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/JA99308FX015

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JASPE2 8(4) 27N-34N 499-672 151 R-l96R Ill I I June 1993 Journal of Analytical Atomic Spectrometry Including Atomic Spectrometry Updates CONTENTS NEWS AND VIEWS 27N Conference Report-J. I Garcia Alonso 30N Benedetti-Pichler Award 30N Book Review-Phil Potts 31 N 33N Papers in Future Issues Diary of Conferences and Courses PAPERS 499 51 7 539 545 551 557 565 571 577 585 591 595 599 Chromatography Coupled With Inductively Coupled Plasma Atomic Emission Spectrometry and Inductively Coupled Plasma Mass spectrometry. A Review- Steve J Hill Martin J Bloxham Paul J Worsfold Background and Background Correction in Analytical Atomic Spectrometry. Part 1. Emission Spectrometry. A Tutorial Review-J B Dawson R D Snook W J Price Measurement of Inductively Coupled Plasma Infrared Atomic Emission of Carbon and Oxygen From Alcohols Using Fourier Transform Infrared Spectrometry-C A Morgan B W Smith J D Winefordner Signal Enhancement of Lead and Thallium in Inductively Coupled Plasma Atomic Emission Spectrometry Using On-line Anodic Stripping Voltammetry-Jack R Pretty Joseph A Caruso Determination of Uranium and Thorium in Basalts and Uranium in Aqueous Solution by Inductively Coupled Plasma Mass Spectrometry-Elizabeth H Bailey Anthony J Kemp K Vala Ragnarsdottir Speciation of Eight Arsenic Compounds in Human Urine by High-performance Liquid Chromatography With Inductively Coupled Plasma Mass Spectrometric Detection Using Antirnonate for Internal Chromatographic Standardization-Erik H Larsen Gunnar Pritzl Steen Honore Hansen Laser Vaporization Inductively Coupled Plasma Mass Spectrometry a Technique for the Analysis of Srnall Volumes of Solutions-R Krishna Prabhu S Vijayalakshmi T R Mahalingam K S Viswanathan C K Mathews Gas Chromatographic Determination of Phosphorus Sulfur and Halogens Using a Water-cooled Torch 'With Reduced-pressure Helium Microwave-induced Plasma Mass Spectrometry-W Charles Story Joseph A Caruso 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-Guanhong Tao Zhaolun Fang Examination of Separation Efficiencies of Mercury Vapour for Different Gas-Liquid Separators in Flow Injection Cold Vapour Atomic Absorption Spectrometry with Amalgam Preconcentration-C P Hanna P E Haigh J F Tyson S Mclntosh Determination of Total Mercury by Single-stage Gold Amalgamation With Cold Vapour Atomic Spectrometric Detection-Lian Liang Nicolas S Bloom Determination of Sodium by Sequential Metal Vapour Elution Analysis With Hydrogen Carrier Gas-Kiyohisa Ohta Takehiko Sugiyama Syn-ya Inui Tohru Suzuki Takayuki Mizuno Mechanisms of Chloride Interferences in Atomic Absorption Spectrometry Using a Graphite Furnace Atolmizer Investigated by Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry.Part 2. Effect of Sodium Chloride Matrix and Ascorbic Acid Chemical Modifier on Manganese-John P Byrne Marc M Lamoureux Chuni L Chakrabarti Tam Ly D Conrad Gregoire continued on inside back cover Typeset by Burgess Thames View Abingdon Oxfordshire 0267-9477C199314:l-161 1 61 5 623 633 637 643 649 655 659 665 671 Increased Performance in Electrothermal Atomic Absorption Spectrometry of Lithium in Renal Tubular Fluid by Use of Tantalum Foil-Peter Boer Rene Fransen Walther H Boer Hein A Koomans Graphite Furnace Atomization Behaviour of Lead Contained in Clinical and Environmental Materials in the Presence of Palladium-induced lsoformation and Citric Acid-Victor A Granadillo Janeth A Navarro Romer A Romero Mechanisms of Atomization of Lead from Nitric Acid Hydrochloric Acid and Sodium Chloride Matrices in Atomic Absorption Spectrometry Using a Graphite Probe Furnace-Glen F R Gilchrist Chuni L Chakrabarti Jianguo Cheng Dianne M Hughes Indium Hydride Generation Atomic Absorption Spectrometry with In Situ Preconcentration in a Graphite Furnace Coated with Palladium-Yiping Liao Anmo LI Determination of Trace Elements in High-purity Molybdenum Trioxide by Slurry Sampling Electrothermal Atomic Absorption Spectrometry-Bohumil Docekal Viliam Krivan Selenium Speciation by High-performance Liquid Chromatography-Fraction Collection-Electrothermal Atomic Absorption Spectrometry Optimization of Critical Parameters-Francisco Laborda Dipankar Chakraborti Jose M Mir Juan R Castillo Speciation of Chromium by the Determination of Total Chromium and Chromium(iii) by Electrothermal Atomic Absorption Spectrometry-E.Beceiro- Gonzalez P Bermejo-Barrera A Bermejo-Barrera J Barciela-Garcia C Barciela-Alonso Determination of Copper Iron Aluminium Lead and Cadmium in Cork Stoppers by Electrothermal Atomic Absorption Spectrometry-M Elisa Soares M Lourdes Bastos Margarida A Ferreira Performance of a Modular Thermospray Interface for Signal Enhancement in Flame Atomic Absorption Spectrometry Coupled On-line to Flow Injection or Liquid Chromatography-Erik H Larsen Jean-Simon Blais On-line Thermospray Continuous Volatilization of Cobalt Aluminium and Chromium Volatile Chelates and Determination by Heated Quartz Tube Atomic Absorption Spectrometry-Maria S Jimenez Jose M Mir Juan R Castillo CUMULATIVE AUTHOR INDEX 151 R Atomic Emission Spectrometry-Barry L. Sharp Simon Chenery Raymond Jowitt Simon T. Sparkes Andrew Fisher 169R References GBC Scientific Equipment U.K Ltd. 13 Frederick Sanger Road The Surrey Tel 0483 304988 Fax 0483 303071 Resea .rch Park Guildford Surrey GU2 5Y D

