-oriented pyrolytic graphite monochromator and a 4 mm diameter Si(Li) energy dispersive (ED) detector. Unfortunately the ED detector could only achieve a resolution of 150 eV (FWHM at 5.9 keV) which compares poorly with a skate-of- the-art system which can deliver resolutions below 130 eV. Notwithstanding this applications where improved per- formance can be achieved in resolving a major element peak overlapping with a trace peak will continue to drive the development of wavelength dispersive detection sys- tems particularly as the poor detector collection efficiency of WD spectrometers can be offset by the much greater power available in the next generation of SR sources.To obtain a detailed overview of the recent work on SR instrumentation the Proceedings of the Seventh National Conference on Synchrotron Radiation Baton Rouge Octo- ber 199 1 (eds. Stockbauer R.L. Poliakoff E.D. and Saile V. North Holland 1992) is to be recommended. 2.2.2. Excitation Heckel and colleagues (92/4633 92/3204) gave further details of their commercially available EDXRF instrument which uses polarized radiation for excitation. The instru- ment comprises a 2 kW X-ray tube a Barkla scatterer polarizing unit and an Si(Li) detector all arranged in orthogonal (Cartesian) geometry. Notwithstanding the high power of the tube which was required to obtain a viable count rate it was still necessary to open up the collimators resulting in some loss of polarization.Despite this loss detection limits were claimed to be a factor of 10 better than conventional EDXRF instruments although the quoted detection limits in the range 0.3-15 pg g-I do not fully bear out this factor of improvement. A group in Bremen (93/ 1973) compared the performance of highly oriented pyrolytic graphite (HOPG) and ordinary graphite as polarizers in a laboratory-built spectrometer with ortho- gonal geometry and similar to that of Heckel et al. referred284R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 to above. The ability of the HOPG unit to act as a Bragg polarizer for Mo K X-radiation was limited by the necessity to operate with relatively wide collimators in order to obtain an adequate count rate from the samples. Under these divergent beam conditions the HOPG unit acted more as a Barkla scatterer and showed no advantage over an ordinary graphite Barkla scatterer in terms of achievable detection limits. Details of this versatile spectrometer at Bremen have been given by Swoboda and co-workers (92/39 14).The spectrometer can be configured for use with Bragg reflectors or Barkla scatterers for polarized X-ray excitation or with secondary targets. The 3-axis orthogonal geometry secondary target spectro- meter at Goeteborg (93/1974) was modified to characterize and reduce the beam inhomogeneity which had been found to be a particular problem when analysing small samples such as those in forensic science investigations. A highly flexible mechanical system was incorporated so that not only could samples be centralized in the most intense beam but different sections of the sample could be irradiated and analysed.Csete (931 1747) presented a measurement of the spectral output of eight different secondary targets and confirmed the importance of using filters in conjunction with secondary-target sources. The problem of obtaining materials that can act as secondary targets of low 2 elements such as calcium or phosphorus was investigated by Lepy and co-workers (93/2777). The targets were made from ion-exchange resin filter-papers which had been loaded with the element of interest and five such targets were investigated. The narrow effective energy range of these targets compared with conventional direct excitation from a side-window molybdenum or rhodium target X-ray tube would appear to be a serious practical disadvantage.Furthermore radiation damage of the filters may limit their useful lifetime when a high-intensity primary beam is used. A number of patents for new and improved X-ray tubes and components have been claimed. Fiebiger (93/1695 93/ 1696) was particularly active and has developed both lanthanum hexaboride and lanthanum-platinum alloy elec- tron emitters specifically for use in X-ray tubes. A complete X-ray tube comprising the lanthanum-platinum emitter was claimed (93/1698) and a complete excitation unit incorporating the new electron emitter and tube technology was claimed (93/1697) by a team at Siemens which included Fieberger. An X-ray tube with a ribbon-like filament and a new type of alumina ceramic mounting was claimed by Yonemitsu and Sigiura (93/1751).Osada (93/1825) claimed a patent for a beryllium window whose outer surface has a beryllium oxide coating layer (over and above the natural one) which was considered to offer increased environmental resistance. Finally a rather inter- esting X-ray tube with a transmission anode was developed by Spitsyn et al. (93/2015). The anode is a self-supporting polycrystalline diamond film onto which the metallic anodeharget material was deposited and the use of such a target in an X-ray tube was described. The fundamentals of low-energy electron induced X-ray spectrometry (LEEIXS) were described by Romand and co- workers (93/2002) who remain at the vanguard in develop- ing the technique. The authors concentrated on the use of LEEIXS for surface analysis and described fully the instrument details offering a detailed comparison of the technique with electron probe microanalysis.Their section on quantitative analysis was particularly comprehensive. As legislation covering the use of radioisotope sources becomes ever-more restrictive there is little if any development to report in this field. However the intrinsic simplicity of XRF using sources and the extensive user base is still sufficient for there to be some development work in areas of the world where legislation is less onerous and where availability and maintenance of X-ray tubes and high voltage sets may be limited. Bai and Wang (93/1837) described a new radioisotope-excited EDXRF instrument for use in the analysis of cement raw mix and alumina.The instrument used an 241Am and an increasingly-rare 238Pu source. Leonev and co-workers (93/2766) described a 57C0 source which they proposed for use in XRF spectrometers. Source activities in the range 1-1 35 mCi were used and the integrity of these high-energy sources was exhaustively tested under a wide variety of physical conditions. The preparation details for a 93mNb radioisotope excitation source were presented by Sevast’yanov et al. (92/3970). The source was formed into the usual annular form and was claimed to provide a factor of 1.4 improvement in detection limits for Co Cu Ga Mn and Sr in aqueous solutions when compared with those using a Io9Cd excitation source. Sanni (93/2838) reviewed the subject of XRF excitation by the mixing of radioisotope source material with samples. Whilst capable of producing very high geometric excitation and detection efficiency when the ‘self-exciting’ sample is placed directly on the beryllium window of an Si(Li) detector the handling and disposal of the subsequent samples is a factor which is unlikely to result in wide acceptance of the technique. Although X-ray tubes have been used for almost a century the increasing interest in fundamental parameter (FP) quantitative analysis calculations over the past 15 years has driven the interest in obtaining a more accurate description of the spectral distribution of the output of X-ray tubes.The group at Atominstituet in Vienna (93/867) used an Si(Li) detector to make careful direct measurements of the output spectrum from an X-ray diffraction tube which they use for TXRF analysis.Sensitivities for thin-film samples excited by X-rays from this tube were calculated from measured data and showed good agreement with those predicted from the measured tube output spectrum. Del- gado and Ortiz (9311971) described how absorption data for a collimated X-ray beam can be used to provide a functional description of the spectral distribution of a low energy X-ray beam. Using the authors’ approach the need for knowledge of the actual energy distribution of the X-ray tube output spectrum is avoided which may simplify substantially some FP calculations with no loss in the accuracy of analytical results. The use of an SEM as a photon excitation XRF instrument is not new but recently Pozsgai (93/2735) provided what is probably the most complete theoretical description of the practice.In such a system the primary electron beam strikes the rear of a foil transmission target whose forward X-ray flux is used as an excitation source for XRF measurement. The benefit of the technique is that much-reduced spectrum backgrounds result from this form of X-ray excitation when compared with direct electron excitation and there can be a substantial improvement in detection limits. The author presented details on the calculation of the X-ray spectrum distribution of this source and showed how this information can be used in FP calculations for samples excited in this way. Although X-ray lasers are the subject of much work the attainable energies have only recently reached levels greater than 1 keV-a level at which they begin to become of interest for use in XRF (93/2799 93/1893 93/2836 9311895 93/1812). Energies up to 1.5 keV albeit with femto- or pico-second pulsed devices are now becoming feasible and Kmetec (9312834) reported the production of X-rays in the energy range 20-1000 keV from a solid tantalum target which was irradiated by the tight focus region of a 60 mJ 120 fs laser.It is unlikely that the XRF community will benefit from such devices in the near future. In addition to X-ray lasers there continues to be a small number of publications which offer yet more exotic X-rayJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 285R sources. The use of exploding wires as a source of X-rays has previously been reported but a new variation-the use of crossed wires in a so-called X-pinch device was described by Christon and Choi (9213962).This device provided X- rays in the energy range 0.1 - 10 keV and was claimed rather enigmatically to offer an ‘ideal source’ for X-ray micros- copy and lithography. Finally Enomoto and Saito (93/1745) reported X-ray triboemission from silicon ni- tride alumina and zirconia ceramics observed during mechanical wearing of these materials at low loads and high sliding velocity. X-rays with energies up to 20 keV were detected and a mechanism for their production was proposed. 2.2.3. Detectors There is a substantial number of papers on X-ray detectors every year. Many of these papers relate to X-ray imaging tomography and astronomical measurements and are omit- ted from consideration in this update as there is little of interest for the XRF practitioner.The past five years have seen much interest in the use of semiconductor detector windows made from materials other than beryllium. Diamond-like carbon has been employed successfully in a number of commercially available detec- tors and the review period has seen patent claims on a variety of such windows (93/1850 92/3992 92/3991 93/2846). The high vacuum integrity and transmission properties in the X-ray energy range from 275 to 750 eV of a ‘diamond’ window were reported by Fischer and Phillips (93/1660). The authors indicated that such windows were superior to those made of other available materials such as beryllium and organic polymers because of their high X-ray transmission at energies t l keV and their favourable physical and chemical properties.Hamilton et al. (93/ 182 1 ) used XRD XRF and SEM techniques to characterize diamond-like carbon thin films produced by a hot-filament chemical vapour deposition method. The X-ray transmis- sion properties were found to be superior to either 2.5 pm Mylar or 6.3 pm polypropylene and these authors also recommended the films for their excellent mechanical chemical and thermal properties. Developments in non-cryogenic semiconductor detectors continue and the best way by far to obtain the latest information is to consult the proceedings of the ‘7th International Workshop on Room Temperature Semicon- ductor X- and Gamma-ray Detectors and Associated Electronics Italy September 199 1 ’ (Nucl.Instrum. Meth. Phys. Res. 1992,322,3). Suffice it to say here that any reader interested in the current state of the art in cadmium telluride mercuric iodide and other room-temperature detector technologies should make this their first stopping place. Although not a non-cryogenic solution Watanabe et al. (93/1982) reported on the characteristics of a Si(Li) detector which needs only to be cooled (with liquid nitrogen) for the duration that measurements are being carried out. Such a ‘cool-on-demand’ approach has the benefit of retaining the high resolution of the Si(Li) detector but does not obviate the need for the bulky Dewar and associated liquid nitrogen handling. A more popular approach is to use a thermoelectric cooler as discussed in a patent by Woldseth and Bosson (93/1998).Their design uses a 5-stage Peltier cooler (which is not new) and a heat shield supported by nylon ‘spiders’ which appear to form the basis ofthe claim. Other additional features of the detector are a motor drive and a proximity sensor on the detector tip employed when it is used as a retractable SEM detector. Anatychuk et al. (9312848) claimed a Soviet patent for a thermoelectrically-cooled semiconductor detector whose fundamental design appears to be similar to many devices that have been available in the West for some years now. The use of Si(Li) detectors predominates in EDXRF spectrometers other than benchtop units where sealed proportional counters remain important. Tribedi and Tan- don (93/1685) determined the efficiency of an Si(Li) detector over the energy range 1-20 keV.The measure- ments were performed using standard radioisotope sources. Selin and colleagues at Chalmers University (9311 972) reported on the very interesting but little-known polariza- tion effects that can be observed in Si(Li) detectors. These effects manifested themselves as a time-dependent increase in detector background and were attributed to the trapping of charges from the electron-hole pairs produced during the X-ray detection process. Unfortunately this work was of necessity limited to one or two detectors (and may not be fully representative of this category of detector) serves as a timely reminder that EDXRF workers seeking the best detection limits should consider all the characteristics of the detection system in addition to the excitation system.It is counter-productive to expend great efforts in optimizing the incident radiation regime in TXRF and SRXRF if the detector makes an inherent contribution to detected back- ground or the spectrum processing becomes adversely affected by the changing characteristics of the detector with time. A comparison of Si(Li) and high purity germanium (HPGe) detectors was made by Rossington et al. (93128 13). Assuming that equivalent capacitance and the electronic contribution to noise are the same resolution of an HPGe detector was expected to be 27% better than for an equivalent Si(Li) detector. The authors confirmed the very high Ge K escape peak fractions for HPGe (8 to 16%) and concluded that these constituted a fundamental limitation to the use of HPGe detectors in the analysis of complex spectra with significant peaks at energies above 1 1.1 keV.The HPGe detector was shown to have a rather severe low energy tail at energies just above the Ge L edge and this was attributed to incomplete charge collection in the 0.2 pm dead layer. Measurements of peak-to-background ratios were made using photon-excited pure metal foils and from these it was seen that the Si(Li) detector had significantly better S/B ratios especially in the range 5-10 keV. The authors rightly concluded that considerations other than just resolution improvements must be taken into account when making the choice between a Si(Li) and HPGe detector for XRF. This work confirms the extreme difficul- ties arising from the high Ge K escape peak intensities when there are X-ray peaks at energies greater than 11.1 keV in the spectrum.There is a continuing development of silicon-based detection technologies other than the traditional Si(Li) X- ray detector. Lengeler et al. (93/ 1805) have investigated a number of silicon p-i-n diodes from several manufacturers and found them to be very well-suited as X-ray detectors for the 5-20 keV energy range. The operational details of such a p-i-n diode which was proposed as an X-ray detector for an XRF instrument destined for the Mars Rover on the Russian 1994-6 Mars mission were reported by Klingelho- efer and co-workers (93/1669). A new theoretical model for the X-ray sensitivity of p-i-n and silicon surface barrier detectors was proposed by Cho et af.(93/2806). The authors considered two charge collection mechanisms in an attempt to explain recent results which were apparently contrary to the usual belief that it is only the thickness of the depletion layer which determines the detector efficiency curve. Rossington and colleagues at Lawrence Berkeley (92/39 10) investigated the X-ray response of a position-sensitive silicon vertex microstrip detector but concluded that although the system is useful for high-energy physics experiments the system noise and measurement electronics will need to be improved if such devices are to be used successfully at energies (60 keV. The properties of three286R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 types of thin film amorphous silicon X-ray detectors were investigated by Wei (93/2026) and the characteristics of a silicon avalanche photodiode were reported (93/2828). The latter devices were found to work well for energies t 2 0 keV but the significant dependence on temperature for this room-temperature device constitutes a major limitation to practical use at the present time. A group at NSLS Brookhaven USA (93/2845) gave details of a 100-element silicon detector array for use in SR experiments. The 10 x 10 array elements were each 4 mm square and laid out on a single piece of high-purity silicon which is cooled by liquid nitrogen. Each detector element had its own signal process- ing channel and the achievable count rate may well exceed values of up to 500 kcps which can currently be obtained using commercially-available arrays of 1 3 HPGe detectors.Silicon charged-coupled devices (CCDs) continue to be of interest in XRF but mainly for their potential use in imaging systems. Tate (92/3911) reviewed this subject and Clarke and co-workers (93/2859) continued their work in this area and investigated SR applications. Of particular interest was their reporting of the radiation hardness characteristics of these devices which is particularly impor- tant when considering use in modern SR beam lines. The quantum efficiency and charge collection characteristics of CCDs in the energy range up to 60 keV was investigated by Francis et al. (93/2858) and a CCD with a thicker depletion layer was studied for use as a position-sensitive detector in X-ray microscopy (92/4037).The latter device provided readout speeds of one million pixel per second and could resolve Ti K from Fe K lines. Karakado (93~778) provided a timely and comprehen- sive review of the nature and performance characteristics of superconducting tunnel junction (STJ) detectors. The mechanism of their operation was presented and current predictions are for a factor of 10 improvement in resolution compared with a conventional (1 50 eV) Si(Li) detector. To date the best consistent resolution appears to be 48 eV at 5.9 keV which is substantially better than that of even the best premium Si(Li) detectors ( t 1 2 8 eV). Kraus et al. (93/ 1748) discussed two different operating mechanisms for STJ devices and showed a device that exhibited resolution of 60 eV (FWHM at 5.9 keV).The limited size of the device was used to advantage and a spatial resolution of 5 pm was claimed. Unfortunately the reported STJ detectors are extremely small ( t 2 0 0 pm square) although the investigation of newer STJ devices such as those based on niobium (Kurakado M. et al. Proc. Matsumura et al. Nucl. Instrum. Meth. Phys Res. 1993 A329 227 X-ray detection with Nb/AlO,/Nb superconducting tunnel junctions and energy diffusion effect on energy resolution SPIE III 1992 1743 351 and 93/2014) appears to offer the prospect of larger devices. Despite the much improved resolution compared with Si(Li) detectors the background in spectra taken from STJ detectors looks rather high and there is much yet to be done before we can expect commercially viable devices to be available for XRF applications.Smith and Bavdaz (92/3919) reviewed the principles of operation and performance characteristics of gas scintilla- tion proportional counters (GSPC) as X-ray detectors. The Coimbra group (93/2812) have continued their work on these detectors and reported on the dependence of resolu- tion on the distance between the scintillation region and photomultiplier. These authors concluded that the com- monly-used configuration represented the worst case! The physical configuration and X-ray detection charac- teristics of an optic fibre bundle coupled to a scintillation detector were described in some detail by Laguesse and Bourdinaud (92/3964). Although designed principally for higher energy X- and gamma-rays the detection system could be of use at energies more typical of XRF work.The increasing interest in silicon photodiodes has prompted a careful study of their efficiency and energy calibration (9312860) using the standard X-ray source radiation available at the BESSY SR facility in Berlin. A simple model describing the spectral response of these devices in the X-ray energy range up to 3.5 keV was proposed and verified experimentally. The features of the recently developed microstrip propor- tional counter technology (MSPC) were described by Budtz- Joergensen (92/39 16 9312037). Energy resolution < 14% (measured at 5.9 keV) a gas gain of lo4 (using xenon gas fill) and a position resolution of 1 mm was shown to be the state-of-the-art at the present time.A highly integrated MSPC detector array on a silicon substrate was prepared using semiconductor fabrication techniques by Nagae and co-workers (9311 788) and shown to offer 15% resolution at 5.9 keV with a gas gain of lo3. Bouclier and co-workers (93/2811) at CERN in Grenoble have developed MSPC detectors which were fabricated on a thin-film polymer support and which offered high gas gain ( lo4) but rather poor resolution of around 20% at 5.9 keV. 2.3. Total Reflection X-ray Fluorescence (TXRF) Once more there has been substantial growth in the literature of TXRF during the review period. This growth is partly as a result of the great increase in the use of TXRF in the semiconductor processing industry and it now seems appropriate to make a clear distinction between the use of TXRF in its conventional bulk chemical analysis guise and its more recent application to surface analysis and depth- profiling.The large number of TXRF reviews during the review period are a sure indicator of the ever increasing spread of the applications of the technique. Highly readable descrip- tions of the instrumentation and full range of applications of TXRF were provided by Klockenkaemper et al. (93/2764) and Reus and Prange (Reus U. and Prange A. Spectrosc. Europe 1993 5 26 An Analyst’s Approach to Total Reflection XRF Features and Applications). Both sets of authors described briefly the nature of the instru- mentation made comparisons with other trace multi- element analytical techniques and stressed the wide range of successful applications of the technique.Reviews of a more comprehensive nature were presented by Klockenka- emper and Von Bohlen (9214632) and Prange and Schwenke (Prange A. and Schwenke H. Adv. X-ray Anal. 1992 35B 899 Trace Element Analysis using Total Reflection X-ray Fluorescence Spectrometry). The former authors covered all aspects of TXRF and included a particularly complete section on biological and clinical applications-an area to which they have made a consider- able contribution. Prange and Schwenke provided a useful discussion and tabulation of the historical development of TXRF and very useful practical details of sample carrier materials; instrument analytical calibration and sample preparation techniques. Recent developments in TXRF were reviewed by members of the TXRF group at Atomin- stituet in Vienna (93/1985 and 9313952).Of particular interest was their recent work on the use of novel excitation and detection systems for the extension of the applicable X- ray energy range of TXRF. The extension to low energies was demonstrated by the determination of oxygen using a windowless X-ray tube and Si(Li) detector and at high energies by the measurement of the K emission lines of selected REE. Current work being carried out at GKSS Geesthacht Germany was reviewed by Schwenke and colleagues (93/1905) who described their progress in surface analysis and depth profiling. The generation of X-ray standing waves by the total reflection of X-rays was reviewed by Bedzyk (93/2767). The fact that the majority of TXRF installations are inJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 287R Germany or Japan is perhaps borne out by publication of reviews in German by Klockenkaemper (93/1653) and in Japanese by Taniguchi and Ninomiya (93/1826) Taniguchi and Nishihagi (93/286 1) and Aoki (93/ 1892). The review by Kim and Kim (93/2761) may be the harbinger of the introduction of TXRF into the burgeoning industries of Korea. Although appearing too late for full inclusion in this Update the Proceedings of the Fourth Workshop on TXRF Spectrometry held at GKSS Geesthacht Germany in May 1992 (Spectrochimica Acta Part B 1993 Volume 48) are highly recommended for readers wishing to discover the latest advances in all aspects of TXRF. Hein et al. (9312744 and 93/1879) have built a new TXRF instrument specifically for the analysis of light elements.The spectrometer comprised a chromium target X-ray tube a primary reflector unit optimized for low energy excitation and a detector equipped with a thin entrance window and low-noise electronics. The system could be operated in a high vacuum and the authors were able to determine oxygen in the pg-ng range. The modification of a commer- cially available X-ray diffractometer to permit TXRF analysis was presented by Nicolosi (92/C38 16) who success- fully applied the spectrometer to the analysis of thin films. Schuster (93/2022) filed a patent application for a TXRF spectrometer designed for the measurement of semiconduc- tor wafer surface contamination The system incorporated an LSM monochromator as the primary beam reflector and a detector for measuring the intensity of the totally-reflected X-ray beam.Detection limits of the order of 10” atoms cm-2 were expected. Workers at GKSS (931 1699) have also filed a patent application for a somewhat similar TXRF spectrometer but which has two LSM mirrors in the primary beam path. Kubota et al. (93/ 19 10) also applied for a patent on a TXRF spectrometer for the measurement of surface contamination on silicon wafers. The key feature of their claim appears to be a sample holder which allows the wafer to be tilted to eliminate Bragg reflections which would otherwise be detected. Bormann and Schwenke (93/ 1797) applied for a patent for a TXRF measurement process in which a fresh analytical surface of a flat specimen was prepared in situ by sputtering or evaporation.A patent for a two-crystal monochromator unit with high-energy cut-off characteristics typical of those used for TXRF applications was applied for by Kojima and Utaka (93/2849). Finally Dixkens and Fissan (93/1744) claimed a patent for an electrostatic precipitator unit which was designed to collect on TXRF sample holders a homogeneous deposit of particles of diameter < 1 pm. Collection of particles < 1 pm was 100% efficient and the sample carriers could be used directly for trace element determinations in a TXRF spectrometer. 2.3.1. Chemical Analysis Guenther et al. (93/1652) made a comparison of TXRF and ICP-MS for the analysis of two biological reference ma- terials (spinach and mussel).Quantitative results were based upon the addition of a single internal reference element (which is all that is required for quantification by TXRF) which required the ICP-MS to be operated in the semiquantitative mode. The TXRF results were both more accurate and precise for elements significantly above the detection limit of the technique. The authors recommended that ICP-MS could be used for screening when used in the ‘semi quant’ mode but accurate analysis would require the use of external calibration or standard additions methods. The detection limits achieved by ICP-MS were substan- tially better than TXRF and ICP-MS offered the additional benefit of being able to determine isotopes. Tolg (93/2816) reviewed the role of trace elements ‘for life’ (related particularly to medical and environmental applications) and reported that TXRF was one of the most promising methods (along with laser spectroscopy ICP-MS and GDMS) to improve the detection capacity of trace elements in clinical biological and environmental samples. Ninomiya et al.(9311795) reported the use of TXRF to determine Cr Cu Fe and Ti in photocopier toners. These workers showed that not only could they discriminate easily between four different toners but they could also determine which toner was used to copy a sheet by removing particles from it. These results were used in a forensic study and clearly show the ability of TXRF to obtain non-destruc- tively elemental composition information from microgram particles of material. Hashimoto et al. (9311841 and 92/C35 1 1) used two internal standard additions elements for the quantitative analysis of liquid samples by TXRF spectrometry.The authors’ data appear to offer no benefit over the existing practice of using a single internal standard element and it is possible that they were unaware of this existing standard practice. Guntay (931 1846) developed a TXRF method for the analysis of I to detection limits of 0.08 pg 1-l in a gas sample derived from experiments performed to investigate the scrubbing effect of I in de- contaminating water pools. Burba (93/752) quantified U and Th by TXRF in a study of these and other elements in relation to the capabilities and limitations of conventional anion-exchange resins functionalized by chelating reagents. Hegedus and Winkler (93/2006) made use of the micro- analytical capability of TXRF for the determination of 0.5-0.6% levels of Nb in small (e.g.50 mg) samples of steel scraped from the walls of pressure vessels used in a nuclear power plant. A simple analytical procedure in which Mo was used as internal standard was developed and the precision of Nb determination was t 4 % relative. And finally Hoffmann et al. (93/765) used TXRF as one of a range of analytical techniques to analyse seven steel samples offered as reference materials. More than 90% of the results were in good agreement with wet chemical data deviations being caused by systematic errors and inhomo- geneity effects. 2.3.2. Surface Analysis and Depth Profiling Growth in this important area has been particularly strong during the current review period and serves to stress the importance of XRF development in the solution of contem- porary industrial analytical problems.In addition to the general TXRF reviews cited in section 2.3 above Matsushita (93/1990) and Yamashita (9312027) reviewed the specific topic of the TXRF measurement of surface contamination on silicon wafers. Streckfuss et al. (93/2745) in their review of TXRF analysis of silicon wafer surface contamination made comparisons of direct TXRF analysis with vapour phase decomposition (VPD) AAS and described the ultra-sensitive technique of VPD-TXRF analysis. Iwamoto et al. (93/1838) provided a brief but wide-ranging review of TXRF instrumentation and its application to surface analysis and depth profiling of semiconductor wafers.The subjects of X-ray standing waves and surface structure were reviewed by Zegenhagen (9 2/40 5 3). De Boer and van den Hoogenhof (93/1896) described the theory underlying TXRF of single and multi-layer thin film samples. These workers constructed a spectrometer for their studies and used it to determine the depth distribution of elements in layered specimens such as a 30 nm layer of cobalt on silicon; a cobalt-gold bilayer on silicon; and a periodic carbon-nickel multilayer (LSM). The authors described the production of X-ray standing waves at surfaces in thin film samples and were able to determine the number of layers in the carbon-nickel LSM from the X-ray288R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 interference fringes it produced.An X-ray standing wave TXRF method was described by Zheludeva et al. (92139 13) for the determination of the thickness and density of the ultra-thin surface layer of carbon-iron LSM devices. The use of monochromatized X-ray excitation for TXRF analysis was described by Schuster (93/1988) who used a molybdenum anode X-ray tube and an LSM monochroma- tor. This arrangement yielded high sensitivity because of the wide bandpass of the LSM for Mo K radiation resulting in detection limits in the range 1010-1012 atoms cm-2. The narrow range of incident X-ray energies provided a well- defined penetration depth which was used to good advan- tage in depth profiling of As implanted in silicon wafers. Nishihagi et al. (9213905) used an LiF200 Bragg crystal monochromator and a 9 kW rotating tungsten anode X-ray tube to generate highly monochromatic W La1 radiation which was used for the determination of silicon wafer surface contaminants.Calibration standards for Cu Fe Ni and Zn were prepared by spin-coating silicon wafers with standard solutions and achievable detection limits ( 1000 s) were in the range 3.2 x lo9-7.4 x lo9 atoms cm-*. The authors' instrument was also equipped to produce 2- dimensional maps of the surface contamination and to provide depth profiling of wafers. Using an instrument of the same type Yakushiji and co-workers (9312874) investi- gated the effect caused by mis-orientation of the crystal planes on the Si K and elastically-scattered W La1 peak intensities from silicon wafers. The Si K peak intensity was found to remain constant for a series of wafers but the W La1 peak changed greatly.The authors presented the theoretical basis for these variations and predicted that a small rotation of the sample would compensate for the W La1 peak intensity variation. The driving force behind the development of TXRF analysis in the semiconductor industry has been the mea- surement of silicon wafer surface contamination. Hockett (9311703) continued his work in this area and reviewed results reported for a round robin check of TXRF analysis. Acid treatments for the preparation of ultra-clean silicon wafer surfaces were investigated in detail by Antilla and Tilli (93/1752). Very dilute (1:lOO to 1:106) mineral acids were used prior to TXRF measurements and limits of detection better than 1Olo atoms cm-2 of Fe were achieved which allowed the authors to study carefully the effects on minority carrier lifetimes of such low levels of contamina- tion.Hockett et al. (9311889) used TXRF analysis to investigate the difficult problem of C1 contamination on wafers and achieved a detection limit of 1 0l2 atoms cm-2 of C1. The data revealed some unexpected sources of C1 contamination and served to demonstrate the value of the simultaneous multi-element measurements which TXRF provide. The determination and depth profiling of impuri- ties in the topmost region of silicon wafers have been studied by Frey et al. (9311 192) and Hockett (9311733). Detection limits of the order of 1011-1012 atoms cm-2 were reported in both studies for elements in the 2 range 26-30.Hack1 et al. (9311791) were able to correlate successfully results from TXRF and deep level transient spectroscopy in their study of Cu Fe and Ni contamination on silicon wafers. Watanabe et al. (93120 12) reported an interesting TXRF study of an indium phosphide surface under an atmosphere of As. The Si(Li) detector was fitted with a Parylene entrance window to increase sensitivity for the L series lines of Ga and As. The authors used the TXRF measurements to determine the number of indium arsenide monolayers grown during a 10 min period. In their study of trace metal surface contamination of gallium arsenide Hockett and co-workers (9311 792) measured 17 elements by TXRF. It is worth mentioning that the use of monochro- matized W L radiation for excitation has benefits in the TXRF determination of the first transition series elements on gallium arsenide because the energy of the incident radiation lies conveniently below the Ga K absorption edge.A simpler alternative to the spin-coating method adopted by Schuster (93/ 1988) for the preparation of calibration curves for wafer surface contamination analysis was de- scribed by Kondo et al. (9311981). The method involved direct deposition of liquid drops on the wafer surface which led to the formation of a central concentrated spot of dried calibrant solution. Despite the obvious difference between the homogeneous distribution of the true surface contamination and calibration spots the method yielded accurate results. Conversely Hashiguchi and Hayashi (9214065) used a spin-coating method to prepare standards which were then used for SR-TXRF analysis of silicon wafer surface contamination.Accurate results were re- ported although despite the use of SR detection limits of 10" atoms cm-2 were obtained which were no better than for contemporary laboratory instruments employing X-ray tube excitation. Finally Kubota and co-workers (9311875) made a patent application for a TXRF spectrometer designed specifically for the analysis of surface contamination on silicon wafers. 2.4 Synchrotron Radiation X-ray Fluorescence (SRXRF) The number and importance of developments in SRXRF spectrometry are sufficient to afford them a separate section in this year's Update. The specific work relating to development and use of SRXRF microprobes is collected together with XRMF work in a separate section (2.2.1) of the Update and is not repeated here.Although SR sources are of special interest for the development of XRF microprobes there is also a consider- able body of work reported where the benefits of SR can be used for analysis of bulk samples. The history of the new third generation SR source at ESRF Grenoble was re- viewed by Haensel (9312760). The same author also detailed the design of the ESRF source with particular stress on the importance of the brightness and the energy ranges available as a consequence of the incorporation of a new generation of insertion devices (9311823 9312759). Yang et al. (9213923) designed and tested a high-precision mono- chromator which provided monochromatized SR over the energy range 0.9-4 keV with a bandpass of 0.9 eV at the Si K edge.A comprehensive description of the nature and characteristics of polarizing optics for SR was given by Hart (9312028) and details of optic elements for high-brilliance SR sources were presented by Joksch (9311676). Carr and colleagues (93117 18) at the SSRL facility in Stanford CA USA made careful calculations and measurements of the correlation between SR X-ray spectra and the magnetic fields in the undulators producing the spectra. Recent developments at the Photon Factory including work on bending magnets and linearly-polarized SR from insertion devices were presented by Ando and Kagoshima (931 1675). The development and application of compact SR sources is becoming more important in view of the higher energies and brightness now being obtained which offer options for uses other than lithography of semiconductor devices.Takada (9311871) described progress in this field and showed how insertion devices can be incorporated into even these compact rings. The author indicated that the use of a modem superconducting ring and a beam-wobbling technique could produce higher energies and exposure areas up to 50 x 50 mm whilst maintaining simplicity of oper- ation. In a similar vein Richter (93/1898) and Uberall et al. (921396 1) described how relatively inexpensive ($1 M) compact LINACS can be used to produce channelling radiation in the X-ray region with intensities which the latter authors claimed would exceed those of conventional SR sources.It remains to be seen if these claims result in theJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 289R more widespread availability of high-brightness tunable SR-like X-ray sources or whether the compact SR rings will be more successful. The high heat load which monochromators and windows in SR beam lines have to withstand was studied theoreti- cally by Tong et al. (921391 5). A team at Argonne has been developing liquid gallium cooled optics for use in the planned third generation SR facilities (93/1967). Liquid gallium was pumped through monochromator silicon crys- tals in which holes had been drilled or channels cut. Using such a cooling system in conjunction with an inclined crystal (93/1663) the usual thermal distortion of the crystal was eliminated and any observed degradation in the rocking curve width was shown to be a result of residual strain in the crystal mounting.Workers at Rockwell International (931 1659) also investigated liquid gallium cooling for SR monochromators. The performance charac- teristics of water and liquid gallium coolants and two different designs of crystal heat exchanger were docu- mented. Although SR facilities are only available at a limited number of sites world-wide a notable feature of this year’s review is the wide variety of applications that are now beginning to appear some of which involved the analysis of geological samples. The synchrotron X-ray microprobe is much better suited for the analysis of sensitive samples than competitive techniques as demonstrated by the analysis of fluid inclusions in geological samples by Rankin et al.(93/855) who used a range of techniques including LA- ICP-AES and SRXRF microprobe to analyse fluid inclu- sions associated with Cu Pb Sn W and Zn mineralized granites of eastern Australia. An and Zhan (92/C4176) undertook a homogeneity study of the Chinese reference sample GSR-5 by SRXRF using a 100 x 100 pm white SR beam with 60 s count times. Iron and Ni impurities in diamond were detected using synchrotron radiation XRF in diamonds grown in a metallic solvent by Wakatsuki et al. (92/4047). Turning now to the characterization of surfaces Iida (93/2000) reviewed the analysis of semiconductor surfaces by grazing incidence XRF which in most cases used a synchrotron radiation source and Zheludeva et al.(93/ 1674) investigated the distribution of heavy (Pb) atoms in a Langmuir-Blodgett film by measuring the Pb fluores- cence signal as a function of the glancing angle of a monochromatic (1 3.5 keV) synchrotron X-ray beam. Archaeological samples were analysed by Nakai et al. (93/1832) using both synchrotron radiation induced XRF to obtain concentration data and XANES spectra obtained by XRF detection to obtain chemical state information. These techniques were applied to the analysis of an antique Chinese clay doll and the determination of the oxidation state of iron in the black glaze of a bowl from a kiln site in southern China. In a further contribution Nakai et al. (921C3508) applied these techniques to an ancient corroded iron implement. The determination of lead in bone is now a common measurement in clinical samples by XRF and Jones et al.(92/4278) used SRXRF to measure the distribution of Pb as well as Ca and Sr in bone by line scan and elemental distribution map. Homma et al. (93/ 17 14 93/2864) mea- sured the distributions of Cu Se and Zn in human kidneys and associated tumours one advantage of this technique being the non-destructive nature of this measurement. These authors extended these studies to the imaging of trace elements in the kidneys of rats that had been administered organic mercury (93/2773). Kwiatek and co-workers (93/1668) used an SR beam line with a spot size of 70 x 100 pm at HASYLAB (Hamburg) for the measurement of ten elements in cancerous kidney tissue samples 10 pm thick. Elevated levels of trace elements were identified in the cancerous tissues although only elemental X-ray line ratios were measured rather than concentrations and results for only two specimens were presented.Wu et al. (92/C4178) used both tube excited XRF and SRXRF to measure changes in the trace elemental composition of the hair of pregnant women the elements determined included Al Br Ca C1 Cu Mg Pb and S. The hair of athletes was analysed by Qian et al. (93/2009) each sample being scanned from point to point at 1.5 mm intervals (each interval corre- sponding to about 5 d of growth). Preliminary results showed that changes in Fe were related to the exercise capacity of the athlete but Ca and Zn showed no observable change. The use of SRXRF in industrial applications was re- viewed by Hormes et al.(93/2762) and Hormes (93/2867). The techniques considered included EXAFS and XANES as well as fluorescence analysis and the application of SR in X-ray lithography for the production of semiconductor microstructures. Isaacs et al. (93/ 1780) studied the compo- sition of metal ions in solutions formed under conditions of localized corrosion in simulated corrosion pits using in situ X-ray absorption and fluorescence measurements to quan- tify concentration gradients within the artificial pit. Cheval- ier et al. (9311 978) determined trace elements in aluminium by SRXRF. An environmental application of SRXRF was described by Torok et al. (93/2746) in the SRXRF analysis of fly ash from Hungarian brown-coal power stations.The toxic metal content of chimney ash was found to be much higher than that of ash removed by an electro-filter. Wang et al. analysed Cu Fe Pb and Zn in three species of macrophyte seaweed from the Tagus estuary in Portugal by SRXRF monochromatized with a curved mosaic crystal and corre- lated levels with industrial pollution. A reasonably good agreement was found between synoptic values of these elements dissolved in the estuarine water and values determined in algae. 