ISSN:0267-9477    

DOI:10.1039/JA99308BX017

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 27N Conference Report 1993 European Winter Conference on Plasma Spectrochemistry January 10-1 5 1993 Granada Spain When I was approached by Judith Egan-Shuttler and Les Ebdon after suggestions by Alfredo Sanz-Medel and asked to write a conference report for JAAS on the 1993 European Win- ter Conference on Plasma Spectroche- mistry I knew I was doomed. That meant that I had to get up early every day of the conference to attend the first plenary lectures and stay late in the evening to get a feeling of the ‘other aspect’ of scientific conferences. I should say that I tried my best but somehow at the end of the week the first part of my duty became harder to perform while the second part seemed easier. Anyway I will try to present you an accurate account of what hap- pened those five days of January in Granada both scientifically and so- cially.The Conference was held in the modem Palacio de Exposiciones y Congresos of Granada which was opened in 1992. In order to give you some statistics (the list of participants and the book of abstracts were my source of data) 263 participants from 25 countries attended the conference. As is the case when the Winter Confer- ence is held in Europe the number of participants from the USA and Canada was reduced (28 participants). However they somehow managed to present almost 50% of the invited lectures. I was told that this is because they produce better looking slides and tell jokes during their presentations. Central and South America was repre- sented by only 5 participants while the rest were mainly European (1 from Australia 2 from Israel and 1 from Korea made up the total).The host country was well represented with 55 participants even if you take into account that at the time of the confer- ence not a single ICP-MS instrument was operative in Spain (a few were under installation I was told). The scientific programme consisted of 6 Plenary lectures 10 Keynote lectures on special topics 8 oral sessions (34 presentations) 3 poster sessions (1 26 posters) and 3 special discussion ses- sions. The Conference was opened by Alfredo Sanz-Medel the Conference organizer on Sunday evening. The first Plenary lecture was held after- wards and addressed by Paul Bour- mans (The Netherlands) on ‘Plasma Spectrochemistry in Search for Inno- vation or Confirmation’.The names of Columbus Granada and the magic dates of 1492 and 1992 were heard that evening and not for the first time during the Conference. The links be- tween Spain and Latin America were confirmed by the second speaker of the evening Daniel Batistoni (Argentina) who gave an account of the develop- ment of ‘Plasma Spectrochemistry in Latin America’. By that time all dele- gates were ready for the welcoming buffet and cocktail reception in the Hotel Saray. That was an early night for all delegates tired of travelling and looking forward to a week of new discoveries in Granada. Monday started with the first session on ‘Plasma Fundamentals and Lasers’. Gary Hieftje (USA) was in charge of the Plenary lecture of the day entitled ‘New Perspectives in Plasma Sources for Spectrochemical Analysis’ where he reviewed the basic features of the inductively coupled plasma (ICP) source and introduced us to a new microwave-induced plasma (MIP) source which contains a cooler central channel and produces a tail similar to the ICP discharge.Jean-Michel Mermet (France) presented the next Keynote lecture on ‘Critical Assess- ment of Laser Ablation ICP Atomic Emission Spectrometry’. He described how the use of UV lasers produced higher ablation rates and lower ele- mental discrimination than IR lasers. From the first oral session mention should be made of the papers from Scott Tanner (Canada) on the deter- mination of plasma temperatures by the measurement of ion kinetic ener- gies and from F.Vanhaecke (Belgium) on the ‘Zone Model’ to explain signal behaviour and interferences in ICP- mass spectrometry (MS). The second oral session was devoted to ‘Alterna- tive Plasma Sources’. Akbar Montaser (USA) gave the Keynote lecture ‘Plas- mas Other Than Argon ICP Dis- charges for Analytical Spectrometry Facts and Fiction’. Helium ICP dis- charges show promise for MS mea- surements of high ionization potential elements and those which are inter- fered with by argon atomic and polya- tomic ions. I was impressed by a novel microwave plasma cavity assembly and torch presented by Henryk Matu- siewicz (Poland) able to work at mod- erate power (300 W) and handle nebulized slurries without problems. The first poster session was devoted to ‘ICP-AES Techniques and Applica- tions’.It seems that ICP-atomic emis- sion spectrometry (AES) is well estab- lished for the analysis of difficult samples like ceramics. Laser ablation slurry nebulization microwave diges- tion techniques and new nebulizer types were all described. New instru- mental developments were presented (Perkin Elmer) on the use of solid-state detectors (CCD) in combination with an Cchelle spectrometer for a simulta- neous ICP-AES instrument. The evening session was dedicated to traditional Spanish music with a splendid guitar and flute concert. In spite of the cold night Joe Brenner could have stayed sitting for two more hours as he was so impressed by the music and the multicultural past of Granada well reflected on the walls of the ‘Carmen de 10s Martires’.The buffet after the concert left every- body satisfied and the wine helped to28N JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 Poster session L to R Sam Houk and Scott Tanner raise the temperature to manageable levels. Tuesday was the ICP-MS day and a sad day. Wojciech Vieth (USA and Poland) died of a heart attack while setting up his poster at 9 a.m. I would like to send here the condolence of all delegates to his family. Gary Horlick (Canada) presented the third Plenary lecture on ‘ICP-MS Has it Matured Already?. The emergence of addi- tional ion sources which are comple- mentary and/or competitive with the ICP is a proof of maturity. It was interesting to see how electrospray MS could allow direct elemental specia- tion to be carried out.Sam Houk (USA) spoke in his Keynote lecture on ‘Recent Developments in ICP-MS In- strumentation’ and compared it with the troubles of Columbus sailing to and from America. However Colum- bus did not know that cryogenic desol- vation drastically reduced some poly- atomic ions and on the other hand that direct insertion nebulizers pro- vided increased sensitivity with low sample consumption. In the following oral session Gary Hieftje (USA) de- monstrated how difficult it is to couple an ICP to a time-of-flight mass spec- trometer and Barry Sharp (UK) showed that high precision isotopic ratios can be obtained even with a quadrupole mass spectrometer. The afternoon session was devoted to ‘Ma- terials Analysis’. I was in charge of the Keynote lecture on ‘ICP-MS for the Analysis of Nuclear Materials’ not an easy task. Afterwards people wanted to know how I managed to make my slides glow in the dark.The analysis of silicate materials using slurry nebuli- zation Joe Brenner (Israel) and cera- mics by ICP-AES Flora Barba (Spain) closed the session. The second poster session included other plasma sources ICP-MS glow discharge (GD) devices MIP-AES and furnace atomic non-thermal excitation spectroscopy (FANES). It was clear that laser ablation ICP-MS is estab- lishing itself as a satisfactory technique for the analysis of solid samples. Also a prototype double focusing multi- collector ICP-MS instrument seemed to be the solution to obtain highly precise isotopic ratios. Other instru- ment manufacturers claimed that dy- namic ranges of up to 10 orders of magnitude can be obtained by the use of both a Faraday and a channel electron multiplier detector.Spectral interferences were identified by the use of a high resolution ICP-MS instru- ment and Gary Horlick presented a data base including all known interfer- ences for natural element analysis. It would be a good idea to extend this spectral interference database to the analysis of non-natural elements (fis- sion products and actinides). In the poster session also GD sources both for MS and AES were described. There is a tendency to use r.f. powered sources for the analysis of non-con- ducting powders. Finally analytical applications of different MIP sources were presented. That night I discovered that given a minimum amount of people you can still eat ‘tapas’ and drink several beers in Spain for less than 1000 pesetas per head.Surprisingly it took some serious pub crawling and samba danc- ing to finish the 14000 pesetas kitty that we had gathered. The next day was devoted to GD and we all managed to hear Jose Broekaert (Germany) give the Plenary lecture on ‘Potential and Use of Low Pressure Discharges for Atomic Spec- trometry’; a review on new develop- ments of low pressure discharges focusing on GD for AES and MS. The use of the GD as a detector for gas chromatography (GC) or hydride generation (HG) was outlined. W. Harrison (USA) presented the next Keynote lecture on ‘Glow Discharge Mass Spectrometry’. Perspectives of this technique were explored in this lecture. In the following oral session two papers caught my attention espe- cially Angelika Raith (UK) studied the conditions where flat-bottomed craters can be formed for depth profil- ing measurements with the GD and Rosario Pereiro (Spain; USA) de- scribed a gas-sampling GD device for the analysis of organic vapours and as a detector for GC.The afternoon was free for all dele- gates except for those lecturing at and attending the seven short courses pro- grammed. Those who did not care for skiing in Sierra Nevada or sightseeing in Granada or those who did but could not were there. Gunter Knapp (Austria) was in charge of ‘Sample Decomposition and Element Precon- centration in Trace Element Analysis’ Sam Houk (USA) of ‘ICP-MS’ Joe Brenner (Israel) of ‘ICP-AES and ICP- MS in Geoanalysis’ Klaus Dittrich (Germany) of ‘ETA Techniques in Atomic Spectrometry’ Lieselotte Moenke (Germany) of ‘Laser Sampl- ing; Atomic Emission and Mass Spec- trometry’ Cameron McLeod (UK) of ‘Trace Metal Speciation’ and Rick Browner (USA) of ‘Nebulizer Charac- teristics Design and Routine Oper- ation’.All courses were well attended and satisfying I was told. For my part I would like to express my personal thanks to Sam Houk for telling me what I did not know about ICP-MS but was afraid to ask. In the evening all delegates gathered for the nocturnal visit to the Alhambra Palace. This splendid piece of Arab architecture overlooking the city was the last refuge of the Spanish Arabs when the city was conquered by the Christian kings Isabella and Ferdi- nand in 1492. Everyone was im- pressed by the rich decorations of the room walls and ceilings.I learned from Fadi Abou-Shakra that you can read without problem the Arabic inscrip- tions in the Alhambra after all these years. After the Alhambra the Confer- ence organizer was able to gather a small group of delegates in order to discover the hidden secrets of down town Granada. In one of the small taverns Gary Hieftje and Gary Hor- lick discovered why Andalusia is well known for its devotion to the Virgin Mary. Not a single square centimetre of the walls of this tavern was free of portraits of the Virgin. At twelve o’clock the whole tavern was singing the ‘Salve’ to the Virgin in a most devoted atmosphere. At ten past twelve back to business as usual! Thursday morning was dedicated to ‘Hybrid Techniques’ this new expres- sion for using expensive instrumenta- tion as a detector for high-perform- ance liquid chromatography (HPLC) and other cheaper techniques.The Plenary lecture of the day was pre- sented by Les Ebdon (UK) on ‘Hybrid Techniques with Plasma Detection’. The low detection limits of ICP-MS and its multi-elemental capabilities makes it an ideal detector for trace metal speciation after chromatogra- phic separation. Examples of applica- tions for tin lead and arsenic specia- tion were presented. In the field of biological materials Carlo Vandecas- teele (Belgium) described in his Key- note lecture ‘ICP-MS of Biological Samples’ the problems in the determi- nation of trace metals in human serum. The direct analysis of the serum after simple dilution is hindered by severe isobaric interferences from polyatomic ions for many elements.The use of a high resolution instru- ment would solve most of those prob-JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 29N Enjoying the sights of Granada are L to R Steve Hill JosP Broekaert Jean-Michel Mermet Barry Sharp Helen Crews and Ramon Barnes lems. The oral session on ‘Hybrid Techniques’ included papers on elec- trothermal vaporization (ETV)-ICP- AES ETV-ICP-MS ion exchange (1C)- ICP-MS HPLC-ICP-MS and HPLC- HG-ICP-AES. As would you I get confused with so many acronyms. The afternoon oral session was de- voted to ‘Isotope and Biological Analysis’. Ramon Barnes opened the session with the Keynote lecture ‘Iso- tope Analysis in Biomedical Research with Analytical Plasma Source Mass Spectrometry’.The environmental sources of lead poisoning in childhood can be investigated by the use of isotopic ratios. Also lead speciation can be carried out after chromatogra- phic separation of serum proteins and combined with isotopic ratio measure- ments. From this paper and others presented later we could see ICP-MS taking over applications where previ- ously only thermal ionization MS could give reliable results. Highly pre- cise isotopic ratios with an ICP ion source can also be obtained with a multi-collector double focusing mass spectrometer . The third and last Poster Session included papers on ‘Environmental and Biological Analysis Flow Injec- tion Separation and Speciation Tech- niques’. It would be impossible to describe all the techniques and appli- cations here but I will try to summar- ize the main trends.The coupling of separation and preconcentration tech- niques with the ICP-MS (or ICP-AES) provides the ultimate detection limits matrix removal and speciation capa- bilities. Supercritical fluid chromato- graphy has been applied with ICP-MS detection. New nebulizers are increas- ingly applied with the ICP-MS (direct injection ultrasonic). The use of ICP- MS in marine geological biological and environmental analysis is increas- ing rapidly. The Congress Dinner was held on Thursday evening in the Corral del Principe. After dinner Alfredo Sanz-Medel thanked all the delegates for coming to Granada and presented the prize for the best poster. The prize was given to Juan Carlos Fariiias (SpaidFrance) for the poster ‘Study of Laser Ablation of Alumina Ceramics in ICP-AES’.The Flamenco show after dinner got everybody moving and somehow tables were towed away and dancing started the same way you ignite a plasma after seeding some dancing electrons from the Mega- Attending thejnal poster session are L to R Francine Byrdy Joe Caruso and Sandra Clelland Viajes girls. When the dancing was over in the Corral del Principe those of us who were in an ionized or metastable excited state were supplied with free tickets for a well known disco in Granada. Neutrals and heavy ele- ments were rejected (voluntarily) at this stage and returned to the hotels. Changing r.f. and d.c. fields were ap- plied in the disco and an ion-trap type of situation was generated.Multiple ion-ion interactions were observed in a space-charge dominated environ- ment. Slowly some ions were able to exit the ion trap and returned to the hotels. Others less (or more) fortu- nate formed polyatomics and could not exit the ion trap till 8 o’clock in the morning. Friday started with a hangover so it was really hard to attend the Plenary lecture of Cameron McLxod (UK) on ‘Field Sampling and Flow Injection Strategies for Plasma Spectrochemical Analysis’. The basic idea of taking the microcolumn to the sample and pre- concentrating in the field instead of taking litres of sample to the labora- tory is most useful. Moreover for speciation work in natural waters it is a nice way to keep the integrity of the species. Joseph Caruso (USA) spoke on ‘The Potential of Liquid Chromato- graphy ICP-MS for Trace Metal Speci- ation’ in his Keynote lecture.Supercri- tical fluid chromatography offers the advantages of liquid chromatographic separation with gaseous sample intro- duction into the ICP which provides the best levels of detection. The oral session after the well needed coffee break was devoted to ‘Separation Speciation and Flow Injection (FI) Techniques’. Five papers were pre- sented on different applications of microcolumns for preconcentration and elimination of matrix and spectral interferences in atomic spectrometry and on FI coupled to plasmas. The L to R Arfredo Sanz-Medel and Ben Fair- man the conference organizers30N session was closed by Chico Krug (Brazil) with the last Keynote lecture on ‘FI On-line Electrodissolution of AIIoys for ICP-AES’. I found this an elegant method of simultaneously dis- solving and analysing conductive samples. The closing ceremony was addressed by Alfredo Sanz-Medel and Ramon Barnes to a worn-out audi- ence. After thanking the delegates for their contributions and wishing them a JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 safe journey back home it was an- nounced that the next Winter Confer- ence will be held again in sunny California (San Diego) in January 1994. Before I finish this report I would like to thank in the name of all delegates Alfredo Sanz-Medel for a perfectly organized Conference; Ben Fairman the Conference Secretary for being there for everything (even on Friday); and to Mega-Viajes S.A. for their extensive support. J. I. Garcia Alonso Commission of the European Corn m un it ies JR C Institute for Transuranium Elements Posqach 2340 7500 Karlsruhe Germany

ISSN:0267-9477    

DOI:10.1039/JA993080027N

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

30N JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 Book Review Handbook of X-ray Spectrometry Methods and Techniques Edited by RenC E. Van Grieken and Andrzej A. Markowicz. Pp xiv+704. Marcel Dekker. 1993. Price $195.00. ISBN 0 8247 8483 9 This book covers all aspects of X-ray fluorescence spectrometry (XRF) and is divided into 13 chapters each writ- ten by eminent experts in their field. There are of course other books deal- ing with particular aspects of the sub- ject but none as far as I know which cover the subject in such a comprehen- sive and authoritative fashion. Al- though this is a multi-authored (and multi-national) volume there is a freshness in the approach in individual chapters. Eight of the 13 chapters cover aspects that one would expect to find in any self-respecting text on XRF.However the book more than justifies its comprehensive nature in the remaining five chapters which cover more specialized techniques in- cluding more specialized XRF methods that offer ultra-trace detec- tion limits and X-ray microanalysis techniques. The volume starts in a relatively conventional manner in that the first chapter by Andrzej Markowicz (Cra- cow Poland) covers X-ray physics (73 pp.) and includes ten appendices con- taining tabulated data for fluorescence lines and selected fundamental para- meters. As well as the expected data these appendices are sufficiently com- prehensive to include collisional cross section data for absorption and scat- tering processes and the wavelengths of K satellite lines. In Chapter 2 J. A.Helsen (Leuven Belgium) and Andrzej Kuczumow (Lublin Poland) cover wavelength dispersive X-ray fluores- cence (75 pp.) and include interesting technical details of X-ray tube anode technology the analytical character- istic of multilayers and deviations in expected line intensity ratios that re- sult from chemical shift and speciation effects. The authors are sufficiently brave to include an intercomparison table of the technical features of named instruments from commercial manufacturers. Joseph Jaklevic and Robert Giauque (Berkeley CA USA) are the authors of the complementary chapter on energy dispersive XRF (EDXRF) in Chapter 3 (30 pp.) and consider mainly Si(Li) and Ge detec- tors and associated pulse processing technology. Tube-excited EDXRF in- strumentation (with direct and secon- dary target configurations) are des- cribed with applications having an environmental bias.Spectrum evalua- tion is the topic of Chapter 4 which is reviewed in some detail by Pierre Van Espen and Koen Janssens (Antwerp Belgium) in no less than 1 13 pages. By spectrum evaluation the authors mean extracting the information con- tent mainly from ED X-ray spectra. The scope of this chapter is compre- hensive and well illustrated covering topics such as Fourier transformation digital smoothing techniques peak search methods background estima- tion net peak area determination by integration fitting reference spectra and analytical functions. Available computer codes are reviewed and For- tran computer codes listed for many of the more important digital manipula- tions.This chapter clearly has wider relevance than just XRF the spectrum evaluation procedures being equally applicable to ED microprobe and par- ticle-induced X-ray emission (PIXE) spectra and some aspects of high reso- lution gamma spectrometry. I first came across a contribution from J. L. de Vries (Eindhoven The Netherlands) in a book on practical X- ray spectrometry published in 1967 in collaboration with Ron Jenkins. His contribution in the present text with Bruno Vrebos (Almelo The Nether- lands) to Chapter 5 (‘Quantification by XRF analysis of infinitely thick samples’ 44 pp.) is therefore all the more welcome. Matrix corrections areJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 31N here described in 106 equations and topics covered range wider than just correction models since the effect of various sources of error is considered including aspects of sample prepara- tion and instrumentation. Compton scatter corrections are summarized rather more briefly than the use of other non-mathematical methods to compensate for matrix effects includ- ing the use of internal standards stan- dard additions procedures and dilu- tion methods.In addition a range of mathematical correction models are described a useful summary being included of the advantages and limita- tions of each. Quantification in the XRF analysis of intermediate-thick- ness samples is covered by Andrzej Markowicz (Cracow Poland) and RenC Van Grieken (Antwerp Bel- gium) in Chapter 6 (20 pp.) considera- tion being given to particular aspects including the emission-transmission method corrections via scattered pri- mary radiation and particle-size ef- fects in granular samples.John Watt (Sidney Australia) describes radioiso- tope X-ray analysis in Chapter 7 (52 pp.) including a comprehensive de- scription of applications mainly in- dustrial some on-line. The second half of the book deals with complementary X-ray techniques starting with Chapter 8 (42 pp.) on synchrotron radiation-induced X-ray emission by Keith Jones (Brook- haven USA). After an overview of the properties of synchrotron radiation and a description of facilities analyti- cal capabilities and applications are reviewed for both collimated and fo- cused X-ray microscopes with a brief discussion of X-ray tomography EX- AFS and XANES.In chapter 9 (37 pp.) Heinrich Schwenke and Joachim Knoth (Geesthacht Germany) de- scribe total reflection XRF covering the pysics of X-ray reflection design of instrumentation and analytical prac- tice including some reference to depth profiling. Richard Ryon (Livermore CAY USA) and John Zahrt (Los Ala- mos NM USA) discuss polarized- beam X-ray fluorescence in Chapter 10 (25 pp.) with particular reference to orthogonal excitation and detection geometries and excitation by charac- teristic radiation diffracted off a crys- tal through a 28 angle of 90". Particle- induced X-ray emission is covered by Willy Maenhaut (Gent Belgium) and Mas Malmqvist (Lund Sweden) in the next chapter (65 pp.) in a contribution that has a fully developed applications section.John Small (NIST MD USA) describes electron-induced X-ray emission in the penultimate chapter (73 pp.) This chapter is particularly strong on modelling the mechanism of X-ray production and attenuation re- levant to electron microprobe analysis and discusses in some detail X-ray mapping applications and composi- tion-composition histograms which provide the analyst with an image that can be used to interpret the numerical relationship between the various com- ponents in the sample. The final chap- ter (36 pp.) by Jasna Injuk and Renk Van Grieken (Antwerp Belgium) con- cerns sample preparation and services all that comes before in terms of procedures appropriate for the prepa- ration of solid liquid aerosol and biological samples including chemical separation procedures. There are reasons why this book must be highly recommended reading for all involved in X-ray spectrometry. One is the comprehensive nature of the text. Another is the high reputation of the contributing authors almost all of whom will be instantly recognized as having made important contribu- tions in their subject area. A third is the fact that the book is well illustrated with many original diagrams as well as those reproduced from other sources. And the fourth is that the text has been well edited. It is usual in these situa- tions for reviewers to draw the reader's attention to some over-sight or defici- ency in the text. To do so in this instance would be churlish. This is an important book in the field of X-ray spectrometry. Other texts may deal with individual topics in greater detail. However it is unlikely that the entire subject will be covered in a competi- tive text as in 'Handbook of X-ray Spectrometry'. Phil Potts Department of Earth Sciences Open University Milton Keynes