2.5. Calibration and Data Processing. Irrespective of the completeness of calculation models for the correction of matrix effects in XRF the need for the accurate determination of net peak intensities remains of critical importance. This requirement for spectrum process- ing is particularly important in the analysis of EDXRF spectra where peak overlaps are the norm.Boman and Isakson (9311906) made a comparison of two computer programs both of which incorporate spectrum processing algorithms. The often-forgotten but important matter of how well the packages correct for variation in zero peak position and spectrometer gain was investigated although correction of peak resolution (FWHM) for countrate was not considered. Soliman and co-workers (9214029) de- scribed a computer procedure for the resolution of over- lapped peaks in EDXRF spectra. This empirical procedure was evaluated in the energy range 3-8 keV for geological and steel samples but the general applicability of the technique was not confirmed. A useful procedure for the resolution enhancement of an EDXRF spectrum was described in detail by Stoev and Vutchkov (Nucl.Instrum. Meth. Phys. Res. 1991 B53 187). The method was based on a non-linear digital filter and appears to offer a robust procedure that does not require extensive computing resources. Campbell and Wang (93/2752) at Guelph con- tinued their excellent work on the characterization of peak shapes in spectra from Si(Li) detectors. The authors recommended the convolution of a Lorentzian function of appropriate width with the Gaussian function (resulting in a Voigt function) if the true peak shape is to be modelled accurately. The Lorentzian component was shown to represent much of the low-energy tailing of peaks which is290R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 normally attributed to incomplete charge collection and other detector imperfections.This Guelph group used their new model with a non-linear least squares fitting procedure to determine the width of the La and LI emission lines of a number of heavy elements (9311897). The width of the La peaks showed good agreement with theoretically-calculated values but the width of the LI lines was found to be as much as 30% lower than predicted. A method for the determina- tion of the Gaussian parameters of X-ray peaks was described by Samat and Evans (93/1779) though the complete and accurate description of the photopeaks in spectra from Si(Li) detectors needs to be extended from the single Gaussian model as ably demonstrated by the work of the Guelph group and Selin (9311 972).In addition to these widely used least squares peak fitting procedures Jin (93/1991) and Naoki and Gohshi (921C3533) proposed peak deconvolution methods which use Fourier transfor- mation techniques and Rhode and Whittenburg (92/C38 12) presented a ‘Bayesian’ deconvolution proce- dure based upon a Lorentzian peak model. Rather than use a traditional least squares approach Bland et al. (93/1963) described a simplex optimization procedure for the fitting of L series peaks in spectra from planar germanium detectors. The peak model that they used was a Lorentzian and a step function both convolved with a Gaussian function which seems very similar to that proposed by the Guelph group. Empirical matrix correction procedures remain widely used where a suite of standards is available.A guide for users of correction methods in XRF was provided by the ASTM (9213969) and this guide can usefully be used to augment the existing textbooks. Work reported by Molcha- nova et al. (9312779) considered the importance of the concentration range over which constant alpha coefficients can be applied. The authors concluded that it was impor- tant to use correction algorithms in which the alpha coefficients vary with concentration-an echo of the long- standing recommendation by Tertian and Claisse to use sliding (or gliding) alpha coefficients to preserve the achievable accuracy of the concentration alphas method. In what looks like a worrying first step in the wrong direction a Soviet patent was claimed (9312871) for a calibration procedure in XRF.It can only be hoped that this is an isolated case especially as it appears only to embody previously developed XRF methodology. Bosch Reig et al. (Fresenius’ J. Anal. Chem. 1992 344 16) addressed the question of correction factors used in the limit dilution method (LDM). The authors showed the importance of the ‘diluent effect’ where in some cases the effect of the very low mass absorption coefficients of the diluent may require a greater correction than the original matrix effects! A method of correcting this ‘diluent effect’ was proposed and shown to be effective for synthetic mixtures of Fe and Zr oxides. In a second paper (93/2754) the authors used the same Fe-Zr oxide system and two clay samples to investigate the true absorption-enhancement effects occurring in samples subject to the LDM.A general equation was developed and included a ‘compensation coefficient’ based upon the ratio of mass absorption coefficients in the original sample and a similar standard. Although the calculation procedure was simple the method relied upon intensity measurements from three standards which are then diluted in exactly the same way as the samples under consideration. For the determination of six elements in the clays accuracies ranged from 8% relative at 410 ppm (CaO) to around 2% relative at 0.5% (A1203 and Si02). In their work on the related total dilution method the same workers (9312020) proposed an algorithm to linearize the intensity-concentration calibration plots for the determination of Sn in tin-lead solders. The correction coefficients could be calculated by a straightforward graphi- cal or numerical method and the resulting calibration yielded good results over a wide concentration range (21-75% Sn).A modification of the emission-transmission method for the correction of matrix effects was described by Markow- icz and Haselberger (93/1738). Rather than using a single element backing target these workers used a multi-element target and split the spectrum into three energy sections in order to avoid errors due to intervening absorption edges of major elements. In the geological samples considered the edges of concern were Ca and Fe and the major corrections were for Fe and Ca (only on itself). The method was also applied to 0.5 g coal samples but insufficient data were presented to permit an assessment of the true accuracy of the method.Markowicz et al. (9311710) also carried out a systematic study of the achievable accuracy of the emis- sion-transmission (E-T) method. The enhancement effect was specially investigated as was the effect of treating a radioisotope source as either mono- or bi-chromatic. Abdunnabi and Wasilewska-Radwanska (Appl. Radiat. Isot. 1993 44 4 659 Particle size effect in XRF by Emission-Transmission Met hod) presented expressions showing how the particle size of samples affects the accuracy of the E-T method. Above 100 pm the simple E-T method showed significant errors for samples of Fe304 and Cu2S and the absolute magnitude of the error was shown to vary depending upon the geometry of the radioisotope- excited EDXRF instrument.The application of chernometrics to EDXRF spectrome- try continues to be explored and Van Espen (931C364) presented the case for using chemometric techniques to retain the intrinsic simplicity of XRF in the face of ever- increasing computational complexity and ‘de-skilling’ of users. Otto and co-workers (931 18 17) presented a general overview of how fuzzy logic and neural networks can be applied to a variety of problems in analytical chemistry including automated qualitative analysis using XRF spec- trometry. A comparison of the training requirements of a backward error propagation (BEP) and a genetic algorithm (GA) neural network system for the generation of quantita- tive XRF calibration models was presented by Bos and Weber (92147 10).The BEP procedure performed as well for an Fe-Cr-Ni system as a conventional XRF procedure when 13 standards were used but like the conventional models was poor when extrapolating outside the range of the training (calibration) set. The GA procedure was slow and performed poorly. A patent for a neural network which processes spectral data was claimed (9311819) but this appears to concentrate on large organic molecular struc- tures and many spectrum types of which the X-ray data seem only to be XRD pattern data. A procedure of optimized scaling was proposed by Karstang and Manne (9311729) who suggested the procedure was as good in its ability to solve XRF analysis equations as partial least squares (PLS) or principal component regression. Partial least squares techniques themselves were used by Swerts et al.(Anal. Chem. 1993,65 1 18 1) for the determination of S in graphite by EDXRF spectrometry. The use of unfiltered Rh-tube excitation yielded a spectrum in which the scat- tered Rh L radiation interfered strongly with the S K spectrum and the AXIL least squares peak fitting software gave unreliable results because the program was unable to model adequately peaks present in the observed spectrum. The PLS method needed no such implicit model and was also able to take multiple scatterldiffraction peak artefacts and S K peak shifts in its stride. The PLS method required no human guidance such as input of background positions and yielded an accuracy better than 8% over a range of S concentrations extending from 2 to 63%.The PLS method was also employed in a portable radioisotope-excited EDXRF system used for the analysis of aluminium alloy,JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 291R stainless steel and zinc concentrate samples (93/ 1992) as well as in the chemical state measurement of S with a double crystal monochromator (931 1 993) and geological samples (9312755). In the latter study PLS was combined with FP calculations in order to reduce the number of standards required. Unfortunately these three interesting applications of PLS are only available in Chinese language journals and as such make their contribution to this important new area rather less than would otherwise be the case. In the case of bulk samples particle size eflects are usually eliminated by sample preparation procedures. Unfortu- nately this is not possible for XRMF work which prompted Lankosz (9311878) to develop a Monte Carlo method for the simulation of XRF processes in spherical microsamples.Calculations for single grains of Fe203 or ZnS indicated that the intensity of the excited characteristic X-rays depended strongly on the diameter of the particle and the diameter and geometric profile of the incident microbeam. Nordberg (92/3000) developed a mathematical model to describe the quantitative XRF spectrometry of small multilayer spheri- cal samples used as targets in inertial confinement fusion experiments. The model showed the effect of changing the sample from flat to a spherical multilayer and was extended to approximate the XRF signals arising from non-uniform shells.Measurements to confirm the validity of the model were performed on a commercially-available EDXRF spec- trometer. Abbruzzese and Di Nunzio (93/2794) took advantage of the XRF signal variation arising from the analysis of a polycrystalline metal sheet to determine grain size. 2.5.1. Fundamental Parameter (FP) calculations. Kuczomow et al. (93/1080) made a valiant attempt to draw together the common features of the intensity-concentration relationships in XRF PIXE and EPMA. The principal common thread identified was that of the absorption of emitted X-ray photons and in all three cases the Beer-Lam- bert relationship held true which led the authors to consider the Laplace transform an ideal starting part for a unified analytical method.The authors confirmed that the Laplace approach was successful in representing accurately the interactions in EPMA and PIXE. In XRF all problems associated with the polychromatic nature of X-ray tube excitation and secondary fluorescence (enhancement) ef- fects were embodied in the solution although tertiary fluorescence (third element effect) which can be substantial in some systems was not explicitly covered. Improvements in the fundamental approach were de- scribed by Afonin et al. (9311 793) and tested for the analysis of silicate rocks by XRF. The improved algorithm corrected for primary and secondary X-ray absorption secondary and tertiary fluorescence excitation by scattered X-rays photo- electrons and the divergent X-ray beam for which full equations were presented.The spectral intensities of X-ray tubes with both thick and electron transmission targets can be calculated using the program developed by the authors. Borkhodoev (93/2789) has developed a complete yet compact FP program for use with a simultaneous WDXRF spectrometer. The program accounted for the polychroma- tic X-ray tube output and for all primary and secondary interactions in the sample. The difficult case of Fe-Ni-Cr ternaries was used to test the program and with the exception of some bias in results for Cr caused by tertiary fluorescence the results were impressive. The program was able to calculate results for 18 analytes and to account for an element by difference. The latter feature was demon- strated by the successful analysis of a series of geological samples with oxygen as the element calculated by differ- ence.In many cases where FP calculations are applied to the results from SRXRF analysis calculations are substantially simplified if the SR beam is monochromatized. The small SR facility ELSA in Bonn however was used without monochromatization and Pantenburg et al. (93/ 1686) had to modify their FP calculations to account for this. The energy distribution of the output ‘white’ spectrum from the SR source was calculated and the Si(Li) detector efficiency was very carefully measured to allow FPXRF analysis of a diverse range of archaeological samples. Data were normal- ized to 100% total and accuracy for the determination of Ag Cd Cu and Pb in a silver alloy was about 5% relative. Software improvements in an ‘effective coefficients’ FP method which can now be used with a number of standards (rather then just one) were described by Broll and colleagues (93/1852).The authors’ improvements also included an extension of their program for the determination of an unanalysed element (e.g. 0) and a specific modification to improve trace element analysis. Szaloki (93/ 1979) de- scribed three different iteration schemes for FP calculations with radioisotope source excitation and Sarkar (93/2667) devised a new scheme for calculating the enhancement effect in thin-film systems. In an Ni-Fe (9 1 ) binary system the enhancement of Ni on Fe was found to approach a constant value for a layer thickness of > 100 ,ug cm-*. The way in which the fundamental algorithm was derived from the original FP equations was briefly described by Rousseau (9213908).The author provided a useful descrip- tion of the simple calibration procedure required by his fundamental algorithm and presented a somewhat tongue- in-cheek checklist against which XRF software should be compared. A program (PROPX) which allowed an X-ray tube spectrum to be subjected to a number of absorption processes was described by Kyrala (93/2804). Different absorption filters and X-ray tube anode materials could be investigated and plots of cross-sections obtained. Bisson- nette and Schreiner (9312868) made a comparison of two semi-empirical models available for the calculation of output spectra from tungsten target X-ray tubes used in clinical investigations.A practical met hod for reconstruct- ing X-ray tube output spectra based on spectra measured with a number of filters was described by Kirichenko and co-workers (93/2827 93/283 1). The provision of the fundamental parameters themselves remains of key importance in the accuracy and advance- ment of FP calculations. Fritzsche et al. (92/3880) de- scribed a database containing mass absorption coefficients for elements up to 2=92 (U). Stoelzel et al. (93/2857) measured fluorescence Coster-Kronig and Auger yields of the samarium L sub-shells. The relative L-shell X-ray line intensities for Au Hg Ir Pb Sm U and W were measured by Darko and Telteh (93/1680) and photo-production cross-sections for the L X-rays of elements in the 2 range 56 to 92 were calculated and confirmed by measurement by Puri et al.(93/2741). The accurate measurement of the fluorescence yield for Fe K lines was reported by Sole (93/1891). A photographic film method was used by Shrivastava and co-workers (93/ 1849 93/20 13) for the measurement of some weak X-ray emission lines in the spectra of selected REE. New designations for some of the observed lines were suggested (93/2742) on the basis of these new measurements. X-ray emission wavelengths and relative intensities were measured for Xe K and L series lines (93/1896) and for Ar L Kr L Xe L Ar K and Cm M (93/1848) lines. The absolute measurement of the efficiency of a Si(Li) detector was reported by Dolbnya et al. (92/39 18) using measurements based on the attenuation of SR beams. In the first of two measurement methods SR was mono- chromatized at various energies and in the second the white SR beam was passed through filters before striking the292R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 detector. There was good agreement between the two methods and the accuracy of the overall measurement was claimed to be better than 10% relative. Deviations from predicted mass absorption coefficients (MAC) when mea- sured for X-ray lines where absorption edges lie very close to the exciting line were reported by Kerur et al. (931 1683). The same group made a careful experimental investigation of variations in the MAC for several elements absorbed by aluminium (9312776). The effect of small angle scattering on the measured MAC was examined using three collima- tors and two sources (55Fe and 57C0) and was found to show good agreement with values predicted theoretically.2.5.2. Matrix correction using scattered radiation. A neglected aspect of X-ray fluorescence was evaluated comprehensively by Fernandez (93/1705) namely that of contributions to fluorescence intensities from Rayleigh and Compton scattering within a thick sample. The proposed model included multiple scatter contributions to the photoelectric effect and presented the theoretical basis of a general model for second-order intensity computations. The chains of interactions considered were Rayleigh- photoelectric phot oelect ric-Rayleigh Compton-photo- electric and photoelectric-Compton. Model calculations for alumino-silicate geological matrices showed that scat- ter can make a larger contribution to the enhancement in fluorescence intensities than secondary fluorescence ef- fects.Indeed the total scattering contribution can cause an enhancement in fluorescence intensities of up to sev- eral tens of percent in light matrices and explains why experimental intensities for these and similar samples are considerably higher than the intensities predicted by an XRF enhancement model which does not include a scat- tering contribution. Fernandez and Molinari (931 1783) provided a comprehensive review of the processes of multiple scattering in XRF spectrometry and how these processes can be calculated successfully within the frame- work of transport theory. On the basis of this theoretical starting point Fernandez and Sumini (93/ 1970) developed SHAPE a computer program which simulates the com- plete EDXRF spectrum taking into account all interac- tions including multiple scattering.Theoretical equations describing the magnitude of secondary XRF emission arising from interactions with Compton electrons were derived by Stoev (93/1900). Binary systems were consi- dered and the effect was compared with that caused by secondary and tertiary enhancement. The magnitude of the Compton peak shgt for Rh Kcx lines scattered by graphite was investigated by Kundra (93/1720) who had observed a significant difference from the theoreti- cal position. The difference increased with sample thickness and incident beam diameter and was attributed to the change in the 'effective' scattering angle.The phenomenon was characteristic of thick samples of light matrices in systems having close-coupled optics such as EDXRF spectrometers. This effect was shown by Greaves et al. (93/168 1) to be useful for the experimental determination of the geometry in a radioisotope-excited XRF spectro- meter. Harvey (93/1886) applied a Compton scatter correction to geological analysis and confirmed the classic limitation that measurements should only be made as far down as the first major element absorption edge. For geological work this usually means the Fe K edge but when concentrations of even hundreds of pg g-' of heavier elements such as Sr are present the validity of the straightforward Compton rela- tion fails. The author proposed an iterative calculation scheme in which absorption corrections were made at each absorption edge in the spectrum.Garcia-Gonzalez et al. (9311037) investigated the use of Rh Kcx Rayleigh Rh Kcr Compton lines and continuum background intensities as sources of scattered radiation for use in matrix corrections in the analysis of iron ores and an alumino silicate material. These authors recommended the use of either the contin- uum background at 14" 28 (LiF200) or the Rh Kcx Rayleigh peak for scatter correction of the Fe data. A new model for Compton scatter correction which included an enhancement term was proposed by Domi (93/2772). This new model was compared with nine other published models and found to yield superior accuracy with little extra calibration effort being required. Although the new enhancement term included the concentration of an interfering element this could be replaced by measured intensities with only a very small loss of accuracy in the it era t ive procedure.A backscatter fundamental parameter model was devel- oped by Aboh et al. (93/2780) for use in EDXRF spectro- metry. The 'dark-matrix' (i.e. unanalysable elements) was attributed to one nominal element and the model was validated by the production of accurate analysis of an IAEA reference soil sample. 2. 6. Applications 2.6.1. Specimen Preparation Reports of innovations in 'conventional' sample prepara- tion have not been as numerous as in previous reviews a feature of this year being the number of patent applications and also of contributions from Russian workers. One such application by Malyutina et al.(93/1765) described the use of glassy carbon crucibles in an XRF method designed for the analysis of zirconium dioxide in mineral raw materials. The method involved the fusion of a sample suspension with a melt comprising lithium metaborate lithium tetra- borate and silica (SO2) at a temperature of 850-880 "C with the application of ultrasound. Luedemann et al. (9312003) also reported on the use of graphite crucibles for the fusion of geological samples using an induction furnace. The method was claimed to be safer easier and less expensive to perform than alternative methods using platinum crucibles and gas burners but mechanical grinding and polishing had to be used to overcome imperfections on the surface of the fused disc. Some innovations in fusion procedures for the prepara- tion of selected minerals and raw materials as glass discs have been reported by a number of workers. Majcen (93/2018) reported a fusion method for the determination of barium sulfate strontium sulfate and calcium sulfate in the mineral barite in which the fusion mixture comprised germanium oxide lithium tetraborate lithium carbonate and lanthanum oxide.Yuan et al. (93/2165) developed a method for the difficult determination of major elements in sulfide minerals in which the sample (0.25 g) was mixed with lithium metaborate (4.4 g) lithium tetraborate (2.4 g) and sodium nitrate (1 g) in a platinum-gold crucible. The mixture was first heated to 700 "C for 10 min to pre- oxidize the sample then after the addition of a small volume of ammonium bromide solution fused at 1050 "C for 10 min.The method was applied to the analysis of raw materials concentrates and slags for the determination of Cu Pb S and Zn. Fujishiro et al. (92/3993) devised a technique for the analysis of SO3 in gypsum based on fusion with sodium borate containing 0.05 to 0.15% strontium iodide at 1000- 1 100 "C for 10 to 20 min before moulding the sample into a glass bead for analysis. Rubi et al. (921C3638) used a conventional fusion technique based on lithium tetraborate as flux to which a small amount of lithium bromide as non-wetting agent was added for the analysis of REE concentrates. However a very high flux to sample ratio (55 1) was used which although virtuallyJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 293R eliminating matrix and particle size effects would have significantly reduced sensitivities and degraded detection limits. An interesting interference was examined by Gazulla et al. (93/1759) caused by the use of sodium bromide (NaBr) as an anti-adherent in the fusion of ceramic samples where the use of sodium iodide (NaI) is not appropriate. Without correction an overlap between the Br L-lines and A1 K-lines caused bias in the XRF determination of the latter element. Iwamoto and Okashita (92/3994) made a patent applica- tion for the design of a sample holder which was claimed to reduce background radiation emanating from the holder the back of which had a heavy metal coating. A modified sample holder was also described by Kochmola and Bondarenko (92/2939) which was suitable for the XRF analysis of powdered samples.Innovations in sample preparation for alloy samples have been reported by several workers. In particular Dorofeeva et al. (93/1775) reported on sample preparation for copper- based alloys in which disintegrated chips were prepared as compressed pellets on a boric acid backing. Difficulties in determining the exact volume ratio between the solid solution and the eutectic phase caused by the presence of fine flakes of eutectic on the surface of coarser particles were minimized by thorough disintegration of the sample. An extraction-concentration method for the XRF analysis of Al Cu and Ni alloys was described by Logunova et al. (92/4406). A low melting-point reagent comprising C17-C20 carboxylic acid and its mixture with di(2-ethylhexy1)hydro- genphosphate was used to separate metals from alloy samples.After solidification this extracted solid solution could be used for direct analysis by XRF or re-dissolved for spectrophotometric analysis and AAS. Mamulova et al. (93/2862) made a patent application for a method of sample preparation for sulfur-containing compounds. After sintering at 800-900°C for 40-50 min with sodium carbo- nate (Na,CO,) and magnesium oxide (MgO) in a crucible the mixture was cooled and compressed into a pellet with binders. Greater reproducibility was obtained by sandwich- ing the specified sample mixture between layers of sintering reagents in the crucible. Finally Arakawa and Hagi (93/2030) described an interesting patent application for an XRF sample preparation procedure in which a gelling agent was used to eliminate almost completely the fluidity of the sample.2.6.2. Chemical analysis Following the trend highlighted in last year’s Update a considerable number of papers have described various sample dissolution and preconcentration procedures in which the analyte products have been determined by XRF. These procedures have been used both to extend the detection limit capability of the technique to levels below those that could be achieved by conventional sample preparation procedures and to apply the XRF technique to sample types such as waters which would be analysed conventionally by solution techniques such as AAS and ICP-AES. For the analysis of solution samples Bezverkhny- aya et al.(93/1689) applied for a Russian patent to cover the design of a cell comprising a cylindrical housing with a cover containing a polymeric window. Particular aspects including preconcentration in the determination of REE were reviewed by Zhang et al. (93/2778). Masi and Olsina (93/27 56) evaluated preconcentration techniques for the determination of trace levels of arsenic in natural waters including coprecipitation liquid-liquid extraction and adsorption on activated charcoal. Goediker et al. (9213898) developed a preconcentration method for XRF analysis involving evaporation and the use of high-purity polycarbo- nate membranes with detection limits for Ca C1 K Mg Na P and S being less than 1 pg g-l. To give a more general overview of the scope and variety of individual chemical separation techniques used with XRF selected procedures are summarized in Table 1.2.6.3. Thin films A range of papers has been published in the current review period covering the analysis of thin films by XRF. A new technique for the evaluation of surfaces and interfaces was described by Sasaki and Hirokawa (93/ 1834) making use of the refraction effect in XRF which can be measured from the variation in scattered X-ray intensity with take-off angle. Information on the uniformity surface roughness and the chemical state of the thin film coated on optically flat substrates could be obtained. Other aspects of analytical techniques used in this field of study were considered by Brumme et al. (93/1704) who reviewed the application of EDXRF using polarized radia- tion in surface analysis and by Knyazev et al.(93/3932). The latter authors considered the EDXRF analysis of materials of intermediate thickness and described a mathe- matical method for correcting matrix effects which was applied to the determination of Sn in SRMs. The continuing interest in analysing borophosphosilicate or phosphosilicate glass films was demonstrated by the work of Levine and Higgins (93/843) who described a new WDXRF method for the simultaneous determination of P and film thickness. The method was based on an analysis of Si and P line intensities corrections being applied to account for peak-shift and peak-height due to chemical bonding. Results agreed with elemental data determined independently by ICP-AES and ellipsometer measurements of thickness.Several other papers have described the analysis of thin films related to semiconductor materials including Johnston et al. (93/1687) who used EDXRF and PIXE to analyse epitaxial layers of Hg,-,Cd,Te grown by metal organic chemical vapour deposition (MOCVD). The EDXRF tech- nique was preferred for routine stoichiometric analysis as might be required in a production environment owing to the cost of PIXE accelerator time and concomitant beam damage. The structure of Cu-In-Se thin films having a chalcopyrite structure was analysed by Kohiki et al. (93/2832) who observed a positive shift in the Cu La X-ray energy with an increase in the number of excess electrons in this material. The excess electrons entered the lower conduction band in n-type Cu-In-Se thin films deposited by a molecular beam method.The TXRF technique was shown by Bergholz et al. (9312017) to be one of the few methods with sufficient sensitivity to analyse contamina- tion by the impurity elements Cu Fe and Ni on silicon ultra-large scale integration technology devices at the 1 010 atoms cm-2 level. The simultaneous determination of composition and thickness of Tb-Fe-Co and of Al-Si-Cu thin films was described by Naganuma et al. (92/4399) using a fundamen- tal parameter XRF method and Mashin et al. (9312033) proposed a method for determining the thickness of two- layer Si-Ge and Ge-Si films on ‘polikor’. Some interesting practical applications have been de- scribed during the current review year. Coppi et al.(93/2822) discussed the use of EDXRF for measuring the thickness of the ethyl cellulose micro-encapsulation of sulfadiazine or salbutanol sulfate drugs based on the attenuation of the S Ka emission peak. Eichler et al. (93/1725) evaluated the feasibility of determining Ag Br and I in silver halide holographic films using 57C0 source excitation and a germanium detector. The relationship between concentration of silver and optical density of the emulsion for various exposures was determined. A new294R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Table 1 CHEMICAL SEPARATION AND PRECONCENTRATION PROCEDURES FOR XRF ANALYSIS Brief details of the procedure Particular features Preconcentration Adsorption procedure Elements analysed Au in ores of low in specified matrix Au content Reference 9312023 9312 75 7 9312038 After roasting samples leach Au with thiourea and adsorb onto activated charcoal for EDXRF analysis Coprecipitate selected trace elements with Al(OH) after adjusting the pH to 7.3 with ammonia Optimization of extraction conditions discussed.Best detection limits were 0.038 pg g-I Au 0.8 pg 1-' with a relative precision of 4-6% EDXRF detection limit was 0.2- Coprecipitation Asv C P Pbn Thw Tiw in water samples Cu Fe Ni in titanium alloy Coprecipitation After dissolving in HCl coprecipitate trace metals with indium hydroxide at pH 9 after masking Ti with H202 as its peroxo complex coprecipitate with hydrated Fem oxide bound with activated charcoal Evaporate SiOz matrix as SiF and precipitate trace elements with hexa- methyleneammoniumhexamethylene- dithiocarbamate and indium Convert P to phosphate and XRF detection limits were Fe 8.1 pg g-'; Cu 0.8 pg g-'; and Ni 1.4 pg g-' 9312 7 58 9312787 Coprecipitation P in waste waters from a paper mill EDXRF detection limit was 0.89 mg of P per g of activated charcoal Ag Au Bi Cd Co Cu Fe Mn Mo Ni Pb Pd Sn TI V Zn in water glasses (technical alkali silicates) Sulfide in waste water REE in xenotime (REE mineral) TXRF used to verify the accuracy of AAS determinations Precipitation Sulfide from production of yeast precipitated as zinc sulfide REE were precipitated from an NH3-NH4Cl solution at pH 9 using 1 -( 2-pyridylazo)-2-naphthol- modified naphthalene filtered and anal ysed containing H202 and spiking with a Zr standard solution precipitate Ta with phenylarsonic acid boil filter and analyse the dried filter-paper Direct analysis of sample solutions contained in polyethylene bottles of wall thickness 0.1 mm After boiling the sample in HCl Precipitation Precipitation EDXRF analysis 931 1 870 921200 Calibration lines were rectilinear up to 1000 pg with RSDs of about 5% Precipitation Ta in rare earth metals Reported detection limit was 7.5 pg g-I Ta with RSD of 2.7% for 200 pg of Ta in 1 g of La203 93/1885 Direct analysis of solution Ce Sr in aqueous solution Matrix effects minimized by using samples of similar composition.Calibration graphs were rectilinear from 10 to 300 pg g-' Sr and from 100 to 3000 pg g-' Ce determination of Hf by WDXRF Alpha coefficient correction used in the 796 931 Hf in Hf-Zr binary solutions Direct analysis of sample solutions presented for analysis in simple pol yet h ylene bottles Direct analysis of nuclear materials in liquors Direct analysis of solution 9 31 931 735 827 Direct analysis of solution Pu Th U in liquors Determinations made on a hybrid K-edgelXRF analyser in the IAEA Safeguards Laboratory Matrix effects caused by various cations and anions were studied Suitable for silicate and aluminate solutions.Typical RSD was 3.5% Direct analysis of solution Evaporation Th U in aqueous A1203 Na20 Si02 solution Direct analysis of sample solutions in simple polyethylene bottles Sample solution (0.1 ml) deposited 9214497 9311881 in technical solutions used in zeolite production on a gravimetric paper and dried at ambient temperature then at 60 "C Sample solution sprayed onto a Mylar or Kapton film using a nebulizer Apply 10-50 pl micro-droplets of sample solution to filter-paper disc Heat sample at 600 "C in a platinum crucible to decompose deliquescent compounds; prepare sample for analysis as a briquette sodium peroxide (2 g) at 700 "C for 15 min after cooling dissolve in water and spot 50 p1 on to filter-paper with waxed ring Aqueous phase (0.4 ml) was applied to a filter-paper and then air dried C1- in natural waters Fe Ti in uranium K and Mg in sea salt (and Ca S042- and Sr) Mo in minerals Fuse mineral sample (0.5 g) with Fifteen rare earth elements and Y in aqueous solution Evaporation Evaporation Evaporation XRF instrument incorporated a 79 mm2 Ge crystal with a 127 pm window Precisions of better than 5% achieved by EDXRF analysis Detection limits were 0.005% (Mg) and 0.0006°/o (K); calibrations were linear up to concentrations of 0.2% Mg and 0.4% K 100% MOO Calibration rectilinear from 0.I to 9312397 9213903 931 1706 9213944 Evaporation 9312 173 9211 8 I Evaporation Correction for background and spectral overlap interferences was discussed. The technique gave detection limits of 0.1% and RSDs of 0.1-5% up to 10 g 1-I and gave detection Calibration lines were rectilinear Evaporation Sn and W in aqueous Sample solution (50 pl) applied to solution the centre of a wax circle on a filter- DaDer then dried L . limits of 0.01 g I-'JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 295R ~~~ ~~~~~~~ Table 1 CHEMICAL SEPARATION AND PRECONCENTRATION PROCEDURES FOR XRF ANALYSIS-continued Preconcentration procedure Evaporation Extraction Extraction Extract ion Ion exchange Ion exchange Ion exchange Sorption Sorption Elements analysed Trace elements in in specified matrix aqueous solution Au in environmental samples Bi in lead concentrates Nb and Ta As Bi Ca Cu Fe Mn Ni Pb Rb Sr Zn in aqueous solution (waste waters) Cr Cu Fe Pb Zn in drinking water P04,- h o d 3 - Si032- SO4*- in natural and waste waters Trace elements in rocks and ores and natural and waste waters Trace heavy metals in water and waste waters Brief details of the procedure Samples were prepared for analysis by evaporation of the sample solution as small dried spots mounted on thin plastic films After aqua regia attack Au was recovered by solid extraction on to a base of tri-butylphosphate.Au was back-extracted with thiourea solution and evaporated to form a thin film for XRF analysis mixture Bi complexed with Na di- ethyldithiocarbamate and extracted into CHCl,. Extract was filtered and evaporated on to a Mylar film After dissolving the sample in HF- aqua regia evaporate to a small volume and extract Nb and Ta into tartaric acid solution (6%). After dilution with tartaric acid solution spot 70 p1 on to a wax-branded filter- paper. After drying in air analyse the filter-paper as a thin film by XRF column (Woffatit MC 50) wash dry and analyse by XRF Sample fused with fluoride-nitrate Concentrate on anion-exchange Water (2 1) was preconcentrated on a chelating ion-exchange resin (Ostsorb-Oxin) which was then dried at 105 "C and pressed into a pellet 50- 100 ml water sample was shaken with fibrous ion exchanger (polyacro- nitrile fibre modified with poly ethylene polyamide) which was then dried and analysed by XRF using Pd tube excitation Characteristics of POLYORGS complexing sorbent discussed specifically its high selectivity towards noble rare earth and heavy metals Preconcentration by sorption onto chemically modified cellulose is reviewed Particular features Reference Detection limits by EDXRF were 9311 987 as low as 1 ng equivalent to 1 ng g-I for sample solutions containing 1000 pg g-' total dissolved solids or less.Typical precision varied from better than 2% (secondary target EDXRF) to 5 to 10% for direct tube excitation The same extraction procedure was used to determine Au in natural waters by INAA 93/ 1666 Suitable for the determination of 10 pg g-' Bi.Concentration varied linearly with the Bi:Hg intensity ratio RSD was about 0.4% 9212950 9214468 Heavy metals > 1 to 3 mg I-' to an RSD 9213 166 of <5'/0 could be determined by EDXRF using a '09Cd radioisotope source Radionuclide EDXRF (z38Pu source) Detection limit for As and P was 10 pg and for SiO,:- and S 25 pg with an RSD of 0. I9 931 1768 9311 672 Schemes for XRF analysis as well as 93/2 I8 1 AAS ICP-AES and NAA were discussed EDXRF determination 93/ 1727 series of 15 jewellery CRMs comprising a thin precious metal foil mounted on a smooth aluminium substrate was described in a conference report by Stankiewicz et al.(931C996). These reference materials were designed with the standardization of XRF instrumentation in mind and will be characterized by interlaboratory examination. In another report Bachmann et al. (9312875) proposed a method for the analysis of samples that are difficult to decompose or which can be easily contaminated in which the pulverized sample was embedded as a thin layer in cold- setting polymer. The method was tested with cobalt oxide (COO) and yttrium oxide (Yz03) and also a mixture of these with silver oxide (Ag,O) and manganese dioxide (Mn02) and the authors reported that between 20 and 60 ng of these elements could be determined by EDXRF with a precision Several groups have reported the use of more specialized forms of instrumentation for the analysis of thin films.Glancing incidence X-ray analysis used in the analysis of layered materials was reviewed by De Boer and Van den Hoogenhof (93/1673) who showed how an X-ray standing wave set-up in layered materials at glancing incidence could be used as a 'nanometric yardstick' (sic) to determine the depth distribution of atoms by a combination of reflectivity and XRF. Noma et al. (9312854) demonstrated the poten- tial of grazing exit XRF spectroscopy for the analysis of thin films of Cu and Ni on glass substrates. The XRF intensity was measured as a function of exit angle for near normal X- Of +_ 2-4%.296R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 ray incidence and showed a sharp increase at the critical angle of Ka radiation for the metal film.Sakurai and Iida (93/ 1980) used a Fourier transform algorithm on measure- ments of interference oscillations observed in the total external reflection from thin films of Si-Si02. The peak position in Fourier space was found to be in good agreement with the layer thickness. A variable exit angle ultra-soft XRF technique was used by Scimeca and Ander- mann (93/2019) for depth profiling of Ni-Fe thin-film multilayers down to a thickness of 10 nm results being in reasonable agreement with those obtained by X-ray photo- electron spectrometry (XPS). The same workers using the same technique (92/4007) also reported on the oxidation of iron based on variations in the Fe L/3/La intensity. The oxidation mechanism was believed to penetrate to a certain depth such that discrete oxide layers are not formed.The analysis of several types of surface coatings has been reported during the current review period including the thickness of zinc-based nickel alloys on a ferrous material and a double-layered organic coating on a zinc substrate using XRF and magnetically-induced Foucault currents (9311 773). An XRF procedure was described by Ziolowski and Glenc (92/4462) for measuring the composition of protective coatings and applied to the analysis of the protective layers on titanium anodes used for the pro- duction of chlorine. Tin-lead coatings were analysed by Roessiger (93/2765) with particular attention being paid to the effect of changes in crystallite size of this electro- deposited coating material during prolonged storage.Once the crystallite size exceeds the wavelength of the applied X- rays the alloy was found to behave no longer as a homogeneous specimen so affecting the XRF results. Nazarov (9213931) developed an XRF method for the determination of composition and thickness of Co-Ni coatings on Cu and Sn-Pb-Bi coatings on brass using 241Am and Io9Cd sources for excitation and reported relative errors of 2 4 % in elemental composition and 6% in thickness determinations. Two environmental applications are worthy of note. Nishioka et a/. (93/18 15) measured the surface salt density on polluted electrical power insulators using simple instru- mentation incorporating a low-power tube excitation source and neon gas-filled proportional counters. A 30 pm polyvinylidene chloride filter was placed in front of the counter to remove interferences on C1 from the K-lines of Ar in air and from composite elements in the insulator glazing material.The technique was evaluated using artifici- ally produced surfaces having 0.0 1-0.1 mg cm-* of sodium chloride and gave a relative error of 1.1% at the 0.1 mg cm-* level for a 100 s count time. And finally Ortiz- Gonzalez et al. (93/ 1 829) used an XRF technique to analyse sulfate-rich weathering materials on natural hydrated sul- fates for a range of major minor and trace elements and presented detection limit data for the elements Ag As Cd Ge Sb and Sn. 2.6.4. Geological The capabilities of XRF in the determination of trace elements in rocks were reviewed by Bruce Chappell (93/2001) a notable contributor to method development in this area of application; advantages and disadvantages of the technique were outlined.Potts and Webb (931 1926) also reviewed comprehensively the theory and practise of both WD and EDXRF in the analysis of silicate rocks and exploration samples covering theory instrumentation calibration and matrix correction procedures and sample preparation. Feather (93X925) reviewed the capabilities of a range of techniques including WDEDXRF used by a large mining and exploration corporation and applicable to exploration geochemistry. The author described a commer- cially available EDXRF instrument which replaced fire assay procedures for the direct determination of Au and of U in ore samples. In a Russian language review Afonin (9311816) discussed the use of XRF in geological and geochemical applications.Publications that describe innovations in the use of XRF in geological applications are relatively few and do not adequately reflect the widespread use of XRF in routine applications. However Heckel et al. (93/1977) described the use of novel instrumentation that is now commercially available in which samples are excited by a polarized beam of X-rays derived by scatter of the primary beam off a low atomic number secondary target. Thirty-six elements could be determined to detection limits in the range 0.3- 15 pg g-l after a total spectrum count time of 1000 s. Eddy et al. (9312007) investigated the use of XRF to determine the PGE following a nickel sulJidejire assay. After dissolution of the nickel button the platinum-group element sulfide residue was filtered redissolved and then precipitated as a metallic residue by reduction with sodium tetrahydroborate.This residue was filtered and analysed by XRF using Au as an internal standard. The elemental concentrations in 20 NIST reference materials of geochemical interest were determined by a variety of techniques including XRF INAA colorimetry and coulometry by Bower et al. (9312771). Data for some elements which had not previously been reported were presented and for others agreement with available results was generally good. Suleimenov et al. (9 3/ 1 8 5 3) presented a patent application for the preparation of a standard for undertaking XRF analysis of rocks. This standard was prepared as a fused glass from a range of materials designed to represent the chemical composition of layered igneous silicate samples.One of the principal geological uses of XRF is in the analysis of silicate rocks. In this area of application Potts et a1 (93/C24) reported the precise determination of Rb / Sr drawing comparisons with WDXRF analysis. One surpris- ing conclusion was that the precision of Rb and Sr data were broadly comparable between WD- and EDXRF at low elemental concentrations ( ( 5 0 pg g-I) owing to it was suggested the beneficial suppression of detected back- ground resulting from the use of a primary beam filter in EDXRF. In another conference presentation LaBrecque (93/C935) described the use of radioisotope-excited XRF in mineral exploration particular interest being shown in the determination of Nb Pb Sr Th Y Zn and Zr in laterite samples using a lo9Cd source and an Si(Li) detector and the K-lines of Ba Ce La and Nd employing a HPGe detector and an 241Am excitation source. Some results were pre- sented for a mercuric iodide detector instrument although determinations of Nb were not as satisfactory owing to the poorer resolution and detection efficiency of the instrument used in this study compared with a Si(Li) detector.Other applications to rocks and sediments included studies of sediments from the Tigre River Venezuela (93/1702) the Rajasthan sands of India (9214025) and in determining the U content of samples in a low energy scintillation gamma spectrometry technique for the direct measurement of 238U (93/1921). Sulfur (0.01 to 0.1%) in rocks was determined by Shvetsov et af.