ISSN:0267-9477    

DOI:10.1039/JA99308030Nb

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 31N Diary of Conferences and Courses 1993 Third Annual Flow Injection Atomic Spectrometry Short Course June 1-3 1993 University of Massachusetts Am herst MA USA The course features hands on experi- ments with all atomic spectrometries including ICP-MS. Topics covered will include hydride generation and appli- cations to environmental and clinical samples. For further information contact Professor Julian Tyson Department of Chemistry University of Massa- chusetts Arnherst MA 01003 USA. Telephone (413) 545 0195; fax (413) 545 4856. 37th Summer Short Course in Radio- isotope Techniques June 20-25,1993 Loughborough University of Technol- ogy UK The department of chemistry at Loughborough University is holding its 37th Summer Short Course in Radioisotope Techniques from June 20-25 1993.This course provides a broad outline of modern radio- chemical methods through lectures and practical sessions and is suitable for scientists in both industry and education. It could also provide appro- priate training as required by the Ionizing Radiations Regulations 1985. The fee course is f840.63 (inc. VAT) which includes full accom- modation in the new Short Course Centre Burleigh Court. For further information contact Miss C. L. Archer Course Secretary Department of Chemistry Lough- borough University of Technology Loughborough Leicestershire UK LE 1 1 3TU. Telephone 0509 22258 1. XXVIII Colloquium Spectroscopicurn Internationale June 28-July 7 University of York UK Details can be found in J. Anal.At. Spectrom. 1993 8 1 IN. For further information contact XXVIII Colloquium Spectroscopicurn Internationale Department of32N JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 Chemistry (CSI Secretariat) Lough- borough University of Technology Loughborough Leicestershire UK LEI 1 3TU. Pre- and Post-CSI Symposia Following the tradition that has been established at recent CSI there are a number of pre- and post-CSI symposia on various specialist topics. These are summarized below. 3rd Kingston Conference Analytical Spectroscopy in the Earth Sciences June 28-29 Kingston University Surrey UK Introductory Chemometrics-Short Course June 29 University of York York UK Vapour Generation Techniques Theory and Practice-Short Course June 29 University of York York UK 5th Surrey Conference on Plasma Source Mass Spectrometry July 4-6 Lumley Castle Hotel Co.Durham UK Spectroscopic Data Handling-Short Course July 4-6 University of York York UK Applications of Glow Discharges in Optical and Mass Spectrometry University of York York UK July 4-7 Graphite Atomizer Techniques in Ana- lytical Spectroscopy July 4-7 University of Durham Co. Durham UK Trace Elements in Clinical Chemistry July 7 University of Durham Co. Durham UK Details can be found in J. Anal. At. Spectrom. 1993 8,12N. For further information on the Pre- and Post-Symposia contact XXVIII Colloquium Spectroscopicum Interna- tionale Department of Chemistry (CSI Secretariat) Loughborough University of Technology Lough- borough Leicestershire UK LEI 1 3TU.39th Canadian Spectroscopy Confer- ence August 16-18 Quebec Canada For further information contact 39th Canadian Spectroscopy Conference Department de Chimie Pavillon Vachon Universite Laval Quebec Canada GlK 7P4. Telephone (418) 656 3282; fax (418) 656 7916. 6th Hungaro-Italian Symposium on Spectrochemistry Advances in Envi- ronmental Sciences August 23-27 Misizok- Lillafured Hungary For further information contact Gy. Zaray L. Eotvos University Institute of Inorganic and Organic Chemistry P. 0. Box 32 H-15 18 Budapest 112 Hungary. Telephone 361 181 9778; fax 361 181 1974. 9th International Conference on Four- ier Transform Spectroscopy Ca,gary Canada Scientific Programme The 9th ICOFTS follows tradition in including all endeavours usually but not exclusively of interest to chemists and physicists that involve Fourier transform spectroscopy at wavelengths from the ultraviolet to the far-infrared.Contributed posters are invited on any such topic. The plenary lectures will include application of FTS in industry analysis chemistry and physics as well as advances in the techniques of FTS. The scientific program will con- sist of three or four plenary lectures each day daily poster sessions and an instrument exhibition. August 23-27 Plenary lectures The following scientists have agreed to present plenary lectures M. A. Chesters University of East Anglia UK; Robert M. Corn University of Wisconsin USA; Therese Encrenaz Observatoire de Paris France; Wil- liam G. Fateley Kansas State Univer- sity USA; Yukio Furukawa Univer- sity of Tokyo Japan; Michael C.L. Gerry University of British Colum- bia Canada; Peter R. Griffiths University of Idaho USA; Hideyuki Ishida Toray Research Centre Japan; Robert T. Kroutil Aberdeen Proving Grounds USA; R. Mendelsohn State University of New Jersey USA; Richard A. Palmer Duke University USA; John F. Rabolt IBM Almaden Research Center USA (1 993 Lippin- cott Award lecturer); Otto Schrems Alfred Wegener Institut Germany; Heinz W. Siesler Universitat Essen Germany; Gordon G. Shepherd York University Canada; Herbert L. Strauss University of California USA; and Gwyn P. Williams Brook- haven National Laboratory USA. Topics The 9th ICOFTS includes the follow- ing topics for discussion and display. Methods absorption emission and reflection spectroscopy; theoretical and practical developments of FTS instrumentation; high resolution spectroscopy and analytical spectro- scopy; time-resolved spectroscopy and polarization techniques; intensity measurements microscopy and ellip- sometry; hyphenated techniques and photoacoustic sampling; surface tech- niques sensors and signal processing; and chemometrics and databases.Applications chemistry physics biology and medicine; chemical analy- sis polymers and industry; space the stratosphere the atmosphere; the envi- ronment and remote sensing; catalysis process and quality control; solid state materials and devices; electrochemis- try and interfaces; catalysts and aggre- gates; surfaces and thin films; and molecular design. Exhibition To date some 20 manufacturers of instruments sampling devices ancil- lary equipment and supplies have booked space at the exhibition accom- panying the conference including all major manufacturers of FT instru- mentation.The exhibition will be located in an area which is directly integrated with the lecture auditorium. the poster displays and the refresh- ment stalls. Registration and accommodation Deadline for registration will be July 1 1993. Late registration will be subject to an additional charge of Can. $50. While the exact registration fee has not yet been set it will not exceed Can. f5OO (about US $400 at current ex- change rates). The price of the Confer-JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 33N ence Proceedings (soft cover) and the registration at a substantially lower tion will be available on the University traditional Thursday evening Confer- rate will be offered but will not in- of Calgary campus offering single or ence Social Event will be included in clude the Conference Proceedings. double occupancy rooms and one- the registration fee. Special student University residence accommoda- bedroom suites.

ISSN:0267-9477    

DOI:10.1039/JA993080031N

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 33N Future Issues will Include Use of the Simplified Generalized Standard Additions Method for Cali- bration in Solid Sampling Electrother- mal Vaporization Inductively Coupled Plasma Atomic Emission Spectrome- try-Sylvie Boonen Peter Verrept Luc Moens and Richard Dams Elimination of the Interfering Effect of Transition Metals in the Determina- tion of Tin by Hydride Generation Atomic Absorption Spectrometry-A. M. Abdallah M. M. El-Defrawy Nagwa Nawar and Manal M. El- Shamy Determination of Lead and Copper in Kerosene by Graphite Furnace Atomic Absorption Spectrometry Stabiliza- tion of Metals in Organic Media by a Three-component Solution-Ivana A. Silva Silvia M. Sella Reinaldo C. Campos and A. J. Curtius On-line Removal of Interferences in the Analysis of Biological Materials by Flow Injection Inductively Coupled Plasma Mass Spectrometry-Les Eb- don Andrew S.Fisher Paul J. Wors- fold Helen M. Crews and Malcolm Baxter Fructose-6-phosphate Kinase Immo- bilized on Controlled Pore Glass as a New Substrate for Selective Separa- tion of Antimony(II1)-M. B. De La Calle-Guntinas Yolanda Madrid and Carmen Camara Determination of Trace Impurity Rare Earth Elements in High-purity Rare Earth Element Samples Using High- resolution Inductively Coupled Plasma Mass Spectrometry-Yuichi Takaku Kimihiko Masuda Takako Takahashi and Tadashi Shimamura Flow Injection Systems for Directly Coupling On-line Digestions With An- alytical Atomic Spectrometry. Part 2. Reactions in a Microwave Field- Thomas J.Gluodenis and Julian F. Tyson Speciation of Mercury by Reversed- phase Liquid Chromatography With Inductively Coupled Plasma Mass Spectrometric Detection-Chung- Wen Huang and Shiuh-Jen Jiang Effect of Nickel and Palladium as Chemical Modifiers and Influence of Urine Matrix on Different Chemical Species of Selenium in Electrothermal Atomic Absorption Spectrometry- Francisco Laborda Jorge Vinuales J. M. Mir and Juan R. Castillo On-line Preconcentration and Deter- mination of Mercury by Flow Injec- tion Inductively Coupled Plasma Atomic Emission Spectrometry-P. Canada Rudner A. Garcia De Torres and J. M. Can0 Pavon The OH ‘Bullet’-a Promising Spatial Reference for the Inductively Coupled Plasma-P. J. Galley and Gary M. Hieftje Ultra-trace Determination of Cad- mium by Vapour Generation Atomic Fluorescence Spectrometry-Phillip Goodall Steve J. Hill and Les Ebdon Furnace Atomization Plasma Excita- tion Spectrometry Effects of Sodium Chloride and Sodium Nitrate on Lead and Silver Emission-T.D. Hettipa- thirana and Michael Blades Performance Characteristics for a Glove Box Inductively Coupled Plasma Mass Spectrometer for the Analysis of Nuclear Materials-Jose Ignacio Garcia Alonso D. Thoby- Schultzendorff Bruno Giovanonne Lothar Koch and Helmut WiesmanRamon M. Barnes Editor Department of Chemistry LGRC Towers University of Massachusetts Am herst MA 01 003-0035 Telephone (413) 545-2294 fax 545-4490 Objective The ICP INFORMATION NEWSLETTER is a monthly journal published by the Plasma Research Group at the University of Massachusetts and is devoted exclusively to the rapid and impartial dissemination of news and literature information re- lated to the development and applications of plasma sources for spectrochemical analysis.Background ICP stands for inductively coupled plasma discharge which duringthe past decade has become the leading spectrochemi- cal excitation source for atomic emission spectroscopy. ICP discharges also are applied commercially as an ion source for mass spectrometry and as an atom and ion cell in atomic fluo- rescence spectrometry. The popularity of this source and the need to collect in a single literature reference all of the pertinent data on ICP stimulated the publication of the ICP INFOR- MATlON NEWSLETTER in 1975. Other popular plasma sources i.e.microwave induced plasmas direct current plasmas and glow discharges atso are included in the scope of the ICP IN- FORMATION NEWSLETTER. Scope As the only authoritative monthly journal of its type toe ICP INFORMATIONNEWSLETTER is read in more than $0 coun- tries by scientists actively applying or planning to use the ICP or other types of plasma spectroscopy. For the novice in the field the ICP INFORMATION NEWSLETTER provides a condse and systematic source of information and background material needed for the selection of instrumentation or the development of methodology. For the experienced scientist it offers a sin- gle-source reference to current developments and literature. Editorial The ICP INFORMATlON NEWSLETTER is edited by Dr. Ramon M Barnes Professor of Chemistry University of Mas- sachusetts at Amherst with the assistance of a 20-member Board of National Correspondents composed of leading plasma spectroscopists.The Board members from around the world report news viewpoints and developments. Dr. Barnes has been conducting plasma research on ICP and other dis- charges since 1968. He also serves as chairman of the Winter Conference on Plasma Spectrochemistry sponsored by the ICP INFORMATION NEWSLETTER. Regular Features .Original submitted and invited research articles by ICP and .Complete bibliography of all major ICP publications. .Abstracts of all ICP papers presented at major US and inter- .First-hand accounts of world-wide ICP developments. .Special reports on dcp microwave glow discharge and other Calendar and advanced programs of plasma meetings *Technical translations and reprints of critical foreign-Ian- guage ICP papers.Critical reviews of plasma-related books and software. Conference Activities The ICP INFORMATION NEWSLETTER has sponsored seven international meetings on developments in atomic plasma spectrochemical analysis since 1980 in San Juan Orlando San Diego St. Petersburg and Kailua-Kona. Meeting pro- ceedings have appeared as Developments in Atomic Plasma Spectrochemical Analysis (Wiley) Plasma Spectrochemistry and Plasma Spectrochemistry I/-IV (Pergamon Press) as well as in special issues of Spectrochimica Acta Parts and Journal of Analytical Atomic Spectrometry. The 1994 Winter Confer- ence on Plasma Spectrochemistry will be held in San Diego California January 10 - 15 1994; its proceedings will be published by Fall 1994.Subscription Information Subscriptions are available for 12 issues on either an annual or volume basis. The first issue of each volume begins in June and the last issue is published in May. For example Volume 18 runsfrom June 1992 through May 1993. Backissues beginning with Volume 1 May 1975 also are available. To begin a subscription complete the form below and submit it with prepayment or purchase information. For additional informa- tion please call (41 3) 545-2294 fax (41 3) 545-4490 or contact the Editor. Credit cards accepted. plasma experts. national meetings. plasma progress. To order complete this section and send it to ICP Information Newsletter %Dr. Ramon M. Barnes Depart- ment of Chemistry Lederle GRC Towers University of Massachusetts Amherst MA 01 003-0035 USA. Start a subscription for the following issue CJ Volurne(s)- (June 19- - May 19- ) or 0 19 (January - December). Enclosed 0 Prepayment 0 Check or money order OVISA 0 Mastercard Account No. (All 13 or 16 digits) ) or 0 Send invoice. Date Cardholder Signature .Amount Due $ - Mail to Name Organization Address City Telephone Te I ex/f ax Nofe For each credit-card transaction a 4 % service charge will be added reflecting our bank charges. Current subscription rates are $60 (North America) $85 (Europe South America) or $94 (Africa Asia Indian/Pacific Ocean Areas Middle East and Russia). Back issue rates available on request. All payments should be made with US dollars by draft on a US bank by international money order or by credit card. Foreign bank checks are not accepted. D Purchase order (No. Card holder Name Expiration date - S t a te/C o u n t r y ZI P/Postalcode --

ISSN:0267-9477    

DOI:10.1039/JA993080033N

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 ATOMIC SPECTROMETRY UPDATE-ATOMIC EMISSION Barry L. Sharp* Chemistry Department Loughborough University of Technology Loughborough LE1 1 3TU Simon Chenery 1 151R SPECTROMETRY Leices te rs hire U K Analytical Geochemistry Group British Geological Survey Keyworth Nottingham UK NE72 5GG Raymond Jowitt British Steel Technical Teesside Laboratories P. 0. Box 1 1 Grangetown Middlesbrough Cleveland UK TS6 6U5 Simon T. Sparkes and Andrew Fisher Department of Environmental Sciences University of Plymouth Drake Circus Plymouth Devon UK PL4 8AA Summary of Contents 1 Arcs Sparks Low-pressure Discharges and Lasers 1 .l. Arcs 1.2. Sparks 1.3. Low-pressure Discharges 1.3.1. Glow discharge lamps 1.3.2. Hollow cathode discharges 1.3.3.Other sources 1.4. Lasers 2 Inductively Coupled Plasmas 2.1. Fundamental Studies 2.2. Sample Introduction 2.2.1. Nebulizers 2.2.2. Flow injection 2.2.3. Chromatography 2.2.4. Electrothermal vaporization 2.2.5. Solid sampling procedures 2.2.6. Chemical vapour generation 2.3.1. Torch and generator design 2.3.2. Spectrometers 2.3.3. Instrument control and chemometrics 2.3. Instrumentation 3 Microwave-induced Plasmas 3.1. Fundamental Studies 3.2 3.3 3.4 Instrumentation Sample Introduction 3.3.1. Direct nebulization 3.3.2. Electrothermal vaporization 3.3.3. Chemical vapour generation 3.3.4. Direct analysis of solids Chromatography 3.4.1. Instrumentation 3.4.2. Gas chromatography-microwave-induced plasma applications 3.4.3. Supercritical fluid chromatography 4 Direct Current Plasmas This review describes developments in all aspects of atomic emission spectrometry including fundamental processes and instrumentation reported in the Atomic Spectrometry Updates References in JAAS Volume 6 (91 /C1688-91/4050) and Volume 7 (92/1-92/1447).The full references names and addresses of authors can be readily found from the Atomic Spectrometry Update References in the relevant issues of JAAS. However as an additional service to readers an abbreviated form of each reference quoted (except those to Conference Proceedings) is given at the end of the review. The most significant developments in emission spectrometry relate to the introduction of commercial instruments that employ two-dimensional solid state detectors (CCDs or CIDs) in place of the conventional photomultiplier tubes.These instruments permit considerable flexibility in wavelength selection allow simultaneous background correction and the use of internal standards to improve precision. Undoubtedly they will be a spur to the routine implementation of more advanced forms of spectral processing which hitherto have been only of academic interest. The early promise of discharges in graphite furnaces remains largely unfulfilled and it seems unlikely that these devices will find the universal application of the established source such as the ICP. As mentioned last year the glow discharge continues to be developed and undoubtedly its simplicity and modest cost have encouraged attempts to extend the range of its application. Solid sampling in general continues to be an active area and there has been renewed interest in laser ablation as a sampling technique for optical spectrometry.152R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL.8 1. ARCS SPARKS LOW-PRESSURE DISCHARGES AND LASERS Four reviews of the atomic emission literature have been produced in the last year. Morozov (92/3085) concentrated on regression coupling equations for the analysis of light alloys Busch and Busch (92/3894) collated analytical applications of flame-furnace IR emission spectrometry Chen (92/3976) covered all aspects of AE citing 581 references although in Chinese and Mermet (93/ 1090) reviewed plasmas as a source of photons and ions in chemical analysis 1.1. Arcs The effects of the presence of chlorine in an arc plasma have been calculated by Radic-Peric (92/4625) in respect of B Ca and Si atomic ionic and molecular forms and their spectral line intensities and Zayakina et al.(93/1170 93/117 1) have shown similar reduced emission intensities for Mg Sn Ti and Zn with increasing concentrations of NaCl in the graphite collector. The effects of NaCl on the electrical parameters of an arc burning in a rotating magnetic field have also been studied (92/ 1782). Electro- thermal vaporization of NaCl into a d.c. arc has been achieved using a tungsten spiral (93/703) and the technique has been used to determine Cu with a detection limit of 2 . 7 ~ 10-Io g pl-1 and an RSD of 4.1%. Florian and Terpakova (92/2983) have proved the halogenating ability of CuCl in a study of the evaporation processes of REE in a d.c.arc whilst the influence of discharge media (Ar-N2 Ar-02) on the line intensities of REE has been investigated by You et al. (92/4345). Characteristics of arc AE such as speed simplicity and high sensitivity have been exploited in two specific methods. Xu (93/1031) determined Au in geological ma- terials down to 0.5 ng g-' after separation of the Au by sorption on foamed plastic in a U-shaped glass tube and using NH41 as a spectrochemical carrier for excitation in gas chamber profile electrodes. Detection limits from 2 x lo-' to 5 x for Al Ca Cu Cr Fe Ga In Mg Mn Ni Pb and Si in special purity red phosphorus were achieved by Zolotoreva (93/796). Reported equipment developments have been limited to a study of electrode geometries (93/C82) aimed at designing a hand held spectrometer to provide a more stable d.c.arc excitation for scrap metal analysis and the introduction of a d.c. arc spectrograph with charge injection device (CID) solid state detector (9212055 92/C4180 93/C 178 93/C295). 1.2. Sparks Instrumentation capable of time and spatial resolution has been developed by Lograsso and Coleman (93/C176) to determine number densities of species in a high voltage uni-directional spark. Bye and Scheeline (93/C378) have used similar equipment to make fundamental measure- ments of single discharges and produce electron number density maps and obtained apparent excitation tempera- tures for both analyte and support gas species. They concluded that limitations in the precision of spark source analysis result from the metallurgy of the sample owing in part to the thermal effect of the spark rather than the reproducibility of the plasma and that method develop- ment rather than fundamental research represented the most fruitful development path for spark methods. Stux (93/C995) has followed this road in the use of time-resolved spark analysis to improve the accuracy of metals analysis.Details of a number of spark based analytical methods have been published. Nygaard et a/. (92/3075) correlated results of the well established rotating disc electrode spark technique for oil analysis with those for ICP. Non- equivalence between the techniques was attributed to the diifferent response of each source to viscosity mismatches between samples and calibration standards and suspended particulates.Improved performance over the rotating disc rnethod was claimed by Saba and Byrd (93/1185) who pipetted 5 p1 oil samples onto a paraffin-coated stationary lower electrode eliminated any matrix effect by ashing and then sparked for 20 s. The wide ranging applications of an aerosol-spark technique have been demonstrated by Zhe- leznova and Kuzmenko (93/C958) where sample solution aerosols passed through a channel in the lower electrode after pneumatic or ultrasonic nebulization. Results pre- sented included the concentrations of Al Cd Co Cu Fe IMn Mo and Ni in copper alloys ocean and still waters aqueous solutions of boric acid chloroform extracts and the concentrations of Br Cl and I in solutions of halogen- containing organic substances.A technique for the rapid spark analysis of small solid samples based on pressing specimens into holes in a copper support disc has been developed by Puttman (93/1087). The eternal problem of the rapid determination of acid-soluble A1 in steel has been ,tackled by workers at Thyssen Stahl (92/1918) by the peak integration method. Success was limited by the samples not being homogeneous with respect to A1 and A1203 distribu- tion rather than by deficiencies in the spectrometric method. Spark ablation (SA) coupled with ICP excitation has been used for tin-lead solders (92/252) low-alloyed steel (92/38 19) and ferro-vanadium (92/4627). Each of these publications demonstrated SA-ICP to be a valid analytical technique. Continued development of spark source spectrometry equipment has been described in four presentations (92/C373 1 92/C3737 92/C3789 93/C393).These deal with long-term stability (92/C373 I) determination of nitro- gen in steel (921C3737 93/C393) and digital techniques in the control of source and data acquisition parameters (92/C 3 7 8 9). 1.3. Low-pressure Discharges 1.3.1. Glow discharge lamps Fundamental aspects of the ionization and excitation characteristics of GDLs have been reported by several workers. Horlick (93/C233) used a Fourier transform spectrometer and atomic absorption measurements in a study of neutral atom and ionic species. Straaten et a/. (92/1629) related etching rate to power density and ob- tained good agreement between calculated and measured results at three Ar pressures.They also reported (93/C1328) on the plasma processes occurring in the cathode dark space and negative glow regions. Emissions for three Cu transi- tions were measured by Levy et al. (92/1627) to study charge-exchange processes. Copper ionic emissions were also used by Wagatsuma and Hirokawa (92/1628) to show the effects of He additions to Ar and Ne GD plasmas. Harrison et al. (92/C37 17 92/4598) highlighted the separa- tion of the sputtering and excitation processes within the GD as the phenomenon that separated it from most other spectroscopic sources. Ionization processes in a pulsed GD were also investigated (93/C359). Marcus and co-workers have again made a significant contribution to GD knowledge particularly in the area of r.f. powered GDs. The effects of support gas flow (92/C3424) anode geometry (92/C3425) line selection (921C3459 92/C3727) plasma characteristics (93/C336) the use of Langmuir probes (93/C230 93/C231) and the bulk analysis of high-purity metals and complex alloys (92/C3730 93/C357) were all reported.An r.f GD was used by Kawaguchi et a/. (92/C3526,93/59 1) as both an emissionJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 153R and ion source. The effects of r.f. power gas pressure and sample thickness on emission and mass spectra were studied. Heintz and Hieftje (921C3729) characterized the effects of changing the r.f. frequency in terms of emission characteristics and effective power for both conductive and non-conductive samples. A magnetic field was also added (931C358) to increase sample sputtering and modify the glow region in order to improve analyte excitation.Plasma electron temperatures in a magnetron r.f. GD were reported by Heco et al. (92/C3647) together with experimental conditions for quantitative analysis. Background equiva- lent concentrations were compared with conventional GD- AES. Sacks et al. (9211626 9212058 93/C232 93/C337 93/C356) have continued their development of a planar magnetron GD. Cathode current densities of greater than 100 mA cme2 were easily achieved for pressures in the range 0.0007-2.5 Torr (lTorr= 133.322Pa) with a plasma voltage below 500 V (92/1626 92/C232 93/C337). Spati- ally resolved emission spectral data showed the effects of plasma current and pressure on line intensities for the plasma gas and cathodically sputtered species from a pure copper cathode and a zinc-based alloy reference material.Analytical application of the source was demonstrated by the determination of Al Mg Mn and Ni in a series of six zinc-based NIST standards (92/2058 93/C356). Detection limits of 0.006 and 0.00055% were achieved for Mn and Ni respectively . Steers et al. (93/C23,93/C84) have shown that microwave boosting of GDs enhances strongly the resonance lines of elements in the sample. A high-resolution Fourier trans- form spectrometer was used to enable mechanisms such as excitation by charge transfer to be shown by comparison of spectra obtained with different carrier gases. Gas tempera- tures and the concentration of excited states of Ar have been calculated by Leis et al.