(9311994) using a vacuum cell for the powdered samples thereby avoiding the need to press samples into pellets or fuse them as glass discs. Relative standard deviations of 9- 1 1 O/o were reported. Corals were analysed by XRF by Yu (92/3947) on samples prepared as powder pellets against standards prepared from RMs diluted with spectroscopically pure calcium carbonate. Detection limits (in pg g-' ) and coefficients of variation (in percent relative) for the ele- ments were reported as follows CaO (20 pg g-I 0.2%),JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993. VOL. 8 297R A1203 (8 p g g-l 2.8%) Si02 (10 pg g-l 1.4%) Fe203 (5 pg g-l 1.0%) P ( 5 pg g-l 1.7%) Sr (2 pg g-’ 0.3%). The XRF method has also made a significant contribu- tion to the characterization of minerals during the current review period including the elemental composition of zeolite (91/4013) where data were in good agreement with determinations by PIXE and Iceland spar (93/ 1 707) where results were comparable to those obtained by chemical analysis and ICP-AES.Yuan et al. (93/2165) determined the major elements in sulfide minerals using an innovative sample preparation procedure for glass discs and reported results for Cu Pb S and Zn with coefficients of variation of between 0.3 and 2.6 O/o relative. Lui and Jing (92/3944) determined Mo in Mo-Ni and Mo-W-Ca ores and molyb- denite by spotting 50 pl of the dissolved sample solution into the centre of a wax-ring filter-paper. The calibration was linear from 0.1 to 100% MOO,.Gleisberg et al. (9214557) determined Th in monazite samples after dissolu- tion of the sample and extraction of Th by chromatography on to HDEHP/Wofatite EP-60 which was analysed directly by EDXRF using a Io9Cd radioisotope source. Manganese nodules have been the subject of several reports including that of Cai et al. (9311851) who fused samples in a graphite crucible at a dilution of 1 :3 with a flux comprising lithium tetraborate (Li2B40,)-lithium carbo- nate (Li2C03)-lithium nitrate (LiNO,) flux and prepared synthetic calibration standards. Wang et al. (93/279 1) used an on-board XRF instrument to analyse samples prepared as powder pellets (no binder) for A1203 CaO K20 MgO Na20 P205 Si02 Ti02 and Ba Fe Mn (alpha coefficient correction) and Co Cu Mo Ni Pb Sr Y Zn Zr (Compton scatter correction) to a precision of better than 1 O/o for most elements.And finally Sun et al. (93/ 1260) used a theoretical alpha correction procedure to determine Al Fe K Mg Mn P Si and Ti in manganese nodules again using synthetic calibration standards. The analysis of ore materials has been the subject of several publications. Savina et al. (92/3933) determined Re from the L-line in the range 0.0005-0.01 Yo in ore and related materials from samples that had been mixed with polystyrene (4 1) and prepared as pressed powder pellets. Deviations of 0.1-0.3% were reported in the analysis of standard samples containing 5-28% Re using a gold anode tube. Ore samples were analysed for Cu Pb and Zn by Stroganov et al.(91/3334) using a palladium anode tube. Coefficients of variation of 0.7-4% were obtained in the range 1-60% which were better than those obtained by AAS. ‘Polymetallic’ ores were analysed by Kierzek et al. (93/1709) for Co Cu Fe Ni Ti and V by both ED- and WDXRF. The EDXRF detection limits for these elements were 40-70 pg g-l data by WDXRF being lower by a factor Several publications have considered the XRF analysis of soils reports in Chinese language journals being particu- larly prevalent. A method for the determination of S in soil to a 4.5 pg g-* detection limit for samples with <25% organic matter was described (93/2748). Major elements were determined by Ren et al. (93/20 10) on pressed powder pellets prepared from a mixture of sample (2.5 g) and methyl cellulose (1.25 g) with an FP correction procedure.In another procedure presented by Yu (93/180 l) major and selected trace elements were determined on samples pre- pared by pelleting 4 g of microcrystalline cellulose in an aluminium ring and re-pelleting after adding 500 mg of soil; detection limits were reported as follows in pg g-l CaO 24; Cu 2.1; Fe203 16; KzO 20; Mn 5.9; P 4.3; and Zn 2.4. Li et al. (92/1157) determined Cu Rb Y and Zn in soil samples prepared as pressed sample briquettes rimmed and backed with low-density polyethylene and reported RSDs of 1.2 0.66 1.2 and 0.66% respectively. Magyar et al. (9311050) used XRF in combination with LA-ICP-MS for of 1.5-2. the analysis of rock samples and suggested that some improvements should be made to the semiquantitative XRF correction program.Aspects of soil and sediment analysis specifically related to pollution are considered in the next section. 2.6.5. Environmental Recent advances in the application of XRF to the environ- mental sciences have been reviewed by Marcoen et al. (93/1654) and in the application of a modern WDXRF instrument to environmental analysis by Bonvin et al. (93/ 1858) with particular consideration of the analysis of Pb and Zn in organic waste and Cr and Zn in air samples collected on filters. In a review of analytical methods appropriate for the analysis of pollutants in air EDXRF was considered (92/4059) along with mass and elemental analysers PIXE INAA AAS and C determination. Appli- cations in the area of environmental analysis were pre- sented in the most recent ASU review of this subject area by Cresser et al.(J. Anal. At. Spectrom. 1993 8 1R). One of the favoured applications of XRF is for the direct analysis of aerosol pollutants collected on a suitable filter. The availability and status of aerosol Jilter reference materials were discussed by Waetjen et al. (92/3876) who considered that the available RMs were unsuitable for validating analytical techniques and recommended the sampling procedure of Dannecker and Naumann ( L u f 1980 40 3 16) as being suitable for the uniform deposition of particulate material on a filter to a variation of 5-1 5% for small pieces of filter. Shesterikov et al. (93/1740) made a patent application for a procedure for preparing stan- dards for XRF analysis of aerosol solid particles based on the deposition of suitable sample solutions of the analyte on a substrate and drying. Salazar (9311682) found that several elements present in glass fibre filters interfered with trace elements in particulates analysed by EDXRF Pb being one of the few elements that could be determined successfully.Determination of Pb as a pollutant has been the subject of a report by Beitelman et al. (93/1772) who evaluated a commercial EDXRF instrument for the determination of Pb in paint on military structures in West Germany. The instrument could detect the presence of lead-based paints hidden beneath non-leaded paint. Lead in urban dust has also been the subject of a conference abstract by Boyer et a/. (92K3684) in which data were presented to identify the minimum mass suitable for analysis by EDXRF.Using the Pb L/3 line ratioed to the Compton intensity the minimum sample mass was found to be 0.4 g for a 3 1 mm sample cup. The EDXRF technique was used to monitor the atmos- phere of industrial environments around Mo-W and Pb-Zn metallurgical plants by Mikhailusova et al. (9212960) using an instrument equipped with lo9Cd 241Am and 238Pu excitation sources and an Si(Li) detector. The elements determined included Cd Fe Mo Sb W and Zn. Koutrakis et al. (92/40 18) used XRF to analyse 16 elements in indoor aerosols in two New York State counties. A physical model was developed to ascertain the contribution of indoor and outdoor sources cigarette smoking being the most impor- tant source of indoor pollution.Chen (92/4023) also developed an XRF method for the determination of As Co Cd Fe Mn Ni Pb Sb Sn and Zn in aerosol samples collected on glass fibre filters. Results of the monitoring of volcanic aerosol originating from Kilauea volcano which polluted two populated areas in Hawaii were presented by Morrow et al. (93/1843). The XRF technique was one of the methods used to characterize this material along with ion chromatography and gravime- tric determinations. This study showed that although the primary pollutant emitted from the volcano is SO2 suffici-298R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 ent oxidation occurs to generate substantial amounts of sulfate particulate material. Soils and sediments contaminated by industrial activities have been the subject of a number of studies.Barci-Funel et al. (93/2035) used gamma and low energy X-ray spectrometry to characterize non-destructively a number of fission products and transuranic elements in sediment samples and compared selected results with those obtained after a radiochemical separation. Crain et al. (93/167 1) described on-going work using XRF and LA-ICP-MS as complementary techniques for the determination of As Ba Cr and Pb in soil samples comparing results of these determinations with those obtained using EPA 3050 and 6010 methods. The determination of toxic elements in soils using a variety of techniques including XRF was reviewed by Kubota (93/2734). Wheeler (92/C376 1) dis- cussed the analysis of contaminated soils in waste disposal sites in which portable EDXRF was used to identify ‘hot- spots’ for subsequent analysis by laboratory-based EDXRF instrument.Rapid multi-element determinations of ‘chemical fuels’ (which can contain motor oil industrial solvents and paint manufacturing residues) can also be undertaken by EDXRF to demonstrate that pollutants (which might subsequent to burning be incorporated in clinker or fly ash and deposited in land-fill sites) are below regulatory limits. Iwatsuki et al. (93/1995) determined Ca K Mg S042- and Sr in sea salt after drying the sample at 110 “C grinding and pressing in an aluminium ring to form a briquet. Good agreement with conventional methods was observed for Ca SO,2- and Sr but significant discrepan- cies were observed in the XRF intensity data for the K and Mg Ka lines.In a contribution to the analysis of waters Kempe at al. (93/2795) undertook a study of the upper layers of water in the Black Sea and used EDXRF to determine Mn in suspended particulate matter comprising finely dispersed microspherules (about 0.5 pm in diameter). Industrial pollution in the Ngong River of Kenya was analysed by Jonnalagadda et al. (9311 845) using a variety of techniques XRF being employed to measure the profiles of various elements in suspended and solution material in aquatic samples. And finally XRF was used by Howe and Bowlt (92/3904) to monitor the recovery of iodine from an anion exchange process as part of a study of the lzSI content of freshwater samples the isotopic content of resins being measured using a thin NaI(T1) well-type scintillation detector.2.6.6. Archaeology and Forensic Two new analysers for the non-destructive analysis of archaeological materials were described by Taguchi and Saito (93/1833 and 92/C3527). One was a high-energy X- ray computerized tomographic scanner which was de- signed to analyse samples of maximum size 600 mm diameter to a spatial resolution of 0.3 mm diameter. Cross- sectional image data were found to be useful in the classification of archaeological materials particularly pot- tery bronzes and slags. The other instrument was a micro- focused X-ray mapping analyser which incorporated a micro-focus X-ray tube operating at 200 kV (maximum) with a spot size of 0.1 mm diameter and a 500 x 500 mm scanning stage. Elemental distribution images were used to classify archaeological samples such as pottery and glazes on old ceramics.The analysis and provenancing of pottery porcelain and clay were the subject of a number of other studies. Eissa et al. (9214259) combined data by XRF and Mossbauer spectroscopy to provenance the clay used in pottery found at excavations at the Mit-Rahina (Memphis) region from the New Kingdom in Egypt. Yap (93/17 15) fingerprinted the geographical origin of porcelain samples from Jingde- zhen in China and elsewhere by PCA using EDXRF data for 12 elements (As Co Cu Fe Mn Nb Ni Rb Sr Y Zn and Zr). Analysis by EDXRF using a radioisotope excita- tion source and Si(Li) detector was used by Yamada et al. (9214539) to provenance clay used to make Japanese earthenware pseudo-3-dimensional maps for Fe and Rb and 2-dimensional maps for Sr being particularly useful.The Pb/Sn ratio of glazes from Middle Age majolica pottery from Italy was determined by Krajewaki et al. (93/1655) variations in this ratio being discussed in relation to sample location. A radioisotope EDXRF instrument was used by Mazo-Gray and Alvarez (93/1830) to measure trace ele- ments in Ming porcelain recovered from a Spanish shipwreck for comparison with two fake reproductions. The relative intensity ratios of Co Mn Nb Rb Sr and Zr were found to be diagnostic with Rb/Sr and Mn/Co varying between 2-5 and 2-4 respectively in antique porcelain. A variety of analytical techniques including XRF PIXE gamma spectrometry and INAA were used by Revel and Lahanier (931390 1) to characterize white clay figurines and moulds from French museums.Results from these tech- niques were often found to be complementary but INAA was the most efficient and effective in providing data for over 20 trace elements. A range of six standards containing ternary mixtures of Ag Au and Cu were prepared by White et al. (92/44 13) for calibration of EDXRF in the analysis of museum artefacts comprising historic gold objects. The non-destructive capa- bilities of EDXRF were also used to good effect by Ferretti et al. (93/1962) in the analysis of grey colours used in three paintings by Correggio. These colours were found to contain significant amounts of Sb the concentration of which was related to the darkness of the colour. Following optical microscopy SEM and electron probe microanalysis the Sb was found to be present in the form of the lead-grey mineral stibnite (Sb2S3).Imitation red ware manufactured in the Netherlands Saxony and England some of which are delusively similar to the 17th/l8th century Chinese original was distinguished by Anders et al. (93/1831) using non-destructive EDXRF analysis on the basis of distinctive differences in the CaO MnO and Pb contents as well as density differences. Turning to a modern forensic application Misra et al. (93/1746) used EDXRF to distinguish samples of Indian nail polish manufactured to imitate a popular brand particularly on the basis of the Fe/Ti Fe/Cu and Ti/Cu ratios. 2.6.7. Industrial During the current review period a large number of papers have addressed industrial applications of XRF reflecting perhaps the continued expansion of the technique in to this area of analysis. Some of these applications are covered in the latest ASU review of industrial analysis by Marshall et al.(J. Anal. At. Spectrom. 1992 7 349R). One of the traditional strongholds of XRF continues to be the metallurgical industries and Holzhey (931 1 867) compre- hensively reviewed the application of a variety of tech- niques including gamma radiation XRF and INAA in process and quality control in this industry. Turning specifically to the iron and steel industries the advantages of an instrument fitted with a number of fixed channels and a universal goniometer were discussed by Bonvin et al. (93/2782) together with the performance of an LSM analyser crystal for the determination of Carbon.Gomez et al. (93/1736) described an XRF procedure for aJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 299R range of ferroalloys which incorporated three sample preparation procedures one based on re-melting the sample in an induction furnace a second based on pelletization of powdered materials and a third based on the preparation of glass discs from pre-oxidized materials. The accuracy and precision of these schemes were evaluated. Molchanova et al. (9312840) described the development of a set of SRMs of steels designed particularly for the calibration of XRF instrumentation. Results were presented for Al Coy Cry Cu Fe Mn Mo Nb Ni P S Si Ti V and W. Bondarchuk et al. (9312643) described the analysis of alloy steel rollings a single determination for Cr Cu Mn Ni Ti taking 40 s.Li and Zhang (9214667) determined As Pb Sb and Sn in bearing steel discussing background and matrix correction procedures and reporting precision of around 10 %. An interesting application of X-ray spectra in process control is described by Schiller and Schiller (9312865) involving industrial electron beam furnaces. The accelera- tion voltage in these furnaces is sufficiently high to excite characteristic X-rays in the melting sample and the authors present initial results from a new WD spectrometer devel- oped for this application. X-ray fluorescence methods for the determination of Al Co Cr Cu Fe Mo Mn Nb Ni P S Si Ti V and W in high temperature and Fe-Ni-based alloys were described by Rozova et al.(9312034) who optimized sample preparation techniques and modelled mathematically the variation of background intensity with composition for several low abundance components. It was reported that the best results for matrix corrections of Ni-based alloys were obtained with the Lucas-Tooth and Price method. Bettinelli et al. (931278 1) undertook a detailed assessment of ICP-AES in comparison with WDXRF for the analysis of nickel-based alloys discussing the relative merits of the techniques in terms of accuracy precision and detection limits. The XRF technique has also been used in other metallurgical applications. Melkonyan et al. (921392 8) used a cation-exchange procedure to recover quantitatively Cu Ni and Zn from copper alloys that had been dissolved in nitric acid; the resin was analysed directly by XRF.Matsumoto (931 176 1 and 931 1882) accurately determined A1 in zinc hot-dip galvanizing bath samples by XRF after preparing the sample with a silicon carbide (Sic) abrasive paper (40 grit). Savina et al. (9213933) used an XRF method to determine Re in metallurgical raw materials by-products and wastes by pelletizing samples with polystyrene (4 1 ) and exciting with a gold anode X-ray tube. Analysis time was 45 min per sample. Zagorodnii et al. (9311883) used an EDXRF technique to analyse Fe Mn and Ti in materials used to prepare powder-core welding wire the total analysis time being 15 min. The analysis of coal has been the subject of a number of XRF reports during the current review period some related to potential environmental problems associated with power generation. Chrusciel et al.(9214445) tested a number of analytical techniques including XRF in the characteriza- tion of coal. Martinez-Tarazona et al. (9312784) determined nine major and minor elements and 13 trace elements in low-volatility bituminous coal by XRF. Various calculation procedures based on either the relationship between elemental concentration and ash content or detrital miner- alogy were used to investigate the organic affinities of these elements. The operation of rapid on-line instrumentation for monitoring the ash and S-content of brown coal from an open cast site was reviewed by Thiede (9214010). The instrumentation was based on the XRF analysis of dust collected by suction from a belt transfer point.Ash content and overall calorific values of Spanish coals were deter- mined by EDXRF in a paper by Cruz et al. (9312842). Determinations were made from the A1 and Si contents and results gave RMS differences of about 1.3 mass-% ash and 124 cal g-' gross calorific value compared with classical combustion techniques. Valkovic et al. (9311 657) deter- mined a number of trace elements in South African and Croatian coal and coal ash by XRF PIXE proton-induced pray emission (PIGE) and gamma spectrometry and reported that XRF and gamma spectrometry were adequate techniques for the determination of elements at concentra- tion levels of environmental significance. Both EDXRF (for trace elements) and WDXRF (for major elements) were used by Evans et al.(921401 7) to analyse eight samples of Argonne premium coal. Determinations were made on ash prepared as glass discs after fusion with lithium borate and briquettes prepared from whole coal after mixing with cellulose results on several RMs being presented. Yoko- kawa et al. (9311200) determined As Cd Cr Cu Hg Mn Ni Pb and Zn by both XRF (on ashes remaining after pyrolysis at 800 and at 185 "C) and ICP-AES (using the Carius method). Results from the two ashing procedures were in agreement except for As and Hg which are volatile and Mn Ni and Pb which seemed to be low by XRF. Fly ash has been analysed by Cooper et al. (931 1 890) who used results to assess the impact on the Grand Canyon of stack emissions from coal-fired power stations. Particulate samples from a designated power station were collected using a plume simulating dilution sampler and analysed by XRF ion chromatography and combustion flame ioniza- tion.A method for the accurate XRF analysis of blast furnace slag was described in a report by Dumarey and Moerkerke (931 1887) in which particular attention was paid to obtain- ing representative samples since the composition of slag varies during the cast. After grinding to a fine powder samples were fused with a 1 1 mixture of sodium and lithium tetraborate in a 1 10 sample-to-flux ratio at 1250 "C using an automatic fluxer. Accuracy and precision were assessed relative to several RMs. Converter slags were analysed by Naumenko et al. (9311731) using an XRF technique in which samples were fused with anhydrous borax and formed by a metal stamp.Impurity elements in blast furnace slags were analysed by Zhadanovskaya and Chumachenko (9311907) for Mn Ti and V (together with other major elements) by a procedure that gave RMS calibration errors of 0.0 12 0.0 17 and 0.0 1 5% respectively. Amerkhanov and Khlevnaya (93/2793) also analysed slags using samples that had been compressed as a disc with a boric acid backing. Conversely Mishra et al. (9311866) used a fusion bead technique to prepare samples of Indian sinter for XRF analysis. A 1:lO fusion with sodium tetraborate was used and XRF results were in good agreement with wet chemical techniques for the determination of A1203 CaO Fey P and Si02 over a wide range of concentrations. In the cement manufacturing industry XRF was used by Gromozova et a1 (9312852) to analyse cement raw mix based on coal wastes optimum results being obtained for samples prepared as glass discs at a dilution with flux of 1 :5.The XRF technique also has a role to play in the nuclear industry as shown in a paper by Guardini et al. (93/2866) who evaluated the performance of several non-destructive techniques including K-edge and X-ray fluorescence densi- tometry in the determination of U and Pu in nuclear materials. Wagner et al. (9312863) described developments by the Euratom Safeguards Directorate for the non- destructive on-site analysis of U and Pu at large nuclear reprocessing plants so avoiding the necessity for shipping samples off site. The design and installation of a hybrid K- edge XRF instrument were discussed which was capable of determining concentrations of U and Pu in undiluted samples of input liquors down to 0.3% U and 0.7% Pu.An XRF procedure for the determination of impurities in nuclear-grade uranium oxides and other uranium com- pounds was described by Al-Ammar and Ali (9312737).300R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Samples were prepared as pellets using starch as binder and standards were prepared in a U308 matrix (this being more stable than other uranium oxides). Limits of detection (in pg g-l) were reported to be As (40) Ca (80) Co (1 7) Cr (8) Cu (3 Fe ( 5 ) Mn (30) Mo (25) Ni (29) Th (7) Ti (lo) V(52) and Zn (5). Dragnev et al. (92/3902) described a combined gamma and passive X-ray fluorescence proce- dure for the determination of both total U and 235U enrichment in nuclear fuel with the advantage that both these parameters were determined reliably and accurately from a single measurement.Matrix effects which influence the enrichment measurement were taken into account. Finally Nitsche et al. (9312820) described a method for the determination of Pu down to levels of 10-lo mol 1-1 in aqueous samples and liquid wastes that posed a possible environmental hazard. The method involved the measure- ment of U L X-rays which follow the alpha decay of Pu a prerequisite being that the isotopic composition of Pu must be known. The procedure was claimed to have advantages in being less labour intensive than alternative radiochemi- cal separation procedures. The analysis of lubricating oils particularly for additive or wear metals has traditionally been another strong-hold of XRF.MacKey et al. (92/3072) reviewed the analysis of additive metals comparing WDXRF with ICP-AES tech- niques. Cheng and Zeng (92/3948) described the simulta- neous determination of trace metals in lubricants in which a filter paper was immersed in 0.5 g of sample dissolved in hexane (5 ml). After drying the filter-paper was analysed by XRF for Ba Ca C1 Cu Fe P S and Zn in the concentration range 0.1-0.6% with coefficients of variation of -4.6%. Brodskii (9311888 93/2788) described a method for the analysis of wear metals in lubricating oils in which the oil samples were filtered using a membrane filter and the residue analysed by EDXRF using a Io9Cd source.A computer code based on the FP approach was used to correct for matrix effects in samples of intermediate thickness and representative detection limits for Ca and Mo were reported to be 140 and 3.7 ng g-l respectively. Price (93/2774) used calibration samples prepared from synthetic standards and an intensity correction procedure to deter- mine Ba Ca C1 Mg P S and Zn in a series of monthly round-robin test samples of lubricating oil that had been analysed by a group of about 17 different laboratories. Goedde et a[. (93/1700) used XRF to validate a method for the determination of C1 in waste oil by an ion-selective electrode technique. The analysis of plastics for metals and other inorganic fillers in plastics was the subject of a number of reports. Martinez et al.(93/1802) proposed a method in which the plastic matrix was first decomposed by fusion with sodium hydroxide in a silver crucible using sodium nitrate to ensure complete oxidation. After cooling the melt was dissolved in dilute hydrochloric acid and elements precipitated by adding a mixture of FelI1 sodium diethyldithiocarbamate and sodium rhodizonate solutions. The residue was filtered and the dried filter paper analysed directly by XRF. Calibration curves were rectilinear to 200 pg (As"' Cd CrlI1 and Hg) except for Pb (1 50 pg) Sb"1 (1 00 pg) and Ba (1000 pg). Rao and Pandey (92/4459) determined the S content of copolymer powders by EDXRF calibration techniques using various standards being described in detail. Sandborg and Shen (92K37 14) described an EDXRF method for the analysis of the inorganic content of polymers in which a modified FP correction program which could accommodate the presumed organic content of the polymer was used to convert X-ray intensities to concentrations. Hoffmann et al.(92/3899) evaluated sev- eral techniques (INAA AAS and XRF) for the analysis of stainless-steel constituents in plastics to determine the abrasion effects or wear in plastics processing equipment presenting analytical details of each method. The XRF analysis of Fe was identified as the best method. Warren (93/284 1) undertook a comparison of various non-destruc- tive techniques including XRF neutron absorption and scattering gamma-ray absorption and ultrasonic methods for the measurement of the fibre content of reinforced engineering plastics and composites.The determination of Ti in paints was described by Lewandowski and Fahsel (9312850) in a patent application in which the ash obtained from a dried and calcined sample was fused with a flux such as sodium borate (Na2B4O7)-li- thium tetraborate (Li2B40,) at 1000 to 1600 "C for 5 to 30 min Ti being determined by XRF on the fused bead. In one of a series of reports on the XRF analysis of raw materials published during the current review period Hong et al. (93/2736) described the analysis of iron ores using a glass bead technique and the De Jongh alpha coefficient matrix correction procedure. Accuracy assessed from a calibration curve made up from 32 standards was estimated to be 20.16 mass-% Fe (la). Imported iron ores were analysed using an XRF method by Jiang and Gao (93/1884).Dried samples (1 g) were fused with lithium tetraborate (2.4 g) lithium metaborate (3.6 g) sodium nitrate (1 g) and ammonium iodide (0.5 g) at 1250 "C for 20 min then moulded as glass discs. The Compton scatter peak was used as an internal standard and RSDs in the determination of the major elements were 0.2-2.3%. The XRF technique was used by Jiang (93/1885) to analyse REE metal for Ta using a chemical separation procedure which involved dissolving the metal and precipitation of Ta with phenylarsonic acid using zirconium as carrier. The precipi- tate was filtered and dried and XRF measurements were made directly on the filter-paper using zirconium as internal standard. The limit of detection for Ta was 0.00075% with a standard deviation of 0.02% achieved in test samples.The REE themselves were determined in REE oxide mixtures by Le (92/3943). Dried samples (0.3 g) were prepared by fusion with 1 1 lithium metaborate-lithium tetraborate (5.5 g) silica (0.5 g) and iodine oxide (I2OS) (0.03 g) at 1 100 "C for 10 min and results showed an RSD of 0.75-3.6%. The XRF technique was one of those used to validate a capillary-tube isotachophoresis method for the analysis of metallic elements in high-temperature supercon- ductors by Kaneko et al. (92/4046). Impurities in refractory carbides nitrides and borides were analysed in a contribution from Kaneko et al. (9214540) using a procedure in which the sample was first taken into solution (nitric-hydrochloric acids for V compounds nitri- c-hydrofluoric acids for Nb and Ta compounds).After evaporating to dryness and heating in an electric furnace at the appropriate temperature the residues were ground prior to analysis by XRF. Impurity standards containing Co Cr Fe Mn and Ni in the range 0.002-0.22% were prepared in a similar manner and standard errors from resultant calibration curves were -t 0.0047-0.C 133%. The analysis of ceramic materials was reviewed by Ishizuka (93/ 1670) who considered the capabilities of a range of analytical techniques including XRF. An XRF method for the analysis of enamel frits was described by Baimurzina et al. (93/2851). The elements Al Ca Cu Fe K Mg Mn Na Ni P Si and Ti were determined and differences in matrix effects were taken into account by using separate calibrations for Ca-rich and Ti-rich frits.Yoshikawa and Ito (931191 1) made a patent application for the determination of oxygen in zirconium fluoride and hafnium fluoride by XRF using a Rh or Cr X-ray tube and an 'artificial cumulative film' as detector. The same workers (92/3995) applied for a second patent for the determination of oxygen in titanium boride by XRF using samples mixed with polyethylene. Two interesting applications have been described inJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 301R which elements that can be analysed by XRF spectrometry were used as ‘markers’. The first was by Davis and Lucas (9311 693) who made a patent application for the addition of elements to roofing materials which could subsequently be analysed to permit the ready identification of production parameters MnO and BaSO being successfully deter- mined by EDXRF after ashing the rubber roofing mem- brane.Nagai et al. (93/1694) also made a patent application for a method of measuring the adhesive on a cardboard box which involved the addition of 0.1 mass-% of an element having an atomic number in the range 30-92 to the adhesive so that determination of this element by XRF could be used to measure the amount of adhesive applied to the cardboard. Two reports describing the use of XRF to analyse brines process solutions and waste water are highlighted here. Samuelson and McConnell (93/2008) described an XRF method for the analysis of high density brines used to control oil and gas well operations. The elements Ca C1 and Zn were determined in brines made up of the chloride and bromide salts of these elements with a matrix correction for the bromine content derived from the Compton scatter ratio technique. Bespalova et al.(93/188 1) described an XRF method using a multi-channel spectrometer for the analysis of process solutions involved in the manufacture of zeolites specifically the AlzOJ and Na20 contents of aluminate solutions where RSDs of 1.55 and 3.42% were reported and the Si02 and Na20 contents of silicate solutions where the RSDs were 3.49 and l.66% respec- tively. The determination of Na in solution was particularly demanding. Other applications of XRF included the determination of I in photographic fixers by EDXRF where detection limits of 8.7 ,ug g-’ were reported using caesium as an internal standard (93/1758) and the use of XRF and other tech- niques to measure the purity of In isolated and preconcen- trated by electrodeposition (92/4013).The EDXRF tech- nique was also used to measure the presence of a filler precipitated directly onto the cell walls of ultra-high ash papers (9311701) and the more general use of XRF for problem solving in the paper industry (93/ 1820). 2.6.8. Clinical and Biological The current review period has seen much XRF activity in clinical and biological applications some of which is covered in the latest ASU review of this topic (9214562). X-ray fluorescence spectrometry has become one of the standard methods for the analysis of human hair and several advances have been reported in this application.Folin et al. (92/4270) determined Cu and Zn in female human hair of two age groups (3-6 and 70-90 years) comparing determinations made by AAS and EDXRF. Good correspondence of results between the two techniques was obtained with an increase in concentration noted with increase in age. Calliari et al. (93/28 17) determined Cu Fe and Zn in hair by EDXRF after microwave digestion of specimens. Mu et al. (9312747) determined Ca Co Cu Fe K Mn Ni Sr Zn by XRF in human scalp hair and reported a positive correlation between drinking water and hair concentrations for Sr but a negative correlation for Cu. Dote et al. (93/1800) analysed A1 and F by XRF in black hair as one of the parameters in evaluating the metabolism of trace elements in patients suffering from dementia and found that F increased with age but A1 decreased. Watan- abe et al.(9312738) analysed Ca Cu F Fe K Mg Na P and Zn by XRF in a large group of rural inhabitants and a more restricted group of medical students they found no differences between sampling areas but found that some variations in concentration correlated with colour of hair sex and age. Wang et al. (92/C4 170) reported an accuracy of 0.1 Yo a precision of 0.74% and a detection limit of 1 ppm in the determination of Zn by a new XRF technique which involved analysis of a compressed disc of hair. Another standard application of XRF in clinical studies is in the in vivo analysis of lead in bone. Todd et al. (93/1769) reported a study in which the radiation dose to the patient’s leg resulting from the in vivo analysis of lead (L-lines) using a Io9Cd excitation source was measured.Results showed that doses varied with the patient’s age in the range 34 to 1100 nSv for measurements with a median precision of 4.9 pg of Pb per gram of bone mineral for a 30 min measurement in an adult. Preiss and Tariq (93/1766) evaluated critically the Lcu line XRF analysis of lead in human bone using the method of Rosen et al. (Procl. Natl. Acad. Sci. 1989 86 685). Armstrong et al. (93/1860) concluded that in vivo XRF measurements of tibia lead concentrations was likely to be used increasingly as a biological monitor of cumulative exposure to lead follow- ing a re-analysis of a group of workers occupationally exposed to lead. Results from this group recorded 5 years after a previous analysis confirmed the reliability of the technique and showed improved precision owing to techni- cal advances.Pella and Soares (93/1999) evaluated the secondary target method of exciting the Pb L-line spectrum for in vivo measurements of lead in bone. The spectrum output from such a source comprised mainly characteristic X-rays which were much lower in intensity than those expected of an X-ray tube. Minimum detection limits the effect of skin and the effective dose equivalent were reported from measurements on a simulated sample. Several other applications of XRF in the analysis of clinical samples have been reported. The use of radioiso- tope XRF for the trace element analysis of biological samples was reviewed by Havranek et al. (92/4003) who showed on the basis of literature data that the main applications in diagnostic and clinical studies were in haematology oncology studies of kinetic processes and the diagnosis of heavy metal intoxication.Methods of sample preparation and their inff uence on analytical results were also discussed. Kaufman et a/ (9312873) discussed an automated EDXRF analysis system for the determination of stable tracers in vitro. Advantages were reviewed in a number of clinical and research investigations where other stable or radioisotope techniques might be used as an alternative (for example the use of caesium as an analogue for potassium in evaluating the function of red blood cells). Nilsson et al. (92/4279) reported that the detection limit for Cd in the course of in vivo measurements in bone was improved by substituting a Si(Li) detector for a germanium detector. Sakai (93/1713) analysed F Ca Mg and P in human dentine by XRF to contribute data to a study of the effect of brushing on the development of dental caries. Xie and Hou (93/1742) described an XRF procedure for measuring directly the metal content of gallstones.The alumino-silicate content of calcium supplements from various carbonate deposits was measured by Bourgoin (93/1776) using XRF who found that fossilized oyster shells contained substantially more A1 than material derived from dolomite. The IUPAC Commission on Toxicology (93/ 177 1 ) reported the results of a cooperative study from 39 laboratories using seven inherently different methods of analysis (including EDXRF) for the measurement of Se in freeze-dried human whole blood.A critical evaluation of results from these techniques and the performance of contributing laboratories was undertaken. The XRF deter- mination of Se in serum plasma and whole blood was reviewed by Robberecht et al. (92/4286); topics covered included sampling storing sample pre-treatment experi- mental conditions and concentrations in population groups. Gresits et al. (93/1767 and 9311653) reported the302R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 construction and operation of a radioisotope EDXRF system incorporating a lZsI radioisotope source and a Si(Li) detector used for the determination of trace elements (Br Cu Fe Sr and Zn) in blood. A number of developments involving the assay of animal tissue have been reported during the current review period.Homma et al. (93/1861) used a non-destructive XRF imaging technique to measure the distribution of trace elements (Cu Hg Se and Zn) in the kidney of infant rats and those that had been administered organic mercury. Li et al. (93/1691) used XRF for the determination of trace elements in animal liver in which matrix effects were accounted for in several ways Br Cu Mo Rb and Zn were ratioed to the Rh-Ka Compton scatter intensity; Ca Fe and Mn to the scattered background intensity at 0.1876 nm; and K Mg Na P and S to the intensity of the Rh-La Rayleigh scatter line. Tariq and Preiss (93/1712) reported on the time-dependent distribution of selenate and selenite in mice using a radioisotope-induced XRF technique based on ’%e.Mertin (93/1692) used EDXRF to determine trace elements (Br Ca Cu Fe K Mn Pb Rb Sr and Zn) in the fur of silver foxes of various ages to evaluate differences that could be correlated with the effects of sex and age. As one of several papers highlighting the analysis offish and sea-food Cu was determined in the dorsal muscle and liver of farmed Chinook salmon by Peterson et al. (93/1102) using AAS and XRF to evaluate the effect of an algicide containing copper oxide as an active ingredient. A range of products from fast-food outlets was analysed for As by Nielsen et al. (9214033) using XRF and positive determinations were found to correlate almost completely with sea foods that had a geometric mean As concentration of 2.1 -t 3.2 pg g-’ (dry mass).Accuracy of results was evaluated using NIST RMs and a dietary assessment of As intake from various sea food dishes was undertaken. A range of elements was determined in mussel reference samples prepared as pressed powder pellets using XRF by Wang et al. (93/1690); river sediment reference materials diluted with cellulose (1:9) were used as calibration standards. In another contribution from this group (92/C4179) the same XRF method was used to assist in the preparation of a mussel RM by the determination of Cu Mn Pb and Sr for homogeneity testing. The analysis of vegetables andfruits has been the subject of a number of reports. In a second contribution Nielsen et al. (92/4032) determined Pb and Sn non-destructively by XRF and found that results exceeded detection limits in only 24 (Pb) and 36 (Sn) samples out of the 525 that were analysed.Coincident detection of these elements occurred in 22 samples indicating a highly significant correlation in their elevated occurrences. Although leaching of Sn from tin cans explained some of the anomalous Sn values the correlated occurrences of Pb and Sn were thought to reflect biological intake from soils. An intercomparison of results on ‘vegetal’ SRMs was published by Moauro and Carconi (93/2396) in which INAA data were compared with those from other techniques including AAS ICP and XRF. As in last year’s review the analysis of rapeseed has been reported in a number of investigations. Wagstaffe et al. (93/2733) reported the certification of the sulfur content of three rapeseed reference materials establishing the suitability of these samples for calibrating XRF spectromet- ers.The relationship between total S (determined by XRF) and the glucosinolate content of rapeseed was reported by Schnug et al. (93/2740). Reference materials from BCR were used for calibration and a transformation proposed to convert previous data to be compatible with data from this new calibration. In a second contribution from this group (93/ 1743) the total glucosinolate content of 36 samples of rapeseed was determined by XRF and HPLC and by the Kjeldahl method for total protein. Correction of the seed protein content in the calculation of the glucosinolate content by XRF improved significantly the agreement between the two methods.In conjunction with an HPLC study Clossais-Besnard et al. (9214055) used XRF to determine total S in rapeseed prepared as pellets from powdered seeds and these data in combination with enzymic calibration were used for the rapid quantitative determination of all glucosinolates. Mao et al. (9213945) described a technique for the determination of P in rape- seed and other vegetable oils by XRF in which 50 pl of sample were deposited onto a filter-paper and analysed when dry. Leaf and other plant material have also been the subject of XRF investigations. Clark et al. (93/ 174 1) developed an XRF technique for the analysis of leaf material where insufficient sample was available for preparing a conven- tional powder pellet. The sample was mixed with cellulose or boric acid in varying proportions.Cellulose was found to be the preferred sample preparation medium when less than 40 mg of material was available for analysis. The mechani- cal shaking of cellulose and sample generally gave higher concentrations than manual mixing. The elements of interest included Al Ca C1 Cu Fe K Mg Mn P S Si and Zn. Kocman et al. (9311 862) described a rapid and precise XRF method for the determination of Al Ca C1 Cu Fe K Mg Mn Na P Pb S Si Sr and Zn in macro and micro- nutrients in leaves and vegetables; the method was applied to a study of acid rain affected forest. Sakata et al. (9311 770 92/C35 18) evaluated the FP method of correcting matrix effects in the XRF analysis of leaves and reported that by using cellulose (C6H as the unanalysed ‘balancing element’ accurate XRF results could be obtained in the analysis of certified leaf RMs.In a further contribution Bumbalova et al. (93/2821) used a radioisotope EDXRF instrument (Io9Cd source + Si(Li) detector) to analyse plant drugs (Nephrosal tea bag) and their water infusion. In the dried sample Br Ca Cu Fe K Mn Ni Pb Rb Sr and Zn could be detected but only Ca Mn Sr and Zn in the aqueous infusion. Belakova et al. (93/1804) used similar instrumentation to determine selected elements (including Br Cu Fe Ni Pb Rb Sr and Zn) in medicinal plant samples also packed in tea bags. Cai and Guo (9311708) analysed ginseng and its soil by XRF and measured the distribution of various elements (including Ca and Sr) in different regions of the plant. The Fe and Mn contents of fresh and brewed tea were determined using XRF by Sahin et al.(9311 865) to evaluate the effect of various growth and processing factors. Finally the detoxication mechanism towards Al Cr and Mn of Pseudomonas syringae was evaluated in a series of controlled laboratory culture experiments by Al-Aoukaty et al. (93128 15). 2.6.9. Chemical eflects Chemical state analysis by soft X-ray emission spectroscopy was reviewed by Kawai (92/3906) with particular emphasis on molecular orbital (MO) calculations for compounds having ‘spectator holes’ in the valence orbitals. Examples considered include ‘shake-off satellite peaks in the C1 Ka spectrum and the multiplet structure of the La spectra of transition metal compounds. The interpretation of spectra without spectator holes was also considered as well as techniques for measuring soft X-ray spectra.Various studies have been undertaken of high T super- conductors. Sakai et al. (93/ 1835) measured profile changes of the 0 K spectra of various copper compounds including superconductors and obtained good agreement between experimental results and theoretical spectra obtained by MO calculations on linear 0-Cu and Cu-0-Cu clusters when the contribution to X-ray spectra of s and p orbitalsJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 303R was taken into account. The Cu L X-ray spectrum of copper compounds including high T superconductors was mea- sured by Nakajima et al. (92/4000) who found a relation- ship between the satellite intensity of the Cu 2p XPS emission and the Cu La line width.The theory of Cu 2p X- ray emission spectroscopy in high T superconductors was examined in relation to emissions observed in the spectra of La2Cu0 and CuO by Tanaka et al. (92/4001). A shoulder structure which appears on the high energy side of the main Cu peak in La2Cu04 and high T superconductors (but not CuO) was shown to originate from the stronger hybridiza- tion between selected symmetry states caused by the existence of apical 0. Charge transfer effects in the spectrum of copper L X-ray emission spectra of CuI1 compounds including high T superconductors were also reported by Kawai and Maeda (92/3999). A shoulder on the high energy side of the main La line was correlated with a transition between poorly screened states in contrast to the main line which involved well-screened states.Bonding egects between Cu and S in BaCu2Sz were examined by Osadchii et al. (93/2853) who correlated features in the La spectrum of Cu the I@ spectrum of S and the valence band X-ray electronic spectrum of BaCuzSz with the presence of CuS4’- clusters having highly covalent Cu-S bonds. Valence state speciation studies of S were undertaken by Li et al. (93/2129) who used the Kalman filter algorithm to resolve overlapping spectra of Svl SIV So and S-I1 recorded on a dual crystal spectrometer. For eleven mixtures of S042- S032- S and S2- recoveries of each state were between 92 and 105%. Further studies of the chemical state of S this time in environmental samples were undertaken by Wang et al. (93/1665). A computer program incorporating a least squares curve fitting method was used to resolve overlapping peaks in spectra recorded from coal peach leaves tea soil etc.recorded on a high resolution XRF spectrometer. The role of charge-transfer in XRF and XPS studies of copper(I1) compounds was studied by Osadchii et al. (9312797) using a theoretical basis to show the presence in the Cu K a spectrum of an intense ‘shake-up’ satellite located about 0.4 eV to the long wavelength side of the main line which in CuO corresponds to transitions associated with the CuOd6- cluster. A number of papers have reported chemical shifts and the presence of satellite peaks in studies of the electronic structure of atoms and bonding effects in molecules. Chemical shifts in the Ca K a and Kp emission spectra were observed by Sugiura (9312830) from a variety of calcium compounds (CaF CaO and CaS) using a two crystal spectrometer.In combination with measurements of the photoelectron spectrum of anion species the first small peak at the Caz+ K line absorption threshold of each of these compounds was identified as a core exciton the energy level of which is formed below the bottom of the conduction band; binding energies of these excitons were estimated. In two further contributions Sugiura (93/ 1899) investigated first high energy satellite peaks in the Ka X- ray spectrum of fluorine measured from various metal fluorides drawing some correlations with XPS spectra of the F- 2p valence bands to explain the transition mecha- nism and second the Kp X-ray emission spectrum of hydrated chlorides of alkaline earth and REE (93/2796) drawing comparisons with the emission spectra of anhy- drous materials (reported previously) to evaluate the influence of the water molecules.Zhu et al. (93/2031) investigated the fine structure present in the B K a X-ray spectrum using a high resolution soft X-ray curved crystal spectrometer. Overlapped bands were resolved with a Fourier self-deconvolution technique with a new type of apodization function. Results correlated with the theory of an sp2 hybrid orbit of boron in Bz03. Kai et al. (92/3954) used a high resolution XRF spectrometer with double crystals to investigated chemical shifts in the Si Ka! and A1 K a lines observed from amorphous films of Alz03 SiO CaO-SiO and A1203-CaO prepared by radiofrequency sputtering.These data were used to examine the structure and composition of the film. Ang et al. (92/C4174) presented data by XPS and XRF for the determination of the bridging and non-bridging oxygen content in glasses based in part on measured shifts in peak position FWHM peak intensity and asymmetry in the Si K spectra. Scimeca and Gohshi (9311 822) continued their novel work in the use of high resolution XRF spectroscopy to study chemical bonding egects in solution. Specifically dramatic changes in the C1 K a and Kp spectra were measured on dissolving sodium chloride in water and these changes were interpreted on the basis of chemical-depen- dent X-ray shake-off satellites which were contrasted with aqueous sulfide measurements.In a further study Scimeca and Gohshi (92/4061) used similar techniques to probe the electron structure of two aqueous systems potassium sulfide [K2S(aq)] and zinc chloride [ZnCl,(aq)] that exhibit long range ordering. Both these studies were also reviewed in a conference abstract (92/C3509).304R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 LOCATION OF REFERENCES The full list of references cited in this Update have been published as follows 9212590-92lC3494 J. Anal. At. Spectrom. 1992 7(5) 247R-277R. 92lC3495-9214073 J. Anal. At. Spectrom. 1992 7(7) 329R-348R. 92/4074-92/4734 J. Anal. At. Spectrorn. 1992 7(8) 389R-411R. 93lCl-93lC997 J. Anal. At. Spectrom. 1993 8( I) 45R-78R. 931998-93jCl354 J. Anal. At. Spectrom. 1993 8(3) 137R-149R. 93lC1355-9312093 J.Anal. At. Spectrom. 1993 8(4) 169R-194R. 9312094-92127 10 J. Anal. At. Spectrom. 1993 8(5) 239R-262R. Abbreviated forms of the literature references quoted (excluding those to Conference Proceedings) are given on the following pages for the convenience of the readers. The full references names and addresses of the authors and details of the Conference presentations can be found in the appropriate issues of JAAS cited above. Abbreviated List of References Cited in Update 9212590. Anal. Proc. 1991 28 312. 9212626. J. Anal. At. Spectrom. 1991 6 283R. 9212950. Zavod. Lab. 1991 57(4) 29. 9212960. Zavod. Lab. 1991 57(1 l) 25.9212998. X-Ray Spectrom. 1 99 1 20,2 1 5.9213000. X-Ray Spectrom. 1991 20 245. 9213072. ASTM Spec. Tech. Publ. 1991 1109 52. 9213166.Chem. Tech. (Leipzig) 1991 43 347. 9213204. LaborPraxis 199 1 15 736 738. 9213244. Seram- ikkusu 1991 26 536. 9213822. J. Anal. At. Spectrom. 1992 7 23. 9213825. J. Anal. At. Spectrom. 1992 7 43. 9213827. J. Anal. At. Spectrom. 1992 7 53. 9213828. J. Anal. At. Spectrom. 1992 7 1R. 9213845. Chem. Geol. 1992 95 1. 9213847. Chem. Geol. 1992 95 63. 9213859. Geochim. Cosmochim. Acta 199 1 55 2075. 9213860. Geochim. Cosmochim. Acta 199 1 55 224 1.9213873. Nucl. Instrum. Meth. Phys. Res. Sect. A 1992,311,240.9213876. Nucl. Instrum. Methods Phys. Res. Sect. B 1990 49 360. 9213877. Nucl. Instrum. Methods Phys. Res. Sect. B 1990 49 551. 9213879. Nucl. Instrum. Methods Phys. Res. Sect. B 1990 50 338. 9213880. Nucl. Instrum. Methods Phys. Res. Sec. B 1990,50 353. 9213884. Int.Lab. 1991 21(3) 50. 9213898. Fresenius’ J. Anal. Chem. 1990 338 917. 9213899. Fresenius’ J. Anal. Chem. 1991 339 230. 9213902. J. Radioanal. Nucl. Chem. 1991 152 161. 9213903. J. Radioanal. Nucl. Chem. 1991 152 251. 9213904. J. Radioanal. Nucl. Chem. 1991 152 347. 9213905. Adv. X Ray Anal. 1991 34 81. 9213906. Adv. X- Ray Anal. 199 1 34 9 1. 9213908. Adv. X-Ray Anal. 199 1 34 157. 9213910. Adv. X-Ray Anal. 1991,34,337.9213911. Adv. X-Ray Anal. 1991 34 357. 92/3913. Rev. Sci. Instrum. 1992,63 15 19. 9213914. Rev. Sci. Instrum. 199 1 62 2980. 9213915. Rev. Sci. Instrum. 1992 63 493. 9213916. Rev. Sci. Instrum. 1992 63 648. 9213918. Rev. Sci. Instrum. 1992 63 685. 9213919. Rev. Sci. Instrum. 1992 63 689. 9213921. Rev. Sci. Instrum. 1992 63 946. 9213923. Rev.Sci. Instrum. 1992 63 1355. 9213928. Zavod. Lab. 1990 56( 12) 37.9213931. Zavod. Lab. 1991 57(9) 27. 9213933. Zavod. Lab. 1991 57(10) 7. 9213943. Lihua Jianyan Huaxue Fence 1991 27 207. 9213944. Lihua Jianyan Huaxue Fence 1991 27 240. 9213945. Fenxi Huaxue 1990 18 1 155. 9213947. Fenxi Huaxue 1991 19 126. 9213948. Fenxi Huaxue 1991 19 Inside back cover. 9213953. Proc. SPIE-Int. SOC. Opt. Eng. 199 1 1440 188. 9213954. Proc. SPIE-Int. SOC. Opt. Eng. 1991 1519. 9213955. Proc. SPIE-Int. SOC. Opt. Eng. 1991 1519 298. 9213956. Proc. SPIE-Int. SOC. Opt. Eng. 1991 1545 116. 9213957. Proc. SPIE-Int. SOC. Opt. Eng. 1992 1547 63. 9213958. SPIE-Int. SOC. Opt. Eng. 1992 1547 221. 9213959. Proc. SPIE-lnt. SOC. Opt. Eng. 1991 1548 160. 9213960. Proc. SPIE-Int. SOC. Opt. Eng. 1991 1550 46.9213961. Proc. SPIE-Int. SOC. Opt. Eng. 1991 1552 198. 9213962. Proc. SPIE-Int. Soc. Opt. Eng. 1991 1552 278. 9213964. Proc SPIE-Int. Soc. Opt. Eng. 1991 1592 96. 9213969. ASTM Stand. 1990 E 1361. 9213970. Appl. Radiat. Isot. 1990 41 1149. 9213978 Fenxi Shiyanshi 1991 10 133. 9213991. Jpn. Kokai Tokkyo Koho JP 03,170,672 (9 1,170672) (Cl. C23C 16/02) 24 Jul 199 1 Appl. 89/308,173 28 Nov 1989 4 pp. 9213992. Jpn. Kokai Tokkyo Koho JPO3,170,673 (91,170,673) (Cl. C23C16/26) 24 Jul 199 1 Appl. 89/308,174,28 Nov 1989,4 pp. 9213993. Jpn. Kokai Tokkyo Kobo JP 03,175,346 (9 1,175,346) (Cl. GOlN23/223) 30 Jul 199 1 Appl. 89/3 13,293,04 Dec 1989 3 pp. 9213994. Jpn. Kokai Tokkyo Koho JP 03,225,267 (9 1,225,267) (Cl. GOlN23/223) 199 1 Appl. 90/2 1,423 1990. 9213995.Jpn. Kokai Tokkyo Koho JP 03,22 1,862 (9 1,22 1,852) (Cl. GO lN23/223) 199 1 Appl. 90/ 16,400 1990. 92/3996. SU 1,427,987 (Cl. GOlN23/223) 23 May 1991 Appl. 4,190,231 15 Dec 1986. From Otkrytzya lzobret 1991 (19) 231. 9213997. U S . US 5,060,247 (Cl. 1988. 9213999. Physica C (Amterdam) 1991 185 981. 92/4000. Physica C (Amsterdam) 199 1 185 983. 92/4001. Pysica C (Amsterdam) 199 1 185 1489. 9214003. Acta Fac. Pharm. Univ. Comenianae 1990 44 67. 9214007. Appl. Surf Sci. 199 1,52 199.9214010. Braunkohle (Duesseldorj 1991 43( 1 l) 27. 9214013. Bull. Soc. Chim. Fr. 1991,677 83. 9214017. Energy Fuels 1990 4 440. 9214018. Environ. Sci. Technol. 1992 26 52 1. 9214023. Huanjing Huaxue 1991 10(6) 56. 9214025. Indian J. Environ. Prot. I991 11 33. 9214028. Int. J. Environ.Anal. Chem. 1990 41(3-4) 27. 9214029. Isotopenpraxis 1991 27 350. 9214031. J. Electrochem. SOC. India 199 1 40 WS.2 1.9214032. J. Food Cornpos. Anal. 1991 4 206. 9214033. J. Food Compos. Anal. 1991 4 285. 9214037. Jpn. J. Appl. Phys. Part 1 1991 30 3540.9214044. Meas. Sci. Technol. 1991 2 183. 92/4046. Mol. Cryst. Liq. Cryst. 1990 184 297. 92/4047. New Diamond Sci. Technol. Proc. Int. ConJ 2nd 1990 (Pub. 1991) 143. 9214049. Opt. Appl. 1990 20 2003. 9214052. Phys. Rev. Lett. 1991 67 3590. 9214053. Phys. Scr. T 1991 T39 328. 9214055. Plant Physiol. Biochem. (Paris) 1990 28 173. 9214059. SCOPE 1991 46 89. 9214061. Solid State Commun. 1991 80 951. 9214065. Tetsu to Hagane 1991 77 2007. 9214069. 2. Phys. A Hadrons Nucl. 1992 341 227. 9214083. Anal. Proc. 1992 29 94.9214084. Anal. Proc. 1992 29 104. 9214091. Analyst 1992 117 3 13. 9214092. Analyst 1992 117 395. 9214100. Analyst 1992 117 577. 9214104. Analyst 1992 378-50 GOlN23/223) 199 1 JP Appl. 88/UT 150 103,JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 305R 117 649.9214259. Acta Phys. Hung. 1991,69,25.9214270. Ann. Chim. (Rome) 199 1 81 39. 9214278. Basic Life Sci. 1990 55 281. 9214279. Basic Life Sci. 1990 55 297. 9214282. Biol. Cell (1981) 1990 70 129. 9214286. Biol. Trace Elem. Res. 1990 25 149. 9214297. Bur. Mines Rep. Invest. 1991 RI 9359 12 pp. 9214299. C. R. Acad. Sci. Ser. 2 1990 311 57. 9214314. Chin. Sci. Bull 1991 36(2) 140. 9214315. Chin. Sci. Bull. 199 1,36 173.9214362. US Par. 4 949 367 filed 29 March 1989. 9214368. Huaxue Tongbao 1991 2 35.9214399. Kinki Aruminyumu Hyomen Shori Kenkyukai Kaishi 1990 146 7. 9214406. Kompleksn. Ispol’z. Miner. Syr’ya 1990 5 87. 9214413. Mater. Res. SOC. Symp. Proc. 1991 185 731. 9214419. Met. Ions Biol. Med. Proc. Int. Symp. Ist 1990 192. 9214422. Metall. Trans. A 1991 22 1969. 9214428. Mineral. J. 1991 15 203. 9214429. Mineral. Mag. 199 1 55 347. 9214440. Nucl. Mater. Manage. 1990 19 199. 9214445. Nucl. Tech. Explor. Exploit. Energy Miner. Resour. Proc. Int. Symp. 1990 (Pub. 1991) 269.9214451. OxfordSer. Opt. Sci. 1990 1 316. 9214459. Polym. Test. 1991 10 31. 9214462. Powloki Ochr. 1989 17(3) 24. 9214471. Proc. Electrochem. Soc. 1991 91 342. 9214478. Prog. SurJ Sci. 199 1,36 35. 9214483. Rare Met. (Beijing) 199 1 10 144.9214494. S. Afi. J. Sci. 1991 87 138.9214497. Sci. Int. (Lahore) 1991 3 19. 9214512. Soil Sci. SOC. ,4m. J. 1991 55 750. 9214528. Trends Anal. Chem. 1991 10 71. 9214531. Vacuum 1991 42 205. 9214539. X-sen Bunseki no Shinpo 199 1 22 8 1. 9214540. X-sen Bunseki no Shinpo 199 1,22 1 13. 9214555. Zentralinst. Kern forsch. Rossendorf Dresden [Ber.] ZjK 1990 ZW-713 63. 9214556. Zentralinst. Kernforsch. Ros- sendorf Dresden [Ber.] ZJK 1990 ZfK-713 64. 9214557. Zentralinst. Kern forsch. Rossendorf Dresden [Bey.] Z f l 1990,ZfK-713 72. 9214562. J. Anal. At. Spectrom. 1992,7 67R. 9214573. J. Anal. At. Spectrom. 1992,7 551.9214576. J. Anal. At. Spectrom. 1992,7 55 7.9214579. Analyst 1992 117 707. 9214585. Analyst 1992 117 869. 9214598. J. Anal. At. Spectrom. 1992 7 75. 9214599. J. Anal. At. Spectrom. 1992 7 81.9214603. J. Anal. At. Spectrom. 1992 7 109. 9214605. J. Anal At. Spectrom. 1992 7 121. 9214629. J. Anal. At. Spectrom. 1992 7 255. 9214630. J. Anal. At. Spectrom. 1992 7 261. 9214632. J. Anal. At. Spectrom. 1992 7 273. 9214633. J. Anal. At. Spectrom. 1992 7 281. 9214648. J. Anal. At. Spectrom. 1992 7 371. 9214667. Lihua Jianyan Huaxue Fence 1991 27 145. 9214668. Lihua Jianyan Huaxue Fence 199 1 27 158. 9214680. Fresenius’ J. Anal. Chem. 1991,341,43.9214682. Fresenius’ J. Anal. Chem. 1991 341 537. 9214684. Anal. Chem. 199 1,63 64 1 A 644A. 9214685. Anal. Chem 1992 64 274. 9214686. Anal. Chem. 1992 64 288. 9214687. Anal. Chem. 1992 64 354. 9214688. Second. Ion Mass Spectrom. SIMS 7 Proc. Int. ConJ 7th 1989 (Pub. 1990) 9. 9214690. Second. Ion Mass Spectrom. SIMS 7 Proc.Int. ConJ 7th 1989 (Pub. 1990) 25.9214692. Second. Ion Mass Spectrom. SIMS 7 Proc. Int. Conf.’ 7th 1989 (Pub. 1990) 45.9214693. Second. Ion Mass Spectrom. SIMS 7 Proc. Int. ConJ 7th 1989 (Pub. 1990) 57.9214696. Second. Ion Mass Spectrom. SIMS 7 Proc. Int. Conf 7th 1989 (Pub. 1990) 793. 9214697. Second. Ion Mass Spectrom. SIMS 7 Proc. Int. Con$ 7th 1989 (Pub. 1990) 809.9214698. Second. Ion Mass Spectrom. SIMS 7 Proc. Int. Con$ 7th 1989 (Pub. 1990) 8 15. 9214699. Second. Ion Mass Spectrom. SIMS 7 Proc. Int. Con$ 7th 1989 (Pub. 1990) 879. 9214704. Spectrochim. Acta Part B 1991 46 1667. 9214705. Spectrochim. Acta Part B 199 1 46 17 1 1. 9214709. Appl. Plasma Source Mass Spectrom. (Sel. Pap. Int. Conf) 2nd 1990 (Pub. 1991) 101. 9214710. Anal. Chim. Acta 1991 247 97.9214715. Spectrochim. Acta Rev. 1991 14 45. 9214717. Appl. Radiat. Isot. 1992 43 271. 9214718. Appl. Radiat. Isot. 1992 43 279. 931409. Analyst 1992 117 971. 931419. Appl. Opt. 1992 31 987. 931457. At. Spec- trosc. 1991 12 239. 931462. Chem. Geol. 1991 94 105. 931528. Spectrochim. Acta. Part B 1992 47 119. 931568. Anal. Sci. 199 1 7 1263.931752. Fresenius’J. Anal. Chem. 1991 341 709. 931765. Fresenius’ J. Anal. Chem. 1992 342 312. 931843. Adv. X-Ray Anal. 1991 34 299. 931855. Geochim. Cosmochim. Acta 1992 56 67. 931864. Surf Interface Anal. 199 1 17 8 75. 931867. X-Ray Spectrom. 1992 21 37. 931998. J. Anal. At. Spectrom 1992 7 25N. 931999. J. Anal. At. Spectrom. 1992 7 579. 9311001. J. Anal. At. Spectrom. 1992 7 595. 9311003. J. Anal. At. Spectrom. 1992 7 605. 9311004.J. Anal. At. Spectrom. 1992 7 61 1. 9311005. J. Anal. At. Spectrom. 1992 7 61 7. 9311006. J. Anal. At. Spectrom. 1992 7 623. 9311008. J. Anal. At. Spectrom. 1992 7 635. 9311009. J. Anal. At. Spectrom. 1992 7 641. 9311020. J. Anal. At. Spectrom. 1992 7 71 1. 9311022. J. Anal. At. Spectrom. 1992 7 719. 9311033. Analyst 1992 117 1 15 1. 9311037. Analyst 1992 117 1169. 9311040. Analyst 1992 117 1477. 9311044. Anal. Proc. 1992 29 274. 9311045. Anal. Proc. 1992 29 276. 9311048. Anal. Proc. 1992 29 280. 9311049. Anal. Proc. 1992 29 281. 9311050. Anal. Proc. 1992,29,282(9). 9311051. Anal. Proc. 1992 29 282. 9311052. Anal. Proc. 1992 29 284. 9311054. Anal. Proc. 1992,29,287.9311070. Can. J. Appl. Spectrosc. 1992 37 22A. 9311074. At. Spectrosc. 1991 12 215. 9311078.At. Spectrosc. 1991 12 235. 9311080. Spectrochim. Acta Part B 1992 47 971. 9311083. Spectrochirn. Acta Part B 1992 47 1001. 9311093. Agrokhimiya 199 1 3 62. 9311102. Aquaculture 1991 99 105. 9311138. Exot. Nucl. Spectrosc. [Proc. Am. Chem. SOC. Div. Nucl. Chem. Technol. Symp.] 1989 11. 9311192. Mater. Sci. Eng. B 1992 B12 195. 9311200. Nenryo Kyokaishi 1991 70 833. 9311208. Opt. Commun. 1 99 1,85 408.9311221. Proc. Rencontre Moriond. 1 99 1,26 329. 9311224. Rapid Commun. Mass Spectrom. 1991 5 586.9311232. Reza Kagaku Kenkyu 1991 13 63.9311252. Tech. Poszukiwan Geol. Geosynoptyka Geoterm. 1989 28 55.9311260. Toyama ken Eisei Kenkyusho Nenpo 1990,14 208. 9311642. Spectrochim. Acta Part B 1992 47 1123. 9311651. Spectrochim. Acta Part B 1992 47 1241. 9311652. Fresenius’ J.Anal. Chem. 1992 342 444. 9311653. ‘4nalytiker Taschenbuch Bd. 10 ed. Gunzler H. Springer-Verlag Berlin 199 1. 9311654. Bull. Rech. Agron. Gembloux 1992 27 133. 9311655. J. Mater. Sci. Lett. 1992 11 848. 9311657. Nucl. Instrum. Methods Phys. Rex Sect. B 1992 69 479. 9311659. Nucl. Instrum. Methods Phys. Res. Sect. A 1992 318 908. 9311660. J. Vac. Sci. Technol. A 1992 10 21 19. 9311661. Nucl. Instrum. Methods Phys. Rex Sect. A 1992 317 597. 9311663. Nucl. Instrum. Methods Phys. Res. Sect. A 1992 319 158. 9311665. Huanjing Huaxue 1992 11(3) 55. 9311666. Process Metall. 1992 7A. 9311668. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 68 122. 9311669. HyperJine Interact. 1992 71 1449. 9311670. Bunseki 1992 4 295. 9311671. Spectroscopy (Eugene Oreg.) 1992 7(5) 40 42.9311672. Zh. Anal. Khim. 1992,47 383.93J1673. Springer Proc. Phys. 1992,61 (Surf X-Ray Neutron Scattering) 1 19. 9311674. Springer Proc. Phys. 1992 61 (Surf X-Ray Neutron Scattering) 125. 9311675. Springer Ser. Opt. Sci. 1992 67 (X-Ray Microsc. 111) 23. 9311676. Synchrotron- strahlung Erforsch. Kondens. Mater. Vorlesungsmanuskr. IFF-Ferienkurses 23rd. 1992 20.1 18. 9311678. Synchro- t ronstra h Iu ng Erforsch . Kondens. Ma ter. Vorlesu ngsma n- uskr. IFF-Ferienkurses 23rd. 1992 38.1 20. 9311679. Springer Ser. Opt. Sci. 1992 47 (X-Ray Microsc. 111) 226. 9311680. X-Ray Spectrom. 1992 21 1 1 1. 9311681. X-Ray Spectrom. 1992 21 127. 9311682. X-Ray Spectrom. 1992 21 143. 9311683. Appl. Radiat. Isot. 1992 43 893. 9311685. Nucl. Instrum. Methods Phys. Rex Sect.B 1992 69 178. 9311686. Nucl. Instrum. Methods Phys. Rex Sect. B 1992 68 125. 9311687. Nucl. Instrum. Methods Phys. Res. Sect. B 1992,69,36 1.93/1688. Springer Ser. Opt. Sci. 1992 67. 9311689. Otkrytiva Izobret. 1991 43 164.306R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 9311690. Guangpuxue Yu Guangpu Fenxi 199 1 11(6) 45. 9311691. Guangpuxue Yu Guangpu Fenxi 1991 11(6) 49. 9311692. Pol’nohospodarstvo 199 1 37 982. 9311693. Eur. Pat. Appl. EP 482,577 (Cl. C08K3/00) 29 Apr 1992 US Appl. 602,543 24 Oct 1990. 9311694. Jpn. Kokai Tokkyo Koho JP 04 50.638 [92 50,6381 (C1. GOlN9/24) 19 Feb 1992 Appl. 90/15 1,569 12 Jun 1990.9311695. Ger. Offen. DE 4,026,30 1 (Cl. HO 1 J35/06) 27 Feb 1992 Appl. 20 Aug 1990. 9311696. Ger. Offen. DE 4,026,300 (Cl.HOl J35/06) 27 Feb 1992 Appl. 20 Aug 1990.9311697. Ger. Offen. DE 4,026,297 (Cl. H05G1/34) 27 Feb 1992 Appl. 20 Aug 1990. 9311698. Ger. Offen. DE 4,026,298 (CI. HOl J35/06) 27 Feb 1992 Appl. 20 Aug 1990; 3 pp. 9311699. Ger. Offen. DE 4,015,275 (Cl. GOlN23/223) 14 Nov 1991 Appl. 12 May 1990. 9311700. GIT Fachz. Lab. 1992 36 373. 9311701. Tappi J. 1992 75 175. 9311702. Acta Cient. Venez. 1991 42 247. 9311703. Proc. Electrochem. SOC. 1992 92 (Proc. Int. Symp. Clean. Technol. Semicond. Device Manuf 2nd 199 l) 324. 9311704. Jahrb. Oberflae- chentech. 1992 48 403. 9311705. X-Ray Spectrom. 1992 21(2) 57. 9311706. Nippon Kaisui Gakkaishi 1992 46(2) 96. 9311707. Fenxi Shiyanshi 1992 11 54.9311708. Nucl. Sci. Tech. 1992 3(1) 19. 9311709. J. Radioanal. Nucl. Chern. 1992,158,40 1.9311710.J. Radioanal. Nucl. Chem. 1992 158 409. 9311711. Biol. Cell (1981) 1992 74 147. 9311712. Nucl. Med. Biol. 1992 19 423. 9311713. Shika Gakuho 1992 92 295. 9311714. Sangyo Igaku 1992 34 142.9311715. Appl. Spectrosc. 1992,46 843.9311718. Rev. Sci. Instrum. 1992,63 3564.9311719. Surf Coat. Technol. 1992 51 273. 9311720. X-Ray Spectrom. 1992 21 115. 9311722. Springer Ser. Opt. Sci. 1992 67(X-Ray Microsc. HI) 338. 9311725. Proc. SPIE-Int. SOC. Opt. Eng. 1992 1600(Int. Symp. Disp. Hologr. 1991) 71. 9311727. Zfl- Mitt. 1991 165 60. 9311728. Chimia 1992 46 186. 9311729. Chemom. Intell. Lab. Syst. 1992 14 165. 9311730. Cornm. Eur. Communities [Rep.] EUR 1992 EUR 141 13 Prog. Anal. Chem. Iron Steel Ind. 125. 9311731. Zavod. Lab. 1992 58(2) 53. 9311733. Proc.Electrochem. Soc. 1992 92 (Proc. Symp. Diagn. Tech. Semicond. Mater. Devices 199 I) 132. 9311735. Sci. Int. (Lahore) 199 1 3 26 1.9311736. Cornm. Eur. Communities [Rep.] EUR 1992 EUR 141 13 Prog. Anal. Chem. Ion Steel Ind. 157. 9311737. Cornm. Eur. Communities [Rep.] EUR 1992 EUR 14 1 13 Prog. Anal. Chem. Iron Steel Ind. 3 1 1. 9311738. Appl. Radiat. Isot. 1992,43 777.9311740. USSR SU 1,695,199 (Cl. GOlN23/223) 30 Nov 1991 Appl. 4,6 15,909 5 Dec 1988. Otkrytiya Izobret. 199 1 44 169. 9311741. Commun. Soil Sci. Plant Anal. 1992 23 569. 9311742. He Dianzixue Yu Tance Jishu 1992 12 86. 9311743. J. Sci. Food Agric. 1992 58 431. 9311744. J. Aerosol Sci. I99 1.22 S375.9311745. Wear Mater. 199 1,8 223. 9311746. Appl. Radiat. Isot. 1992 43 609. 9311747. Appl. Radiat.Isot. 1992 43 767. 9311748. Nucl. Instrum. Methods Phys. Res. Sect. A 1992 315 213. 9311751. Jpn. Kokai Tokkyo Koho JP 04 14,741 [92 14,7411 (Cl. HOlJ35/06) 20 Jan 1992 Appl. 90/115,205 02 May 1990. 9311752. J. Electrochem. SOC. 1992,139 175 1.9311757. X- Ray Spectrum. 1992 21 87. 9311758. X-Ray Spectrom. 1992 21 99. 9311759. Tec. Lab. 1991 13 594. 9311761. ISIJ Int. 1992 32 553. 9311762. USSR SU 1,689,819 (CI. GO1 N23/223) 07 Nov 199 1 Appl. 4,728,O 14,07 Aug 1989. Otkrytiya Izobret. 1991 41 152. 9311763. Eur. Pat. Appl. EP 483,753 (Cl. GOlT1/36) 06 May 1992 JP Appl. 90/293,03 1,30 Oct 1990.9311765. USSR SU 1,696,942 (Cl. GOlN1/28) 07 Dec 1991 Appl. 4,809,990 12 Feb 1990. Otkrytiya Izobret. 1 99 1 45 1 7 1. 9311766. J. Radioanal. Nucl. Chem. 1992 164 38 1. 9311767.J. Radioanal. Nucl. Chem. 1992 164,275.9311768. J. Radioanal. Nucl. Chem. 1992 64 357. 9311769. Environ. Res. 1992 57 117. 9311770. Anal. Sci. 199 1 7(Suppl. Proc. Int. Congr. Anal. Sci. 199 I 1 175. 9311772. Report 199 1 CERI-TR-M- 9 1/16; Order No. ADA232 229 Gov. Rep. Announce. Index (US) 199 1 91( 1 9 Abstr. No. 140,707. 9311773. Galvano Organo 1992 61 225. 9311775. Avtom. Svarka 1991 10 43. 9311776. Bull. Environ. Contam. Toxicol. 1992 48 803. 9311778. Nucl Instrum. Methods Phys. Rex Sect. A 1992,314,252.9311779. Pertanika 199 1,14,20 1.9311780. Proc. Electrochem. SOC. 1992 92 (Proc. Symp. X-ray Methods Corros. Interfacial Electrochem. 199 1 ) 354. 9311782. Nippon Butsuri Gakkaishi 1992,47,293.9311783. Adv. Nucl. Sci. Technol. 1991 22 45. 9311785. Zh.Tekh. Fiz. 1991 61 125. 9311787. Jpn. J. Appl. Phys. Part I 1992 31 1219. 9311788. Univ. Tokyo Inst. Nucl. Study INS-Rep. 1992 INS-Rep.-9 19.9311789. Phvs. Scr. T 1992 41(Proc. Int. Workshop Auger Spectrosc. Electron. Struct. 2nd 1991) 288. 9311791. J. Electrochem. SOC. 1992 139 1495. 9311792. Semi-Insul. III- V Mater. Proc. Conf.’ 6th 1990 281. 9311793. X-Ray Spectrom. 1992 21 69. 9311795. Shikizai Kyokaishi 1992 65 176. 9311796. J. Chem. SOC. Pak. 199 1 13 252. 9311797. Ger. Offen. DE 4,028,043 (Cl. GOlN23/203) 12 Mar 1992 Appl. 05 Sep 1990. 9311800. Biomed. Res. Trace Elem. 1991 2 297. 9311801. Fenxi Huaxue 1992 20 176.9311802. Fresenius’ J. Anal. Chem. 1992 342 586. 9311803. Anal. Div. 1991 25 (Edmonton Spring Symp. 1991) 263. 9311804. Cesi Farm. 1992 40 226. 9311805.Mater. Sci. Forum 1991 79(EPDIC I ) 389. 9311812. Appl. Phys. Lett. 1992 60 2195. 9311815. Appl. Radiat. Isot. 1992 43 615. 9311816. Zavod. Lab. 1992 58 25. 9311817. Pure Appl. Chem. 1992 64 497. 9311818. Comm. Eur. Communities [Rep.] EUR 1991 EUR 13686 Annu. Symp. Safeguards Nucl. Mater. Manag. 13th 199 1 245. 9311819. PCT Int. Appl. WO 92 02,886 (Cl. G06F15/18) 20 Feb 1992 US Appl. 559,649 30 Jul 1990. 9311820. Adv. X-Ray Anal. 1991,34 313. 9311821. Adv. X-Ray Anal. 1991 34 543. 9311822. Phys. Rev. Lett. 1992 68 2243. 9311823. IEEE Trans. Nucl. Sci. 1992 39 44. 9311825. Jpn. Kokai Tokkyo Koho JP 03,266,399 [91,266,399] (Cl. H05G 1/04) 27 Nov 199 1 Appl. 90/63,269 14 Mar 1990. 9311826. Bunseki 1992 2 129. 9311827. Cornm. Eur. Communities [Rep.] EUR 199 1 EUR 13686 Annu.Symp. Safeguards Nucl. Mater. Manag. 13th 1991 149. 9311829. Int. J. Environ. Anal. Chern. 1991 45 275. 9311830. Archaeometry 1992 34 37. 9311831. Archaeometry 1992 34 43. 9311832. Anal. Sci. 1991 7(Suppl. Proc. Int. Congr. Anal. Sci. 1991) 365. 9311833. Anal. Sci. 1991 7(Suppl. Proc. Int. Congr. Anal. Sci. 1991) 659. 9311834. Anal. Sci. 1991 7(Suppl. Proc. Int. Congr. Anal. Sci. 1991) 1375. 9311835. Anal. Sci. 1991 7(Suppl. Proc. Int. Congr. Anal. Sci. 1991) 1207. 9311836. Anal. Sci. 1991 7(Suppl. Proc. Int. Congr. Anal. Sci. 1991 1403. 9311837. Anal. Sci. 1991 7(Suppl. Proc. Int. Congr. Anal. Sci. 199 l) 523.9311838. Anal. Sci. 199 1 7(Suppl. Proc. Int. Congr. Anal. Sci. 1991) 499 9311841. Anal. Sci. 1991 7(Suppl. Proc. Int. Congr. Anal. Sci. 1991) 577.9311843. Proc. Annu. Meet. Air Waste Manage. Assoc. 1991 84 Paper 91/89.2. 9311845. Bull. Chem. SOC. Ethiop. 1991 5(2) 49. 9311846. Proc. Nucl. Therm. Hydraul. 1990 6 213. 9311848. Z. Naturforsch. A Phys. Sci. 1992 47 460. 9311849. Phys. Lett. A 1992 163 188. 9311850. Jpn. Kokai Tokkyo Koho JP 03,282,400 [91,282,400] (Cl. G21K5/00) 12 Dec 1991 Appl. 90/85,960 30 Mar 1990. 9311851. X-Ray Spectrom. 1992 21(1) 17. 9311852. X-Ray Spectrom. 1992 21(1) 43. 9311853. USSR SU 1,672,325 (Cl. GOlN23/223) 23 Aug 199 1 Appl. 4,476,465 30 May 1988. Otkrytiya Izobret. 199 1 31 178. 9311856. Kenkyu Hokoku Kanagawa ken Kokyo Shikensho 199 1 62 90. 9311858. Analusis 1 992 20(3) M50. 9311860. Br. J. Ind. Med. 1992 49 14. 9311861. Biomed. Res. Trace Elem. 1990 1 221. 9311862.Commun. Soil. Sci. Plant Anal. 1991 22 2063. 9311864. Powder Technol. 1992 69 93. 9311865. Int. J. Food Sci. Technol. 1991 26 485. 9311866. Steel India 1991 14 41.JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 307R 9311867. Freiberg. Forschungsh. B 1990 27 1 5. 9311869. Adv. X-Ray Anal. 199 1 34,2 17.9311870. GIT Fachz. Lab. 1991 35 1327. 9311871. Reza Kenkyu 1991 19 1038. 9311872. Int. Congr. Anal. Sci. 1991 373. 9311873. Anal. Sci. 199 1 7(Suppl. Proc. Int. Congr. Anal. Sci. 199 1 ) 36 1. 9311875. Jpn. Kokai Tokkyo Koho JP 03,235,046 [9 1,235,0461 (Cl. GO 1 N23/223) 2 1 Oct 199 1 Appl. 90/30,583 09 Feb 1990. 9311876. J. Radioanal. Nucl. Chem. 1992 157 203. 9311878. X-Ray Spectrom. 1992 21 1 1 9311879. Fresenius’ J. Anal. Chem. 1992 342 19 1.9311881. Zavod. Lab. 1991 57(7) 68. 9311882. Tetsu to Hagane 1992,78 173.9311883. Zh. Anal. Khim. 1991,46 2263. 9311884. Fenxi Shiyanshi 199 1 10(5) 39. 9311885. Fenxi Shiyanshi 1991 10(6) 42. 9311886. X-Ray Spec- trom. 1992 21 3. 9311887. ATB Metall. 1990 30(3) 60. 9311888. Zh. Anal. Khim. 1991,46 2436. 9311889. Mater. Res. SOC. Symp. Proc. 1991 225 (Mater. Reliab. Issues Microelectron.) 329. 9311890. Proc. Annu. Meet. Air Waste Manage. Assoc. 1991 84th Paper 90.5. 9311891. Nucl. Instrum. Methods Phys. Res. Sect. A 1992 312 303. 9311892. Hyomen Gijutsu 1991 42 1240. 9311893. Inst. Pys. Conf Ser. 1991 116(X-rayLasers 1990) 43. 9311895. J. Appl. Phys. 1992,71 1153. 9311896. Phys. Rev. A 1992 45 1531. 9311897. Phys. Rev. A 1992 45(3) 171 1. 9311898. Mater. Sci.Eng. B 1992,11 139.9311899. Jpn. J. App. Phys. Part I 1992 31 3 11. 9311900. J. Phys. D Appl. Phys. 1992 25 131. 9311901. Proc. SPIE Int. SOC. Opt. Eng. 1992 1546(Multilayer Grazing Incidence X-Ray/EUV Opt.) 596. 9311902. Proc. SPIE-Int. SOC. Opt. Eng. 1992 1546(Multilayer Grazing Incidence X- Ray/EUV Opt.) 607. 9311904. Adv. X-Ray Anal. 1991 34 193. 9311905. X-Ray Spectrom. 199 1 20 277.9311906. X-Ray Spectrom. 199 1 20 305. 9311907. Zavod. Lab. 1991 57( 1 I) 70. 9311908. Eur. Pat. Appl. EP 456,897 (Cl. GOlN23/223) 21 Nov 199 1 DE Appl. 4,O 1 5,608 1 5 May 1990.9311909. Eur. Pat. Appl. EP 465,797 (Cl. GOlN23/223) 15 Jan 1992 DE Appl. 4,021,617 06 Jul 1990. 9311910. Eur. Pat. Appl. EP 464,671 (Cl. GOlN23/223) 08 Jan 1992 JP Appl. 90/170,687 28 Jun 1990. 9311911.Jpn. Kokai Tokkyo Koho JP 03,237,344 [91,237,344] (Cl. GOlN23/223) 23 Oct 1991 Appl. 90133,497 14 Feb 1990. 9311913. Geos- tand. Newsl. 1992 16 3. 9311919. Geostand. Newsl. 1992 16 325. 9311921. J. Geochem. Explor. 1992 42 345. 9311925. J. Geochem. Explor. 1992 44 201. 9311926. J. Geochem. Explor. 1992 44 25 1. 9311935. At. Spectrosc. 1992 13 113. 9311942. Anal. Chem. 1992 64 2425. 9311943. Anal. Chem. 1992 64 2444. 9311946. Appl. Spectrosc. 1992,46 894.9311962. Stud. Conserv. 199 1,36 235. 9311963. Nucl. Instrum. Methods Phys. Rex Sect. A 1992 A312 323.9311966. Rev. Sci. Instrum. 1992,63 578. 9311967. Rev. Sci. Instrum. 1992 63 1746. 9311968. Rev. Sci. Instrum. 1992 63 1755. 9311970. X-Ray Spectrom. 1991 20 315. 9311971. X-Ray Spectrom. 1991 20 343. 9311972.X . Ray Spectrom. 199 1 20 325. 9311973. X-Ray Spectrom. 199 1 20 33 1. 9311974. X-Ray Spectrom. 199 1 20 337.9311975. X-Ray Spectrom. 199 1 20,27 1.9311977. X-Ray Spectrom 199 1 20 287. 9311978. X-Ray Spectrom. 1991 20 293. 9311979. X-Ray Spectrom. 1991 20 297. 9311980. .Jpn. J. Appl. Phys. Part 2 1992 31 L113. 9311981. Jpn. J. Appl. Phys. Part 2 1992,31 Ll 1.9311982. KEK Proc. 1991 5(Radiat. Detect. Their Uses) 97. 9311983. Jpn. Kokai Tokkyo Koho JP 03,206,999 [91,206,999] (Cl. G21K1/06) Appl 90/2,732 10 Jan 1990; 4 pp. 9311985. Adv. X-Ray Anal. 199 1 34 1.9311987. Adv. X-Ray Anal. 199 1,34,4 1.9311988. Adv. X-Ray Anal. 199 1 34 7 1. 9311989. Adv. X-Ray Anal. 199 1 34 13 1.9311990. Oyo Butsuri 199 1,60 1 141.9311991. Fenxi Huaxue 199 1 19 11 10. 9311992. Guangpuxue Yu Guangpu Fenxi 1991 11(4) 50.9311993. Guangpuxue Yu Guangpu Fenxi 199 1 11(4) 53 70. 93/1994. Zayod. Lab. 1991 57(11) 24. 9311995. Nippon Kaisui Gakkaishi 199 1 45 294.9311996. USSR SU 1,659,809 (Cl. GO 1 N23/223) 30 Jun 199 1 Appl. 4,703,252 08 Jun 1989. Otkrytiya Izobret. 1991 24 150. 9311997. USSR SU 1,378,571 (Cl. GOlN23/223) 30 Jul 199 1 Appl. 4,042,290 27 Jan 1986. Otkrytiya Izobret. GOlT1/24) 24 Dec 1991 Appl. 565,793 10 Aug 1990. 9311999. Adv. X-Ray Anal. 1991 34 293. 9312000. Adv. X- Ray Anal. 1991 34 23. 9312001. Adv. X-Ray Anal. 1991 34 263.9312002. Adv. X-Ray Anal. 199 1,34 105.9312003. Adv. X-Ray Anal. 199 1,34,2 13.9312004. Adv. X-Ray Anal. 1991 34 57. 9312006. Adv. X-Ray Anal. 1991 34 239. 9312007. Adv. X-Ray Anal. 1991 34 277. 9312008. Adv.X - Ray Anal. 1991 34 285. 9312009. Hejishu 1991 4 493. 9312010. Fenxi Shiyanshi 1991 10(6) 44. 9312012. J. Cryst. Growth 199 1 115 37 1. 93/2013. X-Ray Spectrom. 1992 21 21. 9312014. Nucl. Instrum. Methods Phys. Res. Sect. A 1992 313 173. 9312015. USSR SU 1,653,548 (Cl. H01535/08) 30 May 1991 Appl. 4,796,974 22 Jan 1990. Otkrytiya Izobret. 199 1 20 234. 9312017. Diffus. Defect Data Pt. B 1991 19(Gettering Defect Eng. Semicond. Technol.) 109. 9312018. Vestn. Slov. Kem. Drus. 199 1 38 493. 9312019. Appl. Spectrosc. 1992 46 13 1. 93/2020. Fresnius’ J. Anal. Chem. 1992 342 295. 9312021. Ger. (East) DD 292,540 (Cl. GOlN23/223) 01 Aug 1991 Appl. 338,677 14 Mar 1990. 9312022. Europ. Patent EP 0 456 897 A l 1991. 9312023. Fresenius’ J. Anal. Chem. 1992 343 292. 9312026.Proc. SPIE Int. SOC. Opt. Eng. 1991 1519(Int. Conf Thin Film Phys. Appl. 1991 225. 9312027. Denshi Zairyo 1991 30(8) 32. 9312028. Proc. SPIE Int. Soc. Opt. Eng. 1991,1548 (Prod. Anal. Polariz. X-Rays) 46. 9312030. Jpn. Kokai Tokkyo Koho JP 03,216,532 [91,216,532] (Cl. GOlN1/23) 24 Sep 1991 Appl. 9011 2,9 12 23 Jan 1990. 9312031. Wuli Xuebao 199 1 40 141 1. 9312032. Pis’ma Zh. Tekh. Fiz. 1991 17( 13) 82. 9312033. Zavod. Lab. 1990 56(12) 34. 9312034. Zavod Lab. 199 1 57(9) 3 1.93/2035. Appl. Radiat. Isot. 1992,43 37. 9312037. Nucl. Instrum. Methods Phys. Rex Sect. A 1991 310 82. 9312038. Bunseki Kagaku 1991 40 361. 9312039. J. Anal. At. Spectrom. 1992 7 783. 9312054. J. Anal. At. Spectrom. 1992 7 883. 9312055. J. Anal. At. Spectrom. 1992 7 889. 9312056. J. Anal. At.Spectrom. 1992 7 895. 9312058. J. Anal. At. Spectrom. 1992 7 905. 9312059. J. Anal. At. Spectrom. 1992 7 915. 9312060. J. Anal. At. Spectrom. 1992 7 923. 9312061. J. Anal. At. Spectrom. 1992 7 929. 9312062. J. Anal. At. Spectrom. 1992 7 937. 9312063. J. Anal. At. Spectrom. 1992 7 943. 9312064. J. Anal. At. Spectrom. 1992 7 951. 9312065. J. Anal. At. Spectrom. 1992 7 959. 9312066. J. Anal. At. Spectrom. 1992 7 965. 9312067. J. Anal. At. Spectrom. 1992 7 971. 9312070. J. Anal. At. Spectrom. 1992 7 993. 9312084. J. Anal. At. Spectrom. 1992 7 1099. 9312090. J. Anal. At. Spectrom. 1992 7 1 1 31. 9312091. J. Anal. At. Spectrom. 1992 7 1139. 9312092. J. Anal. At. Spectrom. 1992 7 1147 9312093. J. Anal. At. Spectrom. 1992 7 1 15 1. 9312094. Fresenius’ J. Anal. Chem. 1992 342 15.9312096. Fresenius’ J. Anal. Chem. 1992 342 907. 9312100. Fresenius’ J. Anal. Chem. 1992 343 741. 9312101. Fresenius’ J. Anal. Chem. 1992 343 773. 9312109. Spectrochim. Acta Part B 1991 46 1803. 9312110. Spectrochim. Acta Part B 1991 46 1819. 9312112. Spectrochim. Acta Part B 1992 47 505.9312119. Appl. Spectrosc. 199 1 45 1408. 9312124. Appl. Spectrosc. 1992 46 448. 9312125. Nucl. Instrum. Methods Phys. Res. Sect. A 1990 299 567. 9312128. Nucl. Instrum. Methods Phys. Res. Sect. B 1991 54 433. 9312129. Anal. Chim. Acta 199 1 248 257. 9312130. Anal. Chim. Acta 1992,256 153. 9312132. Anal. Chim. Acta 1992 258 317. 9312153. Anal. Chem. 1992 64 469. 9312154. Anal. Chem. 1992 64 724. 9312155. Anal. Chem. 1992 64 737. 9312156. Anal. Chem. 1992 64 1088. 9312157.Anal. Chem. 1992 64 1164. 9312158. Anal. Chem. 1992 64 320R. 9312159. 199 1 28 262. 9311998. U.S. US 5,075,555 (Cl. 250-370,15;308R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL 8 Anal. Chem. 1992 64 1606. 9312160. Anal. Chem. 1992 64 1819. 9312161. Anal. Chem. 1992 64 2036. 9312162. Anal. Chem. 1992 64 2216. 9312163. Anal. Chem. 1992 64 2253. 9312164. Anal. Chem. 1992 64 2623. 9312165. Fenxi Shiyanshi 1992 11(2) 52.9312173. Fenxi Shiyanshi 1992 11(3) 47. 9312181. Fresenius’J. Anal. Chem. 1991 341 586. 9312203. At. Spectrosc. 1992 13 19.9312204. At. Spectrosc. 1992 13 26. 9312205. At. Spectrosc. 1992 13 29. 9312212. Anal. Chem. 1991 63 2069. 9312218. Anal. Sci. 1991 7 527. 9312219. Anal. Sci. 1991 7 533. 9312220. Anal. Sci. 1991 7 541. 9312221.Anal. Sci. 1991 7 545. 9312223. Anal. Sci. 1991 7 11 17. 9312226. Anal. Sci. 1991 7 1243. 9312230. Anal. Sci. 1991 7 1359. 9312232. Anal. Sci. 1992 8 179. 9312242. Appl. Spectrosc. 1992 46 401. 9312245. Appl. Spectrosc. 1992 6 1327. 9312246. Chem. Geol. 1991 94 85. 9312247. Chem. Geol. 1991 94 137. 9312248. Chem. Geol. 1992 94 193. 9312249. Chem. Geol. 1992,101,71.93l2250. Chem. Geol. 1992 101 1 11. 9312251. Chem. Geol. 1992 101 187. 9312252. Earth Planet. Sci. Lett. 1992 111 257. 9312257. Hejishu 1992 15 122. 9312262. At. Spectrosc. 1992 13 8 1. 9312266. Fenxi Huaxue 1992 20 458. 9312275. Chin. Sci. Bull. 1992 37 469. 9312277. Comm. Eur. Communi- ties [Rep.] EUR 1991 EUR 13686 Annu. Symp. Safe- guards Nucl. Mater. Manage. 13th 1991 165. 9312279. Comm. Eur.Communities (Rep.] EUR 1991 EUR 13686 Annu. Symp. Safeguards Nucl. Mater. Manage. 13th 199 1 2 19. 9312280. Comm. Eur. Communities [Rep.] EUR 199 I EUR 13686 Annu. Symp. Safeguards Nucl. Mater. Manage. 13th 199 1,225,9312281. Comm. Eur. Communi- ties [Rep.] EUR 1991 EUR 13686 Annu. Symp. Safe- guards Nucl. Mater. Manage. 13th 1991 229. 9312282. Comm. Eur. Communities [Rep.] EUR 199 1 EUR 13686 Annu. Symp. Safeguards Nucl. Mater. Manage. 13th 199 1 24 1. 9312283. Comm. Eur. Communities [Rep.] EUR 1992 EUR 141 13 Prog. Anal. Chem. Iron Steel Ind. 8 1. 9312289. C. R. Acad. Sci. Ser. III 1992,315 179. 9312290. Ber. Forschungszent. Juelich 1992 Juel-2628 42. 9312291. Biol. Cell 1992 74 43. 9312292. Biol. Cell 1992 74 75. 9312293. Biol. Cell 1992 74 105. 9312315. Symp.Ser. 1992 479 288.9312318. Anal. Chim. Acta 1992,259 193. 9312319. Anal. Chim. Acta 1992 261 31 5. 9312321. Anal. Biochem. 1992 202 367. 9312322. Anal. Biochem. 1992 205 278. 9312326. Analusis 1992 20 229. 9312327. Appl. Phys. Lett. 1992 60 222. 9312328. Appl. Phys. Lett. 1992 60 1178. 9312330. Appl. Radiat. Isot. 1992 43 881. 9312331. Appl. Spectrosc. Rev. 1992 27 223. 9312339. Ganko 1992 87 107. 9312341. Geochim. Cosmochim. Acta 199 1 55 3709.9312342. Geochim. Cosmochim. Acta 1991 55 3901. 9312344. Geophys. Res. Lett. 1991 18 2165. 9312345. Geophys. Res. Lett. 1991 18 2169. 9312352. Lanthanide Actinide Res. 199 1 3 285. 9312354. Lect. Notes Phys. 199 1 389 (Laser Ablation Mech. Appl.) 344. 9312357. Mass Spectrom. Rev. 1992 11 4 1. 9312359. Mass Spectrom. Rev.1992,11 193.9312360. Mater. Chem. Phys. 1992,31 23. 9312362. Mater. Chem. Phys. 1992,31 127. 9312364. Mater. Elektron. 1991 4 24. 9312365. Mater. Res. Soc. Symp. Proc. 1990 191 85. 9312370. Methods Surf Charact. 1991 2 273. 9312371. Methods Surf Charact. 1991 2 417. 9312373. Microbeam Anal. 1991 26 35. 9312376. Microbeam Anal. 1991 26 344. 9312378. Microchem. J. 1992,46,42.93/2379. Mikrochim. Acta 1992 106 127.9312381. Mikrochim. Acta 1992,107 137. 9312384. Mikrochim. Acta 1992 107 17 1. 9312387. Mikrochim. Acta 1992 108 41. 9312396. J. Radioanal. Nucl. Chem. 1991 151 149. 9312397. J. Radioanal. Nucl. Chem. 1992 158,9 1.9312800. Tech. Instrum. Anal. Chem. 1992 12 97. 93/2401. Tetsu co Hagane 1991 77 1843. 9312412. J. Aerosol Sci. 1991 22 S835. 9312413. J. Am. SOC.Mass Spectrom. 1992,3 10.9312415. J. Am. SOC. Mass Spectrom. 1992 3 122. 9312416. J. Am. Soc. Mass Spectrom. 1992 3 128. 9312417. J. Appl. Phys. 1991 70 7602. 9312419. J. Autom. Chem. 1991 13 273. 9312423. J. Chromatogr. 1992 576 297. 9312424. J. Chromatrogr. 1992 594 275. 9312425. J. Chromatogr. Libr. 1991 47 101. 9312426. J. Clin. Lab. Anal. 1992,6 190. 9312429. J. High Resolut. Chromatogr. 1992 15 387. 9312431. J. Inst. Electron. Telecommun. Eng. (New Delhi) 1991 37 235. 9312434. J. Microbiol. Methods 1992 15 167. 9312435. J. Mod. Opt. 1992 39 243. 9312436. J. Mod. Opt. 1992,39 257. 9312437. J. Pharm. Biomed. Anal. 1992 10 279. 9312438. J. Radioanal. Nucl. Chem. 1992 156 201. 9312439. J. Radioanal. Nucl. Chem. 1992 157 239. 9312440. J. Radioanal. Nucl. Chem.1992 157 281. 9312441. J. Radioanal. Nucl. Chem. 1992 158 13. 9312442. J. Radioanal Nucl. Chem. 1992 160 119. 9312443. J. Radioanal. Nucl. Chem. 1992 160 191. 9312446. J. Res. Natl. Inst. Stand. Technol. I99 1 96 61 7. 9312448. J. Tech. Phys. (Warsaw) 1992,33 67. 9312454. J. Vac. Sci. Technol. A 1992 10 2880. 9312455. J. Vac. Sci. Technol. A 1992 10 2887. 9312464. J. Vac. Sci. Technol. B 1992 10,380.9312465 J. Vac. Sci. Technol. B 1992,10 385. 9312467. J. Vac. Sci. Technol. B 1992 10 1633. 9312469. Scanning 1992 14 160. 9312470. Second. Ion. Mass Spectrom. SIMS 7 Proc. Int. Conf 1989 (Pub. 1990) 6 1. 9312471. Second. Ion Mass Spectrom. SIMS 7 Proc. Int. Conf 7 1989 (Pub. 1990) 259.9312474 Second. Ion Mass Spectrom. SIMS 7 Proc. Int. Conf 7 1989 (Pub. 1990) 7 1 5.9312479. Shitsuryo Bunseki 1 99 1 39 26 1. 9312482. Shitsuryo Bunseki 199 1 39 3 15. 9312483. Shitsuryo Bunseki 199 1 39 337. 9312484. Shitsuryo Bunseki 1992 40 173. 9312485. Spectroscopy (Eugene Oreg.) 1992,7( I) 22. 9312489. Springer Ser. Surf Sci. 1992 23 97. 9312490. Springer Ser. Surf Sci. 1992 23 1 17. 9312494. Surf Sci. 1992 266,48 1.9312496 Surf Sci. 1992,266,506.9312497. Surf Sci. 1992 266 517. 9312499. Surf Sci. 1992 271 64 1. 9312500. Indium Phosphide Relat. Mater. Process. Technol. Devices 1992 45. 9312501. Inst. Phys. Con$ Ser. 1991 113 141. 9312502. Inst. Pys. Conf Ser. 1991 113 1 63. 9312504. Int. J. Mass Spectrom. Ion Processes 199 1 111 355. 9312505. Int. J. Mass Spectrom. Ion Processes 1992 112 19. 9312506. Int. J. Mass Spectrom. Ion Pro- cesses 1992 113 213.9312508. Int. J. Mass Spectrom. Ion Processes 1992 114 47. 9312509. Int. J. Mass Spectrom. Ion Processes 1992 114 209. 9312510. Int. J. Mass Spectrom. Ion Processes 1992 115 123. 9312511. Int. J. Mass Spectrom. Ion Processes 1992 116 7 1. 9312512. Int. J. Mass Spectrom. Ion Processes 1992 116 87. 9312515. Nucl. Instrum. Methods Phys. Rex Sect. B 1992 64 149. 9312517. Nucl. Instrum. Methods Phys. Res. Sect. B 1992. 64 321. 9312518. Nucl. Instrum. Methods Phys. Rex Sect. B 1992 64 330. 9312519. Nucl. Instrum. Methods Pys. Res. Sect. B 1992 64 609. 9312520. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 64 614. 9312521. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 64 621. 9312522. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 64 626. 9312523. Nucl.Instrum. Methods Phys. Res. Sect. B 1992 64 632. 9312524. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 64 636. 9312525. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 64 646. 9312528. Nucl. Instrum. Methods Phys. Rex Sect. B 1992 64 659. 9312530. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 66,48. 9312531. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 66 118. 9312532. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 67 495. 9312534. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 68 235. 9312535. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 68 309. 9312536. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 68 313. 9312537. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 68 319. 9312538. Nucl. Instrum. Methods Phys. Rex Sect. B 1992 69 503. 9312541. Nucl. Instrum. Methods Phjx Res. Sect. B 1992 70 358. 9312542. Nucl. Instrum.JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 309R Methods Phys. Res. Sect. B 1992 70 451. 9312543. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 70 464. 9312544. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 70 490. 9312546. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 70 541. 9312549. Pis’ma Zh. Tekh. Fiz. 1992 18(7) 28. 9312550. Phys. Med. Biol. 1992 37 1349. 9312557. Proc. Aust. Conf Nucl. Tech. Anal. 1991 7 66. 9312560. Proc. Aust. Conf Nucl. Tech. Anal. 1991 7 206. 9312561. Proc. Int. Sch. Phys. ‘Enrico Fermi’ 1989 (Pub. 1991) 111 169.9312564 Pure Appl. Chem. 1992,64 485. 9312567. Sur- Interface Anal. 199 1 17 95 1.9312568. Surf Interface Anal. 1991 17 965. 9312569. Surf Interface Anal. 1992 18 23.9312570. Surf Interface Anal. 1992,18 52. 9312571. Surf Interface Anal. 1992 18 8 1. 9312572. Surf Intersace Anal. 1992 18 103. 9312574. Surf Interface Anal. 1992 18 147. 9312575. Surf Interface Anal. 1992 18 229. 9312576. Surf Interface Anal. 1992 18 306. 9312577. SUI$ Interface Anal. 1992,18 539.9312578. Surf Interface Anal. 1992 18 561. 9312581. Surf Interface Anal. 1992 19 232. 9312583. Spectrochim. Acta Part B 1992,47 107.9312585. Spectrochim. Acta Part B 1992,47 517. 9312588. Spectrochim. Acta Part B 1992 47 591. 9312589. Spectrochim. Acta Part B 1992 47,633.9312590. Spectrochim. Acta Part B 1992 47 1259. 9312595. Vacuum 1992,43 159.9312602. Vysokochist. Veshchestva 1991 6 21 1. 9312605. Youkuangye 1991 10(3) 53. 9312606. Yuanzineng Kexue Jishu 199 1,25,66.9312607. Z. Naturforsch. A Phys. Sci. 1992,47 748. 9312608. Z. Phys. A Hadrons Nucl. 1991 340 41 1. 9312609. Zavod. Lab. 199 1 57( 12) 27.9312610 Zfl Mitt. 199 1 166 7. 9312613. Zh. Anal. Khim. 1991 46 2222. 9312614. Oceanis 1991 17 421. 9312617. Radiocarbon 1991 33 297. 9312619. Radiocarbon 1992 34 2 1. 9312625. Rare Met. (Beijing) 1991 10 248. 9312626. Rare Met. (Beijing) 1992 11 47. 9312637. Rev. Sci. Instrum. 1992 63 2469. 9312638. Rev. Sci. Instrum. 1992 63 2472. 9312639. Rev. Sci. Instrum. 1992 63 2485. 9312643. Zavod. Lab. 1991 57 72. 9312647. NATO ASI Ser. Ser. B 1992 289 399. 9312648. Nature 1992 356 50. 9312650. Nippon Seramikkusu Kyokai Gakujutsu Ronbunshi 1992 100 1038. 9312656. Nucl. Sci. Tech. 1990 1 19. 9312657. Nucl. Sci. Tech. 1990 1 149.9312659. Trans. R. Microsc. SOC. 1990 1 31. 9312660. Tree Physiol. 1992 10 209. 9312662. Trends Anal. Chem. 1 992 1 1 142. 9312665. Anal. Spectrosc. Libr. 1991 5 191. 9312667. Appl. Radiat. Isot. 1991 42 789. 9312703. SIA Surf Interface Anal. 199 1 17 855. 9312708. Wiss. Z. Tech. Univ. Dresden 1991 40 101. 9312713. Analyst 1992 117 1585. 9312733. Fresenius’ J. Anal. Chem. 1992 344 1. 9312734. Bunseki 1992 7 544. 9312735. X-ray Spectrom. 1992,21,249.9312736. Anal. Sci. Technol. 1991 4 83. 9312737. X-Ray Spectrom. 1992 21 2 1 1. 9312738. Fluoride 1992 25 55. 9312740. Fett Wiss. Technol. 1992 94 246. 9312741. X-Ray Spectrom. 1992 21 17 1.9312742. X-Ray Spectrom. 1992 21,201.9312743. Appl. Phys. Lett. 1992 61 1019. 9312744. Fresenius’ J. Anal. Chem. 1992 343 760. 9312745. Fresenius’ J. Anal. Chem. 1992,343,765.9312746. Con$ Proc. Ital. Phys. SOC. 1990 25 875. 9312747. He Dianzixue Yu Tance Jishu 1992 12,. 249. 9312748. Guangpuxue Yu Guangpu Fenxi 1992 12 119. 9312751. AIP Con. Proc. 1992 258 419. 9312752. X-Ray Spectrom. 1992 21 223.9312754. Fresen- ius’ J. Anal. Chem. 1992,344 22.9312755. Fenxi Huaxue 1992,20 1074. 9312756. An. Asoc. Quim. Argent. 1990,78 265. 9312757. Anal. Chim. Acta 1992 268 177. 9312758. Fresenius’ J. Anal. Chem. 1992 344 118. 9312759. AIP Con$ Proc. 1992 258 665. 9312760. Acta Phys. Pol. A 1992 82 33. 9312761. Anal. Sci. Technol. 1990 3 131. 9312762. Acta Phys. Pol. A 1992 82 37. 9312764. Anal. Chem. 1992 64 1 1 15A. 9312765. Galvanotechnik 1992 83 3 140. 9312766. At. Energ. 1992,72,403.9312767. Conf Proc. Ital. Phys. SOC. 1990 25 463. 9312768. Conf Proc. Ital. Phys. SOC. 1990 25 395. 9312771. Geostand. Newsl. 1992 16 27. 9312772. X-Ray Spectrom. 1992 21 163. 9312773. Biomed. Res. Trace Elem. 199 1 2 5 1. 9312774. Erdoel Kohle Erdgas Petrochem. 1992 45 239. 9312776. X-Ray Spectrom. 1992 21 133. 9312777. Appl. Radiat. Isot. 1992 43 847. 9312778. Guangpuxue Yu Guangpu Fenxi 1992 12 89. 9312779. X-Ray Spectrom. 1992 21 149. 9312780. X-Ray Spectrom. 1992 21 119. 9312781. Comm. Eur. Communities [Rep.] EUR 1992 EUR 14 1 13 Prog. Anal. Chem. Iron Steel Ind. 362. 9312782. Comm. Eur. Communities [Rep.] EUR 1992 EUR 141 13 Prog. Anal. Chem. Iron Steel Ind. 519. 9312784. Fuel 1992 71 909. 9312787. Fresenius’ J. Anal. Chem. 1992 343 362. 9312788. Zh. Anal. Khim. 1991 46 2436. 9312789. Zh. Anal. Khim. 1992 47 438. 9312790. Analusis Mag. 1992 20(8) M48. 9312791. Mar. Min. 1991 10 259. 9312793. Zavod. Lab. 1992 58(7) 52. 9312794. Mater. Sci. Forum 1992 94. 9312795. NATO ASI Ser. Ser. C 1991 351 89. 9312796. J. Phys. Chem. Solids 1992 53 1049. 9312797. Zh. Eksp. Teor. Fiz. 1992 101 1259. 9312798. Pover- khnost 1992 4 69. 9312799. Inst. Phys. ConJ Ser. 1992 126 119. 9312801. Nucl. Instrum. Methods Phys. Res. Sect. A 1992 A319 320. 9312802. FR. Demande FR 2,668,263 (Cl. GOlN23/223) 24 Apr 1992 Appl. 90/13,000 19 Oct 1990. 9312803. Proc. Copper 91-Cobre 91 Int. Symp. 1991 2 483. 9312804. Rev. Sci. Instrum. 1992 63 4768. 9312806. J. Appl. Phys. 1992 72 3363. 9312811. Proc. Jt. Int. Lepton Photon Symp. Europhys. Conf High Energy Phys. 1991 (Pub. 1992) 1 242. 9312812. IEEE Trans. Nucl. Sci. 1992 39 541. 9312813. IEEE Trans. Nucl. Sci. 1992 39 570. 9312815. Microbios 1992 70(282) 13. 9312816. Met. Compd. Environ. Lve. 4 Sel. Pap. IAEAC Workshop Toxic Met. Compd. 4th 1991 (Pub. 1992) 1. 9312817. Met. Compd. Environ. Lve 4 SeL Pap. IAEAC Workshop Toxic Met. Compd. 4th 1991 (Pub. 1992) 47. 9312820. J. Radioanal. Nucl. Chem. 1992 161 401. 9312821. J. Radioanal. Nucl. Chem. 1992 166 55. 9312822. Pharm. Ind. 1992 54 293. 9312827. Prib. Tekh. Eksp. 1992 3 206. 9312828. Kenkyu Hokoku Toyama Daigaku Suiso Doitai Kino Kenkyu Senta 1991 10 69. 9312830. Jpn. J. Appl. Phys. Part I 1992,31,28 16.9312831. Prib. Tekh. Eskp. 1992 3 199. 9312832. Phys. Rev. B Condens. Matter 1992 46 79 1 1. 9312834. IEEE J. Quan- tum Electron. 1992 28 2382.9312836. Proc. SPIE Int. SOC. Opt. Eng. 1992 1671 373. 9312838. J. Trace Microprobe Tech. 1991 9 229. 9312840. Zavod. Lab. 1992 58(4) 28. 9312841. Nondestr. Charact. Mater. I V (Proc. Int. Symp.) 4th 1990 (Pub. 1991) 307.9312842. Nucl. Geophys. 1991 5 513. 9312843. Springer Ser. Opt. Sci. 1992 67 212. 9312844. Nucl. Instrum. Methods Phys. Res. Sect. B 1992 B71 92. 9312845. Nucl. Instrum. Methods Phys. Res. Sect. A 1992 A319 408. 9312846. Jpn. Kokai Tokkyo Koho JP 04,127,100 [92,127,100] (CI. G2 1 W O O ) 28 Apr 1992 Appl. 90/249,846 18 Sep 1990. 9312848. U.S.S.R. SU 1,7 16,409 (Cl. GO lN23/22) 28 Feb 1992 Appl. 4,753,628 30 Oct 1989. Izobreteniya 1992 8 18 1. 9312849. U.S. US 90/236,127 05 Sep 1990. 9312850. U.S. US 5,115,457 (Cl. 378-45; GOlN23/223) 19 May 1992 Appl. 591,122 01 Oct 1990. 9312851. Zavod. Lab. 1992 58( 2) 54. 9312852. Tsement 1991,9 65. 9312853. Zh. Strukt. Khim. 1992,33 68. 9312854. Jpn. J. Appl. Phys. Part 2 1992 31 L900. 9312856. Kagaku to Kogyo (Tokyo) 1992,45,234.9312857. J. Phys. B At. Mol. Opt. Phys. 1992 25 2295. 9312858. Inst. Phys. Con$ Ser. 1992 121 9. 9312859. Inst. Phys. Conf Ser. 1992 121 297. 9312860. Springer Ser. Opt. Sci. 1992 67 321. 9312861. Kagaku Kogyo 1992 43 149. 9312862. U.S.S.R. SU 1,673,935 (Cl. GOlN23122) 30 Aug 199 1 Appl. 4,673,944 06 Apr 1989 Otkrytiya Izobret 1991 32 149. 93i2863. Proc. lnt. Conf Facil. Oper. Safeguards InterJace 4th 199 1 (Pub. 1992) 164.9312864. 5,132,997 (Cl. 378-85; G21K1/06) 21 Jul 1992 JP Appl.310R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Sangyo Igaku 1992,34 268. 9312865. Proc. ConJ Electron 9312869. Nucl. Instrurn. Methods Phys. Rex Sect. A 1992 Beam Melting Rejn. State of the Art 199 1 67. 9312866. A317 383. 9312870. Springer Ser. Opt. Sci. 1992 67 2 17. Proc. Int. Con$ Facil. Oper. Safeguards Interface 4th 199 1 9312871. U.S.S.R. SU 1,702,268 (Cl. GO 1 N23/22) 30 Dec (Pub. 1992) 448. 9312867. Synchrotronstrahlung Erforsch. 199 1 Appl. 4,7 15,19 1 07 Jul 1989. Otkrytiya Izobret Kondens. Mater. Vorlesungsmanuskr. IFF-Ferienkurses 199 1 48 174. 9312873. Invest. Radiol. 1976 11 2 10. 23rd 1992 12.1. 9312868. Med. Phys. 1992 19 519. 9312874. Jpn. J. Appl. Phys. 1992 31 2872. 9312875. Mikrochim. Acta 1992 108 299.