(93/C234) from the shape of lines emitted by a microwave boosted GD through which a tuned diode laser beam was directed. The laser wavelength was scanned through & 5 half-widths of the Ar line at 8 10.6 nm. The jet-assisted GD has been further investigated by Broekaert et al. (93/C354); increased sputter rates were confirmed and the nature of sample ablation studied with the aid of electron microprobe and X-ray analysis. Self absorption problems associated with high sputter rates and axial viewing have been tackled by Banks and Blades (93/C355) with a source modified to allow side viewing of the jet-induced plasma plume. Park et al. (931828) capital- ized on the high proportion of ground state atoms in ajet- assisted GD and optimized its design as a source for direct solid analysis by AA.Larkins (9211630) used AA measure- ments to detect the reduced number of free atoms produced when 140 ppm of water vapour was present in the Ar used for a GD. Steel aluminium brass and zinc alloys all showed the same effect; the reduction in absorbance varied from 12% for Ni in steel to 77% for Cr in aluminium. The effect was more pronounced at lower sputtering currents. In- creases in sputtering rate for Si and C resulting from H2 additions to Ar have been reported (92/4523). Glow discharges have for some time been regularly used as ion sources for mass spectrometry; most commonly in d.c. form combined with quadrupole MS. Duckworth (93lC1329) has now developed an r.f. powered GD as an ion source for a magnetic sector mass spectrometer to be used for the direct analysis of insulators.A GD has also been used as a detector for GC. Piepmeier and Kizuya (93/C280) found that a GD cell made to oscillate in the frequency range 0.1-10 MHz and operating at 1.8 Torr could be used to detect fmol amounts of analyte. Hieftje and Starn (93/C334) have described an atmospheric sampl- ing GD used as a detector for SFC. A particularly novel GD development has been described by Sacks et al. (92/1625). Ion bombardment heated a graphite cathode to temperatures suitable for the vaporiza- tion of solution residues from the cathode surface. Cylindri- cal post- and hollow-cathode designs gave maximum temperatures of 2500 and 2100 "C respectively for a 250 mA discharge in Ar at 4.0 Torr. Longer vapour residence times were given by the hollow cathode form.The effect of an axial magnetic field on cathode heating was also considered. Quantification of depth profile measurements using GD have been investigated by Nickel et al. (9213864 92/4626). Reference pellets were produced from powder mixtures of copper with Cr Mn and/or Ti and from Cr203 Mn02 and Ti02. Sputtering rate and discharge current corrections were determined using the base metal as reference and the method was applied to the analysis of oxide scales on Ni-Cr alloys. Another major problem in depth profile analysis crater shape has prompted an examination of the influence of anode geometry on the electric field distribution and crater profile of a GDL (93/1019 93/1187). A ceramic spacer was used for the anode tube to restrict the burn spot which together with optimization of the discharge voltage and pressure resulted in an almost flat crater profile.Kliment (93/C884) also determined optimal experimental conditions for depth profiling of different elemental films on metallic samples. Two Japanese steel companies Kawa- saki (92/3122) and Nippon (9213262) have reported on the use of GDs for depth profiling. In the former work the discharge gas supply was cut off and a preliminary dis- charge used to remove extraneous substances before surface analysis was performed. Workers at Nippon (92/3262) confirmed iron oxide film measurements by GD-AES using Auger electron spectroscopy XPS or SIMS. Bulk analysis of a wide range of iron and nickel alloys has been achieved by Glick and Hieftje (93/723) using an artificial neural network and multivariate calibration of GD emission spectra.More conventional narrow range calibra- tions were used in the anlysis of an iron-based alloy (92/1858) and the effects of microstructure were examined (92/1934). Steel analysis by GD-AES was used to illustrate the performance of a photodiode array spectrometer (92/1688). Limits of detection were poorer by an order of magnitude than those reported for multi-channel photomul- tiplier spectrometers. Sputter rate correction based on the Bengtson model ( see J. Anal. At. Spectrum. 1990 5 563) was demonstrated by O'Gram et al. (93/C83) and similar equipment was used by McGeorge et al. (92/C3724) for cast iron analysis. Small samples of powdered steel ( 1 - 100 mg) were analysed by Luft (91/3549) after diluting to more than 200 mg with copper powder at ratios of between 1:20 and 1:lOO; disks 10 mm in diameter and 0.3 mm thick were pressed surrounded by more copper and pressed again.Measurements of Al Cr Fe Mn Mo Nb Ni Si Ti and V were made using copper as an internal standard. A universal powder technique based on specimens mixed and pressed with copper powder was reported by Ehrlick (92/1623). A comparison of GD and spark AES for the analysis of heat-treated steels (92/4572) illustrated the effectiveness of the GD in producing universal calibrations for a wide range of steel types after sputter rate correction. Precision values for the techniques were similar. A novel technique in which a device containing an aqueous sample was moved towards a GD generated with He flowing at atmospheric pressure was reported (92/4485) to provide solvent vaporization charring atomization excitation and emission.Elements determined were Ag Cd Cr Cu Hg K Na Pb and Zn. 1.3.2. Hollow cathode discharges A short review of plasma processes and some analytical applications of hollow cathode discharges has been pro-154R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 duced in Hungary (92/2974). The authors also reported their work on the changes in plasma characteristics caused by EIEs (92/2683). Reduced line intensities were observed for Sr I1 at 430.54 and 407.7 1 nm A1 I at 494.40 and 396.15 nm and He I at 41 2.1 nm. Senofonte et al. (92/2662) have continued their work on the basic phenomena of the microwave boosted hollow cathode by the quantification of mass variations of cathode bottoms and walls over a 2 h operation with and without microwave boost.Overall mass loss was considerably lower with microwave coupling but emission output for Ag Al C Cu Fe and Ni was much increased. Improved performance was also demonstrated by the determination of Cr in steel (92/2973). Detection limit improvement from the region of 1 x 10-4-1 x loe7 to 1 x 10-6-1 x lo-* mass-% by optimization of excitation processes using magnetic fields and pulsed power has been shown by Maximov et al. (93/C975) for metals oxides and semiconductor materials. Hollow anode FANES has been further characterized by Riby et al. (93/C229 92/C246) with an investigation of the effects of cathode temperature and thermionic electrons on emission signals.1.3.3. Other sources The tandem emission techniques FANES and FAPES have been examined by Falk (92/26 17) and their character- istics compared with other techniques such as ICP. He concluded that separation and hence optimization of the atomization stage and excitation process could not be completely achieved; GDs were more prone to matrix influences than exitation sources working at atmospheric pressure; analyte and matrix concentrations in the excita- tion source were relatively high; and tandem sources needed elaborate procedures for analytical application. Dittrich (92/2496) compared FANES with ETAAS and reported lower detection limits for FANES. Demeny and Bernard (93/1188) however obtained similar detection limits for Cd by the two techniques although FANES provided a wider dynamic range of 6 orders of magnitude.A comprehensive investigation of the influence of experi- mental variables on the analytical characteristics of FAPES has been made by Sturgeon et al. (9212750 93/C157). Forward powers of 50 W were used to establish He plasmas at 13.6 27 40 and 54 MHz and Ar plasmas at 27 and 40 MHz. Excitation temperatures for the Ar and He plasmas were similar = 3400 K. Detection limits were independent of frequency whereas sensitivities increased with frequency and were consistently greater in Ar plasmas for Ag Cu Fe Mn Ni and Pb. Further work on the excitation and detection of molecular species was also reported (92/4642 93/C243). Temporal emission behaviour of Ag Al Mn and Pb in a FAPES source were examined by Blades and Hettipathirana (93/C247) and related to simultaneous absorption measurements.A FAPES type source developed by Kitagawa and Katoh (92/4571) used r.f. power to heat a graphite cup located centrally in a grounded stainless-steel cylinder. The sample in solution or powder form was placed into the cup that was heated to a temperature of about 1900 "C resulting in thermal vaporization/atomization of the sample into the reduced pressure Ar plasma surrounding the cup. Analytical capability was demonstrated by the direct determination of Cl Cu and Zn in standard biological samples. A similar device has been proposed by Winefordner et al. (92/1994) in which a microwave plasma surrounded the graphite cup heating it to vaporize the sample into the plasma.Detection limits of 10-20 pg were obtained for Ag Ba Cd Cu Ga Ge In Li Mg Mn Rb and Zn with RSDs of less than 12%. Goldberg and Robinson have continued development of a plasma gun (9212393) which atomizes the sample in a discharge tube and emits a plasma plume created by 6 kV 50 pF discharges. Emission lines of Ag and V were used to characterize the source which was later coupled to ICP and :MIP for excitation of the atomized sample (93lC333 9 3 x 3 7 7). Plasmas for AE have been generated at atmospheric and reduced pressures using a standard d.c. plasma spraying torch with Ar-H mixtures (93/833). A current of 600 A at 50 V with pressures of 100 and 53 kPa produced local thermodynamic equilibrium conditions in what would appear to be a very substantial source.An a.c. plasma utilizing He support gas between two copper electrodes was used by Colon and Barry (92/2407 92/2630) for the determination of 14 elements in aqueous solution intro- duced via a glass frit nebulizer or a thermospray interface. The role of charge transfer in He plasmas was examined by Camanan (93/C264) who noted the intense line emission of non-metal positive ions not observed in Ar plasmas. Huang and Blades (92/2753 93/C335) tabulated the intensities of near-IR atomic and ionic lines of Br C C1 F I N and 0 in an He capacitively-coupled r.f. plasma between parallel plates. Flames have been used as AE sources for the determina- tion of A1 at the ppb level (92/1692) B via diborane generation and emission in a hydrogen diffusion flame (92/ 1709) and K using a sophisticated statistical method for calibration (92/4309).Cresser et al. (92/2455) attempted to overcome deficiencies in the flame source by movement of the burner height with synchronized AE and AA measure- ment to ensure detection of chemical or incomplete atomization interferences. Segmented flow techniques for cool flame emission were investigated by the same group (93/C88). A combined flame-arc high frequency discharge developed by Prudnikov (92/2280) gave improved stability and a three-fold improvement in the detection limits of A1 and Si. The convenience of using a flame emission source for AA measurements has been demonstrated by Calloway and Jones (921C3750) with results for multi-element anlay- sis and internal standardization. Detectors for gas chromatography have been proposed by Wu et al.