ISSN:0267-9477    

DOI:10.1039/JA993080261R

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 31 1R Glossary of Abbreviations Whenever suitable elements may be referred to by their chemical symbols and compounds by their formulae. The following abbreviations are used extensively in the Atomic Spectrometry Updates. a.c. AA AAS AE AES AF AFS AOAC APDC ASV BCR CCP CMP CRM cv cw d.c. DCP DDC DMF DNA ECD EDL EDTA EDXRF EIE EPMA ETA ETAAS ETV EXAFS FAAS FAB FAES FAFS FI FPD FT FTMS GC GD GDL GDMS Ge( Li) HCL h.f. HG HPGe HPLC IAEA IBMK ICP ICP-MS ID alternating current atomic absorption atomic absorption spectrometry atomic emission atomic emission spectrometry atomic fluorescence atomic fluorescence spectrometry Association of Official Analytical Chemists ammonium pyrrolidinedithiocarbamate anodic-stripping voltammetry Community Bureau of Reference capacitively coupled plasma capacitively coupled microwave plasma certified reference material cold vapour continuous wave direct current d.c.plasma diethyldithiocarbamate N,N-dimethylformamide deoxyribonucleic acid electron capture detection electrodeless discharge lamp ethylenediaminetetraacetic acid energy dispersive X-ray fluorescence easily ionizable element electron probe microanalysis electrothermal atomization electrothermal atomic absorption electrothermal vaporization extended X-ray absorption fine structure flame AAS fast atom bombardment flame AES flame AFS flow injection flame photometric detector Fourier transform Fourier transform mass spectrometry gas chromatography glow discharge glow discharge lamp glow discharge mass spectrometry lithium-drifted germanium hollow cathode lamp high frequency hydride generation high-purity germanium high-performance liquid chromatography International Atomic Energy Agency isobutyl methyl ketone (4-methylopentan-2- inductively coupled plasma inductively coupled plasma mass spectrometry isotope dilution (ammonium pyrrolidin-1-yl dithioformate) spectrometry spectroscopy one) IR IUPAC LA LC LEAFS LEI LMMS LOD LTE MECA MIP MS NAA NaDDC NIES NIST NTA OES PIGE PIXE PMT PPb PPm PTFE QC r.f.REE(s) RIMS RM RSD SIB SEC SEM SFC Si(Li) SIMAAC SIMS SIN SR SRM SSMS STPF TCA TIMS TLC TMAH TOP0 TXRF u.h.f. uv VDU vuv WDXRF XRF infrared International Union of Pure and Applied Chemistry Laser ablation liquid chromatography laser-excited atomic fluorescence laser-enhanced ionization laser-microprobe mass spectrometry limit of detection local thermal equilibrium molecular emission cavity analysis microwave-induced plasma mass spectrometry neutron activation analysis sodium diethyldithiocarbamate National Institute for Environmental National Institute of Standards and nitrilotriacetic acid optical emission spectrometry particle-induced gamma-ray emission particle-induced X-ray emission photomultiplier tube parts per billion parts per million polytetrafluoroethylene quality control radiofrequency rare earth element(s) resonance ionization mass spectrometry reference material relative standard deviation signal to background ratio size-exclusion chromatography scanning electron microscopy supercritical fluid chromatography lithium-drifted silicon simultaneous multi-element analysis with a continuum source secondary ion mass spectrometry signal to noise ratio synchrotron radiation Standard Reference Material spark source mass spectrometry stabilized temperature platform furnace trichloroacetic acid thermal ionization mass spectrometry thin-layer chromatography tetra methlammonium hydroxide trioctylphosphine oxide total reflection X-ray fluorescence ultra-high frequency ultraviolet visual display unit vacuum ultraviolet wavelength dispersive X-ray fluorescence X-ray fluorescence spectrometry Studies Technology

ISSN:0267-9477    

DOI:10.1039/JA993080311R

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

313R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 ATOMIC SPECTROMETRY UPDATE REFERENCES The address given in a reference is that of the first named author and is not necessarily the same for any co-author. 931271 1. 93/27 12. 93127 13. 93/27 14. 93/27 15. 9312716. 9312717. 93127 18. 93/27 19. 9312720. 931272 1. 931 2 722. Charalampopoulos T. T. Hahn D. W. Chang H. Role of metal additives in light scattering from flame particu- lates Appl. Opt. 1992 31 6519. (Dept. Mech. Eng. Louisiana State Univ. Baton Rouge LA 70803-641 3 USA). Eames J. C. Cosstick R. J. Determination of forms of sulfur in coals and related materials by Eschka digestion and inductively coupled plasma atomic emission spec- trometry Analyst 1992 117 1581. (CSIRO Div. Ex- plor. Geosci. P.O. Box 136 North Ryde New South Wales 2 1 13 Australia).Durrant S. F. Multi-elemental analysis of environ- mental matrices by laser ablation inductively coupled plasma mass spectrometry Analyst 1992 117. 1585. (Dept. Chem. Univ. Surrey Guildford Surrey IJK GU2 5XH). Amaud J. Favier A. Determination of ultrafiltrable zinc in human milk by electrothermal atomic absorp- tion spectrometry Analyst 1992 117 1593. (Lab. Biochim. C Centre Hosp. Reg. Univ. Grenoble B.P. 2 17 38043 Grenoble Cedex 9 France). Mateeva N. Arpadjan S. Deligeorgiev T. Mitewa M. Extraction systems for the flame atomic absorption spectrometric determination of trace amounts of mer- cury and palladium Anal-vst 1992 117 1599. (Dept. Chem. Univ. Sofia 1126 Sofia Bulgaria). Chen H.-w. Brindle I. D. Zheng S.-g. Combined generator-separator.Part 2. Stibine generation com- bined with flow injection for the determination of antimony in metal samples by atomic emission spectro- metry Analyst 1992 117 1603. (Dept. Chem. Hang- zhou Univ. Hangzhou Zhejiang 3 10028 China). Tsalev D. L. Sperling M. Welz B. On-line microwave sample pre-treatment for hydride generation and cold vapour atomic absorption spectrometry Analyst 1992 117 1729. (Dept. App! Res. Bodenseewerk Perkin- Elmer GmbH W-7770 Uberlingen Germany). Tsalev D. L. Sperling M. Welz B. On-line microwave sample pre-treatment for hydride generation and cold vapour atomic absorption spectrometry. Part 2. Chemistry and applications Analyst 1992 117 1735. (Dept. Aqpl. Res. Bodenseewerk Perkin-Elmer GmbH W-7770 Uberlingen Germany). Mohd A A.Dean J. R. Tomlinson W. R. Factorial design approach to microwave dissolution Analyst 1992 117 1743. (Sch. Appl. Sci. Inst. Teknol. Mara Shah Alam 40000 Malaysia). Espinosa Almendro J. M. Bosch Ojeda C. Garcia de Torres A. Can0 Pavon J. M. Determination of cadmium in biological samples by inductively coupled plasma atomic emission spectrometry after extraction with I ,5-bis(di-2-pyridylmethylene) thiocarbonohydra- zide Analyst 1992 117 1749. (Dept. Anal. Chem. Fac. Sci. Univ. Mdlaga 2907 1 Mdlaga Spain). Brindle I. D. Zheng S.-g. Improvement of accuracy for the determination of transient signals using the Kalman filter. Part I. Simulations Analyst 1992 117 1925. (Chem. Dept. Brock Univ. St Catharines On- tario Canada L2S 3A1). Shijo Y.Mitsuhshi M. Shimizu T. Sakurai S. Determination of bismuth in sea-water by electrother- mal atomic absorption spectrometry after liquid-liquid extraction and micro-volume back-extraction Analyst 1992 117 1929. (Dept. Appl. Chem. Fac. Eng. Utsunomiya Univ. Ishii-cho Utsunomiya 32 1 Japan). 9 312 72 3. 9312724. 9 312 72 5. 931 2726. 9312727. 931 2728. 9 312 72 9. 9 312 7 30. 931273 1. 9312732. 9 31 273 3. 931 2734. 931 2735. Arpadjan S. Vassileva E. Momchilova S. Preconcen- tration methods for determination of trace amounts of impurities in high-purity copper salts by atomic absorp- tion spectrometry and inductively coupled plasma atomic emission spectrometry Analyst 1992 117 1933. (Fac. Chem. Univ Sofia 1126 Sofia Bulgaria). Krushevska A. Momtchilova S. Gantcheva V.Amara- siriwaradena C. Comparison of different procedures for the analysis of high-purity potassium nitrate by inductively coupled plasma atomic emission spectrome- try Analyst 1992 117 1939. (Inst. Specialty Chem. Vladaya Sofia 174 1 Bulgaria). Kotrljr S. Sramkovai J. Chadima R. Cermak J. Microanalysis of bismuth indium selenide thermo- electric materials by X-ray fluorescence spectrometry with reference assays of indium Analyst 1993 118 79. (Dept. Anal. Chem. Univ. Chem. Technol. 532 10 Pardubice Czechoslovakia). Satake M. Nagahiro T. Puri B. K. Column precon- centration of cobalt in alloys and pepperbush using 2-(5- bromo-2-pyridylazo)-5-diethylaminophenol and am- monium tetraphenylborate adsorbent supported on nap- thalene with subsequent determination using atomic absorption spectrometry Analyst 1993 118 8 5 .(Fac. Eng. Fukui Univ. Fukui 9 10 Japan). Lan C.-R. Direct determination of cadmium in sea- water by electrothermal atomic absorption spectrometry with sodium hydroxide as a chemical modifier Analyst 1993 118 189. (Chem. Lab. Power Res. Inst. Taiwan Power Taipei 23802 Taiwan). Kumar M. Srivastava P. K. Determination of lan- thanum by flame atomic emission spectrometry in rare earth concentrates Analyst 1993 118 193. (Chem. Lab. At. Min. Div. Dept. At. Energy West Block-VII R. K. Puram New Delhi-110066 India). Torrades F. Garcia Raurich J. Study of the coprecipi- tation of calcium potassium sodium and chloride with barium sulfate using atomic spectrometry and visible spectrophotometry Analyst 1993 118 197.(Lab. Anal. Quim. ETSEI de Terrassa Univ. Politec. Catalunya CIColom 11 08222 Terrassa Spain). Hill S. J. Advances in coupled techniques for specia- tion studies Anal. Proc. 1992,29 399. (Plymouth Anal. Chem. Res. Unit Dept. Environ. Sci. Univ. Plymouth Plymouth Devon PL4 8AA UK). Tyson J. F. Flow injection techniques for improving the precision and accuracy of analytical atomic spectro- metry Anal. Proc. 1992 29 436. (Dept. Chem. Univ. Massachusetts Amherst MA 01003 USA). Li Z. McIntosh S. Slavin W. Simultaneous determi- nation of hydride and non-hydride forming elements by inductively coupled plasma atomic emission spectrome- try Anal. Proc. 1992,29 438. (Perkin-Elmer 761 Main Avenue Norwalk CT 06897-237 USA). Wagstaffe P. J. Boenke A. Schnug E. Lindsey A. S.Certification of the sulfur content of three rapeseed reference materials Fresenius’ J. Anal. Chem. 1992 344 1. (Community Bur. Ref. Comm. Eur. Communi- ties B- 1049 Brussels Belgium). Kubota M. Determination of toxic eiements in soils Bunseki 1992 7 544. (Agric. Coll. Ibaraki Univ. Japan). Pozsgai I. Characterization of an X-ray source for the fundamental parameter method X-ray Spectrom. 1992 21 249. (Res. Inst. Tech. Phys. Hung. Acad. Sci. 1325 Budapest Hungary).314R 9312736. 9 3/27 37. 9312 7 3 8. 9312739. 9312740. 9312741. 9312742. 9312743. 9312744. 9312 74 5. 9312746. 9312747. 9312748. 9312749. JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Hong K. J. Moon K. H. Lee J. J. Lee D. H. X-ray fluorescence analysis of iron ores using de Jongh’s theoretical a correction coefficients Anal.Sci. Technol. 1991 4 83. (Anal. Lab. Res. Inst. Ind. Sci. Technol. Pohang 790-330 South Korea). Al-Ammar A. S. Ali F. H. Determination of impuri- ties in nuclear-grade uranium compounds by X-ray fluorescence spectrometry X-Ray Spectrom. 1 992 21 21 1. (Chem. Dept. Nucl. Res. Cent. Iraqi At. Energy Comm. Baghdad Iraq). Watanabe H. Yoshida Y. Kono K. Watanabe M. Inoue S. Tanioka Y. Dote T. Orita Y. Umebayashi K. Nagaie H. Fluorine and other trace elements in hair by X-ray fluorescence analysis Fluoride 1992 25 5 5 . (Dept. Hyg. Public Health Osaka Med. Coll. Tatatsuki 569 Japan). Wang J. X. Chevallier P. Carvalho M. L. Ferreira J. G. SRXRF analysis of iron copper zinc and lead in macrophyte algae from a polluted estuary a compara- tive study ConJ Proc.Ztal. Phys. SOC. 1990 25 1013. (Dep. Phys. Univ. Guelph Guelph Ontario Canada NlG2W). Schnug E. Haneklaus S. Zhao F. Evans E. J. Relations between total sulfur and glucosinolate content in rapeseed-calibration of the X-ray fluorescence (XRF) method Fett Wiss. Technol. 1992 94 246. (Dept. Agric. Univ. Newcastle upon Tyne Newcastle upon Tyne UK NE1 7RU). Puri S. Chand B. Garg M. L. Singh N. Hubbell J. H. Trehan P. N. Physical parameters for L X-ray production cross-sections X-Ray Spectrom. 1992 21 17 1. (Dept. Phys. Panjab Univ. Chandigarh 160014 India). Shrivastava B. D. Singh D. Shrivastava B. D. Identification of the lines in the L emission spectrum of cerium and samarium X-Ray Spectrom. 1992 21 201. (Sch. Stud. Phys. Vikram Univ.Ujjain 456010 India). Piestrup M. A. Boyers D. G. Pincus C. I. Li Q. Ho A. H. Maruyama X. K. Snyder D. D. Skopik D. M. Silzer R. M. Observation of the focusing of X-ray transition radiation using cylindrical optics Appl. Phys. Lett. 1992 61 1019. (Adelphi Technol. Palo Alto CA 94306 USA). Hein M. Hoffmann P. Lieser K. H. Ortner H. M. Application of X-ray fluorescence analysis with total- reflection (TXRF) in material science Fresenius’ J. Anal. Chem. 1992 343 760. (Tech. Hochsch. Darm- stadt W-6 100 Darmstadt Germany). Streckfuss N. Frey L. Zielonka G. Kroninger F. Ryzlewicz C. Ryssel H. Analysis for trace metals on silicon surfaces Fresenius’ J. Anal. Chem. 1992 343 765. (Fraunhofer Arbeitsgruppe Integr. Schaltungen W- 8520 Erlangen Germany). Torok S. Sandor S.Demeter I. Le Huong Quynh Szokefalvi-Nagy Z. Chemical characterization of fly ash samples by synchrotron radiation X-ray fluores- cence and other X-ray emission techniques Conf Proc. Ztal. Phys. Soc. 1990,25 875. (Cent. Res. Inst. Phys. H- 1525 Budapest Hungary). Mu B.-f. Xue Z.-n. Li L.-w. Cheng G.-p. He G.-z. Zhao Y.-h. Determination by XRF of trace elements in human scalp hair from districts with two different terrestrial hot water supplies He Dianzixue Yu Tance Jishu 1992 12 249. (Dept. Phys. Nankai Univ. Tianjin 30007 1 China). Wang X.d. Huang Y.-c. Pang S.-w. Determination of total sulfur in soil by X-ray fluorescence analysis Guangpuxue Yu Guangpu Fenxi 1992 12 119. (Res. Cent. Eco-Environ. Sci. Acad. Sin. Beijing China 100085). Zhou S.-c. Xie T.-z. Ge L.-g. Total content X-ray fluorescence method for prospecting copper deposits 9312750. 931275 1.9312752. 9312753. 9312754. 9312 7 55. 9312756. 9312757. 9312758. 9312 7 59. 9312760. 931276 1. 9312 7 62. 9 312 763. 9312764. 9312 765. Hejishu 1992 15 181. (Chengdu Coll. Geol. Chengdu China 6 10059). Haschke M. Brumme M. Heckel J. Waste analysis by energy-dispersive X-ray spectroscopy GIT Fachz. Lab. 1992 36 803. (Spectro X-Ray Instrum. W-1000 Berlin 42 Germany). Goulon J. Goulon C. Gauthier C. Emerich H. X-ray excited fluorescence correlation spectroscopy a new tool for molecular dynamics studies AZP Cunf Proc. 1992 258 419. (Eur. Synchrotron Radiat. Lab. F- 38043 Grenoble France). Campbell J. L. Wang J. X. Lorentzian contributions to X-ray lineshapes in lithium-drifted silicon spectros- copy X-Ray Spectrorn.1992 21 223. (Dept. Phys. Univ. Guelph Guelph Ontario Canada NlG 2Wl). Kwiatek W. M. Synchrotron radiation induced X-ray emission-SRIXE Acta. Phys. Pol. A 1992 82. (Dep. Nucl. Spectrosc. Inst. Nucl. Phys. 31-342 Krakow Poland). Bosch Reig F. Bosch Mossi F. Peris Martinez V. Gimeno Adelantado J. V. Correction parameters in X- ray fluorescence analysis applying the limit dilution method (LDM). 11. Correction of the interelemental effect Fresenius’ J. Anal. Chem. 1992 344 22. (Fac. Chem. Univ. Valencia Burjassot Spain E-46 100). Luo L. Ma G.-z. Ji A. Study of partial least squares regression and fundamental parameters method in X- ray fluorescence analysis Fenxi Huaxue 1992 20 1074. (Inst. Rock Miner. Anal. Chin. Acad. Geol.Sci. Beijing 100037 China). Masi A. Olsina R. Evaluation of different preconcen- tration methodologies for the X-ray determination of arsenic microamounts in natural waters An. Asoc. Quim. Argent. 1990 78 265. (Fac. Quim. Bioquim. Farm. Univ. Nac. San Luis 5700 San Luis Argentina). Eltayeb M. A. H. Van Grieken R. E. Coprecipitation with aluminium hydroxide and X-ray fluorescence determination of trace metals in water Anal. Chim. Acra 1992 268 177. (Dept. Chem. Univ. Antwerp B-26 10 Antwerp Belgium). Peraniemi S. Vepsalainen J. Mustalahti H. Ahlgren M. Determination of phosphorus in waste water by EDXRF Fresenius’ J. Anal. Chem. 1992 344 118. (Dept. Chem. Univ. Joensuu SF-80 10 1 Joensuu Finland). Haensel R. ESRF and the third generation of synchro- tron radiation sources AIP Conf Proc. 1992 258 665.(ESRF F-38043 Grenoble France). Haensel R. European Synchrotron Radiation Facility Acta Phys. Pol. A 1992 82 33. (ESRF 38043 Greno- ble France). Kim Y. O. Kim Y. S. TXRF (total reflection X-ray fluorescence) its principles and analytical perform- ances Anal. Sci. Technol. 1990 3 131. (Dept. Chem. Bochum Univ. Dortmund Germany). Hormes J. Chauvistre R. Schmitt W. Pantelouris M. Examples of the industrial use of synchrotron radiation Acta Phys. Pol. A 1992 82 37. (Phys. Inst. Univ. Bonn D-5300 Bonn 1 Germany). Xie D. Yan Z.-z. Germanium KX escaping peak and its differentiation of highly pure germanium detector Hebei Shifan Daxue Xuebao Ziran Kexueban 1992 1 36. (Dept. Phys. Univ. Shijiazhuang Shijiazhuang Chin a). KlockenkHmper R.Knoth J. Prange A. Schwenke H. Total-reflection X-ray fluorescence Anal. Chem. I 992 64 1 1 15A. (Inst. Spektrochem. Angewandte Spekttosk. D-4600 Dortmund Germany). Roessiger V. Analysis of tin-lead coatings by X-ray fluorescence. Systematic errors due to sample ageing,JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 315R 9312166. 9312161. 9312768. 9312169. 931 2710. 93/21 71. 931 2 7 72. 931 2 7 73. 93/27 14. 9312775. 93/27 16. 931 2777. 93/27 78. 931 271 9. Galvanotechnik 1992 83 3 140. (Helmut Fischer W- 7032 Sindelfingen Germany). Leonov A. I. Meshcheryakov V. G. Tyamin G. V. Gamma-ray sources with cobalt-57 for X-ray fluores- cence analysis At. Energ. 1992 72 403. (FEI Russia). Bedzyk M. J. X-ray standing waves generated by total external reflection Con$ Proc.ftal. Phys. SOC. 1990,25 463. (Sch. Appl. Eng. Phys. Cornell Univ. Ithaca NY 14853 USA). Gauthier C. Ascone I. Goulon J. Cortes R. Bark J. M. Guilard R. First experimental evidence of circu- larly polarized X-ray excited optical luminescence (XEOL) from chiral europium(3 +) complexes. Con$ Proc. Ztal. Phys. SOC. 1990 25 395. (Lab. Chim. Theor. Interact. Mol. Univ. Nancy-1 F-54506 Vandoeuvre- les-Nancy France). Nicoli G. Andouart R. Barbier C. Dagneaux D. De Santis M. Raoux D. Lithium-doped silicon multide- tector for X-ray anomalous scattering Conf Proc. Ztal. Phys. Soc. 1990 25 351. (DAM 91590 Cerny France). Breon S. R. Hopkins R. A. Nieczkoski S. J. X-ray spectrometer-a cryogenic instrument on the advanced X-ray astrophysics facility Adv.Cryog. Eng. 199 1 37 1 193. (Goodard Space Flight Cent. NASA Greenbelt MD USA). Bower N. W. Lewis C. M. Neifert P. E. Gladney E. S. Elemental concentrations in twenty NIST standards of geochemical interest Geostand. Newsl. 1992 16 27. (Chem. Dept. Colorado Coll. Colorado Springs CO 80903 USA). Domi N. X-ray fluorescence intensity of an element in multicomponent ores and the use of Compton radiation for matrix effect correction X-Ray Spectrom. 1992 21 163. (Inst. Nucl. Phys. Tirana Albania). Homma S. Shimojo N. Non-destructive synchrotron radiation X-ray fluorescence imaging of trace elements in the kidney of rats administered organic mercury Biomed. Res. Trace E l m . 1991 2 51. (Grad. Sch. Doct. Program. Med. Sci. Univ. Tsukuba Tsukuba 305 Japan). Price B.J. X-ray fluorescence method for lubricating oil analysis Erdoel Kohle Erdgas Petrochem. 1992,45 239. (Ind. Anal. Group Oxford Instrum. Abingdon UK OX14 ITX). Kirchnawy F. Modem instrument-assisted analysis in a mobile laboratory for the monitoring of transport of hazardous materials-experiences after three years of practical application Ber. Znt. Kolloq. Verhuetung .4rbe- itsunfaellen Berufskrankh. Chem. Ind. 1991 14th (Ge- faehrliche Arbeitsst. Sicherh. Tramp. Lagerung) 125. (Bundespruefanstalt Kraftfahrzeuge Vienna Austria). Kerur B. R. Thontadarya S. R. Hanumaiah B. Effect of the photon intensity selected at various positions under the photopeak on the mass attenuation coeffici- ent X-Ray Spectrom. 1992 21 133. (Dept. Phys. Karnatak Univ. Dharwad 580 003 India).Lepy M. C. De Sanoit J. Alvarez R. Set of low energy X-ray sources including ion-exchanged membranes as Auorescence targets a qualitative study Appl. Radiat. hot. 1992 43 847. (Lab. Primaire Rayonnem. Ionis. CE Saclay 9 1 193 Gif-sur-Yvette France). Zhang Q.-h. He C.-f. Ren H.-x. X-ray fluorescence spectrometric analysis for rare earth elements Guang- puxue Yu Guangpu Fenxi 1992 12 89. (Changchun Inst. Appl. Chem. Changchun 130022 China). Molchanova E. I. Smagunova A. N. Gunicheva T. N. Smagunov A. V. Dependence of the accuracy of the results of steel X-ray fluorescence analysis on the method of considering the variation of a coefficients with samde chemical comDosition X-Ray Smctrom. 931 2 780. 931218 1. 9 312 782. 931 2783. 9312184. 9312785. 931 2786. 9312181.931 2788. 9312789. 9312790. 9312791. 9312792. 9312 7 9 3. 9312794. 931 21 9 5 . Aboh I. J. K. Bamford S. A. Tetteh G. K. Model for the multi-element analysis of Prestea gold ore with energy-dispersive X-ray fluorescence analysis X-Ray Spectrom. 1992 21 119. (Ghana At. Energy Comm. Legon Ghana). Bettinelli M. Taina P. Bilei F. Baroni U. Bizzarri G. Comparison of the ICP-AES and XRF methods of analysing nickel-base alloys Comm. Eur. Communities [Rep.] EUR 1992 EUR 141 13 Prog. Anal. Chem. Iron Steel Znd. 362. (DCO Cent. Lab. ENEL 29100 Pia- cenza Italy). Bonvin D. Adamson B. W. Juchli K. Use of X-ray fluorescence spectrometry as an analytical technique in the iron and steel industry Comm. Eur. Communities [Rep.] EUR 1992 EUR 141 13 Prog. Anal. Chem. Iron Steel Znd.519. (Appl. Res. Lab. 1024 Ecublens Switzerland). Caola S. Precontrol an efficient alternative to control charts Comm. Eur. Communities [Rep.] EUR 1992 EUR 14113 Prog. Anal. Chem. Iron Steel Ind. 536. (Allegheny Ludlum Brackenridge PA 1 50 14 USA). Martinez-Tarazona M. R. Spears D. A. Tascon J. M. D. Organic affinity of trace elements in Asturian bituminous coals Fuel 1992 71 909. (Inst. Nac. Carbon Deriv. CSIC Oviedo Spain 33080). Osborne P. L. Totome R. G. Influences of oligomixis on the water and sediment chemistry of Lake Kutubu Papua New Guinea Arch. Hydrobiol. 1992 124 427. (Biol. Dept. Univ. Papua New Guinea Papua New Guinea). Boiko V. I. Gorbachev E. A. X-ray emission from converters with various configuration At. Energ. 1992 72 178. (Tomsk. Politekh. Inst.Tomsk Russia). Buehler A. Jackwerth E. Multi-element preconcentra- tion from technical alkali silicates Fresenius’ J. Anal. Chem. 1992 343 362. (Dept. Chem. Anal. Chem. Ruhr Univ. Bochum W-4630 Bochum Germany). Brodskii S. M. X-ray fluorescence determination of metals in oils from aircraft engine lubrication systems Zh. Anal. Khim. 1991 46 2436. (All-Union Techn. Phys. Autom. Res. Inst. Moscow Russia). Borkhodoev V. Ya. Software for X-ray fluorescent analysis by the method of fundamental parameters for an analytical system of an SRM-25 spectrometer Zh. Anal. Khim. 1992 47 438. (Northeast Complex Sci. Res. Inst. Russian Acad. Sci. Far-East Branch Maga- dan Russia). Uhlig S. Peter M. State-of-the-art in modem X-ray fluorescence analysis Analusis Mag. 1992 20(8) M48. (Siemens Analy.X-ray Systems PO Box 21 1262 W- 7500 Karlsruhe 2 1 Germany). Wang Y. M. Liang G. L. Teng Y. Y. Determination of multiple elements in manganese nodules on board using X-ray fluorescence spectrometry Mar. Min. 1991 10 259. (Inst. Rock Miner. Anal. Chin. Acad. Geol. Sci. Beijing China 100037). Kim S.-w. Lee C. Choi S. W. Quantitative interpreta- tion of overlapped X-ray fluorescence spectra by target transformation factor analysis J. Korean Chem. Soc. 1992 36 720. (Dept. Chem. Hanyang Univ. Seoul 133-79 1 South Korea). Amerkhanov M. A. Khlevnaya M. G. X-ray fluores- cence analysis of slags in the Karaganda Metallurgical Works Zavod. Lab. 1992 58(7) 52. (Russia). Abbruzzese G. Di Nunzio P. E. Development of an X- ray technique for measuring grain size as a function of orientation in polycrystalline materials Mater.Sci. Forum 1992 94. (Cent. Sviluppo Mater. Rome Italy). Kempe S. Diercks A. R. Liebezeit G. Prange A. - - 1992 21,-149. (State Univ.,-Irkutsk; CIS). Geochemical and structural aspects of the pycnocline in316R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 9312796. 9312797. 9312798. 9312799. 9 312 800. 931280 1. 9312802. 9312803. 9 312 804. 9312805. 9312806. 9312807. 9312808. the Black Sea (RIV KNORR 134-8 LEG 1 1988) NATO ASI Ser. Ser. C 1991 351 89. (Inst. Biogeo- chem. Mar. Chem. Univ. Hamburg 2000 Hamburg 13 Germany). Sugiura C. Chlorine Kj? X-ray emission spectra of hydrated metal chlorides J. Phys. Chem. Solids 1992 53 1049. (Fac. Eng. Utsunomiya Univ. Utsunomiya 321 Japan).Osadchii M. S. Murakhtanov V. V. Fomin E. S. Mazalov L. N. Role of the charge-transfer process in the formation of the X-ray fluorescence and X-ray photoelectron spectra in copper(I1) compounds Zh. Eksp. Teor. Fiz. 1992 101 1259. (Inst. Neorg. Khim. Russia). Bushuev V. A. Orudzhaliev M. N. Sarkisov S. R. Sarkisov E. R. Peculiarities of the transportation of X- ray radiation in a curved band-like waveguide Pover- khnost 1992 4 69. (Mosk. Gos. Univ. Moscow Russia). Mysyrowicz A. Chambaret J. P. Antonetti A. Aude- bert P. Geindre J. P. Gauthier J. C. Femtosecond X- ray emission from laser irradiated aluminium targets Inst. Phys. Con5 Ser. 1992 126 119. (Lab. Opt. Appl. Ec. Polytech. 9 1 120 Palaiseau France). Lee W. K. Macrander A. T. Mills D. M. Rogers C.S. Smither R. K. Berman L. E. Performance of a gallium-cooled 85" inclined silicon monochromator for a high power density X-ray beam Nucl. Instrum. Methods Phys. Res. Sect. A 1992 A320 381. (Adv. Photon Source Argonne Natl. Lab. Argonne IL 60439 USA). Thompson A. C. Chapman K. L. Ice G. E. Sparks C. J. Yun W. Lai B. Legnini D. Vicaro P. J. Rivers M. L. Focusing optics for a synchrotron-based X-ray microprobe Nucl. Instrum. Methods Phys. Rex Sect. A 1992 A319 320. (Lawrence Berkeley Lab. Berkeley CA USA). Pierre G. Marielle B. Method and apparatus for rapid X-ray tluorescence analysis of a material with low- content elements FR. Demande FR 2,668,263 (CI. GOlN23/223) 24 Apr 1992 Appl. 90113,000 19 Oct 1990. (Institut de Recherches de la Siderurgie Francaise (IRSID)).Holt G. Tily P. J. Development of an on-line XRF- based control system for pyrometallurgical reactors and its application to copper refining Proc. Copper 91-Cobre 91 Int. Symp. 1991 2 483. (Warren Spring Lab. Stevenage Herts UK). Kyrala G. A. PROPX an X-ray manipulation program Rev. Sci. Instrum. 1992 63 4768. (Phys. Div. Los Alamos Natl. Lab. Los Alamos NM 87545 USA). Hokin S. Fonck R. Martin P. Simple multifoil spectrometer for routine carbon and oxygen measure- ments Rev. Sci. Instrum. 1992,63 5038. (Dept. Phys. Univ. Wisconsin Madison WI 53706 USA). Cho T. Hirata M. Takahashi E. Teraji T. Yamagu- chi N. Matsuda K. Takeuchi A. Kohagura J. Ogura K. Theory on the X-ray sensitivity of a silicon surface- barrier detector including a thermal charge-diffusion effect J.Appl. Phys. 1992 72 3363. (Plasma Res. Cent. Univ. Tsukuba Tsukuba 305 Japan). Daillaat J. Belorgey O. Surface scattering of X-rays in thin films. Part I. Theoretical treatment J. Chem. Phys. 1992 97 5824. (Serv. Phys. Etat Condens. Cent. Etud. Saclay 9 1 19 1 Gif-Sur-Yvette France). Ddllant J. Belorgey O. Surface scattering of X-rays in thin films. Part 11. Experiments on thin soap films J. Chem. Phys. 1992 97 5837. (Serv. Phys. Etat Con- dens. Cent. Etud. Saclay 91 191 Gif-Sur-Yvette France). 9312809. 93/28 10. 93/28 1 1. 93/28 12. 93/28 13. 93/28 14. 93/28 15. 93/28 93/28 93/28 18. 93/28 19. 9 312 8 20. 931282 1. 9312822. Yamanaka T. Hanada T. Ino S. Daimon H. Glanc- ing angle dependence of the X-ray emission measured under total reflection angle X-ray spectroscopy (TRAXS) condition during reflection high energy elec- tron diffraction observation Jpn.J. Appl. Phys. Part 2 1992 31 L1503. (Fac. Sci. Univ. Tokyo Tokyo 1 1 3 Japan). Moran M. J. X-ray generation by the Smith-Purcell effect Phys. Rev. Lett. 1992 69 2523. (Lawrence Livermore Natl. Lab. Univ. California Livermore CA 94550 USA). Bouclier R. Florent J. J. Million G. Gaudaen J. Sauli F. Shekhtman L. Microstrip gas chambers on thin plastic supports Proc. Jt. Int. Lepton Photon Symp. Europhys. ConJ High Energy Phys. 199 1 (Pub. 1992) 1 242. (CERN Geneva Switzerland). Dos Santos J. M. F. Bento A. C. S. S. M. Conde C. A. N. Dependence of the energy resolution of gas propor- tional scintillation counters on the scintillation region to photomultiplier distance IEEE Trans.Nucl. Sci. 1 992 39 541. (Phys. Dept. Univ. Coimbra Coimbra Portu- gal P-3000). Rossington C. S. Giauque R. D. Jaklevic J. M. Direct comparison of germanium and lithium-drifted silicon detectors in the 2-20 keV range IEEE Trans. Nucl. Sci. 1992 39 570. (Lawrence Berkeley Lab. Univ. Califor- nia Berkeley CA 94720 USA). Foerster E. Gaebel K. Uschmann I. New crystal spectrograph designs and their application to plasma diagnostics Rev. Sci. Instrum. 1992 63 5012. (Phys. Astron. Dept. Friedrich Schiller Univ. 0-6900 Jena Germany). Al-Aoukaty A. Appanna V. D. Huang J. Aluminium chromium and manganese detoxification mechanisms in Pseudomonas syringae. An X-ray fluorescence study Microbios 1992 70(282) 13. (Dept. Chem. Biochem. Laurentian Univ. Sudbury Ontario Canada P3E 2C6).Tiilg G. Role of trace elements for life from the point of view of an analytical chemist Met. Compd. Environ. Life 4 Sel. Pap. IAEAC Workshop Toxic Met. Compd. 4th 1991 (Pub. 1992) 1. (Inst. Spektrochem. Angew. Spektrosk. D-4600 Dortmund 1 Germany). Calliari I. Tommaseo M. Caravello G. U. Volpe A. Attempt to determine the hair metal content in the Asmat population (Irian Jaya Indonesia) Met. Compd. Environ. Lge 4 Sel. Pap. lAEAC Workshop Toxic Met. Compd. 4th 1991 (Pub. 1992) 47. (Interdept. Cent. Serv. Univ. Padua Italy). Kent M. S. Bosio L. Rondelez F. Homopolymer adsorption at the liquid-air interface by XEWIF Macromolecules 1992 25 623 1. (Lab. Phys. Chim. Surf. Interfaces Inst. Curie 75005 Paris France). Mishra C. D. Pandey H. D. Prasad B.Mediratta S. R. Method for rapid characterization of fly ash Resi- dues Effluents Process. Environ. Consid. Proc. Int. Symp. 1992 149. (Res. Dev. Cent. Iron Steel Steel Auth. India Ranchi 834002 India). Nitsche H. Gatti R. C. Lee S. C. Low-level determi- nation of plutonium by gamma and L X-ray spectros- copy J. Radioanal. Nucl. Chem. 1992 161 401. (Lawrence Berkeley Lab. Univ. California Berkeley CA 94720 USA). Bumbulova A Komova M. Dejmkova E. Identifica- tion of elements in plant drugs and their aqueous infusion using X-ray fluorescence analysis J. Radioanal. Nucl. Chem. 1992 166 55. (Fac. Pharm. Comenius Univ. 832 32 Bratislava Czechoslovakia). Coppi G. Vandelli M. A. Forni F. Bernabei M. T. Control of the microcapsule wall by energy-dispersive X-ray analysis Pharm.Ind. 1992 54 293. (Dept. Pharm. Sci. Univ. Modena 1-4 I 100 Modena Italy).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 317R 9 31282 3. 9312824. 9312825. 9312826. 9 3/28 2 7. 9 312 8 2 8. 9312829. 9312830. 931283 1. 9312832. 9312833. 9312834. 93/28 35. 9312836. Hammel B. A. Keane C. J. Kania D. R. Kilkenny J. D. Lee R. W. Pasha R. Turner R. E. K- and L-shell X-ray spectroscopy of indirectly driven implosions Rev. Sci. Instrum. 1 992 63 50 1 7. (Lawrence Livermore Natl. Lab. Livermore CA 94550 USA). Barnsley R. Brzozowski J. Coffey I. H. Lawson K. D. Patel A. Patel T. K. Peacock N. J. Schumacher U. Bragg spectroscopy of impurities during the JET Preliminary Tritium Experiment Rev. Sci. Instrum. 1992,63 5023. (JET Jt. Undertaking Abingdon Oxon UK OX14 3EA).Da Cruz D. F. Jr. Meijer J. H. Donne A. J. H. Electron velocity distributions measured with soft X-ray PHA at RTP Rev. Sci. Instrum. 1992 63 5026. (Inst. Plasmafys. ‘Rijnhuizen’ FOM 3430 BE Nieuwegein The Netherlands). Zwicker A. P. Finkenthal M. Huang L. K. Regan S. P. May M. J. MOOS H. W. Lippmann S. Soft X-ray multilayer mirror scanning monochromator for magnet- ically confined fusion plasmas Rev. Sci. Instrum. 1992 63 5035. (Dept. Phys. Astron. Johns Hopkins Univ. Baltimore MD 2 12 18 USA). Kirichenko N. N. Lyapidevskii V. K. Perezhogin V. B. Salakhutdinov G. Kh. Samoilova L. B. Comparison of the amplitude analysis and filter methods in recording X-rays Prib. Tekh. Eksp. 1992 3 206. (Mosk. Inzh. Fiz. Inst. Moscow Russia). Matsuyama M.Arai H. Yamazaki T. Watanabe K. In situ measurements of high level tritium by bremsst- rahlung counting method. (I). Feasibility tests of silicon- avalanche photodiode Kenkyu Hokoku Toyama Dai- gaku Suiso Doitai Kin0 Kenkyu Senta 1991 10 69. (Hydrogen Isot. Res. Cent. Toyama Univ. Toyama 930 Japan). Boesl U. Grotemeyer J. Mueller-Dethlefs K. Neus- ser H. J. Selzle H. L. Schlag E. W. Multiphoton and soft X-ray ionization mass spectrometry Int. J. Mass Spectrom. Ion Processes 1992 118 19 1. (Inst. Phys. Theor. Chem. Tech. Univ. Munchen W-8046 Garch- ing Germany). Sugiura C. X-ray spectroscopic studies of calcium fluoride calcium oxide and calcium sulfide Jpn. J. Appl. Phys. Part I 1992 31 2816. (Fac. Eng. Utsunomiya Univ. Utsunomiya 32 1 Japan). Kirichenko N. N.Lyapidevskii V. K. Perezhogin V. B. Determination of the equivalent energy spectra of X- ray by a subtraction (filter) method Prib. Tekh. Eskp. 1992 3 199. (Mosk. Inzh. Fiz. Inst. Moscow Russia). Kohiki S. Nishitani M. Negami T. Wada T. Sakai M. Gohshi Y. X-ray fluorescence spectroscopy of copper-indium-selenide-chalcopyrite structure thin films Phys. Rev. B Condens. Matter 1992 46 791 1. (Cent. Res. Lab. Matsushita Electr. Ind. Co. Morigu- chi 570 Japan). Tong X.-m. Munekawa S. Yamaoka H. Re-emitted spectra of X-rays traversing a solid material Nucl. Instrum. Methods Phys. Rex Sect. B 1992 71 427. (Riken Wako 35 1-0 1 Japan). .Kmetec J. D. Ultrafast laser generation of hard X-rays IEEE J. Quantum Electron. 1992 28 2382. (E. L. Ginzton Lab. Stanford Univ. Stanford CA 94305 USA).Buckens P. F. Veatch M. S. High performance peak detect and hold circuit for pulse height analysis IEEE Trans. Nucl. Sci. 1992 39 753. (Kevex Instrum. San Carlos CA 94070 USA). Fedosejevs R. Bobkowski R. Broughton J. N. Har- wood B. keV X-ray source based on high repetition rate excimer laser-produced plasmas Proc. SPIE Int. SOC. Opt. Eng. 1992 1671 373. (Dept. Electr. Eng. Univ. Alberta Edmonton Alberta Canada T6G 2G7). 931283 7. 9 312838. 9 3/28 39. 9312840. 9312841. 9312842. 9 3/2 8 43. 9312844. 9312845. 9312846. 9312847. 9312848. 9312849. 93/28 50. Pufall R. Roeser K. Stockinger H. Methods for non- destructive determination of semiconductor crystals in housings Ger. Offen. DE 4,100,680 (CI. GO1 N231207) 23 Jul 1992 Appl. 1 1 Jan 1991. (Siemens A.G. Germany). Sanni A. O. Theory and practice of radioactive implant induced X-ray emission J. Trace Microprobe Tech. 1991 9 229. (Dept. Phys. Univ. Ibadan Ibadan Nigeria). Abbas K. Midy P. Brissaud I. Chevallier P. New method of depth profile determination by synchrotron radiation Nucl. Instrum. Methods Phys. Res. Sect. B 1992 71 204. (LURE Univ. Paris XI 91405 Orsay France). Molchanova E. I. Smagunova A. N. Pliner L. N. Ustinova V. I. Smagunov A. V. Pospelov A. L. Development of a set of standard reference materials for calibration of X-ray fluorescence spectrometers in ana- lysis of steels Zavod. Lab. 1992,58(4) 28. (Gos. Univ. Irkutsk Russia). Warren P. L. Comparison of nondestructive tech- niques for the measurement of fibre content in rein- forced engineering plastics and composites Nondestr. Charact.Mater. IV (Proc. Int. Symp.) 4th 1990 (Pub. 1991) 307. (Wilton Mater. Res. Cent. ICI Middlesborough Cleveland UK). Cruz Alvarez M. Dopico T. Riesgo J. L. Determina- tion of ash content and gross calorific value of Spanish coals by energy dispersive X-ray fluorescence (EDXRF) Nucl. Geophys. 1991 5 513. (Dep. Energ. Univ. Oviedo Oviedo Spain 33004). Rivers M. L. Sutton S. R. Jones K. W. X-ray fluorescence microscopy Springer Ser. Opt. Sci. 1992 67 212. (Dept. Geophys. Sci. Univ. Chicago Chicago IL 60637 USA). Dudchik Yu. I. Komarov F. F. Lobotskii D. G. Solov’ev V. S. Tishkov V. S. Kumakhov M. A. Mechanism of bremsstrahlung photon capture to gener- ate waveguide mode of motion Nucl. Instrum. Methods Phys. Rex Sect.B 1992 B71 92. (Inst. Appl. Phys. Probl. Minsk Russia). Furenlid L. R. Kraner H. W. Rogers L. C. Cramer S. P. Stephani D. Beuttenmuller R. H. Beren J. NSLS 100 element solid state array detector Nucl. Instrum. Methods Phys. Res. Sect. A 1992 319 408. (Natl. Synchrotron Light Source Brookhaven Natl. Lab. Upton NY 11973 USA). Imai T. Fujimori N. X-ray window elements and manufacture thereof Jpn. Kokai Tokkyo Koho JP 04,127,100 [92,l27,IOO] (CI. G2 1 K5100) 28 Apr 1992 Appl. 901249,846 18 Sep 1990. (Sumitomo Electric Ind. Japan). Sung H. J. Kim T. S. Chung K. S. Functional expansion of analytical instrument (interfacing of XRF PW1400 with IBM PC-AT) Punsok Kwahak 1988 1 80. (Instrum. Anal. Lab. Korea Inst. Energy Resour. Seoul South Korea). Anatychuk L. I. Vitryuk S.A. Kostin V. A. Mel’nik A. P. Tutkevich K. O. Sensor for X-ray radiometric analyser with semiconductor detector U.S.S.R. SU 1,716,409 (Cl. GOlN23122) 28 Feb 1992 Appl. 4,753,628 30 Oct 1989. Izobreteniya 1992 8 181. (Chernovtsy State University CIS). Kojima S. Utaka T. X-ray spectroscopic analysing apparatus U.S. US 5,132,997 (Cl. 378-85; G21K1/06) 2 1 Jul 1992 JP Appl. 901236,127 05 Sep 1990. (Rigaku Industrial Japan). Lewandowski B. P. Fahsel M. J. Determining titan- ium dioxide in paints U.S. US 5,115,457 (CI. 378-45; GOlN231223) 19 May 1992 Appl. 591,122 01 Oct 1990. (du Pont de Nemours E. I. USA).318R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 9312851. Baimurzina N. S. Naumenko N. N. Tarasova E. G. Filippova R. A. Chalyi K. I. Shokhov B.S. X-ray fluorescence analysis of enamel frits Zavod. Lab. 1992 58(2) 54. (Russia). 93/2852. Gromozova I. K. Bakhtina E. A Volkova S. S. Brylina L. A. Characteristics of X-ray spectrometric analysis of a cement mix based on coal wastes Tsement 199 1 9 65. (Giprotsement CIS). 9312853. Osadchii M. S. Kravtsova E. A. Mazalov L. N. Asanov I. P. Parygina G. K. Savel’eva M. V. Dikov Yu. P. Peculiarities of the copper-sulfur bonding in barium copper sulfide (BaCuzSz) Zh. Strukt. Khim. 1992 33 68. (Inst. Neorg. Khim. CIS). 93/28 54. 9 3/28 5 5. 9312856. 93/28 5 7. 9312858. 9312859. 9312860. 931286 1. 9312862. 9312863. 9 312 8 64. 9312865. Noma T. Miyata H. Ino S. Grazing exit X-ray fluorescence spectroscopy for thin-film analysis Jpn. J. Appl. Phys. Part 2 1992 31 L900.(Res. Center Canon Inc. Atsugi 243-01 Japan). Bassaler J. M. Capdevila J. M. Gal O. Laine F. Nguyen A. Nicolai J. P. Umiastowski K. Rhodotron an accelerator for industrial irradiation Nucl. Instrum. Methods Phys. Res. Sect. B 1992 B68 92. (CEN Saclay CEA F-9 1 19 1 Gif-sur-Yvette France). Hayakawa S. X-ray microscopy with synchrotron radiation Kagaku to Kogyo (Tokyo) 1992 45 234. (Fac. Eng. Univ. Tokyo Tokyo I13 Japan). Stoetzel R. Werner U. Sarkar M. Jitschin W. Fluorescence Coster-Kronig and Auger yields of the samarium L subshells measured with the synchrotron photoionization method J. Phys. B At. Mol. Opt. Phys. 1992 25 2295. (Fachbereich MNI Fachhochsch. Gies- sen 6300 Giessen Germany). Francis H. J. Flint I. Holland A. D. Wells A. High- energy X-ray detection using EEV CCDs Inst.Phys. Conf. Ser. 1992 121 9. (Dept. Phys. Univ. Leicester Leicester UK LE1 7RH). Clarke R. Dos Passos W. Lowe W. MacHarrie R. A. Brizard C. Rodricks B. CCD pixel array detectors for synchrotron radiation applications Inst. Phys. Conf Ser. 1992 121 297. (Randall Lab. Phys. Univ. Michi- gan Ann Arbor MI 48 109 USA). Kuehne M. Krumrey M. Tegeler E. Characterization of soft X-ray detectors Springer Ser. Opt. Sci. 1992,67 32 1. (Phys. Tech. Bundesanst. W- 1000 Berlin 10 Germany). Taniguchi K. Nishihagi K. Total reflection X-ray fluorescence Kagaku Kogyo 1992 43 149. (Osaka Electro Commun. Univ. Neyagawa 572 Japan). Mamulova T. P. Savina E. V. Blashchuk T. P. Kostin V. G. Method for sample preparation in multicompo- nent X-ray spectral analysis of sulfur-containing com- pounds U.S.S.R.SU 1,673,935 (Cl. GOlN23122) 30 Aug 199 1 Appl. 4,673,944 06 Apr 1989 Otkrytiya Izobret 199 1 32 149. (State Sci. Res. Inst. Nonferrous Metals CIS). Wagner H. G. Goerten J. Louis P. Poersch W. Schenkel R. Ottmar H. Eberle H. Koch L. Ougier M. On-site analytical measurements for input accoun- tancy verification in a large reprocessing plant by hybrid K-edge Proc. In?. Con$ Facil. Oper. Safeguards Inter- face 4th 199 1 (Pub. 1992) 164. (Euratom Safeguards Direct. CEC Luxembourg L-2920 Luxembourg). Homma S. Shimojo N. Sasaki A. Non-destructive synchrotron radiation X-ray fluorescence imaging of trace elements in human kidney tumours Sangyo Igaku 1992,34 268. (Univ. Tsukuba Tsukuba 305 Japan). Schiller S. Schiller N. On-line composition control in electron beam melting Proc.Conf Electron Beam Melting ReJin. State of the Art 199 1,67. (Forschungsges. Elektronenstrahl-,Plasmatech. mbH 0-805 1 Dresden Germany). 9312866. Guardini S. Bignan G. Harry R. J. S. Ottmar H. Smith B. G. R. Wells G. ESARDA performance values of non-destructive assay techniques applied in safeguards Proc. Int. ConJ Facil. Oper. Safeguards Interface 4th 1991 (Pub. 1992) 448. (Inst. Safety Technol. Ispra Italy). 9312867. Hormes J. Industrial applications of synchrotron radi- ation Synchrotronstrahlung Erforsch. Kondens. Mater. Vorlesungsmanuskr. IFF-Ferienkurses 23rd 1992 12.1. (Phys. Inst. Univ. Bonn 5300 Bonn 1 Germany). 9312868. Bissonnette J. P. Schreiner L J. Comparison of semiempirical models for generating tungsten target X- ray spectra Med.Phys. 1992 19 519. (Dept. Oncol. McGill Univ. Montreal Quebec. Canada H3G 1A4). 9312869. 93/28 70. 931287 1. 9312872. 9312873. 9312874. 9 31 28 7 5. 9312876. 9312877. 9312878. 9312879. . Van Langevelde F. Janssens K. H. Adams F. C. Vis R. D. Prediction of the optical characteristics and analytical qualities of an X-ray fluorescence microprobe at the European Synchrotron Radiation Facility (Greno- ble) Nucl. Instrum. Methods Phys. Res. Sect. A 1992 A317 383. (Cent. Micro-Trace Anal. Univ. Antwerp Belgium). Erko A. Khzmalyan E. Panchenko L. Redkin S. Zinenko V. Chevalier P. Dhez P. Malek C. Khan Freund A. Vidal B. First test of a Bragg-Fresnel X-ray fluorescence microscope Springer Ser. Opt. Sci. 1 992 67 2 17. (Inst. Microelectron.Technol. High Purity Mater. Chernogolovka CIS). Skripnikov Yu. s. Peshikova L. S. Skripnikov 0. Yu. Te V. Kh. Calibration method of X-ray radiometric analysis U.S.S.R. SU 1,702,268 (Cl. GOIN23122) 30 Dec 1991 Appl. 4,715,191 07 Jul 1989. Otkrytiya Izobret 1991 48 174. (Central Asian Sci. Res. Inst. Nonferrous Metall. Russia). Von Ardenne A. Maedler E. Wehner B. Richter K. Schiller N. Tobisch J. Haehnel G. X-ray method for determining elements in electron-beam melting Ger. Offen. DE 4,032,628 (Cl. GOlN231207) 16 Apr 1992 Appl. 15 Oct 1990. (Forschungsinstitut Manfred von Ardenne Germany). Kaufman L. Deconinck F. Price D. C. Guesry P. Wilson C. J. Hruska B. Swann S. J. Camp D. C. Voegele A. L. Friesen R. D. Nelson J. A. An automated fluorescent excitation analysis system for medical applications Invest.Radiol. 1976 11 2 10. (Dept. Radiol. Univ. California Sch. Med. San Fran- cisco CA USA). Yakushiji K. Ohkawa S. Yoshinaga A. Harada J. Main peak profiles of total reflection X-ray fluorescence analysis of Si(O0 1) wafers excited by monochromatic X- ray beam W-L/? (I) Jpn. J. Appl. Phys. 1992 31 2872. (Showa Denko Silicon K.K. Shimokagemori 1505 Chichibu Saitama 369-1 8 Japan). Biichmann K. Steigerwald K. Klenk H. Development of a method for direct determination of solids as thin films by energy dispersive X-ray fluorescence analysis Mikrochim. Acta 1992 108 299. (Fachbereich Chem. Tech Hochsch. Darmstadt D-W 6 100 Darmstadt Germany). LaBaw C. C. Spectrum-imaging detector array with integrated filter Appl. Opt. 1993 32 780.(Caltech Pasadena CA USA). Hoover R. B. Multilayer monochromator for hard X- rays and gamma rays Appl. Opt. 1993 32 785. (Marshall Space Flight Center AL USA). Axner O. Rubinsztein-Dunlop H. Detection of trace amounts of Cr by two laser-based spectroscopic tech- niques laser-enhanced ionization in flames and laser- induced fluorescence in graphite furnace Appl. Opt. 1993 32 867. (Dept. Phys. Chalmers Univ. Technol. Univ. Goteborg S-4 12 96 Goteborg Sweden). Axner O. Ljungberg P. Malmsten Y. Laser-based spectroscopic technique for fast and reliable measure-JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 319R 9312 8 80. 931288 1. 9312882. 9 31288 3. 9 312 8 84. 9 312 8 8 5. 9312886. 9 3/28 8 7. 9 312 8 8 8. 93/28 89. 9312 8 90. 931289 1.9312892. ments of lifetimes of atomic metastable states in combustive situations Appl. Opt. 1993 32 899. (Anal. Laser Spectrosc. Group Dept. Phys. Chalmers Univ. Technol. Univ. Goteborg S-4 12 96 Goteborg Sweden). Reckers W. Huwel L. Griinefeld G. Andresen P. Spatially resolved multispecies and temperature analy- sis in hydrogen flames Appl. Opt. 1993,32 907. (Max- Planck-Institut fur Stromungsforschung Gottingen Germany). Nyholm K. Maier R. Aminoff C. G. Kaivola M. Detection of OH in flames by using polarization spectroscopy Appl. Opt. 1993 32 919. (Dept. Tech. Phys. Helsinki Univ. Technol. Rakentajanaukio 2 C SF-02 1 50 Espoo Finland). Simeonsson J. B. Miziolek A. W. Time-resolved emission studies of ArF-laser-produced microplasmas Appl. Opt. 1993 32 939. (U.S.Army Ballistic Res. Lab. SLCBR-IB-I Aberdeen Proving Ground MD Baer D. S. Hanson R. K. Semiconductor laser-based measurements of quench rates in an atmospheric pres- sure plasma by using saturated-fluorescence spectros- copy Appl. Opt. 1993 32 948. (High Temperature Gasdynamics Lab. Dept. Mech. Eng. Stanford Univ. Stanford CA 94305 USA). Umetani S. Matsui M. Solvent extraction of alkaline- earth metals with 4-acyl-5-pyrazolones and polydentate phosphine oxides Anal. Chern. 1992 64 2288. (Inst. Chem. Res. Kyoto Univ. Uji Kyoto 61 1 Japan). Mandjukov P. B. Vassileva E T. Simeonov V. D. Regular solution theory in model interpretation of the analyte losses during pre-atomization sample treatment in the presence of chemical modifiers in electrothermal atomization atomic absorption spectro- metry Anal.Chern. 1992 64 2596. (Chair Anal. Chem. Fac. Chem. Univ. Sofia J. Rourchier Blvd 1 I 126 Sofia Bulgaria). Nornura M. Trace element analysis using X-ray absorp- tion edge spectrometry Anal. Chern. 1992 64 271 1. (Photon Factory Natl. Lab. High Energy Phys. Oho Tsukuba 305 Japan). Ratliff J. Majidi V. Simultaneous measurement of the atomic and molecular absorption of aluminium copper and lead nitrate in an electrothermal atomizer Anal. Chem. 1992 64 2743. (Dept. Chem. Univ. Kentucky Lexington KY 40506 USA). Strijckmans K. Lodewyckx W. Dewaele J. Dams R. Determination of tin in copper by radiochemical proton activation analysis Anal. Chern. 1992 64 2904. (Lab. Anal. Chem. Inst. Nucl. Sci. Univ. Gent Proeftuin- straat 86 B-9000 Gent Belgium).Blotcky A. J. Claassen J. P. Roman F. R. Rack E. P. Badakhah S. Determination of aluminium by chemical and instrumental neutron activation analysis in biologi- cal standard reference material and human brain tissue Anal. Chern. 1992 64 2910. (Med. Res. Dept. Veter- ans Affairs Medical Center Omaha NE 68 105 USA). Dittmar T. B. Fernando Q. Leavitt J. A. McIntyre L. C. Jr. Surface concentrations of indium phosphorus *and oxygen in indium phosphide single crystals after exposure to Gamble solution Anal. Chern. 1992 64 2929. (Dept. Chem. Univ. Arizona Tucson AZ 8572 1 USA). Herzner P. Heumann K. G. Trace determination of uranium thorium calcium and other heavy metals in high-purity refractory metal silicides niobium and silicon dioxide with isotope dilution mass spectro- metry Anal.Chern. 1992 64 2942. (Inst. Anorgan. Chem. Univ. Regensburg Universitatsstr. 3 1 D-8400 Regensburg Germany). Adriaens A. G. Fassett J. D. Kelly W. R. Simons D. S. Adams F. C. Determination of uranium and 2 1005-5066 USA). 9312893. 9312894. 9312 89 5. 9 312 896. 9312897. 9312 89 8. 9312899. 9312900. 9312901. 9312902. 9312903. 9312904. 9312905. thorium concentrations in soils comparison of isotope dilution-secondary-ion mass spectrometry and isotope dilution-thermal ionization mass spectrometry Anal. Chern. 1992 64 2945. (Dept. Chem. Univ Antwerp Universiteitsplein 1 B-26 10 Wilrijk Belgium). Vieth W. Huneke J. C. Analysis of high-purity gallium by high-resolution glow discharge mass spectrometry Anal. Chern. 1992,64,2958. (Charles Evans Assoc.301 Chesapeake Dr. Redwood City CA 94063 USA). Nogar N. S. Estler R. C. Conia J. Jackson P. J. Detection of copper in isolated plant cells by reson- ance ionization mass spectrometry Anal. Chern. 1992 64,2972. (Chem. Laser Sci. Div. MS 5565 Los Alamos Natl. Lab. Los Alamos NM 87545 USA). McDowell W. J. Case G. N. McDonough J. A. Bartsch R. A Selective extraction of caesium from acidic nitrate solutions with didodecylnaphthalenesul- fonic acid synergized with bis( tert-butylbenzo)-2 1 - crown-7 Anal. Chern. 1992 64 3013. (Chem. Div. Oak Ridge Natl. Lab. Oak Ridge TN 3783 1 USA). Sperling M. Xu S. Welz B. Determination of chromium(m) and chromium(w) in water using flow injection on-line preconcentration with selective ad- sorption on activated alumina and flame atomic absorp- tion spectrometric detection Anal.Chem. 1992 64 3 101. (Dept. Appl. Res. Bodenseewefk Perkin-Elmer GmbH Postfach 101 76 1 D-88647 Uberlingen Ger- many). High K. A. Azani R. Fazekas A. F. Chee Z. A. Blais J. S. Thermospray-microatomizer interface for the determination of trace cadmium and cadmium- metallothioneins in biological samples with flow injec- tion and high-performance liquid chromatography atomic absorption spectrometry Anal. Chern. 1992,64 3 197. (McGill Univ. Macdonald Campus Dept. Food Science Agric. Chem. 2 1,111 Lakeshore Rd. Ste-Anne- de-Bellevue Quebec Canada H9X 3V9). Peters G. R. Beauchemin D. Characterization of an interface allowing either nebulization or gas chromato- graphy as the sample introduction system in ICP-MS Anal.Chern. 1993 65 97. (Dept. Chem. Queen’s Univ. Kingston Ontario Canada K7L 3N6). Gelinas Y. Youla M. Beliveau R. Schmit J. P. Multi-element analysis of biological tissues by induc- tively coupled plasma mass spectrometry healthy Spra- gue Dawley rats Anal. Chim. Acta 1992 269 1 1 5 . (Dept. Chim. Univ. Quebec Montreal Montreal Que- bec Canada H3C 3P8). Pin C. Bassin C. Evaluation of a strontium-specific extraction chromatographic method for isotopic analy- sis in geological materials Anal. Chirn. Acta 1992 269 249. (Dept. Geol. URA 10 CNRS Univ. Blaise Pascal 5 rue Kessler 63038 Clermont-Ferrand France). Imai N. Microprobe analysis of geological materials by laser ablation inductively coupled plasma mass spectro- metry Anal. Chim. Acta 1992 269,263. (Geol. Survey Japan 1 - 1-3 Higashi Tsukuba Ibaraki 305 Japan).Al-Swaidan H. M. Determination of lead and nickel in Saudi Arabian crude oils by ICP-MS using MIBK for sample pretreatment Anal. Lett. 1992,25 2157. (Coll. Sci. King Saud Univ. Riyadh 1 145 1 Saudi Arabia). Park C. J. Lee K. W. Minimization of error propaga- tion in isotope dilution mass spectrometry Anal. Sci. Technol. 1990 3 25. (Inorg. Anal. Lab. Korea Stand. Res. Inst. Taejon 305-606 South Korea). Lee K.-b. Kim H.-j. Park C. J. Moon D.-w. Lee K.- w. Direct solid analysis by the measurement of relative ion yield with glow discharge mass spectrometry Anal. Sci. Technol. 1990 3 215. (Inorg. Anal. Chem. Lab. Korea Stand. Res. Inst. Taejeon 305-606 South Korea). Kim Y.-s. Choi J.-m. Kim T.-j. Optimization of instrumental parameters and matrix effects in induc-320R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 9312906. 9312907. 9312 908. 9 312909. 93/29 10. 93/29 1 1. 93/29 12. 93/29 93/29 93/29 93/29 93/29 17. 93/29 18. 93/29 19. tively coupled plasma mass spectrometry (ICP-MS) I. Instrumental operating parameters Anal. Sci. Technol. 1991 4 177. (Dept. Chem. Korea Univ. Jochiwon Choongnam 339-700 South Korea). Kim Y.-s. Choi J.-m. Kim T.-j. Optimization of instrumental parameters and matrix effects in induc- tively coupled plasma mass spectrometry. 11. Non- spectroscopic matrix effects Anal. Sci. Technol. 1991 4 185. (Dept. Chem. Korea Univ. Jochiwon Choong- nam 339-700 South Korea). Park C.-j. Fundamentals and application of induc- tively coupled plasma mass spectrometry Anal.Sci. Techno/. 1992 5 51A. (Korea Stand. Res. Inst. South Korea). Woo J.-c. Lim H.-b. Moon D.-w. Lee K.-w. Kim H.- j. Development of the ion source of glow dis- charge mass spectrometry for the determination of trace elements Anal. Sci. Technol. 1992,5 169. (Inorg. Anal. Chem. Lab. Korea Stand. Res. Inst. Sci. Taejon 305- 606 South Korea). Wooderck H. Ha J.-h. Nam Y.-j. Quality assessment of honey by stable carbon isotope analysis Anal. Sci. Technol. 1992 5 229. (Korea Food Res. Inst. Song- nam 463-420 South Korea). Vaai Vaeck L. Van Roy W. Gijbels R. Laser ioniza- tion mass spectrometry for the characterization of solid materials Analusis 1992 20(7) 29s. (Dept. Chem. Univ. Antwerp B 2610 Wilrijk Belgium). Petit A Mauchien P. Laser-resonant ionization Analusis 1992 20(7) 35s.(DCC CEN Saclay 91 191 Gif-sur-Yvette France). Siefering K. Berger H. Whitlock W. Certification of ultra-clean distribution systems at the ppt level with APIMS Annu. Tech. Conf Proc. SOC. Vuc. Coaters 1992 35 397. (BOC Group Airco Research Triangle Park NC USA). Moro L. Lazzeri P. Prudenziati M. Morten B. Savigni P. Interactions between beryllia and high-lead glasses Appl. Phys. Lett. 1992 61 2299. (IRST Pante’ di Povo Trento Italy). Meirav O. Adam M. Boaretto E. Dias S. A. Johnson R. R. Paul M. Venczel E. Measurements of iodine-129 in a nuclear power reactor by accelerator mass spectrometry Appl. Radiat. Isot. 1992 43 1420. (TRUIMF Vancouver British Columbia Canada). Crain J. S. Mikesell B. L. Detection of sub-ng I-’ actinides in industrial waste water matrixes by induc- tively coupled plasma mass spectrometry Appl.Spec- trosc. 1992 46 1498. (Chem. Laser Sci. Div. Los Alamos Natl. Lab. Los Alamos NM 87545 USA). Fan C.-z. Jiang N. Qian W.-j. Quantitative SIMS analysis based on the ‘combined LTE-bond breaking’ model Appl. Sur- Sci. 1992 62 131. (Lanzhou Inst. Phys. Lanzhou 730000 China). Buckley W. T. Budac J. J. Godfrey D. V. Koenig K. M. Determination of multiple selenium stable isotope tracers by inductively coupled plasma mass spectrome- try Biol. Mass Spectrom. 1992 21,473. (Agric. Canada Res. Stn. Agassiz British Columbia Canada VOM IAO). Yarasheski K. E. Smith K. Rennie M. J. Bier D. M. Measurement of muscle protein fractional synthetic rate by capillary gas chromatography-combustion isotope ratio mass spectrometry Biol.Mass Spectrom. 1992 21 486. (Sch. Med. Washington Univ. St. Louis MO 631 10 USA). Good P. F. Olanow C. W. Perl D. P. Neuromelanin- containing neurons of the substantia nigra accumulate iron and aluminium in Parkinson’s disease a LAMMA study Brain Res. 1992 593 343. (Dept. Pathol. Mt. Siani Med. Cent. New York NY USA). 9312920. 931292 1. 9312922. 9312923. 9 312 92 6. 9 3/29 24. 9 31292 5. 9312927. 9 31292 8. 9312929. 9312930. 931293 1. 9312932. 9 31293 3. 9312934. 9312935. Chiba K. Mass spectrometry for elemental analysis of steel Bunseki 1992 71 1. (Shinnippon Seitetsu K. K. Japan). Mizota T. Nakamura T. Iwasaki K. Determination of trace elements in high-purity molybdenum by glow discharge mass spectrometry Bunseki Kagaku 1992 41 425.(Mater. Charact. Lab. Kanagawa High-Tech- nol. Found. Kawasaki 2 13 Japan). Sharp Z. D. In situ laser microprobe techniques for stable isotope analysis Chem. Geol. 1992 101 3. (Inst. Mineral. Univ. Lausanne CH- 10 15 Lausanne Switzer- land). Elsenheimer D. Valley J. W. In situ oxyyen isotope analysis of feldspar and quartz by neodymium-doped YAG laser microprobe Chem. Geol. 1992 101 21. (Dept. Geol. Geophys. Univ. Wisconsin Madison W1 53706 USA). Hervig R. L. Oxygen isotope analysis using extreme energy filtering Chem. Geol. 1992 101 185. (Cent. Solid State Sci. Arizona State Univ. Tempe AZ 85287 USA). Yates P. D. Wright 1. P. Pillinger C. T. Application of high-sensitivity carbon isotope techniques-a ques- tion of blanks Chem. Geol. 1992 101 8 1.(Dept. Earth Sci. Open Univ. Walton Hall Milton Keynes UK MK7 6AA). Palacz Z. A. Freedman P. A. Walder A. J. Thorium isotope ratio measurements at high abundance sensitiv- ity using a VG 54-30 an energy-filtered thermal ioniza- tion mass spectrometer Chem. Geol. 1992 101 157. (V. G. Isotech Middlewich Cheshire UK CW 10 OHT). Lorin J. C. Oxygen isotope analysis on the Cameca ims-300 Chem. Geol. 1992,101 193 (Lab. Phys. Solid Univ. Paris-Sud F-9 1405 Orsay France). Lyon I. Turner G. Isolab 54 ion microprobe Chem. Geol. 1992 101 197. (Dept. Geol. Univ. Manchester Manchester UK M13 9PL). KUSS H. M. Miiller M. Bossmann D. Interferences caused by high matrix element concentrations in ICP mass spectrometry Chem. Listy 1992 86 523. (Univ. Duisburg Duisburg Germany). Huang Q.-w.Lin Y.-z. New method for absolute determination of trace element boron Chin. Sci. Bull. 1992 37 750. (Beijing Syntone Sci. Instrum. Beijing 100080 China). Kershisnik M. M. Kalamegham R. Ash K. O. Nixon D. E. Ashwood E. R. Using oxychloride to correct for chloride interference improves accuracy of urine arsenic determinations by inductively coupled plasma mass spectrometry Clin. Chem. (Washington D. C.) 1992 38 2197. (Dept. Pathol. Univ. Pathol. Salt Lake City UT 84 132 USA). Barrett J F. R. Whittaker P. G. Williams J. G. Lind T. Absorption of non-haeme iron in normal women measured by the incorporation of two stable isotopes into erythrocytes Clin. Sci. 1992 83 213. (Princess Mary Matern. Hosp. Univ. Dept. Obstet. Newcastle- upon-Tyne UK). Luo F.C. H. Huneke J. C. Glow discharge mass spectrometry (GDMS) elemental analysis of coal fly ash Elem. Anal. Coal Its By-Prod. Int. Con$ Proc. 2nd 199 1 (Pub. 1992) 17. (Charles Evans Assoc. Redwood City CA 94603 USA). Lichte F. E. Analysis of coal by laser ablation induc- tively coupled plasma mass spectrometry Elem. Anal. Coal Its By-Prod. Int. Conf Proc. 2nd 1991 (Pub. 1992) 80. (Denver CO 80225 USA). Conrad V. B. Krofcheck D. S. ICP-MSdetermination of trace elements in coal and other geological materials Elem. Anal. Coal Its By-Prod. Int. Conf Proc. 2nd 1 99 1 (Pub. 1992) 97. (Consol. Coal Library PA 15 129 USA).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 321R 93/29 36. 93/29 3 7. 9312938. 9312939 9312940. 931294 1. 9312942. 9312943. 9312944.9 312945. 9312946. 9312947. 9 312948. 9312949. Hittle L. R. Sharkey A. G. Hercules D. M. Morsi B. Elemental composition of coal surfaces by laser desorp- tion mass spectrometry Elem. Anal. Coal Its By-Prod. Int. ConJ Proc. 2nd 1991 (Pub. 1992) 149. (Dept. Chem. Univ. Pittsburgh Pittsburgh PA 15260 USA). Davidson G. R. Bassett R. L. Application of boron isotopes for identifying contaminants such as fly ash leachate in groundwater Environ. Sci. Technol. 1993 27 172. (Dept. Hydrol. Water Resour. Univ. Arizona Tucson A2 85721 USA). Muller J. F. Krier G. Millon E. Analytical tools using laser ablation Eur. Mater. Res. SOC. Monogr. 1992 4 167. (Lab. Spectrom. Masse Chim. Laser Univ. Metz 57070 Metz France). Wang Zi.-s. Sui X-y. Liu J . 4 Quantitative analysis of atmospheric dusts by isotope dilution spark source mass spectrometry Fenxi Shiyanshi 1992 11( 3) 5 1.(Changchun Inst. Appl. Chem. Acad. Sin. Changchun 130022 China). Saumer M. Gantner E. Reinhardt J. Ache H. J. Determination of molybdenum in plant reference ma- terial by thermal ionization isotope dilution mass spectrometry Fresenius’J. Anal. Chem. 1992,344 109. (Inst. Radiochem. Kernforschungszent. Karlsruhe GmbH D-7500 Karlsruhe Germany). Bordat P. Freyer H. D. Kobel K. Vissac T. HPLC preparation of nitrate from ice cores for mass spectro- metric nitrogen- 1 5-nitrogen- 14 measurements Fresen- ius’ J. Anal. Chem. 1992 344 279. (Inst. Chem. Dyn. Geosphaere Forschungszent. Jiilich GmbH D-5 1 70 Julich Germany). Kohl C. P. Nishizumi K. Chemical isolation of quartz for measurement of in situ-produced cosmogenic nu- clides Geochim.Cosmochim. Acta 1992 56 3583. (Dept. Chem. Univ. California San Diego La Jolla CA Seki S. Sumiya H. Tamura H. Hirose H. Analysis of surface contamination by a new combined technique of SIMS and ESDMS Hyomen Kagaku 1992 13 249. (Fac. Eng. Takushoku Univ. Hachioji 193 Japan). Matsuo Y. Maeda H. Takami M. High resolution laser spectroscopy of metallic atoms and molecules storage of singly and doubly charged ions transferred from externally generated laser plasmas Hyperfine Interact. 1992 74 269. (Inst. Phys. Chem. Res. Wako 35 1-0 I Japan). Xiao Y. K. Zhang C. G. High-precision isotopic measurement of chlorine by thermal ionization mass spectrometry of the caesium chloride (Cs,CI+) ion Int. J. Mass Spectrom.Ion Processes 1992 116 183. (Qinghai Inst. Salt Lakes Acad. Sinica Xining 8 10008 China). Kaesdorf S. Hartmann M. Schroder H. Kompa K. L. Influence of laser parameters on the detection efficiency of sputtered neutrals mass spectrometry based on non- resonant multiphoton ionization Int. J. Mass Spectrom. Ion Processes 1992 116 219. (Max Planck Inst. Quantenopt. D-8046 Garching Germany). Marshall A. G. Schweikhard L. Fourier transform ion cyclotron resonance mass spectrometry technique de- velopments Int. J. Mass Spectrom. Ion Processes. 1992 118 37. (Dept. Chem. Ohio State Univ. Columbus OH 43210 USA). March R. E. Ion trap mass spectrometry Int. J . Muss Spectrom. Ion Processes 1992 118 71. (Dept. Chem. Trent Univ. Peterborough Ontario Canada K9J 7B8). Pillinger C.T. New technologies for small sample stable isotope measurement static vacuum gas source mass spectrometry laser probes ion probes and gas chromatography-isotope ratio mass spectrometry Int. J. Mass Spectrom. Ion Processes. 1992 118 477. (Dept. 92093-03 1 7 USA). 9312950. 931295 1 9 312 9 52. 9312953. 9312954. 931295 5. 9 3/29 5 6. 931295 7. 9312958. 93/29 5 9. 9312960. 931296 1. 9312962. Earth Sci. Open Univ. Walton Hall Milton Keynes UK MK7 6AA). Hieftje G. M. Norman L. A. Plasma source mass spectrometry Int. J. Mass Spectrom. Ion Processes 1992 118 5 19. (Dept. Chem. Indiana Univ. Bloom- ington IN 47405 USA). Heumann K. G. Isotope dilution mass spectrometry Int. J. Mass Spectrom. Ion Processes 1992 118 575. (Inst. Anorg. Chem. Univ. Regensburg D-8400 Regensburg Germany).Hervig R. L. Williams P. Thomas R. M. Schauer S. N. Steele I. M. Microanalysis for oxygen isotopes in insulators by secondary-ion mass spectrometry Int. J. Mass Spectrom. Ion Processes 1992 120 45. (Cent. Solid State Sci. Arizona State Univ. Tempe AZ 85287 USA). Dubois J. C. Retali G. Cesario J. Isotopic analysis of rare earth elements by total vaporization of samples in thermal ionization mass spectrometry Znt. J. Mass Specctrom. Ion Processes 1992 120 163. (Dept. Pro- cedes Enrich. Cent. Etud. Nucl. Saclay F91191 Gif- sur-Yvette France). Krueger D. A. Stable carbon isotope ratio method for detection of corn-derived acetic acid in apple cider vinegar collaborative study J. AOAC Int. 1992 75 725. (Krueger Food Lab. Cambridge MA 02 139 USA).Becker J. S. Dietze H. J. Laser ionization mass spectrometry in inorganic trace analysis Fresenius’ J. Anal. Chem. 1992 344 69. (Zentralab. Chem. Anal. Forschungszent. Jiilich GmbH D-5 I70 Julich I Ger- many). Guerrero-Ruiz A. Blanco J. M. Aguilar M. Rodri- guez-Ramos I. Fierro J. L. G. Mechanistic study of the oxygen insertion into molybdena crystals as revealed by SIMS and TPSR techniques J. Catal. 1992 137 429. (Fac. Cienc. UNED Madrid 28040 Spain). Story W. C. Caruso J. A. Heitkemper D. T. Perkins L. Elimination of the chloride interference on the determination of arsenic using hydride generation in- ductively coupled plasma mass spectrometry J. Chro- matogr. Sci. 1992 30 427. (Dept. Chem. Univ. Cincinnati Cincinnati OH 4522 1-0 1 72 USA). Song K. Yi J.-h.Lee J.-m. Determination of trace lead by laser resonance ionization spectroscopy. I. Dependence of detection limit on ionization schemes J. Korean Chem. SOC. 1992,36 832. (Dept. At. Spectrosc. Korea At. Energy Res. Inst. Taejon 305-606 South Korea). Scandurra A. Licciardello A. Torrisi A. La Mantia A. Puglisi O. Fatigue failure in lead-tin-silver alloy during plastic deformation a 3D-SIMS imaging study J. Mater. Res. 1992 7 2395. (Inst. Metodol. Tecnol. Microelettron. CNK Catanai Italy). Surano K. A. Hudson G. B. Failor R. A. Sims J. M. Holland R. C. MacLean S. C. Garrison J. C. Helium- 3 mass spectrometry for low-level tritium determination in environmental samples J. Radio-anal. Nucl. Chem. 1992 161 443. (Environ. Prot. Dept. Lawrence Liver- more Natl. Lab. Livermore CA 9455 1 USA).Hopkins L. C. Nagle J. Malik R. J. Secondary-ion mass spectrometry analysis of beryllium doped gallium arsenide-aluminium gallium arsenide heterostruc- tures J. Vac. Sci. Technol. A 1992 10,2843. (AT and T Bell Lab. Murray Hill NJ 07974 USA). Schroeder F. Storm W. Altebockwinkel M. Wied- mann L. Benninghoven A. Analysis of passivating oxide and surface contaminants on gallium arsenide ( 100) by temperature-dependent and angle-resolved X- ray photoelectron spectroscopy and time-of-flight sec- ondary-ion mass spectrometry J. Vuc. Sci. Technol. B,322R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 9312963. 9312964. 9 31296 5. 9312966. 9312967. 9312968. 9312969. 9312970. 9312978. 931297 1. 9312 972. 93t2973. 9312974. 931 297 5.9312976. 1992 10 1291. (Phys. Inst. Univ. Miinster 4400 Munster Germany). Albers P. Freund B. Seibold K. Wolff S. Characteri- zation of carbon black surfaces by combined XPS and SIMS measurements Kautsch. Gummi Kunstst. 1992 45 449. (Phys. Chem. Forsch. Degussa AG Hanau- Wolfgang Germany). Fichtner M. Depth resolved analysis of salts Kernfor- schungszent. Karlsruhe [Ber.] K f l 1992 KfK 5017 9 1 pp. (Inst. Radiochem. Kernforschungszent. Karlsruhe GmbH Karlsruhe Germany). McConville P. Reynolds J. H. Trial of static Fourier- transform mass spectroscopy of xenon Mantle Meteo- rites 1990 7 1. (Dept. Phys. Univ. California Berkeley CA 94720 USA). Bortoli A. Gerotto M. Marchiori M. Palonta R. Troncon A. Applications of inductively coupled plasma mass spectrometry to the early detection of potentially toxic elements Microchem.J. 1992,46 167. (Environ. Chem. Sect. PMP 30125 Venice Italy). Graham M. J. Study of oxide scales using SIMS Microsc. Oxid. Proc. Int. Conf lst 1990 (Pub. 1991) 10. (Div. Chem. Natl. Res. Counc. Canada Ottawa Ontario Canada KIA OR9). Montgomery M. Harrison P. L. Lees D. G. SIMS investigation of the oxidation of iron in oxygen Mi- crosc. Oxid. Proc. Int. Conf lst 1990 (Pub. 1991) 36. (Manchester Mater. Sci. Cent. Manchester Univ. Man- Chester UK M1 7HS). Quadakkers W. J. Speier W. Holzbrecher H. Nickel H. SIMS investigations of the transport phenomena in chromia and alumina scales on ODS alloys Microsc. Oxid. Proc. Znt. Conf lst 1990 (Pub. 1991) 149. (Inst. React. Mater. Res. Cent. Julich D-5 170 Jiilich Ger- many).Harris A. W. Atkinson A. Moon D. P. Mountfort S. SIMS studies of the transport of oxygen tracer in growing nickel oxide scales formed at 600-900 "C Microsc. Oxid. Proc. Znt. Conf Is? 1990 (Pub. 1991) 31 1. (Mater. Dev. Div. Harwell Lab. Didcot Oxford- shire UK OX1 1 ORA). Beukens R. P. Radiocarbon accelerator mass spectro- metry background precision and accuracy Radiocar- bon Four Decades [Pap. ConJ] 1992 230. (Is0 Trace Lab. Univ. Toronto Ontario Canada M5S 1A7). Danninger H. Atari A. Lux B. Kny E. Friedbacher G. Grasserbauer M. Identification of embrittling trace impurities in tungsten heavy alloys by SIMS Mikro- chim. Acta 1992 108 163. (Inst. Chem. Technol. Anorg. Stoffe Tech. Univ. Wien A- 1060 Vienna Austria). Nakada Y. Koutsuka T. Mine K. Suga H.Factors affecting the quantification of carbon and oxygen in silicon by secondary-ion mass spectrometry (SIMS) Nippon Kinzoku Gakkaishi 1992,56 1 174. (Cent. Res. Inst. Mitsubishi Mater. Ohmiya Japan). Morgan C. G. Telle H. Resonance ionization spec- troscopy Phys. World 1992 5(12) 28. (Dept. Phys. Univ. Coll. Swansea Swansea UK SA2 8PP). Kremkov M. V. Khasanov U. Ion-sputtering cluster- component analysis of solid-state surface elemental composition Poverkhnost 1992 6 7 1. (Inst. Energ. Avtom. Tashkent Uzbekistan). Galana J. Z. Ma C. Haider A. Shadman F. Gilbert S. L. Ultratrace analysis of helium by atmospheric pressure ionization mass spectrometry Proc. Electro- chem. Sac. 1992 92. (Univ. Arizona Tucson AZ 85721 USA). Pavlov A K. Kogan V. T. Gladkov G. Y.Tandem mass-spectrometric method of cosmogenic isotope ana- 9312977. 9312979. 9312980. 9312981. 9312982. 9312983. 9312984. 93t2985. 9312986. 931298 7. 9312988. 9312989. 9312990. 931299 1. 9312992. lysis Radiocarbon 1992 34 271. (A. F. Ioffe Phys. Tech. Inst. St. Petersburg 19402 1 Russia). Cove H. E. History of AMS its advantages over decay counting applications and prospects Radiocarbon Four Decades [Pap. Conf] 1992 214. (Nucl. Struct. Res. Lab. Univ. Rochester Rochester NY 14627 USA). Attrep M. Jr. Roensch F. R. Aguilar R. Fabryka- Martin J. Separation and purification of plutonium in uranium ores for mass spectrometric measurement Radiochim. Acta 1992 57 15. (Los Alamos Natl. Lab. Los Alamos NM 87545 USA). Poupard D. Juery A. Isotope fractionation of pluto- nium in thermal ionization mass spectrometry.Direct deposition and resin bead Radiochim. Acta 1992 57 21. (CEA.RC 91680 Bruyeres le Chatel France). Hung T.-y. Su C.-s. Laser microprobe and resonance ionization mass spectrometry for the analysis of trace elements in solids Rev. Sci. Instrum. 1992 63 5299. (Inst. Nucl. Sci. Natl. Tsing Hua Univ. Hsinchu 30043 Taiwan). Valaskovic G. A. Morrison G. H. Quantitative imag- ing ion microscopy a short review Scanning Microsc. 1992,6 305. (Baker Lab. Chem. Cornell Univ. Ithaca NY 14853 USA). Ludwig K. R. Simmons K. R. Szabo B. J. Winograd I. J. Landwehr J. M. Riggs A. C. Hoffman R. J. Mass-spectrometric thorium-230-uranium-234-ura- nium-238 dating of the Devils Hole calcite vein Science (Washington D. C. 1883-) 1992 258 284.(Fed Cent. US Geol. Survey Denver CO 80225 USA). Addinall R. Newman R. C. Okada Y. Orito F. Calibration of the localized vibrational mode absorp- tion line due to isovalent boron impurities in gallium arsenide Semicond. Sci. Technol. 1992 7 1306. (Inter- discip. Res. Centre Semicond. Mater. Imp. Coll. Sci. Technol. Med. London UK SW7 2BZ). Liu Y. P. Mulvaney R. L. Diffusion of Kjeldahl digests for automated nitrogen- 1 5 analysis by the Rittenberg techniques Soil Sci. SOC. Am. J. 1992 56 1151. (Dept. Agron. Univ. Illinois Urbana IL 61801 USA). Liu Y. P. Mulvaney R. L. Automated nitrogen-15 analysis of ammonium in diffusion disks by the Ritten- berg technique Soil Sci. SOC. Am. J. 1992 56 1185. (Dept. Agron. Univ. Illinois Urbana IL 61801 USA). Miiller P. Dulski P.Luck J. Determination of rare earth elements in sea-water by inductively coupled plasma mass spectrometry Spectrochirn. Acta Part B 1992 47 1379. (Hahn Meitner Inst. Berlin D-1000 Berlin Germany). Miller-Ihli N. J. Comparison of ICP atomic spectro- metry techniques Spectroscopy (Eugene Oreg.) 1992 7(7) 12 14 18. (Nutr. Compos. Lab. US Dept. Agric. Beltsville MD 20705 USA). Ruth K. Schmidt P. Mori E. J. ICP-MS applications in silicon semiconductor manufacturing Spectroscopy (Eugene Oreg.) 1992 7(9) 36. (MEMC Electron. Mater. St. Peters MO 63376 USA). Beucher E. Lenglet M. Weber S. Scherrer S. Oxidation mechanisms on a-brasses (1 0 and 30 at. O/o zinc) by optical methods and SIMS Surf Interface Anal. 1992 18 673. (Lab. Physicochim. Mater. Univ. Rouen 76137 Mont Saint Aignan France).Moro L. Canteri R. Anderle M. Sputtered neutral and molecular-ion mass spectrometries in the character- ization of multilayer samples Surf. Interface Anal. 1992 18 765. (Div. Sci. Mater. IRST 38050 Povo Italy). Gillen G. High dynamic range SIMS depth profiling on in situ ion-beam-generated mesas using the ion micro- scope Surf Interface Anal. 1992 18 777. (Chem. Sci.JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 323R 9 3/299 3. 9 3/2 994. 9 3/29 9 5. 93r2996. 9312 99 7. Technol. Lab. Natl. Inst. Stand. Technol. Gaithers- burg MD 20899 USA). Schild C. Wokaun A. Baiker A Transformation of amorphous glassy metal-zirconium alloys into carbon dioxide hydrogenation catalysts an XPS SIMS and SNMS investigation Sur- Sci. A 1992 269,520.(Phys. Chem. 11 Univ. Bayreuth D-8580 Bayreuth Germany). Li S.-l. Gao S.-q. Mass spectrometric determination of boron isotope in boron carbide Tongweisu 199 1 4 18 1. (China Inst. At. Energy Beijing China). Ustyuzhanina G. V. Pakhovnichishin S. V. Chernysh I. G. Pokrovsku V. A. Study of the surface of disperse graphites by the temperature-programmed desorption and secondary ionic mass spectrometry Ukr. Khim. Zh. (Russ. Ed.) 1992 58 636. (Inst. Khim. Poverkhn. &ev The Ukraine). Rossmann A. Luellmann C. Schmidt H. L. Mass spectrometric determination of carbon and hydrogen isotope ratios for honey authenticity control Z. Le- bensm.-Unters. Forsch. 1992 195 307. (Tech. Univ. Muenchen W-8050 Freising Germany). Kinaeva I. V. Ramendik G. I. Tyurin D. A.Isotope dilution technique in spark source mass spectrometric analysis Zh. Anal. Khim. 1992,47 820. (V. I. Vernaskii Inst. Geochem. Anal. Chem. Moscow Russia). Papers 93x2998-93x30 15 were presented at the 34th Rocky Mountain Conference on Analytical Chemistry Denver Colorado 93K2998. Boss C. B. Recent advances in analytical chemical measurements in microwave induced plasmas (Dept. Chem. North Carolina State Univ. Raleigh NC 27695- 8204 USA). 93lC2999. Krushevska A. Martines L. Amarasiriwaradena C. Barnes R. M. Open focused microwave digestion system for preparation of biological samples for induc- tively coupled plasma spectrometry (Univ. Massachus- etts Dept. Chem. Lederle Grad. Res. Center Amherst 93/C3000. Brenner I. B. Review of the detection capabilities of ICP-AES for the determination of A1 in biological and environmental materials (Geolog.Survey Israel 30 Malkhe Israel St. Jerusalem 9550 1 Israel). 93/C3001.Hotz N. J. Bauer W. F. Determination of the elemental composition of lithium aluminate ceramics by inductively coupled plasma atomic emission spec- troscopy with slurry sample introduction (Idaho Natl. Eng. Lab. EG&G Idaho P.O. Box 1625 Idaho Falls ID 834 15 USA). 93/C3002. Rayson G. D. Evaluation of the inductively coupled plasma as a source for atomic absorption measure- ments (Chem. Dept. 3C New Mexico State Univ. Box 30001 Las Cruces NM 88003 USA). 93/C3003. McNew E. B. Bauer W. F. Siemer D. D. Determina- tion of lithium and trace elements in lithium aluminates using electrothermal furnace atomization with AA-ICP detection (Idaho Natl.Eng. Lab. EG&G Idaho P.O. Box 1625 Idaho Falls ID 8341 5 USA). 93K3004. Rayson G. D. Duarte M. W. Excitation temperature measurement in the ICP independent of LTE assump- tions (Chem. Dept. Box 30001 New Mexico State Univ. Las Cruces NM 88003 USA). 93K3005. Brenner I. B. Erlich S. Sc and Mg ion:atom ratios as diagnostic tools for the discrimination of EIE and physical transport effects due to high concentrations of Ca Mg and Na using ultrasonic nebulization (Geol. Survey Israel 30 Malkhe Israel St. Jerusalem 95501 Israel). 93K3006. Manabe R. Foster R. Pilon M. Application of a solid state detector for the observation of atomic spectra from an ICP source (Thermo Jarrell Ash 175 Jefferson Dr. Menlo Park CA 94025 USA). August 2-6 1992.MA 01003-0035 USA). 93/C3007.McGinty S. Ayala S. Govorchin S. Hughes S. Analysis of ultratrace contaminants in a high tungsten matrix (Bandgap Technology 325 Interlocken Parkway Broomfield CO 8002 I USA). 931C3008. Henry R. Rettberg T. Application of ICP-MS to the analysis of radionuclides in environmental samples (Fisons Instrum. 145 13 Spotswood Furnace Rd. Fred- ericksburg VA 22407 USA). 93/C3009.Taylor H. E. Garbarino J. R. Beckett R. Utilization of inductively coupled plasma mass spectrometry as a detector for sedimentation field-flow fractionation (US Geol. Survey Boulder CO USA). 93/C3010. Dahlquist R. Tasker D. Osborne S. Gower G. Fry 93/C30 93/C30 93/C30 93lC30 w c 3 0 B. Recent improvements in the factors governing basic ICP stability (Fisons Instruments ARL Ecublens Switzerland).l.Covorchin S. Ayala S. McGinty S. Hughes S. Extensions of ICP-MS dynamic range by simultaneous detection of ions and optical emissions (Bandgap Technol. 325 Interlocken Pky. Broomfield CO 8002 I USA). 2. Cantle J. Walsh A. Henry R. Analysis of ‘difficult’ matrices using high resolution ICP-MS (Fisons Instru- ments 145 13 Spotswood Furnace Rd. Fredericksburg VA 22407 USA). 3.Otsuka K. Iwanaga M. Musselman B. Detection of rare earth elements by ICP-MS (Jeol Akishima Tokyo Japan 196). 4.Henry R. Abell I. Gregson D. McCurdy E. Q- Switched Nd YAG laserprobe for ICP-MS analysis (Fisons Instruments 145 13 Spotswood Furnace Rd. Fredericksburg VA 22407 USA). 5.Henry R. Hulmston P. Olsen S. Ringdal O. Appli- cation of electrothermal vaporization ICP-MS to the analysis of petroleum samples (Fisons Instruments I45 13 Spotswood Furnace Rd.Fredericksburg VA 22407 USA). Papers 93lC30 16-93K3029 were presented at the 204th American Chemical Society Material Meeting Washington D. C. August 93K3016. Vocke R. D. Murphy K. E. Paulsen P. J. Fassett J. D. Certification of Pb in blood using isotope dilution inductively coupled plasma mass spectrometry (Chem. Sci. Technol. Lab. Natl. Inst. Standards Technol. Gaithersburg MD 20899 USA). 93/C3017. Slavin W. Making the fruits of atomic spectroscopy research available for analytical chemistry (Bonaire Technol. Box 1089 Ridgefield CT 06877 USA). 93/C30 18. Mermet J. M. Can academic research be of interest to the analytical chemist? (Lab. Anal. Sci. Univ. Lyon 1 69622 Villeurbanne Cedex France).93/C3019. Winefordner J. D. Linking principles with detection power in atomic spectrometry. How far can we go? (Dept. Chem. Univ. Florida Gainesville FL 3261 1 USA). 93/C3020. Caruso J. A. Selective chromatographic detection by plasma mass spectrometry (Dept. Chem. Univ. Cincin- nati Cincinnati OH 45221 USA). 93/C302 1. Olesik J. W. Hobbs S. E. New insights for practical analysis using ICP-OES and ICP-MS from time and space resolved measurements (Lab. Plasma Spectro- chem. Dept. Geol. Sci. Ohio State Univ. 1090 Car- mack Rd. Columbus OH 432 10 USA). 93/C3022.Montaser A. Cai M. Hsiech C. Nam S. Liu H. Zhang H. Understanding processes on the fundamen- tal basis academic exercises or useful studies for practical analytical spectrometry? (Dept.Chem. Ge- orge Washington Univ. Washington DC 20052 USA). 23-28 1992.32413 JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 93K3023. Harnly J. M. Multi-element furnace spectrometry the search for photons in the UV (US Dept. Agric. Nutrient Compos. Lab. Beltsville MD 20705 USA). 93/C3024.McLaren J. W. Lam J. W. H. Berman S. S. Use of mixed-gas plasmas in inductively coupled plasma mass spectrometry (Inst. Environ. Chem. Natl. Res. Council Canada Ottawa Canada K 1 A OR6). 93/C3025. Barnes R. M. Academic-industrial interface in spec- trochemical analysis (Dept. Chem. Lederle Grad. Res. Center Univ. Massachusetts Amherst MA 0 1003- 0035 USA). 93K3026. Marcus R. Development of r.f. powered glow discharge devices a balancing act between the university manu- facturers and the funding agencies (Dept.Chem. Howard L. Hunter Chem. Lab. Clemson Univ. Clem- son SC 29634-1905 USA). 93/C3027.Uden P. C. Seeley J. A. Slowick J. J. Zeng Y. Chromatographic exploration of the periodic table with atomic spectroscopic detection (Dept. Chem. Lederle Graduate Res. Tower A Univ. Massachusetts Amherst MA 01003 USA). 93K3028. Sullivan J. J. Quimby B. D. Element selective detec- tion in GC with atomic emission spectroscopy (Hewl- ett-Packard Avondale PA 193 1 1 USA). 93K3029.St. Louis R. Little J. L. Cook L. A. Use of gas chromatography with atomic emission detection (GC- AED) in the qualitative identification of unknown species (Phys. Anal. Res. Eastman Chemical King- sport TN 37662 USA). Papers 93/C3030-93/C3038 were presented at the 22nd Interna- tional Roland Frei Memorial Symposium on Environmental Analyt- ical Chemistry Dortmund Germany June 9-1 2 1992.93K3030. Lobinski R. Adams F. C. Capillary gas chromatogra- phy-atomic emission spectrometry as a tool for ultra- trace speciation analysis of organometallic species in environmental samples (Dept. Chem. Univ. Antwerp (UIA) Universiteitsplein 1 B-26 10 Wilrijk Antwerp Belgium). 93K303 1. Scholze H. Stephanowitz H. Hoffmann E. Ludke ChR. Comparison of ICP-AES and ICP-MS for deter- mination of selected elements in soils (Inst. Spektro- chem. angew. Spektrosk. Lab. Spektrosk. Methoden Umweltanal. Rudower Chaussee 5 D-0 1 199 Berlin Germany). 93/C3032.Lee M. L. Beinrohr E. Tschopel P. Tiilg G. Pre- concentration of palladium platinum and rhodium by on-line sorbent extraction for graphite furnace atomic absorption spectrometry and inductively coupled plasma atomic emission spectrometry (Inst.Spektrosk. (ISAS) Bunsen Kirchhoff Str. 1 1 D-4600 Dortmund 1 Germany). 