(92/4619) and by Webster and Boss (93K338). The former work used an He r.f. plasma for selective determination of N and the latter electric field measure- ments of surface wave launched plasmas. A universal ionization/spectral emission detector was developed by Vasnin et al. (92/C3721) which used a pulsed high-voltage discharge in He to ionize all substances including the permanent gases. Hofmann et al. (93/ 107 1) have added a constriction fabricated from molybdenum to a deuterium lamp to intensify the plasma and improve this standard UV light source. Detailed spectroscopic measurements of elec- tron densities and gas temperatures were reported. 1.4.Lasers Selected applications of lasers in atomic spectrometry have been reviewed by Thiem Lee and Sneddon (93/478) who gave 208 references. To further the understanding of laser- material interactions which are fundamental to the use of lasers in spectroscopic analysis Chan and Russo (931 1 184) have used ICP-AES to study the effects of laser power density the pressure pulse generated by expansion of the laser plasma and sample transport characteristics. Reduced self absorption of the Cu I lines 324.7 and 327.4 nm has been demonstrated by Kuzuya and Mikami (92/4564) with reduced Ar pressure in a laser microprobe. A linear calibration for Cu in aluminium was obtained over the range 1-9.8% at a pressure of 150 Torr. High pressure He has also proved effective as a medium for laser-induced plasmas (92/2752) used as an AE source. High energy densities 1 x 10'' W ern- produced by 80 fs laser pulseshave excited X-ray emissions in the 0.7-0.9 nm range from solid targets (9212699). The possibilities for CW laser radiation combined with an arc as an AE source have been established by Toktogonov et al.(93/793). Laser-induced plasma AE methods have been reported for a wide range of materials. Particulate matter in fluids has been analysed in Japan (92/C3555) and France (9213858 92/4021). A time gated multichannel analyser was used by Petit et al. (921C3352) to determine Mg in aluminium alloys over the range 1 - 10% with a 2% RSD. Microanalysis of steel has been performed by Niemax (92/4335) with particular reference to Cr and Si and similar work on alloys and minerals by Pershin (92/3083) included a comparison with arc excitation of the products of LA.Laser atomic emission and LA-ICP-AES were used in the microanalysis of geolo- gical samples (9213849). Grant et a/. studied iron ore analysis (92/ 1690) and produced calibrations for Al Ca Mg Si and Ti with precision values from 2 to 25% and detection limits of the order of 0.01%. Transfer of the technique to on-site application was discussed. Equipment developed for in situ liquid steel analysis has been adapted by Lorenzen and Carlhoff (92/C335 I ) to scan a pulsed laser over rubber slabs to determine spatial element distribution and provide on- line control of compound homogeneity. Contaminants on electronic microcircuits fabricated on A1203 substrates have been analysed by laser emission (931725) with a degree of depth profile information also being obtained.Experimental characterization of photon detection based on pulsed laser enhanced ionization (LEI) and photo- ionization has been carried out by Winefordner’s group (92/4563) using Mg in a miniature air-C2H2 flame. This resonance ionization detector was used to detect weak Raman scatter of CCl. CHC13 and CH3SOCH3. Interference of the OH radical in the detection of trace metals such as Pb in air-C2H2 flames by LEI was observed by Yan et al. (93/676). Electrothermal vaporization into an air-C,H flame has been used for the determination of T1 in water by LEI (931559). A 200-fold preconcentration by non-aqueous extraction yielded a detection limit of 0.043 ng ml-I.High- purity orthophosphoric acid germanium Cd-Hg-Te alloys and silver nitrate have been analysed by LEI combined with flame and graphite furnace atomizers1ionizers (92/4623). For standard aqueous solution both systems gave detection limits down to the 1 x 10-I6 g level but these were imporoved 1 00-fold when solid specimens ofthe Cd-Hg-Te alloys were used owing to reduced background signal. Detection limits of 2 ng ml-’ of Sm were achieved by Zhang (92/3276) using LEI. A number of other novel uses of lasers have been reported. Electrothermal atomization in a graphite furnace into which a pulsed Nd:YAG laser was focused has yielded detection limits of 5 and 50 pg for Co and Cd with an RSD of 5% using AE detection (93/C331). A pulsed ion gun for laser atomic ionization spectrometry was constructed by Kuz’mina et al.(9213232) and achieved a detection limit of for Ga in indium. Geological samples were evapo- rated with a CW laser (931C927) and introduced into a flame or inert gas jet to be transported for analysis by AA or AE using flame arc spark or ICP excitation. The mecha- nisms involved in multiphoton absorption spectroscopy were described by Ashford (92/2597). Laser-induced fluo- rescence has been used by Westblom et al. (92/2687) to detect N in flames whilst Hollberg et al. (931C250) described the characteristics of the rapidly developing diode lasers and their potential applications to a range of spectrometries. 155R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 2. INDUCTIVELY COUPLED PLASMAS 2.1.Fundamental Studies A number of reviews of ICP-AES have been produced in the last year covering the subject in either a general fashion or concentrating on its fundamental properties and analyti- cal abilities. Gerasimov et al. (9213084) reviewed 107 references on the physical properties and production of the plasma as well as its analytical applications with special reference to sample introduction. Sanz-Medel (92/4520) commented on the past present and future of ICP-AES citing six references and also (9213068) assessed the latest developments and expectations in eliminating the current limitations of the technique (28 references). All plasmas whether ICP d.c.-arc or LA are potential sources of photons and ions. Mermet (93/I 090) reviewed excitation mecha- nisms sample introduction and analytical parameters of different plasmas but also (92/C37 18) discussed why ICP-AES still continues to dominate when compared with AAS and ICP-MS and suggested its future lay with CCD and CID detector systems that allow real-time background correction.Dale (92/C4 194) also compared and contrasted the advantages of ICP-AES and ICP-MS and concluded that AES is more versatile for geochemical environmental and metallurgical analysis when major minor and trace element analyses are all required as opposed to ultra-trace analysis. This will no doubt be agreed upon by exponents of both techniques and is the result of the superior ability of AES to handle high levels of matrix. Wagatsuma (9213093) discussed the effect of r.f generator frequency on the spectral characteristics of the ICP and its analytical per- formance with 12 references while Stern (931 12 19) briefly reviewed (3 references) the application of the ICP-AES to environmental monitoring and process control.Hieftje and his group looked forward to where they believe improve- ments in ICP-AES will be made in the future (92/4597). Topics such as overcoming matrix effects automating and minimizing sample preparation adding diagnostics to instrumentation as well as precision were all considered targets for research and development. Yang and Barnes (9212544) have produced a very comprehensive (1 25 references) review of the advances in plasma process modelling and computer simulation since 1984. Blades (92/C3392) specifically reviewed plasma excitation mechanisms and observed that comparisons between models and experimental results are complicated by three types of plasma inhomogeneity spatial temporal and compositional. Zheng et al.(931495) considered the factors influencing matrix ion1electron number density and plasma temperature. The effects of concentration observa- tion height plasma power and carrier gas flow on the continuum from calcium magnesium and aluminium matrices were noted. Results showed that the continuum intensity varied in a complex way with these parameters. Sun et al. (93/789) produced axial profiles of the degree of ionization in plasmas. The effect of plasma power and carrier gas flow rate on the profiles were determined and they concluded that the degree of ionization was not related to the excitation characteristics of the ICP directly and surprisingly the influence of matrix elements was insignifi- cant.Huang and Hieftje (92K4110) used laser light scattering to study fundamental excitation parameters such as electron temperature electron number density and gas kinetic temperature. Galley and Hieftje (93/C26 1) calcu- lated spatial distributions of excited atomic and ionic states using Abel inversion asymmetric Abel inversion and computer tomography. The computer tomography although time consuming and complex was considered to provide the most accurate models. Computer simulation was also used by Cai and Montaser (931C2 10) to predict the effect of156R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL.8 He ICP operating conditions on fundamental plasma properties. This was then compared with experimental data. A different approach to measuring fundamental ICP parameters was taken by Strother et al. (9212627) who measured temperature profiles using two colour IR optical pyrometry. Position- and power-dependent temperatures between 1668 and 2543 K were recorded. The spatial dependence of the temperature closely resembled that of the electron number density suggesting that this plays a significant role in determining the thermodynamic temper- ature in an ICP. The importance of the atomization step (occurring on a millisecond time scale) as opposed to the excitation stage (on a nanosecond time scale) has perhaps been underplayed in the past. Mermet observed (931C207) that departures from LTE and matrix effects can be related to parameters influencing the atomization step.These parameters include the size and state of the test material its residence time in the plasma and the efficiency of energy transfer. Some of the most significant work this year on the fundamental pro- cesses of atomization and excitation in the ICP has been described by Olesik and co-workers (9211978 9211979 and 931C206). They demonstrated how the presence of incom- pletely desolvated droplets resulted in changes in the Ca I and Ca I1 emission intensity by factors of 25 and 2.5 respectively. In the region near a solvated droplet Ca I emission was enhanced while Ca I1 was depressed and this directly affected the vertical emission profile. Further to this at the observation height of peak emission intensity (either Ca I or Ca 11) the number of desolvated droplets remained constant regardless of plasma power or injector gas flow rate.The result of these effects was that the time resolved Ca 1:Ca I1 ratio varied by a factor of 70 and was controlled by the fraction of time during which an incom- pletely desolvated droplet was in the observation zone. Farnsworth and Ogilvie (931C204) and Wu and Hieftje (931C258) also studied excitation mechanisms by observing the response of atom and ion lines when large droplets passed through the plasma. In both studies correlation spectroscopy was used to show the relationship between atom and ion line intensities. Wu and Hieftje estimated how droplet size distributions changed vertically in the central channel with respect to plasma power and injector gas flow rate.The measured vaporization rate of particles was compared with that predicted and modelling suggested that particle vaporization was rate limited. Browner et al. (931C259) and Blades and Wier (931C260) both considered the effect of solvent load on fundamental ICP parameters particularly with reference to organics and this