93K3033. Szpunar-Lobinska J. Ceulemans M. Lobinski R. Adams F. C. On-line sample preparation for organotin speciation analysis of water by gas chromatography- atomic emission spectrometry (GC-AES) (Dept. Chem. Univ. Antwerp (UIA) Univ. 1 B-2610 Wilrijk Antwerp Belgium). 93K3034. Hoffmann E. Liidke ChR. Skole J. Application of laser ablation in the analysis of biological samples (Inst. Spektrochem. angew. Spektrosk. Lab. Spektrosk. Meth- oden Umweltanal. Rudower Chaussee 5 D-0 1199 Berlin Germany). 93K3035. Rubio R. Alberti J.Rauret G. Photo-oxidation of arsenobetaine and arsenocholine to generate arsines previous to ICP-AES measurement (Dept. Quim. Anal. Univ. Barcelona Avda. Diagonal 647 08028 Barce- lona Spain). 93K3036. Hoffmann E. Liidke ChR. Skole J. Direct determina- tion of elements in airborne particulates by FANES and ICP-MS (Inst. Spektrochem. Angew. Spektrosk. Lab. Spectrosk. Methoden Umweltanal. Rudower Chaussee 5 D-0 1199 Berlin Germany). 93K3037. Paul M. Briickner P. Water analysis by ICP-MS (Perkin-Elmer M-MSD Postfach 101761 D-88647 Uberlingen Germany). 93/C3038. Siemens V. Klockow D. Broekaert J. A. C. Continu- ous determination of vaporous mercury by micro- wave induced plasma optical emission spectrometry (MIP-OES) (Inst. Spectrochem. Appl. Spectrosc. (ISAS) Dortmund Germany).Papers 93/C3039-93/C3040 were presented at the 6th International Symposium on Resonance Ionization Spectroscopy and Applica- tions Santa Fe NM USA May 24-29 1992. 93K3039. Omenetto N. Interactions of laser induced fluore- scence and ionization techniques in atomic and molecu- lar spectroscopy (CEC Joint Res. Centre Environ. Inst. Ispra Varese Italy). 93K3040. Tiilg G. Limitations of extreme trace analysis from the standpoint of analytical chemistry (Inst. Spektrochem. angew. Spektrosk. Lab. Reinstoffanal. Max Planck Inst. Metall. Stuttgart Dortmund Germany). Papers 9 3 ~ 3 0 4 1-93K3045 were presented at the 10th European Society Conference for Environment Ecochemistry and Health Edinburgh UK April 12- 15 1992. 93/C304 1. Delves H. T. Identification and apportionment of sources of lead in human tissue (Trace Element Unit General Hospital Tremona Rd.Southampton UK SO9 4x7). 93/C3042.Rae J. E. Lidiard H. M. Parker A. Trace-element responsive diseases in the Heasley Mill area North Devon UK the significance of Mn oxides (Postgrad. Res. Inst. Sedimentol. P.O. Box 227 Univ White- knights Reading UK RG6 2AB). 93K3043. Li X.-d. Thornton I. As Sb and Bi in soil and pasture herbage in some old metalliferous mining areas England (Environ. Geochem. Res. Centre Environ. Technol. Royal Sch. Mines Imperial Coll. London UK SW7 2BP). 93K3044. Dong D. Thornton I. Ramsey M. Influence of soil pH on the uptake of aluminium from soil into the soybean plant (Environ. Geochem. Res. Centre Environ. Tech- nol. Imperial Coll. Prince Consort Rd.London UK SW7 2BP). 93/C3045. Kim K.-w. Thornton I. Cadmium molybdenum and selenium in soils and crop plants in the Deog-Pyoung area of Korea; influence of uraniferous black shales (Environ. Geochem. Imperial Coll. Prince Consort Rd. London UK SW7 2BP). Papers C/3046-C/3064 were presented at the IVth National Conference on Atomic Spectroscopy Xiamen China November 93K3046. Ma X.-g. Zhang Z.-x. Qian H.-w. Determination of trace ytterbium in vanadium using Kalman filtering in PDA-ICP-AES (Dept. Chem. Zhongshan Univ. Guangzhou 5 10275 China). 93K3047. Ni Z.-m. Coupled chromatography-atomic spectrome- try for the determination of trace organometallic com- pounds in environmental and biological samples. A review (Res. Center for Eco-Environmental Sci.Acade- mia Sin. China). 93K3048. Zheng J.-g. Zhang Z.-x. Simulation of nebulization and evaporation processes in ICP-AES using Monte Carlo method (Dept. Chem. Zhongshan Univ. Guangzhou 5 10275 China). 93/C3049.Ma X.-g. Zhang Z.-x. Li W.-c. Determination of mixed rare earth element using computer spectrum- stripping method with PDA-ICP-AES (Dept. Chem. Zhongshan Univ. Guangzhou 5 10275 China). 93/C3050. Zheng J.-g. Zhang Z.-x. Simulation of ionization and excitation processes in ICP-AES using Monte Carlo 1-6 1992.JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY. OCTOBER 1993 VOL. 8 325R method (Dept. Chem. Zhongshan Univ. Guangzhou 5 10275 China). 93/C305 1. Sun D.-h. Zhang Z.-x. Optimization of analytical conditions for eliminating matrix effects in ICP-AES (Dept.Chem. Zhongshan Univ. Guangzhou 5 10275 China). 93/C3052. Guo X.-w. Investigation of new techniques in HG-AAS (Northwest Res. Inst. Geol. CNNC Xian 710054 China). 93/C3053.Yang C.4 Zhuang Z.-x. Wang X.-r. Yang P.-y. Determination of ultra-trace heavy metals by ETAAS-studies on FI on-line ion-exchange preconcen- tration of copper (Chem. Dept. Xiamen Univ. Xi- amen 361005 China). 93K3054. Yan X.-m. Wang X.-r. Yang P.-y. Huang B.4 Multi- functional integrated software for the detection and processing of multichannel transient signals of ICP-AES systems (Chem. Dept. Xiamen Univ. Xiamen 361005 China). 93/C3055. Deng Z.-w. Wang X.-r. Hu Z.-w. Huang B . 4 Multi- element determination in sea-water by flow injection (FI) electrochemical preconcentration ICP-AES (Chem. Dept.Xiamen Univ. Xiamen 361005 China). 93/3056. Liu M.-z. Guo T.-z. Application of flow injection hydride generation (FI-HG) techniques in atomic fluo- rescence spectrometry (AFS) (Beijing Haiguang Instru- ment Inst. Rock Mineral Testing Chinese Geol. Acad. Beijing 100027 China). 93/C3057. Fang Z. Expansion of analytical range for flame atomic absorption spectrometry using flow injection tech- niques (Flow Injection Anal. Res. Center Inst. Appl. Ecol. Acad. Sin. Box 417 Shenyang 11001 5 China). 93K3058. Fang Z. Expansion of analytical range for flame atomic absorption spectrometry using flow injection tech- niques (Flow injection Anal. Res. Center Inst. Appl. Ecol. Acad. Sin. Box 417 Shenyang 110015 China). 93/C3059. Memon M. A. Wang X.-r. Zhuang Z.-x. Huang B. Flow injection on-line solvent extraction with atomic spectrometry (Chem.Dept. Xiamen Univ. Xiamen 36 1005 China). 93jC3060. Guo L. Fang Z. Determination of trace amounts of gold by FI on-line preconcentration ICP-AES (Inst. Appl. Ecol. Acad. Sin. Shenyang 1 1001 5 China). 931C306 1. Song L.-m. Determination of palladium and gold in waste waters by on-line chelation ion-exchange precon- centration FAAS (Liaoning Inst. Environ. Prot. Shen- yang 1 1003 I China). 931C3062. Comisarow M. B. Fourier transform ion cyclotron resonance mass spectroscopy (Dept. Chem. Univ. British Columbia Vancouver British Columbia Canada). 93/C3063.Chen H.-w. Tang FA. Gu C. lnfluence of chelating reagents on the plumbane generation determination of lead by HG-AAS in the presence of PAN-S (Dept.Chem. Hangzhou Univ. Hangzhou 3 10028 China). 931C3064. Kawaguchi H. Recent topics in ICP and glow discharge mass spectrometry (Dept. Mater. Sci. Eng. Nagoya Univ. Japan). Papers 93/C3065-93/C3077 were presented at the Proceedings of' the International Symposium of Overseas Chinese Scholars on Analytical Chemistry Wuhan China October 20-24 1992. 93K3065. Xu Z.-p. Tian LA. Study of laser ablation solid sampling for inductively coupled plasma spectrometry (ICP-AES) (Nanjing Lab. Rock Miner. Res. Ministry Geol. Miner. Resources Nanjing 2 100 1 8 China). 93K3066. Jin Q.-h. Some most impressive new advances in analytical atomic spectrometry (Dept. Chem. Jilin Univ. Changchun 130023 China). 93/C3067. Zhang L. Mcintosh S. Slavin W. Hydride generation ICP-AES for the simultaneous determination of hydride and non-hydride forming elements (Perkin-Elmer 76 1 Main Ave.Norwalk CT 06897 USA). 931C3068. Jiang Z.C. Application and potentiality of electro- thermal vaporization ETV-ICP-AES with a poly- (tetrafluoroethylene) slurry fluorinating reagent for trace analysis (Dept. Chem. Wuhan Univ. Wuhan 430072 China). 93/C3069. Fang Z. Sun L.-i. Xu S. Potentials for flow injection on-line preconcentration techniques for flame atomic absorption spectrometry (Flow Injection Anal. Res. Center Inst. Appl. Ecol. Acad. Sin. Box 41 7 Shenyang 1 1001 5 China). 931C3070. Yang P.-y. Nygaard D. Analytical evaluation of an end-on viewing inductively coupled plasma for AES with modified torch and optical system (Dept. Chem. Xiamen Univ. Xiamen 36 1005 China).93/C307 1. Xin R.-x. Mechanism of the enhancement effect of solvents on the spectral intensity in lower power ICP- AES (Inst. Nucl. Energy Technol. Tsinghua Univ. Beijing 100084 China). 93/C3072.Lu B.-v. Zou J.-c. Study of clearing up spectral interference and selecting optimum conditions for de- termining trace rare earth imputity elements in high- purity europium oxide with ICP-AES (Nanjing Inst. Geol. Min. Resources Nanjing 2 100 16 China). 93/C3073.Hu B. Jiang Z.-c. Zeng Y. Study on vaporization behaviours of niobium tantalum uranium and zircon- ium in graphite furnace for sample introduction into an inductively coupled plasma using poly(tetra- fluoroethylene) as fluorinating agent (Dept. Chem. Wuhan Univ. Wuhan 430072 China). 93/C3074. Pen& X.-j.Jiang Z.-c. Zen& Y. Design and evaluation of an on-line microcolumn preconcentration and desol- vation technique for flow injection ICP-AES (Dept. Chem. Wuhan Univ. Wuhan 430072 China). 93/C3075.Zeng X.-b. Zhong Y.4 Liang S.-c. High temperature reaction of aluminium compound on graphite substrate the reason for altering the atom formation processes of precious metals (Dept. Chem. Wuhan Univ. Hubei 430072 China). 93/C3076. Deng B. Liu Q.-a. Determination of bismuth with probe atomization in graphite furnace atomic absorp- tion spectrometry using fuzzy orthogonal design (Dept. Chem. Tsinghua Univ. 100084 Beijing China). 93/C3077. Wang G.-w. He H.-w. Study on the determination of scandium by graphite furnace atomic absorption spec- trometry (Hunan Inst.Rare Earth Metals and Mater. Res. Changsha Hunan 4 100 14 China). 9 31307 8. 9313079. 93/3080. 931308 1. 9313082. Chen M. Direct determination of trace phosphorus in low segregation superalloys by ICP-AES At. Spectrosc. 1992 13 190. (Dept. Chem. Anal. Inst. Metal Res. Acad. Sin. Shenyang I 100 1 5 China). Reichardt M. S. Determination of trace elements in high-temperature alloys by Zeeman-effect electrother- mal atomic absorption At. Spectrosc. 1992 13 178. (Carpenter Technol. Corp. Res. Devel. Center P.O. Box 14662 Reading PA 19612-4662 USA). Chung S.-w. Tsai W.-c. Atomic absorption spectrome- tric determination of heavy metals in foodstuffs using a simple digester At. Spectrosc. 1992,13 185. (Div. Food Technol. Food Ind. Res. Dev. Inst. Hsinchu Taiwan). Ashley D.Polyatomic interferences due to the pre- sence of inorganic carbon in environmental samples in the determination at mass 52 by ICP-MS At. Spectrosc. 1992 13 169. (Natl. Rivers Authority Nottingham UK). Shuttler I. Application of a transversely heated elec- trothermal atomizer with longitudinal Zeeman-cffcct background correction to the determination of vana-326R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 9313083. 9313084. 9313085. 9313086. 93 93 3087. 3088. 9313089. 9313090. 931309 1. 9313092. 9313093. 93 93 3094. 3095. dium in urine At. Spectrosc. 1992 13 174. (Boden- seewerk.. Perkin-Elmer GmbH Postfach 10 176 1 D- 88647 Uberlingen Germany). Calzada M. D. Quintero M. C. Gamero A. Cotrino J. Sanchez Uria J. E. Sanz-Medel A. Determination of bromide by low power surfatron microwave induced plasma after bromine continuous generation Tuluntu 1992 39 341.(Dept. Appl. Phys. Fac. Sci. Univ. Cordoba Spain). Miirer A. J. L. Abildtrup A. Poulsen 0. M. Christen- sen J. M. Estimation of the method evaluation function for the determination of hydride-generating arsenic compounds in urine by flow injection atomic absorption spectrometry Tulunta 1992,39,469. (Dan- ish Natl. Inst. Occup. Health Dept. Chem. Biochem. Lend Parkalle 105 DK-2 100 Copenhagen Denmark). Asp T. N. Lund W. Elemental analysis of bovine liver by inductively coupled plasma atomic emission spectro- metry by using a simple dissolution procedure Tulunta 1992 39 563. (Dept. Chem. Univ. Oslo Box 1033 N- 0315 Oslo Norway). Xu S.-k. Sun L.-j. Fang Z.Application of the slotted quartz tube in flow injection flame atomic absorption spectrometry Tuluntu 1992 39 58 1. (Flow Injection Anal. Res. Centre Inst. Appl. Ecol. Acad. Sin. Box 41 7 1 100 1 5 Shenyang China). Vanhaecke F. Vanhoe H. Dams R. Vandecasteele C. Use of internal standards in ICP-MS Tulantu 1992,39 737. (Lab. Anal. Chem. Inst. Nucl. Sci. Univ. Ghent Proeftuinstr. 86 B-9000 Ghent Belgium). Ghaffari S. Ingle J. D. Jr. Optimization of atomic fluorescence measurements with a microcomputer- based time-multiplex multiple-slit spectrometer Tuluntu 1992 39 749. (Dept. Chem. Oregon State Univ. Gilbert Hall 153 Corvallis Oregon 9733 1-4003 USA). Goyal N. Purohit P. J. Page A. G. Sastry M. D. Direct determination of beryllium copper and zinc in A1-U matrices by electrothermal atomization atomic absorption spectrometry Tuluntu 1992,39,775. (Radi- ochem.Div. Bhabha At. Res. Centre Trombay Bom- bay 400 085 India). hemark U. Pettersson J. O h A Determination of total selenium in water by atomic absorption spectrome- try after hydride generation and preconcentration in a cold trap system Tuluntu 1992 39 1089. (Univ. Uppsala Dept. Anal. Chem. P.O. Box 531 S-751 21 Uppsala Sweden). Welz B. Schubert-Jacobs M. Guo T.-z. Investigations for the determination of tin by flow injection hydride generation atomic absorption spectrometry Taluntu 1992 39 1097. (Dept. Appl. Res. Perkin-Elmer Post- fach 10 176 1 D-88647 Uberlingen Germany). Cathum S. J. Atomization efficiency of a Massmann- type graphite furnace Tulunta 1992 39 12 19.(Centre Anal. Environ. Chem. Dept. Chem. Carleton Univ. Ottawa Ontario Canada K1S 5B6). Murakami M. Takada T. Application of APCD-DIBK extraction system in strongly acidic me- dia determination of traces of copper and nickel in titanium metals by extraction-flame atomic-absorption spectrometry Tuluntu 1992 39 1293. (Dept. Chem. Coll. Sci. Rikkyo Univ. Nishi-Ikebukuro Toshima-ku Tokyo 171 Japan). MacRae N. D. Bottazzi P. Ottolini L. Vannucci R. Quantitative REE analysis of silicates by SIMS conven- tional energy filtering versus specimen isolation mode Chem. Geol. 1993 103 45. (Dept. Geol. Univ. West- em Ontario London Ontario Canada N6A 5B7). Lea D. W. Boyle E. A. Determination of carbonate- bound barium in foraminifera and corals by isotope dilution plasma mass spectrometry Chem. Geol.1993 9313096. 9313097. 9313098. 9313099. 9313 100. 9313 101. 9313 9313 02. 03. 9313 104. 9313 105. 9313 106. 9313 107. 103 73. (Dept. Geol. Sci. Marine Sci. Inst. Univ. California Santa Barbara CA 93 106-9630 USA). Yokoyama T. Takahashi Y. Tarutani T. Simulta- neous determination of arsenic and arsenious acids in geothermal water Chem. Geol. 1993 103 103. (Gen- eral Educ. Coll. Kyushu Univ. Ropponmatsu Chuo- ku Fukuoka S 10 Japan). Totland M. Jarvis I. Jarvis K. E. Determination of the platinum group elements and gold in solid samples by slurry nebulization ICP-MS Chem. Geol. 1993,104 175. (School of Geol. Sci. Kingston Univ. Penrhyn Rd. Kingston-upon-Thames Surrey UK KT 1 2EE). Bohlke J. K. Irwin J. J. Laser microprobe analyses of noble gas isotopes and halogens in fluid inclusions analyses of microstandards and synthetic inclusions in quartz Geochim.Cosmochim. Actu 1992 56 187. (MS 43 1 Natl. Center US Geol. Survey Reston VA 22092 USA). Xiao Y.-k. Sun D.-p. Wang Y.-h. Qi H.-p. Jin L. Boron isotopic compositions of brine sediments and source water in Da Qaidam Lake Qinghai China Geochim. Cosmochim. Acta 1992 56 156 1. (Qinghai Inst. Salt Lakes Acad. Sin. China). Burruss R. C. Ging T. G. Eppinger R. G. Samson I. M. Laser-excited fluorescence of rare earth elements in fluorite initial observations with a laser Raman micro- probe Geochim. Cosmochim. Actu 1992,56 27 13. (US Geol. Survey Box 25046 MS 973 Denver CO 80225 USA). Anbar A. D. Creaser R. A. Papanastassiou D. A. Wasserburg G. J. Rhenium in sea-water confirmation of generally conservative behaviour Geochim.Cosmo- chim. Actu 1992 56 4099. (Lunatic Asylum Charles Arms Lab. Div. Geol. Planetary Sci. California Inst. Technol. Pasadena CA 91 125 USA). Perkins W. T. Pearce N. J. G. Jeffries T. E. Laser ablation inductively coupled plasma mass spectrometry a new technique for the determination of trace and ultra-trace elements in silicates Geochim. Cosmochim. Actu 1992 57 475. (Inst. Earth Studies Univ. Wales Aberystwyth Wales UK SY23 3DB). Saran R. Basu Baul T. S. Srinivas P. Khathing D. T. Simultaneous determination of trace heavy metals in waters by atomic absorption spectrometry after precon- centration by solvent extraction Anal. Lett. 1992 25 1545. (Chem. Lab. Dept. At. Energy At. Miner. Div.Reg. Centre Explor. Res. Shillong 793 01 1 India). Noelte J. Reliable inductively coupled plasma atomic- emission spectroscopic (ICP-AES) results. Optimization with aimed searching routines LuborPruxis 1992 16 332 3!4 338. (Perkin-Elmer Postfach 10 176 1 D- 88647 Uberlingen Germany). Zucheng J. Schramel P. Determination of trace amounts of molybdenum in water samples by induc- tively coupled plasma atomic emission spectrometry after cobalt-dithiocarbamate coprecipitation Fresen- ius’ J. Anal. Chem. 1992 343 600. (Inst. Ecol. Chem. GSF Res. Centre Environ. Health D-8042 Neuherberg Germany). Hoppstock K. Garten R. P. H. Tschopel P. Tolg G. Purification of reagents and separation of element traces by electrodeposition onto a graphite-tube cathode Fresenius’ J. Anal.Chem. 1992 343 778. (Lab. Rein- stoffanal. (LRA) Max Planck Inst. Metallforsch. 4600 Dortmund 1 Germany). Giinther H. Bock T. Frank C. Jacobs K. Determina- tion of foreign atoms in mercury cadmium telluride (Hg -,Cd,Te) by means of flameless AAS Fresenius’ J . Anal. Chem. 1992 343 756. (Versuchs Lehranstalt Brauereiwesen Spirituosenfabrikation Fermentation D- 1000 Berlin 65 Germany).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 327R 9313 108. 9313 109. 9313 1 10. 93/31 11. 9313 1 12. 93131 13. 9313 1 14. 9313 1 15. 9313 1 16. 9313 1 17. 9313 1 18. 9313 1 19. 9313 120. Meckel L. Analytical determination of trace element concentrations of precious metals and colouring oxides in optical glasses and communication light guides Fresenius’ J. Anal.Chem. 1992 343 751. (Schott Glaswerke D-6500 Mainz Germany). Pesch H.-J. Bloss S. Schukrt J. Seibold H. Mercury cadmium and lead content of cigarette to- bacco. Comparative analytical-statistical studies in 1987 and 1991 employing Zeeman AAS Fresenius’ J. Anal. Chem. 1992 343 152. (Inst. Pathol. Fac. Med. Univ. Erlangen-Nuremberg D-8520 Erlangen Ger- many). Sperling M. Yin X. We4 B. Determination of ultra- trace concentrations of elements by means of on-line solid sorbent extraction graphite furnace atomic absorp- tion spectrometry Fresenius’ J. Anal. Chem. 1992,343 754. (Dep! Appl. Res. Perkin-Elmer Postfach 101 76 1 D-88647 Uberlingen Germany). Wienke D. Kateman G. Multiresponse calibration with canonical variates in atomic emission spectro- scopy of powders Fresenius’ J.Anal. Chem. 1992,343 797. (Lab. Anal. Chem. Cathol. Univ. Nijmegen 6525 Nijmegen The Netherlands). Schierle C. Otto M. Wegscheider W. Neural network approach to qualitative analysis in inductively coupled plasma atomic emission spectroscopy (ICP-AES) Fre- senius’ J. Anal. Chem. 1992 343 561. (Dept. Chem. Inst. Chem. Bergakad Freiberg D-9200 Freiberg Germany). Sandoval L. Herraez J.-C. Steadman G. Mahan K. I. Determination of lead and cadmium in sediment slurries by ETAAS comparison of methods for the preparation and analysis of sediment slurries Mikro- chim. Ada 1992 108 19. (Dept. Chem. Univ. South- ern Colorado Pueblo CO 81001 USA). Schramel P. Xu L.-Q. Knapp G. Michaelis M. Application of an on-line preconcentration system in simultaneous ICP-AES Mikrochim.Acta 1992 106 19 1. (Inst. Oekolog. Chem. Gesellschaft Strahlen Um- weltforsch D-8042 Neuherberg Germany). Sdorra W. Brust J. Niemax K. Basic investigations for laser micro-analyis. IV. Dependence on the laser wavelength in laser ablation Mikrochirn. Acta 1992 108 1. (Inst. Spektrochem. Angew. Spektrosk. (ISAS) D-4600 Dortmund 1 Germany). D’Agostino A. T. Determination of thin metal film thickness by X-ray diffractometry using the Scherrer equation atomic absorption analysis and transmis- sion-reflection visible spectroscopy Anal. Chim. Acta 1992 262 269. (Dept. Chem. Univ. South Florida Tampa FL 33620 USA). Lobinski R. Adams F. C. Sensitive speciation analysis of lead in environmental waters by capillary gas chro- matography-microwave-induced plasma atomic emis- sion spectrometry Anal.Chim. Acta 1992 262 285. (Dept. Chem. Univ. Antwerp (UIA) 2610 Wilrijk Belgium). Posta J. Berndt H. Derecskei B. Comparison of droplet-size distribution and matrix effects in flame atomic absorption spectrometry applying hydraulic high-pressure performance nebulization and pneumatic nebulization Anal. Chim. Acta 1992 262 261. (Inst. Spektrochem. Angew. Spektrosk. D-4600 Dortmund 1 Germany). Zheng Y. Zhang D. Factors influencing the atomiza- tion of germanium in graphite furnace atomic absorp- tion spectrometry Anal. Chem. 1992 64 1656. (Dept. Chem. Jilin Univ. Changchun 130023 China). Fernando R. Calloway C. P. jun. Jones B. T. Continuum source atomic absorption spectrometry in an air-acetylene flame with improved detection limits 93/31 2 1.9313 122. 9313 123. 9313 124. 9313 125. 9313 126. 9313 127. 9313 128. 9313 129. 9313 130. 9313 13 1. 9313 132. 9313 133. 9313 134. Anal. Chem. 1992 64 1556. (Dept. Chem. Wake Forest Univ. Winston-Salem NC 27 109 USA). Su E. G. Irwin R. L. Liang Z. Michel R. G. Background correction by wavelength modulation for pulsed laser-excited atomic fluorescence spectrometry Anal. Chem. 1992 64 1710. (Dept. Chem. Univ. Connecticut Storrs CT 06269-3060 USA). Jin Q. Zhang H. Duan Y. Yu A Liu X. Wang L. Trace determination of sulfide and sulfur dioxide by vapour molecular absorption spectrometry using mag- nesium and tellurium hollow cathode lamps Talanta 1992 39 967. (Dept. Chem. Jilin Univ. Changchun China). Borszeki J. Knapp G. Halmos P. Bartha L. Sample preparation procedure for the determination of sulfur and trace metals in oil products by the ICP with a minitorch using emulsions Mikrochim.Acta 1 992,108 157. (Dept. Anal. Chem. Univ. Veszprem 8201 Veszprem Hungary). Zaray G. Kantor T. Wolff G. Zadgorska Z. Nickel H. ICP-AES detection of silicon carbide impurities volatilized in a graphite furnace with the use of carbon tetrachloride vapour Mikrochim. Acta 1992 107 345. (Dept. Inorg. Anal. Chem. L. Eotvos Univ. 1518 Budapest Hungary). Sdorra W. Niemax K. Basic investigations for laser micro-analysis. 111. Application of different buffer gases for laser-produced sample plumes Mikrochirn. Acta 1992 107 3 19. (Inst. Spektrochem. Angew. Spektrosk. D-4600 Dortmund 1 Germany). Chai 2. F. Synchrotron radiation X-ray fluorescence analysis technique Fenxi Shiyanshi 1992 11( 6) 39.(Inst. High Energy Phys. Acad. Sin. Beijing 100080 China). Kozuka S. Kon M. Hayashi M. Matsunaga H. Determination of uranium and thorium in high-purity titanium by ICP-MS after ion-exchange separation Bunseki Kagaku 1993 42 T19. (Res. Dev. Centre Toshiba Kanagawa 2 10 Japan). Xiong C. H. Jian B. L. Wang M. S. Determination of ultratraces of germanium in ground-water by hydride- generation ICP-AES after enrichment with tannic cellu- lose Fenxi Ceshi Tongbao 1992 11 64. (China). Du Y. Tang Y. Zhu M. Determination of elements in nickel naphthenate by air-argon ICP-AES Fenxi Ceshi Tongbao 1992 11 83. (Qiqihar Inst. Light Ind. Qiqihar China). Liu H. S. Direct ICP-AES determination of cerium praseodymium neodymium and samarium in lan- thanum oxide of optical grade 4N Lihua Jianyan Huuxue Fence 1992,28 298.(Beijing Gen. Inst. Chem. Eng. and Metall. Beijing 101 149 China). Fan J. Wang S. AAS determination of zinc in zinc concentrates Lihua Jianyan Huaxue Fence 1992 28 292. (Dept. Chem. Central-South Polytech. Univ. Changsha 4 10083 China). Liu B. L. Application of the sulfidation reaction in AES. Combined receiving-direct determination of tung- sten molybdenum tin bismuth and lead in geological samples Lihua Jianyan Huaxue Fence 1992 28 282. (Jiangxi Inst. Non-Ferrous Metals Geol. Nanchang 33020 1 China). Guo J. Elimination of interference in the AAS determi- nation of nickel (in ores) Lihua Jianyan Huaxue Fence 1992 28 307. (Southwest Geol. Prospect Bur. Inst. Minist.Metal]. Ind. Chengdu 6 1005 1 China). Lu Y. L. Non-dispersive AFS determination of traces of mercury in human hair and plants Lihua Jianyan. Huaxue Fence 1992 28 294. (Inst. Geogr. Chinese Acad. Sci. Beijing 100 10 1 China).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 328R 9313 135. 9313 136. 9313 137. 9313 9313 38. 39. 9313 140. 9313 14 1. 9313142. 9313 143. 9313 144. 9313 145. 9313 146. Zhang H. Y. Liu F. Y. Atomic-absorption spectropho- tometric determination of silver in high-purity cathode copper after its separation on mercaptoacetoxycellulose Lihua Jianyan Huaxue Fence 1992 28 280. (Beijing Gen. Res. Inst. Miner. Metall. Beijing 100037 China). Liu J. P. Chen Y. H. Zhu B. Determination of gold (in ore) by atomic absorption spectrometry with re- duced-pressure plastic foam absorption and thiourea desorption Fenxi Huaxue 1992 20 982.(Central Dept. Instrum. Tests Xinjiang Univ. Urumqi 830046 China). Deng S. L. Li X. F. Direct injection of suspension for determination of cadmium in soil by platform graphite furnace atomic absorption spectrometry Fenxi Huaxue 1992 20 985. (Changsha Inst. Agric. Modernization Chinese Acad. Sci. Changsha 410 125 China). Mei E. W. Jiang 2. C. Liao 2. H. Tungsten spiral electrothermal vaporization sample introduction-in- ductively coupled plasma atomic emission spectrometry for the determination of trace elements Fenxi Huaxue 1992 20 932. (Dept. Chem. Wuhan Univ. Wuhan 430072 China). Wang Y. M. Jiang 2 . M. Liang Y. Z. Han C. Jing B. New automatic atomic absorption spectrophoto- meter controlled by microcomputer with a Chinese processing system Fenxi Huaxue 1992 20 976.(Inst. Metal Res. Chinese Acad. Sci. Shenyang 11001 5 China). Chen K. R. Wang D. C. Standard additions method involving matrix calculation for the simultaneous deter- mination of multiple components (by ICP-AES) Fenxi Huaxue 1992 20 925. (Natl. Res. Centre Certified Reference Mater. Beijing 10001 3 China). Brooks D. S. Flatt J. R. Copper iron and sodium interferences in the determination of gold by atomic absorption spectrometry with particular reference to cyanide solutions Anal. Chim. Acta 1992 264 107. (Metal. Dept. Univ. South Australia Pooraka 5095 South Australia Australia). Rucandio M. I. Determination of lanthanoids and yttrium in rare earth ores and concentrates by induc- tively coupled plasma atomic emission spectrometry Anal.Chim. Acta 1992 264 333. (Centro Invest. Energ. Medioambientales Tecnol. (CIEMAT) 28040 Madrid Spain). Kojima I. Kato A. Iida C. Microwave digestion of biological samples with acid mixture in a closed double PTFE vessel for metal determination by ‘one-drop’ flame atomic absorption spectrometry Anal. Chim. Acta 1992 264 101. (Lab. Anal. Chem. Nagoya Inst. Technol. Nagoya 466 Japan). Franek M. Krivan V. Multi-element characterization of silicon nitride powders by instrumental and radioche- mica1 neutron activation analysis Anal. Chim. Acta 1992 264 345. (Sekt. Anal Hochstreinigung Univ. Ulm D-7900 Ulm Germany). Barth P. Krivan V. Hausbeck R. Cross-interferences of hydride-forming elements in hydride generation atomic absorption spectrometry Anal.Chim. Acta 1992 263 11 1. (Sekt. Anal. Hochstreinigung Univ. Ulm D-7900 Ulm Germany). Ali A. H. Winefordner J. D. Micro-sample introduc- tion by tungsten filament electrode into capacitively coupled microwave plasma for atomic emission spec- troscopy diagnostics Anal. Chirn. Acta 1992,264,3 19. (Chem. Dept. Univ. Florida Gainesville FL 326 1 1 USA). 9313 146a. Ali H. Winefordner J. D. Microsample introduction by tungsten filament electrode into capacitively coupled microwave plasma for atomic emission spectroscopy analytical figures of merit Anal. Chim. Acta 1992 264 9313147. 9313 148. 9313 149. 9313 150. 9313 15 1. 9313 152. 9313 153. 9313 154. 9313 155. 9313 156. 9313 157. 93/31 58. 9313 9313 59. 60.327. (Chem. Dept. Univ. Florida Gainesville FL 3261 1 USA). Postma G. J. Kateman G. Quality of analytical information contained within abstracts and papers on new analytical methods Anal. Chim. Acta 1992 265 133. (Dept. Anal. Chem. Univ. Nijmegen 6525 ED Nijmegen The Netherlands). Mincey D. W. Williams R. C. Giglio J. J. Graves G. A. Pacella A. J. Temperature controlled micro- wave oven digestion system Anal. Chim. Acta 1992 264 97. (Dept. Chem. Youngstown State Univ. Youngstown OH 44555 USA). Cumpson P. J. Seah M. P. Random uncertainties in AES and XPS (X-ray photoelectron spectroscopy). 11. Quantification using either relative or absolute measure- ments SIA Surf Interface Anal. 1992 18 361. (Div. Mater. Metrol. Natl. Phys. Lab. Teddington Middle- sex UK TW11 OLW).Evans S. Estimation of the uncertainties associated with XPS (X-ray photoelectron spectroscopy) peak- intensity determination SIA Surf Interface Anal. 1992 18 323. (Chem. Centre. Dept. Biochem. Univ. Coll. Wales Penglais Aberystwyth Dyfed SY23 3DD UK). Harrison K. Hazell L. B. Determination of uncertain- ties in quantitative XPS (X-ray photoelectron spectros- copy) AES and its impact on data acquisition strategy SIA Surf Interface Anal. 1992 18 368. (Sunbury Res. Centre BP Research Sunbury on Thames Middlesex UK TW16 7LN). Cumpson P. J. Seah M. P. Random uncertainties in AES and XPS (X-ray photoelectron spectroscopy). I. Uncertainties in peak energies intensities and areas derived from peak synthesis SIA Surf Interface Anal. 1992 18 345. (Div. Mater. Metrol.Natl. Phys. Lab. Teddington Middlesex UK TW 1 1 OLW). Aguilera J. A Aragon C. Campos J. Determination of carbon content in steel using laser-induced break- down spectroscopy Appl. Spectrosc. 1992 46 1382. (Catedra Fis. At. Fac. Cienc. Fis. Univ. Complutense Madrid 28040 Madrid Spain). Veber M. Koropchak J. A. Conver T. S. Herries J. Matrix-effects studies with fused-silica aperture ther- mospray sample introduction to ICP-AES Appl. Spec- trosc. 1992 46 1525. (Dept. Chem. and Biochem. Southern Illinois Univ. Carbondale IL 6290 1 USA). Chowdary G. S. Satyanarayana K. Mathur N. Deter- mination of beryllium by ICP-AES in beryl samples and silicate rocks At. Spectrosc. 1992 13 213. (At. Miner- als Div. Dept. At. Energy Hyderabad 500 116 India). Ericson S. P. Tips for aluminium determination (in pharmaceuticals) at ultra-trace levels At.Spectrosc. 1992 13 208. (Baxter Healthcare Round Lake IL 60073 USA). Davidson R. A. Gold determination in geological materials by amyl acetate extraction and flame AAS At. Spectrosc. 1992 13 199. (Salt Lake City Res. Center Bur. Mines US Dept. Interior Salt Lake City UT 84108 USA). Neubauer J. Maier K. Comparison of the flow injection hydride system with a continuous-flow system for on-line determination of bismuth At. Spectrosc. 1992 13 206. (MTU Motoren. Turbinen-Union Mun- chen GmbH D-8000 Munich 50 Germany). Roelandts I. Determination of ten rare earth elements in rare earth ores by inductively coupled plasma atomic emission spectrometry At. Spectrosc. 1992 13 193. (Dept. Geol. Petrol. Geochem.Univ. Liege Liege 1 Belgium). An Y. Willie S. N. Sturgeon R. E. Flow injection hydride generation determination of arsenic with in situJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 329R 9313 1 6 1. 9313 162. 93t3163. 9313 164. 9313 9313 65. 66. 9313 167. 9313 168. 9313169. 9313 170. 9313 I 7 1. 93/31 72. 9313 173. concentration in a graphite furnace Spectrochim. Acta Part B 1992 47B 1403. (Inst. Environ. Chem. Natl. Res. Council Canada Ottawa Ontario KIA OR9 Canada). Ganeyev A. A. Sholupov S. E. New Zeeman atomic absorption spectroscopy approach for mercury isotope analysis Spectrochim. Acta Part B 1992 47B 1325. (Inst. Chem. St. Petersburg State Univ. St. Petersburg 199034 Russia). Irwin R. L. Wei G.-T. Butcher D. J. Liang Z. Su E. G.Takahashi J. Walton A. P. Michel R. G. Transverse Zeeman background correction for graphite furnace laser-excited atomic fluorescence spectrometry determination of lead and cobalt in standard reference materials Spectrochim. Acta Part B 1992 47B 1497. (Dept. Chem. Univ. Connecticut Storrs CT 06269 USA). Tang Y. Q. Du Y. P. Shao J. C. Liu C. Tao W. Zhu M. H. Air-argon inductively coupled plasma for organic solution analysis spectral characteristics and analytical performances Spectrochim. Acta Part B 1992 47B 1353. (Anal. Res. Centre East China Inst. Chem. Technol. Shanghai 200237 China). L’vov B. V. Polzik L. K. Fedorov P. N. Slavin W. Extension of the dynamic range in Zeeman graphite- furnace atomic absorption spectrometry Spectrochim. Acta Part B 1992 47B 141 1.(Dept. Anal. Chem. St. Petersburg Tech. Univ. St. Petersburg 19525 1 Russia). Ivaldi J. C. Tracy D. Bamard T. W. Slavin W. Multivariate methods for interpretation of emission spectra from the inductively coupled plasma Spectro- chirn. Acta Parf B 1992 47 1361. (Perkin-Elmer Norwalk CT 06859-0293 USA). Yang J. Piao Z. Zeng X. Zhang Z. Chen X. Evaluation of the reliability of Kalman filtering results in inductively coupled plasma atomic emission spectro- metry Spectrochim. Acta Part B 1992 47 1055. (Changchun Inst. Appl. Chem. Acad. Sin. Changchun 130022 China). Wang P. X. Holcombe J. A. Pressure-regulated elec- trothermal atomizer for atomic absorption spectrome- try Spectrochim. Acta Part B 1992 47 1277. (Dept. Chem. and Biochem. Univ. Texas Austin TX 78712 USA).Fukumoto N. Kobayashi Y. Kurahashi M. Develop- ment of a high spatial resolution X-ray fluorescence element mapping spectrometer for non-destructive ana- lysis of biological samples Bunseki Kagaku 1992 41 545. (Natl. Chem. Lab. Ind. Ibaraki 305 Japan). Maruta T. Yokoyama S. Kobayashi H. Yamane T. Simultaneous determination of the major and minor elements in high-purity mullite by XRF analysis Bun- seki Kagaku 1992 41 589. (Central Res. Lab. Chi- chibu Cement Saitarna 360 Japan). Yonemori S. Ichikura E. Sugizaki M. Determination of the comonomer content in tetrafluoro- ethylene-perfluoro(propylviny1 ether) copolymers by XRF analysis Bunseki Kagaku 1992 41 593. (Res. Centre Asahi Glass Kanagawa 22 1 Japan). Zagorodnii V. V. Influence of physico-mechanical characteristics of powdered materials on the intensity of XRF spectra of elements Zh.Anal. Khim. 1992 47 1428. (E. 0. Paton Inst. Electric Welding Ukrainian Acad. Sci. Kiev The Ukraine). Eksperiandova L. P. Kvyatkovskii S. F. Kravtsova K. F. Shevtsov N. I. Blank A. B. Non-destructive XRF determination of titanium in ticor monocrystals Zh. Anal. Khirn. 1992 47 937. (Inst. Monocrystals Ukr. Acad. Sci. Kharkov The Ukraine). Liu G. Q. Wang C. X. Xie B. Wu W. H. Determina- tion of arsenic by flow injection analysis with hydride generation spectrophotometry Fenxi Huaxue 1992,20 9313 174. 93/31 75. 9313 176. 9313177. 9313 178. 9313 179. 9313 180. 9313 18 1. 93/3 182. 9313 183. 9313 184. 9313 185. 9313 186. 810. (Dept. Environ. Eng. Hebei Inst. Chem. Technol. Light Ind. Shijiazhuang 05001 8 China).Luo X. G. Guo M. X. Zhu D. X. Simultaneous determination of high concentration phosphorus and other major elements in phosphate rocks and phospho- rus-containing fertilizers by inductively coupled plasma atomic emission spectrometry Fenxi Huaxue 1992 20 866. (Inst. Compd. Fertilizer Shanghai Chem. Eng. Inst. Minist. Chem. Ind. Shanghai 200062 China). Qi W. D. Yuan F. Determination of praseodymium samarium dysprosium holmium thulium and yttrium in high-purity erbium oxide by inductively coupled plasma atomic emission spectrometry Fenxi Huaxue 1992 20 787. (Changchun Inst. Appl. Chem. Chinese Acad. Sci. Changchun 130022 China). Wang J. Zheng Y. Determination of strontium by micro-sampling acetylene-air flame atomic absorption spectrometry in the presence of sulfosalicylic acid Gaodeng Xuexiao Huaxue Xuebao 1992 13 163.(Pharm. Teach. Group Dalian Med. Officer Sch. Dalian 1 1601 3 China). Koenig H. P. Hertel R. F. Koch W. Rosner G. Determination of platinum emissions from a three-way catalyst-equipped gasoline engine Atmos. Environ. Part A 1992 26 741. (Fraunhofer Inst. Toxicol. Aerosol Res. D-3000 Hannover 6 I Germany). Shuman L. M. Bandel V. A. Donohue S. J. Isaac R. A. Lippert R. M. Sims J. T. Tucker M. R. Compari- son of Mehlich- 1 - and Mehlich-3-extractable soil boron with hot-water-extractable boron Commun. Soil Sci. Plant Anal. 1992 23 I. (Dept. Agron. Univ. Georgia Georgia Exp. Stn. Griffin GA 30223 USA). Miaokang S. Yinyu S. Determination of lanthanum europium and ytterbium in food samples by electrother- mal atomic absorption spectrometry J.AOAC Int. 1992,75,667. (Hangzhou Health & Anti-Epidemic Stn. Hangzhou 3 10006 China). Coleman M. E. Elder R. S. Basu P. Koppenaal G. P. Trace metals in edible tissues of livestock and poultry J. AOAClnt. 1992 75 61 5. (Food Safety Insp. Sen. US Dept. Agric. Washington D.C. 20250 USA). Wall P. Standardless XRF analysis solves waste dis- posal control problem Lab. Equip. Dig. 1992,30(3) 15. (Philips Analytical Almelo The Netherlands). Sun S. Q. Zhu J. Y. Application of XRF in the field analysis of carbon steels alloy steels and slags Lihua Jianyan Huaxue Fence 1992,28,300,3 17. (East China Inst. Chem. Tech. Shanghai 200237 China). Gries W. H. Angle-resolved self-ratio technique for surface depth-profile investigations by XFS (X-ray fluorescence spectroscopy) EMA (electron micro-beam analysis) XPS (X-ray photoelectron spectroscopy) and AES (Auger electron spectroscopy) Mikrochim.Acta 1992 107 117. (Res. Inst. Deutsche Bundespost TE- LEKOM D-6 100 Darmstadt Germany). Van Grieken R. E. Markowicz A. A. Handbook of X- ray Spectrometry. Methods and Techniques Marcel Dekker New York NY USA. (Dept. Chem. Univ. Antwerp (UIA) Universiteitsplein I B-26 10 Antwerp- Wilryk Belgium). Filimonov L. N. Neiman E. Ya. Volkovinskii V. V. Specifications of International Standards Organisation standards relating to chemical analysis Zavod. Lab. 1992 58 6. (State Sci. Res. Inst. Rare Metals Ind. Moscow Russia). Vershinin S. L. Mishina E. I. Pimenov V. G. Churbanov M. F. Atomic emission analysis of high- purity xenon difluoride Vysokochist.Veshchestva 199 1 6 173. (Inst. Chem. High-Purity Mater. Acad. Sci. Nizhnii Novgorod Russia).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 330R 9313 187. 9313 188. 9313 189. 9313 190. 93/3191. 9313 9313 92. 93. 9313 194. 9313 195. 93/ 3 1 96. 9313197. 9313 198. 9313 199. 9313200. 93/320 1. Southgate D. A. T. Trace elements databases and food composition compilations Food Chem. 1992 43 289. (AFRC Inst. Food Res. Colney Norwich UK NR4 7UA). Liebmann L. W. Robinson J. A. Mann K. G. Dual beam total internal-reflection fluorescence spectrometer for dynamic depth resolved measurements of biochemi- cal liquid/solid interface binding reactions in opaque solvents Rev. Sci. Instrum. 1991 62 2083. (Dept.Biochem. Given Bldg. Health Sci. Complex Coll. Med. Univ. Vermont Burlington VT 05405 USA). Hwang 2. W. Teng Y. Y. Characterization and some further observations of a laser-ablated plasma Spec- trosc. Lett. 1991 24 1173. (Dept. Phys. Univ. Lowell Lowell MA 01 854 USA). Masamba W. R. L. Smith B. W. Winefordner J. D. Direct introduction of steel samples into a capacitively coupled microwave plasma for atomic emission spectro- metry Appl. Spectrosc. 1992 46 1741. (Dept. Chem. Univ. Florida Gainesville FL 326 1 1 USA). Eames J. C. O’Keefe C. J. Dotter L. E. Practical design for an ICP demountable plasma torch Appl. Spectrosc. 1992 46 1745. (Div. Explor. Geosci. CSIRO North Ryde New South Wales 2113 Australia). Milella E. Sentimenti E. Mazzetto G. Analysis of impurities in high-purity copper by Zeeman graphite furnace AAS At.Spectrosc. 1993 14 1. (Centro Nazl. Ric. Sviluppo Mater. (CNRSM) 72023 Mesagne Italy). Bertagnolli J. A. Neylan D. L. Hammargren D. D. Effect of surfactants on ICP analytical performance At. Spectrosc. 1993 14 4. (Salt Lake City Res. Center Bur. Mines US Dept. Interior Salt Lake City UT 84108- 1283 USA). Morales-Rubio A Salvador A. De la Guardia M. Ros R. Determination of cadmium and nickel in rice plants by flame atomic absorption spectrometry At. Spectrosc. 1993 14 8. (Dept. Quim. Anal. Dept. Biol. Vegetal Univ. Valencia 46 100 Burjassot Spain). Kharbade B. V. Agarwal K. C. Determination of tin in ancient copper art objects by flame atomic absorption spectrometry-solvent extraction method At. Spectrosc.1993 14 13. (Natl. Res. Lab. Conserv. Cultural Pro- perty Lucknow 226 020 India). Lust A. Atomic spectroscopy bibliography for July- December 1992 At. Spectrosc. 1993 14 16. (Perkin- Elmer Norwalk CT 06859-0105 USA). Fujimoto K. Okano T. Matsumura Y. Determination of trace elements in solid samples by ICP-AES utilizing direct sample insertion technique Bunseki Kagaku 1992 41 609. (Tech. Res. Div. Kawasaki Steel Chiba 260 Japan). Ichikawa G. Kubota Y. Tsukahara R. Analysis of non-ferrous metals. Vanadium chromium manganese cobalt and nickel Bunseki 1992 6 458. (Japan). Liang Y. Application of the three-point regression method in atomic absorption spectrometric analysis Yankuang Ceshi 199 1 10 282. (Bose Prefect. Ind. Res. Inst. Bose 533000 Guangxi Prov. China).Koval’chuk L. I. Kobeleva L. V. Sorption concentra- tion and atomic emission determination of some trace elements in fresh waters Khim. Tekhnol. Vody 1992 14,418. (A. V. Bogatskii Phys. Chem. Inst. Odessa The Ukraine Russia). Chmilenko F. A. Baklanov A. N. Atomic absorption determination of toxic and biologically active trace elements in dairy products with use of ultrasonics for acceleration of digestion Zh. Anal. Khim. 1992 47 1 322. (Dnepropetfovsk State Univ. Dnepropetrovsk The Ukraine). 9 3/32O2. 93/ 3203. 9 313204. 9313205. 9313206. 9313207. 9313208. 9313209. 93/32 10. Pupyshev A. A. Muzgin V. N. Vasil’eva N. L. Kostenko T. K. Mel’nikova E. K. Thermodynamic simulation of element atomization in acetylene-air acetylene-nitrous oxide propane (butane)-nitrous oxide and methylacetylene-air flames Zh.Anal. Khim. 1992 47 1378. (Ural Polytech. Inst. Sverdlovsk Russia). Bortlisz J. Krone R. Vollenberg U. Experiences with a computer-supported inductively coupled plasma atomic emission spectrometer Gewaesserschutz Was- ser Abwusser 199 1 124 89. (Emschergenossensch. Lipperverband D-4300 Essen Germany). Lavrinenko A. I. Finegold M. I. Accelerated atomic absorption analysis of lead in petrols with self-atomiza- tion of samples Znt. Labmate 1991 16(4) 25. Leeman Labs Increased sample throughput using an kchelle ICP AES spectrometer Int. Lab. 1993 23 25 28. (Leeman Labs Lowell MA USA). Lopez-Artiguez M. Camean A. Repetto M. Precon- centration of heavy metals in urine and quantification by inductively coupled plasma atomic emission spectro- metry J.Anal. Toxicol. 1993 17 18. (Inst. Nacl. Toxicol. 4 1080 Seville Spain). Burkhard E. G. Mehmood G. Husain L. Determina- tion of trace elements in cloud water and aerosols using instrumental neutron activation analysis and hydride generation with atomic absorption spectrometry J. Radioanal. Nucl. Chern. 1992 161 101. (Dept. Envi- ron. Health Toxicol. Sch. Public Health State Univ. New York Albany NY 1220 1-0509 USA). Phelan V. Plasma-emission (AES) for multiple ele- ments Lab. Equip. Dig. 1992 30(7) 27 29. (Instru- ments SA Stanmore Middlesex UK). Lower S. What’s in a NAMAS (National Measurement Accreditation Service) certificate? Lab. Equip. Dig. 1992 30( lo) 47. (NAMAS Executive Teddington Middlesex UK). Cammann K. Analytical chemistry-today’s definition and interpretation Fresenius’ J. Anal.Chern. 1992 343 812. (Inst. Chem. Biochem. Sensor Res. Westfal- ishe Wilhelms Univ. D-4400 Munster Germany). 93/32 1 Oa. Valcarcel M. Analytical chemistry-today’s definition and interpretation Fresenius’ J. Anal. Chem. 1992 343 8 14. (Dept. Anal. Chem. Fac. Sci. Univ. Cordoba 14004 Cordoba Spain). 931321 1. Zuckerman A. M. Analytical Chemistry-today’s de- finition and interpretation Fresenius’ J. Anal. Chem. 1992 343 817. (Inst. History Sci. Technol. Russian Acad. Sci. Moscow 1030 12 Russia). 93/32 1 la. Nan. 2.. Analvtical chemistrv-todav’s definition and 93/32 93/32 93/32 93/32 interpretation,. Fresenius’ J. -Anal. dhem. 1992 343 8 19. (Shanghai Res. Inst. Mater. 200025 Shanghai China). 2. Koch K. H. Analytical chemistry-today’s definition and interpretation Fresenius’ J.Anal. Chem. 1992 343 821. (Chem. Lab. Hoesch Stahl AG D-4600 Dortmund Germany). 2a. Perez-Bustamanate J. A. Analytical chemistry-to- day’s definition and interpretation Fresenius’ J. Anal. Chem. 1992,343 823. (Dept. Quim. Anal. Fac. Cienc. Univ. Puerto Real Cadiz Spain). 3. Ortner H. M. Analytical chemistry-today’s definition and interpretation Fresenius’ J. Anal. Chem. 1992 343 825. (FB 2 1 Materialwissenschaft Fachgebeit Chem. Anal. Tech. Hochsch. Darmstadt D-6 100 Darmstadt Germany). 3a. Darner K. Analytical chemistry-today’s definition and interpretation Fresenius’ J. Anal. Chem. 1992 343 827. (Lehrstuhl Anal. Chem. Fak. Friedrich Schiller Univ. D-6900 Jena Germany).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 331R 93/32 14. Green J. D. Analytical chemistry-today’s definition and interpretation Fresenius’ J. Anal. Chem. 1992 343 829. (Hull Res. Centre BP Chemicals Hull UK). 93132 14a. Stulik K. Zyka J. Analytical chemistry-today’s definition and interpretation Fresenius’ J. Anal. Chem. 1992 343 832. (Dept. Anal. Chem. Charles Univ. I2840 Prague 2 Czechoslovakia). 9313215. Ducauze C. J. Bermond A. P. Application of the standard additions method to the determination of specific and non-specific absorption in atomic absorp- tion spectrometry Analusis 1992,20 493. (Lab. Chim. Anal. Inst. Natl. Agronomique Paris-Grignon 7523 1 Paris 05 France). 93132 15a. Kuznetsov. V. I. Analytical chemistry-today’s defini- 93132 93132 93132 93/32 19.9313220. 931322 1. 9 3/32 22. 9313223. 9313224. 9 31322 5 . tion and interpretation; Fresenius’J. Anal. Chem. 1992 343 834. (Inst. History Sci. Technol. Russian Acad. Sci. Moscow Russia). Steiner J. D. ICP-AES instrumentation a new concept Analusis 1992 20( 8) M38. (ARL Applied Research Laboratories SA 1024 Ecublens Switzerland). Auffray A. Good laboratory practice and accreditation Analusis 1992 20(9) M14. (Lab. SGS Qualitest Agro- alimentaire 75024 Paris France). Le Bihan A. Cabon J. Y. Elleouet C. Spectral interference related to the presence of nitrate and nitrogen monoxide in Zeeman-corrected atomic absorp- tion spectrometry with electrothermal atomization An- alusis 1992 20 601. (Fac. Sci. Univ. Bretagne Occi- dentale 29275 Brest France). Hill S. J. Bloxham M.J. Worsfold P. J. Chromato- graphy coupled with inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. A review J. Anal. At. Spectrom. 1993 8 499. (Dept. Environ. Sci. Univ. Plymouth Plymouth Devon UK PL4 8AA). Dawson J. B. Snook R. D. Price W. J. Background and background correction in analytical atomic spectro- metry. Part 1. Emission spectrometry-a tutorial re- view J. Anal. At. Spectrom. 1993 8 517. (Dept. Instrum. Anal. Sci. Univ. Manchester Inst. Science Technol. P.O. Box 88 Manchester M60 IQD UK). Morgan C. A. Smith B. W. Winefordner J. D. Measurement of inductively coupled plasma infrared atomic emission of carbon and oxygen from alcohols using Fourier transform infrared spectrometry J. Anal. At. Spectrom. 1993 8 539.(Dept. Chem. Univ. Florida Gainesville FL 326 1 1 USA). Pretty J. R. Cmso J. A Signal enhancement of lead and thallium in inductively coupled plasma atomic emission spectrometry using on-line anodic stripping voltammetry J. Anal. At. Spectrom. 1993 8 545. (Dept. Chem. Univ. Cincinnati Cincinnati OH 4522 I - 0172 USA). Bailey E. H. Kemp A. J. Ragnarsdottir K. V. Determination of uranium and thorium in basalts and uranium in aqueous solution by inductively coupled plasma mass spectrometry J. Anal. At. Spectrom. 1993 8 551. (Dept. Geol. Univ. Bristol Wills Memorial Bldg. Queens Rd. Bristol BS8 lRJ UK). Larsen E. H. Pritzl G. Hansen S. H. Speciation of eight arsenic compounds in human urine by high- performance liquid chromatograpy with inductively coupled plasma mass spectrometric detection using antimonate for internal chromatographic standardiza- tion J.Anal. At. Spectrom. 1993 8 557. (Natl. Food Agency Central Lab. 19 Mdrkhdj Bygade DK-2860 Sdborg Denmark). Krishna Prabhu S. Vijayalakshmi S. Mahalingam T. R. Viswanathan K. S. Mathews C. K. Laser vaporization inductively coupled plasma mass spectro- metry a technique for the analysis of small volumes of solutions J. Anal. At. Spectrom. 1993 8 565. (Radio- 9313226. 9313227. 9313228. 9313229. 9313230. 931323 1. 9313232. 93/32 33. 9313234. 9313235. 9313236. chem. Prog. Indira Gandhi Centre At. Res. Kalpakkam 603 102 India). Story W. C. Caruso J. A. Gas chromatographic determination of phosphorus sulfur and halogens using a water-cooled torch with reduced-pressure helium microwave-induced plasma mass spectrometry J.Anal. At. Spectrom. 1993 8 571. (Dept. Chem. Univ. Cincinnati Cincinnati OH 4522 1-0 173 USA). Tao G.-h. Fang 2.-h. Determination of trace and ultra-trace amounts of germanium in environmental samples by preconcentration in a graphite furnace using a flow injection hydride generation technique J. Anal. At. Spectrorn. 1993 8 577. (Flow Injection Anal. Res. Centre Inst. Appl. Ecol. Chinese Acad. Sci. Box 417 1 I00 15 Shenyang China). Hanna C. P. Haigh P. E. Tyson J. F. McIntosh S. Examination of separation efficiencies of mercury va- pour for different gas-liquid separators in flow injection cold vapour atomic absorption spectrometry with amal- gam preconcentration J. Anal. At. Spectrom. 1993 8 585. (Chem.Dept. Univ. Massachusetts Amherst MA 01003 USA). Liang L. Bloom N. S. Determination of total mercury by single-stage gold amalgamation with cold vapour atomic spectrometric detection J. Anal. At. Spectrom. 1993,8 59 1. (Brooks Rand 3950 6th Ave. NW Seattle WA 98 107 USA). Ohta K. Sugiyama T. Inui S.-y. Sumki T. Mizuno T. Determination of sodium by sequential metal va- pour elution analysis with hydrogen carrier gas J. Anal. At. Spectrom. 1993 8 595. (Dept. Chem. Mater. Mie Univ. Mie Tsu 514 Japan). Byme J. P. Lamoureux M. M. Chakrabarti C. L. Ly T. Gregoire D. C. Mechanisms of chloride interfer- ences in atomic absorption spectrometry using a graph- ite furnace atomizer investigated by electro- thermal vaporization inductively coupled plasma mass spectrometry.Part 2. Effect of sodium chloride matrix and ascorbic acid chemical modifier on manganese J. Anal. At. Spectrom. 1993 8 599. (Dept. Chem. Univ. Technol. Sydney P. 0. Box 123 Broadway New South Wales 2007 Australia). Boer P. Fransen R. Boer W. H. Koomans H. A. Increased performance in electrothermal atomic absorp- tion spectrometry of lithium in renal tubular fluid by use of tantalum foil J. Anal. At. Spectrom. 1993 8 61 1. (Univ. Hosp. Utrecht Dept. Nephrol. Hypertension P.O. Box 85500 3508 GA Utrecht The Netherlands). Granadillo V. A. Romero R. A. Graphite furnace atomization behaviour of lead contained in clinical and environmental materials in the presence of palladium- induced isoformation and citric acid J. Anal. At. Spectrom. 1993 8 615. (Lab. Instrum. Anal.Fac. Exper. Cienc. Univ Zulia Maracaibo Zulia Venezu- ela). Gilchrist G. F. R. Chakrabarti C. L. Cheng J.-g. Hughes D. M Mechanisms of atomization of lead from nitric acid hydrochloric acid and sodium chloride matrices in atomic absorption spectrometry using a graphite probe furnace J. Anal. At. Spectrom. 1993 8 623. (Centre Anal. Environ. Chem. Dept. Chem. Carleton Univ. Ottawa Canada KlS 5B6). Liao Y.-p. Li A.-m. Indium hydride generation atomic absorption spectrometry with in situ preconcentration in a graphite furnace coated with palladium J. Anal. At. Spectrom. 1993 8 633. (Dept. Chem. Peking Univ. Beijing 10087 1 China). Docekal B. Krivan V. Determination of trace elements in high-purity molybdenum trioxide by slurry sampling electrothermal atomic absorption spectrometry J.Anal. At. Spectrom. 1993 8 637. (Sekt. Anal. Hochstreini- gung Univ. Ulm Albert Einstein Allee 11 D-W-7900 Ulm Germany).332R 9313237. 9313238. 9313239. 9313240. 931324 1. 9313242. 9313243. 9313244. 9313245. 9313246. 9313247. 9313248. 9313249. JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Laborda F. Chakraborti D. Mir J. M. Castillo J. R. Selenium speciation by high-performance liquid chro- matography-fraction collection-electrothermal atomic absorption spectrometry optimization of critical para- meters J. Anal. At. Spectrom. 1993,8,643. (Dept. Anal. Chem. Univ. Zaragoza 50009 Zaragoza Spain). Beceiro-Godlez E. Bermejo-Barrera P. Bermejo- Barrera A Barciela-Garcia J. Barciela-Alonso C. Speciation of chromium by the determination of total chromium and chromium(I1x) by electrothermal atomic absorption spectrometry J.Anal. At. Spectrom. 1993,8 649. (Anal. Chem. Nutr. Bromatol. Dept. Fac. Chem. 15706 Santiago de Compostela Spain). Soares M. E. Bastos M. L. Ferreira M. A. Determi- nation of copper iron aluminium lead and cadmium in cork stoppers by electrothermal atomic absorption spectrometry J. Anal. At. Spectrom. 1993,8 655. (Fac. Pharm. R. Anibal Cunha 164 4000 Porto Portugal). Larsen E. H. Blais J.-S. Performance of a modular thermospray interface for signal enhancement in flame atomic absorption spectrometry coupled on-line to flow injection or liquid chromatography J. Anal. At. Spec- from. 1993 8 659. (McGill Univ. Macdonald Cam- pus Dept. Food Sci.1Agric. Chem. 2 1 1 1 1 Lakeshore Rd.Ste-Anne de Bellevue Quebec Canada H9X 3V9). Jimenez M. S. Mir J. M. Castillo J. R. On-line thermospray continuous volatilization of cobalt alumi- nium and chromium volatile chelates and determina- tion by heated quartz tube atomic absorption spectro- metry J. Anal. At. Spectrom. 1993,8 665. (Dept. Anal. Chem. Sci. Fac. Univ. Zaragoza 50009-Zaragoza Spain). Mei E.-w. Jiang Z.-c. Liao Z.-h. Determination of trace amounts of rare earth and other elements in rice samples by ICP-AES with sample introduction by tungsten-coil electrothermal vaporization Fresenius’ J. Anal. Chem. 1992 344 54. (Dept. Chem. Wuhan Univ. Wuhan China 430072). Vidal J. C. Sang J. M. Castillo J. R. Speciation of chromium(vI)-chromium(xx1) by electrothermal atomi- zation AAS after electrodeposition on a L‘vov platform Fresenius’ J.Anal. Chem. 1992 344 234. (Fac. Sci. Univ. Zaragoza Zaragoza Spain E-50009). Luecke W. Systematic investigation of aluminium interferences with the alkaline earths in flame atomic absorption spectrometry. Part 11. Behaviour of magne- sium and calcium Fresenius’ J. Anal. Chem. 1992,344 242. (Inst. Petrogr. Geochem. Univ. Karlsruhe D-7500 Karlsruhe Germany). Vollrath A. 0% T. Hohl C. Seiler H. G. Compari- son of dissolution procedures for the determination of cadmium and lead in plastics Fresenius’J. Anal. Chem. 1992 344 269. (Kanton. Lab. Basel-Stadt CH-4012 Basel Switzerland). Ohlsson K. E. A. Iwamoto E. Frech W. Cedergren A. Transfer of aluminium compounds and spike atomi- zation in a spatially isothermal graphite atomizer Spectrochim.Acta Part B 1992 47 1341. (Dept. Anal. Chem. Univ. Umea S-901 87 Umea Sweden). Jacksier T. Jahl M. J. Barnes R. M. Noise power spectral characteristics of a sealed inductively coupled plasma for atomic emission spectroscopy Spectrochim. Acta Part B 1992,47 1373. (Lederle Grad. Res. Cent. Univ. Massachusetts Amherts MA 0 1003-0035 USA). Ogilvie C. M. Famsworth P. B. Correlation spectros- copy as a probe of excitation and ionization mecha- nisms in the inductively coupled plasma Spectrochim. Acta Part B 1992 47 1389. (Dept. Chem. Brigham Young Univ. Provo UT 84602 USA). Blain L. Salin E. D. Application of silver chloride as a thermochemical additive for the determination of re- fractory elements in solid sediment samples by direct 9313250. 931325 1.9313252. 9 3/32 5 3. 9313254. 93/32 5 5. 931325 6. 9313257. 9 3/32 5 8. 931325 9. 9313260. 931326 1. sample insertion inductively coupled plasma atomic emission spectrometry Spectrochim. Acta Part B 1992 47 1471. (Dep. Chem. McGill Univ. Montreal Que- bec Canada H3A 2K6). Bacon J. R. Ellis A. T. McMahon A. W. Potts P. J. Williams J. G. Atomic spectrometry update- atomic mass spectrometry and X-ray fluorescence spec- trometry J. Anal. At. Spectrum. I992,7,279R. (Macau- lay Land Use Res. Inst. Craigiebuckler Aberdeen UK AB92QJ). Kitagawa K. Electronics and computer techniques in analytical chemistry. Applications to atomic spectrome- try Bunseki 1992 8 594. (Eng. Coll. Nagoya Univ. Nagoya Japan). Su Z.-x. Chang X.-j. Xu K.-l. Luo X.-y. Zhan G.-y. Efficiency and mechanism of macroporous poly(viny1thiopropionamide) chelating resin for adsorb- ing and separating noble metal ions and determination by atomic spectrometry Anal. Chim.Acta 1992 268 323. (Dept. Chem. Lanzhou Univ. Lanzhou China 730000). Fang Z.-h. Sperling M. Welz B. Comparison of three propulsion systems for application in flow injection zone penetration dilution and sorbent extraction pre- concentration for flame atomic absorption spectrome- try Anal. Chim. Acta 1992 269 9. (Dept. Appl. Res. Bodenseewerk Perkin-Elmer GmbH Postfach 10 176 1 D-88647 uberlingen Germany). Ng K. C. Ayala N. L. Simeonsson J. B. Winefordner J. D. Laser-induced plasma atomic emission spectro- metry in liquid aerosols Anal. Chim. Acta 1992 269 123. (Dept. Chem. Univ. Florida Gainesville FL 3261 1 USA).Cheam V. Lechner J. Sekerka I. Desrosiers R. Nriagu J. Lawson G. Development of a laser-excited atomic fluorescence spectrometer and a method for the direct determination of lead in Great Lakes waters Anal. Chim. Acta 1992 269 129. (Res. Appl. Branch Natl. Water Res. Inst. Burlington Ontario Canada L7R 4A6). Salacinski H. J. Riby P. G. Haswell S. J. Coupled flow injection analysis-flame atomic absorption spectro- metry for the quantitative determination of aluminum in beverages and waters incorporating on-line cation exchange Anal. Chim. Acta 1992 269 1. (Adv. Cent. Biochem. Eng. Univ. Coll. London London UK WCl 7JE). Hwang Z.-w. Teng Y.-y. Li K.-p. Sneddon J. Studies of space and time resolved emission measurements of an argon monofluoride excimer laser ablated plasma Anal.Lett. 1992 25 2143. (Dept. Phys. Univ. Massa- chusetts Lowell MA 01854 USA). Martinez M. Miralles N. Sastre A. Herranz C. Determination of the equilibrium constants of alkyl- phosphinic acids by inductively coupled plasma atomic emission spectrometry Anal. Sci. 1992,8 613. (Chem. Eng. Dept. Univ. Politec. Catalunya Barcelona Spain Kim S.-t. Son K.-s. Park J.-a. Baik S.-w. Lim J.-h. Acid effect on the determination of metals by the flame atomic absorption spectrometry Anal. Sci. Tech- nol. 1990 3 77. (Chem. Anal. Lab. Korea Inst. Sci. Technol. Seoul South Korea). Rhee J.-s. Kim T.-j. Lim J.-h. Diagnosis of mastitis by ion chromatography and atomic absorption spectro- metry Anal. Sci. Technol. 1990 3 237. (Chem. Anal. Lab. Korea Inst.Sci. Technol. South Korea). Lim H.-b. Cho MA. Han MA. Lee K.-w. Kim Y.-s. Introduction of organic sample with extended torch and modified sample injector in inductively coupled plasma atomic emission spectrometer Anal. E-08028).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 333R 9313262. 9313263. 9313264. 9313265. 9313266. 931326 7. 9313268. 9 313269. 9313270. 93/327 1. 9313272. 93/32 7 3. 9313274. 9 3/32 7 5 . Sci. Technol. 1991 4 267. (Inorg. Anal. Lab. Korea Res. Inst. Stand. Sci. Taejeon 305-606 South Korea). Park H.-s. Kim SA. Jin HA. Ryoo S.-s. Choi B.-s. Determination of arsenic in human scalp hair by hydride generation-inductively coupled plasma spectro- metry Anal. Sci. Technol. 1992 5 51. (Dept. Chem. Kyung Hee Univ. Yongin 449-701 South Korea).Kim H.-j. Woo J.-c. Lim H.-b. Moon D.-w. Lee K-w. Direct analysis of steels with a gas-jet assisted glow discharge lamp for atomic absorption spectro- metry Anal. Sci. Technol. 1992 5 185. (Inorg. Anal. Chem. Lab. Korea Stand. Res. Sci. Inst. Taejon 305- 606 South Korea). Casabianca H. Use of coupled SFE-GC-AED for the analysis of sulfide and halide pesticides Analusis 1992 20 S9. (Serv. Cent. Anal. CNRS 69390 Vernaison France). Vidal Marin M. Garcia Mata M. Tenorio Sans M. D. Copper levels in drinking water of Madrid An. Broma- tol. 1991 43 51. (Fac. Farm. Univ. Complutense Madrid Madrid Spain E-28040). Mazzucotelli A. Frache R. Magi E. Rivaro P. Gerbino T. Separation and determination of trace amounts of inorganic tin and tributyltin using high- pressure liquid chromatography inductively coupled plasma atomic emission spectroscopy Ann.Chim. (Rome) 1992,82 379. (Inst. Chim. Gen. Univ. Genoa Italy). Lee Y.-i. Thiem T. L. Kim G.-h. Teng Y.-y. Sneddon J. Interaction of an excimer-laser beam with metals. 111 the effect of a controlled atmosphere in laser-ablated plasma emission Appl. Spectrosc. 1992 46 1597. (Dept. Chem. Univ. Massachusetts Lowell MA 01 854 USA). Merkushev V. A. Orlov V. V. Razyapov A. Z. Possibilities of instrumental methods for determination of noble metals with assay preconcentration Blagorod. Met. i Almazy v Nov. Obl. Tekhn. Ginalmazzoloto M. 1991 159. (State Sci. Res. Dev. Inst. Rare Metal Ind. Moscow Russia). Ryazapov A. Z. Evaluation of the sensitivity of atomic absorption and fluorescence spectroscopy with elec- trothermal sample atomization Blagorod.Met. i Al- mazy v Nov. Obl. Tekhn. Ginalmazzoloto M . 1991 173. (CIS). Radhakrishna I. Anbanathan N. Rao K. N. Lakshma- nan A. S. Electrodeposition of (mercury cadmium) telluride films Bull. Electrochem. 199 1 7 567. (Cent. Electrochem. Res. Inst. Karaikudi 623 006 India). Mihalikova E. Miskovic P. Determination of organic stannous substances in the atmosphere Cesk. Hyg. 1992 37 34. (Spec. Ustav Hyg. Epidemiol. Banska Bystrica Czechoslovakia). Hulanicki A. Bulska E. Wrobel K. Determination of manganese lead and cadmium in zinc sulfate by electrothermal atomic absorption spectrometry Chem. Anal. (Warsaw) 1992 37 93. (Dept. Chem. Univ. Warsaw Warsaw Poland). Tadani I. Watanabe H. Aihara M.Kiboku M. Determination of copper in aluminium alloys by ICP- AES after solvent extraction with potassium xanthates Chem. Express 1992 7 825. (Ind. Res. Inst. Kure Japan 737). Pak C.-s. Pak J.-s. Studies on the relationship between blackness and concentration in under-exposed portion of a spectrophotographic plate Choson Minju- juui Inmin Konghwaguk Kwahagwon Tongbo 1991 6 32. (North Korea). Al-Rashdan A. Investigation into speciation of inor- ganic and organolead compounds by high performance liquid chromatography with plasma spectrometric de- 9313276. 9313277. 9313278. 9 31 32 79. 9313280. 931328 1. 9313282. 9313283. 9313284. 9313285. 93/3286. 931328 7. 9313288. 9313289. tection Diss. Abstr. Int. B 1992 52 3568. (Univ. Cincinnati Cincinnati OH USA). Sheppard B.S. Helium-argon mixed-gas plasma as an alternative source for plasma spectrometry Diss. Abstr. Int. B 1992 52 3576. (Univ. Cincinnati Cincinnati OH USA). Roshdy S. M. M a t h S. A. Long-acting hormonal agents analysis of thallium residues in steroid esters following thallium-mediated coupling Egypt. J. Pharm. Sci. 1991 32 575. (Fac. Pharm. Cairo Univ. Cairo Egypt). United States Environmental Protection Agency Guide- lines establishing test procedures for the analysis of pollutants; microwave digestion Fed. Regist. 1992 57 4 1 830. (Washington DC 20460 USA). Zhang H.-q. Ye D.-m. Yu A,-m. Duan Y.-x. Jin Q.-n. Zhang J.-s. Determination of phosphorus by microwave-induced plasma atomic emission spectrome- try using an ultrasonic nebulizer Fenxi Huaxue 1992 20 1065. (Dept.Chem. Jilin Univ. Changchun China 130023). Chen R.-h. Xin H.-m. Determination of copper lead zinc magnesium and calcium in nickel sulfate by atomic absorption spectrometry after matrix separation by precipitation using 2,3-butanedione dioxime Fenxi Huaxue 1992 20 1232. (Zhejiang Prov. Inst. Chem. Eng. Hangzhou China 3 10023). Yu A.-m. Fan F.-l. Jin Q.-h. Determination of trace mercury in water by metastable transfer emission spectroscopy Fenxi Shiyanshi 1992 11 36. (Dept. Chem. Jilin Univ. Changchun China 130023). Wang F.-y. Wan J.-l. Lu H.-b. Xia W. Mechanism of enhancement of surfactants on manganese in flame atomic absorption spectrometry Gaodeng Xuexiao Hu- axue Xuebao 1991 12 1581. (Dept. Chem. Huazhong Norm. Univ. Wuhan China 430070). Tauson V. L. Men’shikov V.I. Zubkov V. S. Use of thermal atomic absorption analyses of synthetic crystals for identifying the form of mercury in minerals Geokhi- miya 1992 8 1203. (Inst. Geokhim. Irkutsk Russia). Lei J. Fu HA. Spatially resolved spectroscopic diag- nostics of a low pressure helium microwave-induced plasma sustained by a surfatron Guangxue Xuebao 1992 12 491. (Dept. Phys. Yunnan Univ. Kunming China 65009 1). Fan Y.-c. An C.-w. Ning B. Lu D.-s. Li Z.-g. Optical emission spectroscopic studies of laser-induced plasma from the ablated yttrium barium copper oxide (YBa,CuJO,) superconducting target Guangpuxue Yu Guangpu Fenxi 1992 12 57. (Natl. Lab. Laser Tech- nol. Huazhong Univ. Sci. Technol. Wuhan China 430074). Zhang Z.-y. Piao Z.-x. Zeng X.-j. Correction of line overlap interference in ICP-AES by self-modeling curve resolution-effect of measurement errors on results Guangpuxue Yu Guangpu Fenxi 1992 12 63.(Changchun Inst. Appl. Chem. Acad. Sin. Changchun China 130022). Yuan F. Qi W.-d. Chen X.-h. Determination of trace rare earth impurities in high purity metallic cerium by inductively coupled plasma atomic emission spectrome- try and correction of spectral interferences Guangpuxue Yu Guangpu Fenxi 1992 12 75. (Changchun Inst. Appl. Chem. Acad. Sin. Changchun China 130022). Mi R.-h. Advances in atomic absorption spectrometry of ytterbium Guangpuxue Yu Guangpu Fenxi 1992,12 105. (Cent. Anal. Comput. Nankai Univ. Tianjin China 30007 1). Qin Lj. Fang K.-w. Wu T.-z. Semiauto demount- able recirculating nebulizer for ICP-AES Guangpuxue334R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL.8 9313290. 931329 1. 9313292. 9313293. 9313294. 9313295. 9313296. 9313297. 9313298. 9313299. 93/3300. 9313301. 9 313 302. 9313303. 9313304. 9313305. Yu Guangpu Fenxi 1992 12 123. (Inst. Rock Miner. Anal. Chin. Acad. Geol. Sci. Beijing China 100037). Bona M. A. Castellano M. Plaza L. Fernandez A. Determination of heavy metals in human liver Hum. Exp. Tuxicol. 1992 11 311. (Fac. Med.,Univ. Zara- goza Zaragoza Spain). Schmolke G. Elsenhans B. Ehtechami C. Forth W. Arsenic-copper interaction in the kidney of the rat Hum. Exp. Tuxicol. 1992 11 315. (Walther Straub Inst. Pharmakol. Toxikol. Ludwig Maximilians Univ. D-8000 Munich 2 Germany). Bhatt H. V. Amin R. J. Pandya C. B. Elemental contents of roots of Anacyclus pyrethrum Indian J.Chem. Sci. 1991 5 77. (Dept. Agric. Health Ind. Hyg. Natl. Inst. Occupat. Health Ahmedebad 380 016 India). Urasa I. T. Mavura W. J. Influence of sample acidification on the speciation of iron(@ and iron(rrr) Int. J. Environ. Anal. Chem. 1992 48 229. (Dept. Chem. Hampton Univ. Hampton VA 23668 USA). Moitra J. K. Pandey G. S. Trace metals in tin extraction plant wastes Int. J. Environ. Anal. Chem. 1992 48 241. (Dept. Chem. Ravishankar Univ. Raipur 492 010 India). Fudagawa N. Kubota M. Cooperative experiment on the determination of cadmium in rice Kagaku Gijutsu Kenkyusho Hokoku 1992 87 2 17. (Natl. Chem. Lab. Ind. Tsukuba Japan). Chmilenko F. A. Baklanova A. N. Ultrasound in sample preparation for determination of zinc in water brine and common salt Khim.Tekhnol. Vody 1992,14 109. (State Univ. Dnepropetrovsk The Ukraine). Shevchuk I. A. Makhno A. Ya. Extraction concentra- tion and atomic absorption determination of cadmium in waters Khim. Tekhnol. Vody 1992 14 740. (Don- etsk. Univ. Donetsk The Ukraine). Hauptmann C. Priem P. Glatzel E. Schneider M. Reference values for the urinary excretion of calcium (Ca) magnesium (Mg) phosphorus (P) and creatinine in children Klin. Labor 1992 38 21 1. (Kinderklin. (Charite) Humboldt Univ. D- 1040 Berlin Germany). Namiki H. Analytical method of surface active agents Kogyo Yosui 1992 405 32. (Fac. Educ. Yokohama Natl. Univ. Yokohama Japan 240). Hoffmann H. J. Spectrometric methods in the frame- work of legislational water analysis LaborPruxis 1 992 16 790.(Bayer. Staatsminist. Landesentwickl. Umwelt- fragen D-8000 Munich 8 1 Germany). Bloedorn W. Rippert T. Thierig D. Unger H. Trace and elemental analysis of steels and ferroalloys. Emis- sion spectroscopy with inductively coupled plasma LaborPraxis 1992,16,878,880,884,886. (Spectro A. I. G.m.b.H. D-4 1 90 Kleve Germany). Bloedorn W. Rippert T. Thierig D. Unger H. Trace and elemental analysis of steels and ferro alloys. Emission with inductively coupled plasma (ICP) excita- tion. Part 2 LaborPraxis 1992 16 982. (Spectro A. I. G.m.b.H. D-4 190 Kleve Germany). American Society of Brewing Chemists USA Alumi- nium in beer by graphite furnace atomic absorption spectrophotometry J. Am. SOC. Brew. Chem. 1992,50 142. (American Society of Brewing Chemists USA).Merkle L. D. Gruber J. B. Seltzer M. D. Stevens S. B. Allik T. H. Spectroscopic analysis of thulium( 3 +)- doped sodium lanthanum molybdate [Tm3+:NaLa- (MOO,),] J. Appl. Phys. 1992 72 4269. (Lasers Photonics Div. Night Vision Electro Opt. Dir. Fort Belvoir VA 22060 USA). Clouet F. Shi M. K. Interactions of polymer model surfaces with cold plasmas hexatriacontane as a model 9313306. 9 313 30 7. 9313308. 9 313 309. 93/33 10. 93/33 1 1. 93/33 12. 93/33 13. 9313314. 93/33 93/33 93/33 17. 9313318. molecule of high-density polyethylene and octadecyl octadecanoate as a model of polyester. I. Degradation rate versus time and power J. Appl. Polym. Sci. 1992 46 1955. (Inst. Charles Sadron 67083 Strasbourg France). Memtt K. Margevicius R. W. Brown S. A. Storage and elimination of titanium aluminium and vanadium salts in vivo J.Biomed. Muter. Res. 1992 26 1503. (Dept. Biomed. Eng. Case Western Reserve Univ. Cleveland OH 44106 USA). Wu M.-g. Gehlhausen J. M. Carnahan J. W. Atomic emission spectrometry with helium plasmas an emerging approach for non-metal determinations J. Chem. Educ. 1992 69 757. (North. Illinois Univ. DeKalb IL 601 15 USA). Chen J.-j. Lou Y.-c. Whang C.-w. Determination of tributyltin in sea-water by hydride generation atomic absorption spectrometry J. Chin. Chem. Soc (Taipei) 1992,39,46 1. (Dept. Chem. Tunghai Univ. Taichung Taiwan 40703). Bicchi C. Frattini C. Pellegrino G. Rubiolo P. Raverdino V. Tsoupras G. Determination of sulfu- rated compounds in Tagetes patula cv. nana essential oil by gas chromatography with mass spectrometric Four- ier transform infrared and atomic emission spectrome- tric detection J.Chromatogr. 1992,609 305. (Dip. Sci. Tecnol. del Farm. Via P. Giuria 9 10125 Turin Italy). Ray A. K. Lal B. Mago V. K. Rao P. R. K. Resonantly enhanced single-colour multiphoton ioniza- tion of the uranium atom J. Opt. SOC. Am. B Opt. Phys. 1992,9 1979. (Bhabha At. Res. Cent. Bombay 400 085 India). Kenney J. Schmiedl U. Maravilla K. Starr F. Graham M. Spence A. Nelson J. Measurement of blood-brain bamer permeability in a tumor model using magnetic resonance imaging with gadolinium- DTPA Magn. Reson. Med. 1992 27 68. (Sch. Med. Univ. Washington Seattle WA 98 195 USA). Graf Harsanyi E. Feher S. Flow-through atomic absorption determination of metals after enrichment Magy.Kem. Foly. 1992,98,323. (Altalanos Anal. Kem. Tansz. Budapesti Musz. Egy. 152 1 Budapest Hun- gary). Borszeki J. Halmos P. Kovacs L. Tilky P. Method for the determination of active sulfur in the graphite packing of a nuclear power station Ma#. Kem. Foly. 1992 98 330. (Anal. Kem. Tansz. Veszpremi Egy. 8200 Veszprem Hungary). Sarzanini C. Mentasti E. Abollino O. Fasano M. Aime S. Metal ion content in Sepia officinalis melanin Mar. Chem. 1992 39 243. (Dip. Chim. Anal. Univ. Torino 10 125 Turin Italy). Bello M. A. Martin L. Martin A Microchemical identification of Macael white marble in some Spanish monuments Muter. Constr. (Madrid) 1992 42(225) 23. (Fac. Quim. Univ. Sevilla Seville Spain 41012). Giordano R. Costantini S. Vernillo I. Moramarco A. Rasi V. Giustolisi R.Gabrieli C. B. Calcium potassium zinc and copper determinations in catarac- tous human lenses Microchem. J. 1992 46 184. (1st. Super. Sanita 00 16 1 Rome Italy). Anwar J. Anzano J. M. Petrucci G. A. Effect of some organic solvents and acids on the laser-induced atomic fluorescence of tin in air-hydrogen flames Mikrochim. Acta 1992 108 285. (Chem. Dept. Univ. Florida Gainesville FL 326 1 1 USA). Goto K. Taguchi S. Kasahara I. Hata N. Methods developed in Toyama University for the examination of water. 11 Mizu Shori Gijutsu 1992 33 355. (Fac. Sci. Toyama Univ. Toyama Japan 930).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 335R 93/33 19. 9313320. 931332 1. 9313322. 9313323. 9313324. 9313 32 5. 9 313 3 26. 9313 327. 9313328. 9313329. 9313330.931333 1. 9313332. Ishii Y. Shibata T. Yoshino Y. Ichimura H. Kobay- ashi K. Active plasma species in titanium nitride film formation process by plasma CVD method Nippun Seramikkusu Kyokai Gakujutsu Ronbunshi 1992 100 1184. (Cent. Res. Lab. Sumitomo Met. Min. Ichikawa China 272). Hardjoutomo W. Munechika H. Kurniawan H. Hat- tori I. Kobayashi T. Kagawa K. Compact TEA carbon dioxide laser for field-based spectrochemical analysis of geological samples Opt. Laser Technol. 1992 24 273. (Fac. Educ. Univ. Fukui Fukui Japan 9 10). Sasaki K. Nishigaki H. Atomic absorption spectros- copic analytic apparatus Eur. Pat. Appl. EP 507,182 (C1 GOIN2117I) 07 Oct 1992 J P Appl. 91193,515 30 Mar 1991; 10 pp. (Shimadzu Kyoto Japan). Suzanne P. Guene G. Portable and automated appara- tus for in situ analysis of a gaseous composition by flame spectrophotometry Demande FR 2,672,996 (Cl.GOlN21/72) 21 Aug 1992 Appl. 9111,729 14 Feb 199 I ; 14 pp. (Etat Francais; Proengin SA France). Cordova A. Changes on plasma and erythrocyte magne- sium levels after high-intensity exercises in men Phy- siul. Behav. 1992 52 819. (Fac. Med. Univ. Valla- dolid Soria Spain 42003). Orishich A. M. Shaikhislamov I. F. Spectral diagnos- tics of a plasma expanding into a background gas and a magnetic field PMTF Prikl. Mekh. Tekh. Fiz. 1992 3 13. (Novosibirsk Russia). Piron-Frenet M. Bureau F. Pineau A. Lead accumu- lation in roadside soil and correlation with traffic density Pollut. Atmos. 1992 134 101. (Lab. Biogeol. Biostratigr. Chemin Houssiniere Fac. Sci.44035 Nantes France). McOmber J. I. Davies J. T. Howden J. C. Liston E. Optical emission and vacuum ultraviolet spectroscopy comparison of non-line of sight ashing using microwave and r.f. plasma generation Pruc. Electruchem. Suc. 1992,92-18 104. (GaSonicslIPC San Jose CA 91 534 USA). Zoellner M. J. Emmel H. W. Nelson L. D. Robotic automation of procedures used for preparing environ- mental samples for the analysis for metals Pruc. Int. Symp. Lab. Autum. Rub. 1991 (Pub. 1992) 402. (Anal. Sci. Lab. Dow Chem. Midland MI 48674 USA). Park M.-y. Current and future prospects of microana- lysis and depth profiling Punsuk Kwahak 1989,2 401. (Chem. Dept. Keonkuk Univ. South Korea). Palivan C. Rughinis D. Ciohodaru G. Niculete E. Effect of cation contamination on the stability of injectable solutions by atomic absorption spectrometry Rev.Chim. (Bucharest) 1992 43 275. (Inst. Cercet. Chim. Fam. Bucharest Romania). Chera I. Iova I. Ganciu-Petcu M. Gruia I. Diplasu C. On the excitation mechanism of metal vapor spectral lines in a hollow cathode discharge in noble cases Rev. Roum. Phys. 1992,37,31. (Fac. Phys. Univ. Bucharest Bucharest-Magurele Romania). Forrest M. J. Winfield R. J. Improved signal-to-noise in fluorescence scattering by means of non-linear pump- ing with a frequency modulated dye laser Rev. Sci. Instrum. 1992 63 5005. (Culham Lab. Euratom Fusion Assoc. Abingdon Oxfordshire UK OX14 3DB). Grad R. Clark R. E. H. Dadusc G. Davara G. Duvall R. E. Fisher A. Fisher V. Foord M. E. Fruchtman A. Visible-light spectroscopy of pulsed power plasmas Rev. Sci.Instrum. 1992 63 5127. (Dept. Phys. Weizmann Inst. Sci. 76100 Rehovot Israel). 9313333. 9313334. 9313 3 3 5. 93/33 36. 93/33 37. 9 313 3 38. 9313 3 39. 9313340. 9313341 9313342. 9313343. 9313344. 93J3345. 9313346. Stinson T. J. Jaw S. Jeffery E. H. Plewa M. J. Relationship between nickel chloride-induced peroxida- tion and DNA strand breakage in rat liver Toxicol. Appl. Pharmacol. 1992 117 98. (Inst. Environ. Stud. Univ. Illinois Urbana IL 6 180 1 USA). Osipov N. N. Panichev N. A. Charykov A. K. Concentrations of heavy metals in the intrusion lense of the Mediterranean Sea water based on the results of atomic absorption analysis Vestn. St. Peterb. Univ. Ser. 4 Fiz. Khim. 1992 1 62. (St. Petersburg Gos. Univ. St. Petersburg Russia).Guo X.-w. Progress in atomic absorption spectrometry and atomic fluorescence spectrometry Yankuang Ceshi 1992 11 6 . (Northwest Res. Inst. Nonferrous Geol. CNNC Xian China 7 10054). Chen L.-m. Advances of sample introduction tech- niques in ICP-AES Yankuang Ceshi 1992 11 16. (Hangzhou Anal. Cent. Minist. Geol. Miner. Resour. Hangzhou China 3 10007). Guan J.-s. Shi Y.-q. Gao B.-h. Liu Y.-m. Determi- nation of 25 trace impurity elements in uranium oxide (U,O,) by horizontal ICP-AES after separation with TBP levextrel resin chromatography Yuanzineng Kexue Jishu 1991 25(6) 8 . (China Inst. At. Energy Beijing China). Monque R. Parisi A. Gonzalez S. Giannetto G. Analytical method for the determination of intra- and extra-framework gallium species in zeolite catalyst Zeolites 1992 12 806.(Dept. Desarrollo Procesos INTEVEP S.A. Caracas Venezuela 1070A). Filichkina V. A. Abroskin A. G. Zharikova 0. M. Proskurnin M. A. Savostina V. M. Thermal-lens spectrometric determination of microquantities of nickel as a-dioximates Zh. Anal. Khim. 1992,47 660. (M. V. Lomonosov Moscow Univ. Moscow Russia). Avramenko L. I. Gudzenko L. V. Zdotovitskaya E. S. Trubaeva T. N. Shelikhina E. I. Antonovich V. P. Blank A. B. Spectrophotometric and atomic emission determination of molybdenum in tungsten oxide after solvent extraction separation Zh. Anal. Khim. 1992 47 737. (Inst. Monocryst. Kharkov The Ukraine). Burmaa G. Potapov V. A. Amosova S. V. Khlebni- kova A. A. Comparison of dibutyl sulfide dibutyl selenide and dibutyl telluride as extractants for gold(1Ix) and silver(I) Zh.Anal. Khim. 1992 47 930. (Inst. Org. Chem. Irkutsk Russia). Grikit I. A. Kozhevnikova A. S. Pugach N. N. Multicrater electrode and its application to the atomic- emission analysis of powders Zh. Prikl. Spektrusk. 1992 57 14. (Nauchno-Issled. Inst. Titana Zaporozhe Russia). Currey N. A. Benko W. I. Yaru B. T. Kabi R. Determination of heavy metals arsenic and selenium in barramundi (Lutes calcar$er) from Lake Murray Papua New Guinea Sci. Total Envirun. 1992 125 305. (Natl. Anal. Lab. P.N.G. Univ. Technol. Lae Papua New Guinea). Kunihiro T. Method of estimating sulfated ash in engine oils by metal element analyses Sekiyu Gak- kaishi 1992 35 460. (Idemitsu Kosan Co. Ltd. Ichihara Japan 299-01). Yin C.-y. Sun M.-w. Determination of the compo- sition of atmospheric particulates by ICP-AES Shan- ghai Huanjing Kexue 1992 11 29.(Liaoning Prov. Environ. Monit. Cent. China). Liang L.-I. Hu X . 4 Atomic absorption spectrometric determination of six metal ions in residual oil-carbon black slurry and ashy water Shiyuu Huagong 1992 21 263. (Res. Inst. Lanzhou Chem. ind. Lanzhou China 730060).336R 9313347. 9313348. 9313349. 9313350. JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY OCTOBER 1993 VOL. 8 Tsalev D. Mandzhukov P. Draganova D. Optimiza- tion study of plumbane generation and preconcentra- tion in hydride generation graphite furnace atomic absorption spectrometry Spectrosc. Lett. 1992,25,943. (Fac. Chem. Univ. Sofia 1126 Sofia Bulgaria). Stojkovic S. R. Strbac N. D. Zivkovic 2. D. IR spectroscopy in determination of enrichment of low quality bauxites Spectrosc. Lett.1992,25 1037. (Tech. Fac. Bor Univ. Belgrade Bor Yugoslavia). Banks P. R. Liang D. C. Blades M. W. Graphite furnace-capacitively coupled plasma spectrometry a new fast furnace technique Spectroscopy (Eugene Oreg.) 1992,7(8) 36 38,40. (Aurora Instrum. Vancou- ver BC Canada). Fridman G. I. Timofeeva L. N. Osipova V. A. Gusarskii V. V. Basic characteristics of the develop- ment of methods for analysis of multicomponent metal- lic systems by inductively coupled plasma atomic 931335 1. 9313 3 52. 9313353. emission spectroscopy Spektr. Anal. Tr. Mosk Kollok. 1990 AN USSR. Otd-nie Obshch. Fiz. i Astron. Nauch. Sov. PO Spektroskopii M. 1991 2 163. (USSR). Goulter J. Determination of minor and trace elements in silicon carbide by slurry sample presentation ICP Sprechsaal 1992 125 508. (Spectro Anal.Instrum. D- 4 190 Kleve Germany). Deavor J. P. Becerra E. Smith B. W. Winefordner J. D. Laser excited atomic fluorescence determination of sub-microliter aqueous samples of lead using a planar cathode discharge Can. J. Appl. Spectrosc. 1993 38 7. (Dept. Chem. Univ. Florida Gainsville FL 3261 1 USA). Ni Z.-m. He B. Han H.-b. Selenium determination in human urine by hydride generation graphite furnace AA Can. J. Appl. Spectrosc. 1993 38 11. (Research Center Eco-Environ. Sci. Acad. Sin. P.O. Box 2871 Beijing China).

ISSN:0267-9477    

DOI:10.1039/JA993080313R

出版商:RSC    

年代:1993

数据来源: RSC