has pro- vided useful baseline data. The study of noise in ICP-AES has been of perennial interest and its reduction is the key to improving the quality of analytical data. Snook (931C22) has characterized noise and separated additive and multiplicative components. The dominant noise was multiplicative and resulted from pneumatic nebulization and desolvation processes.Sharp (931C3 931C266) discussed the origins of noise and the influence of the interaction between the sample and analytical system. It was noted that flicker noise cannot be removed by increasing measurement time. Previous noise studies have concentrated on noise above 10 Hz however measurements were made typically on the 1 - 10 s time scale. Both conventional and novel signal processing strategies for reducing the effect of very low frequency noise were discussed. Of practical help Easley et al. (9212633) demon- strated that noise in the 200-500 Hz region could be reduced by the use of a chimney over the plasma. Unfortunately this had Iittle effect on the magnitude of the 11’ noise. Novel fundamental investigations have included the measurement of space-time emission profiles from a pulsed plasma (9311084).A comparison of the performance of various mixed gas plasmas that appear to offer better detection limits has been presented (92/2975) whilst Barnes (931 10 1 1) has described a sealed and static ZCP-AES system for the analysis of gases specifically arsine. A Fourier transform spectrometer has been used to character- ize spectral sources (93/C3394) its rapid acquisition of multi-line intensity data aided the excitation temperature measurements. An AES facility has been added to an ICP- MS instrument by coupling the radiative output with a fibre optic (921 1984) and it was concluded that compromise ICP parameters had to be used. The use of the ICP as a fluorescence source has never really taken off but Ng et al.(931668) have demonstrated that dye lasers are an ideal excitation source for optimal sensitivity. If dual laser double resonance excitation is used the result is highly element specific. The analytical performance of ICP- LEAFS was evaluated for 17 elements using both atomic and ionic lines. Detection limits ranged from 0.2 ppb (Sc) to 364 ppb (W). Freedom from spectral interference can give this technique special advantages for trace element analysis in complex matrices. 2.2. Sample Introduction Borsier (9214726) has conducted a review of sample introduction with respect to the so called hyphenated techniques (spark and LA FI ETV and chromatography) with 12 references. Cassagne et al. (921C4183) have also reviewed the factors limiting the precision of ICP-AES analysis with particular reference to sample introduction.2.2.1. Nebulizers The fundamentals of sample introduction in particular nebulizers have preoccupied Browner and co-workers for many years. They considered (921C3283) that much of the current understanding of nebulizer sample introduction is based on unsound theory and described the importance of a correct understanding of aerosol generation because of its effects on transport parameters. It was felt that optimal aerosol generation would have a significant impact on future developments in ICP/MIP spectrometry. Data were presented linking the droplet size distribution with preci- sion and accuracy. It was suggested (931C183) that for nebulization the key parameters are optimum mean drop size optimum size distribution and the ratio of solvent to vapour.Using the best available data predictions were made on the ideal aerosol and how it might be achieved. Zheng et al. (921C4113 92/C4114) reported on the use of Monte Carlo techniques in nebulization and aerosol tran- sport. They simulated different solution properties operat- ing conditions and nebulizer dimensions to obtain data on nebulization efficiency and total mass transport rate. Simulations of the rate of aerosol droplet evaporation suggested that this has a minimal effect on transport processes and four fifths of the total transported mass is evaporated in the plasma. Luan et al. (921C3286) studied the noise characteristics of various nebulizers and spray chambers using laser light scattering from the aerosol.Power spectra were produced from the scattered radiation by a spectrum analyser. Evidence suggested that pumping was the main source of discrete noise frequencies and that this could be eliminated by the use of pulse-free pumps. The Scott type spray chamber was found to suppress white noise while llf noise was a major cause of instability with ultrasonic nebulization. Ultrasonic nebulizers (USN) have provided much inter- est this year and have continued their revival. A number of new devices with particular characteristics have beenJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 157R produced. For example a geyser type made from a low cost humidifier (92/1671) has been described. The USNs are often expensive but equivalent performance to conven- tional designs has been obtained from a device with simplified cooling and reduced production costs (921C3289). An ultra-sonic transducer sprayed with a jet of test solution that allowed increased aerosol production while minimizing wash-out time was described and the fundamentals of aerosol production and performance dis- cussed (921C3290 921C3759 93/C40 1).A multi-stage cryogenic method for removing volatile organic solvents such as methanol and acetonitrile after ultrasonic nebuliza- tion has been reported (9213 105). Several commercial units have been described and evaluated (9212460 921C33 13 921C3809 931C309 92x33 1 1 9213801 92K4184 93/C95 1). Applications of USNs have included the analysis of metals in waters by Bannister and Te Hennepe (92/C1953) where the use of a USN avoided preconcentra- tion a time-consuming and potentially contaminating process.It was concluded that great care was needed with optimization and QA/QC procedures should be used. Interestingly the USN was found to yield different recover- ies of metal present in solution and associated with suspended matter when compared to a pneumatic nebu- lizer. Chan and Geil(921C3803) used a USN to achieve the EPA required detection limits for As Pb Se and TI under a QA/QC regime and reported (92/C3312) that As Cr Mo Se and Sn could all be easily detected in biological samples produced by a veterinary laboratory. They also compared oil samples analysed after acid digestion organic solvent dissolution and ultrasonic emulsification (921C3359).Botto (921C3316) investigated the use of a USN for petroleum and petrochemicals and concluded that the high nebulization efficiency offset the degradation of analytical quality arising from residual solvent loading after desolva- tion. Fukaza et al. (921C3708) found that this technique could reach the detection limits of ETV-AAS but was easier faster and more precise for the determination of As Bi Pb Sb Se Sn and Te in copper after indium coprecipitation. A significant amount of work is now being produced on the thermospray nebulizer. It is hoped that this will result in more efficient coupling of HPLC to ICP-AES as this is an area ripe for exploitation. Coetzee and Robinson (9212554) developed a thermospray nebulizer using a stainless-steel capillary heated spray chamber and a desolvator.This produced an 8-fold increase in sensitivity over conventional nebulization but direct injection resulted in flicker at liquid flow rates above 0.1 ml min-l. Elgersma (9211988) investi- gated a thermospray nebulizer specifically designed for coupling either a micro-HPLC or an FI system to ICP-AES. This used a 50 pm fused silica capillary expansion chamber and desolvator. The system could be optimized for a 120 pl min-l flow rate of a methanol-water mixture (8:2). When using FI carrier flow rates of 100-500 pl min-l could be used very reproducibly. An optimum flow rate of 400 pl min-l for carrier and 80 pl sample injections yeilded ppm- level detection limits for 10 elements. Koropchak et al. (93/C399) used a silica capillary with a diameter of 150 pm but this had a short length of 20 m capillary fused to the end.The characteristics and capabilities of this nebulizer were discussed for a variety of matrices. Peng et al. (931649) found that although the thermospray nebulizer had superior detection limits compared with a Babington type nebulizer it suffered from serious matrix effects. A number of new nebulizers have been described. Ivaldi et al. (92/1641) designed and evaluated a conespray nebu- lizer as proposed by Sharp. Short term precisions of < 1% RSD and long term (8 h) precisions of approximately 1 Yo RSD for both simple and high salt matrices were reported. Sensitivity and detection limits were similar to those produced with a cross-flow nebulizer. It was considered to provide a similar performance to the best of the Babington type nebulizers.Guo and Li (93/5 15) tested the GMK stop- flow nebulizer with high salt solutions and found it successful in avoiding clogging and memory effects. Beres et al. (921C3805) have produced a new cross-flow nebulizer with polished sapphire tips inserted into polyether ether ketone (PEEK) bodies. It was found to resist attack from all common acids and solvents including HF and HC104. This was an interesting use of an old methodology im- proved by the use of new materials. Berndt and Schaldach (92/2086) used hydraulic high-pressure nebulization for both aqueous and organic solvents. Relative signal intensi- ties were compared with those from conventional nebuliza- tion. Todoli et al. (93/C79) also used a high pressure pneumatic nebulizer where gas and liquid streams both passed through the same orifice.The droplet size distribu- tion and detection limits were measured at various gas and liquid flow rates. Fischer and Rademeyer (93/C972) used a heated nebulizer system to determine directly metal concen- trations in waxes greases and fats. Problems and para- meters affecting efficiency and sample transport were considered as were the problems of reference materials and calibration. Spray chambers are often considered the junior partners of a sample introduction system but they make an important contribution. Wu and Fu (931650) produced a multi-function spray chamber that could be used in a variety of modes. The spray path was selectable to obtain the best S/B and stability.No matter which combination of nebulizer and spray chamber is used there is always a certain amount of wasted time while the signal stabilizes prior to analysis and decays afterwards. Brown et al. (93/C2 1 1) suggested that this wasted time could be used if a dual multiplexed sample introduction system was used. This configuration overlaps the data aquisition time of one sampling system with the equilibrium cycle of another. 2.2.2. Flow injection The advantages limitations principles and applications of flow injection methods are discussed in a review by Fan and Fang (92/2253) and again by Fang in another paper (9212105). Flow injection has been used by several workers to effect analyte preconcentration. For example Moss and Salin (93/722 92K3281) used a chelating column and direct sample insertion incorporating a cup specifically designed for liquids. The overall detection limits improved by a factor of 140-1200 for Cu Pb and Zn.Gold at the ng ml-I level in natural waters has been preconcentrated on microcolumns of either Amberlyst-A26 or sulfydryl cotton. Detection was by ICP-AES and ICP-MS (93K27). A new and interesting approach to sample collection and preservation has been described by Gomez et al. (921C3484). Microcolumns of ion-exchange resins were used to collect analyte species at the sampling point and the columns were then returned to the laboratory for elution and quantification. Sulfur in steels has been determined using a microcolumn of activated alumina (9311012). The S was collected as the sulfate ion whilst the iron passed through the column.The detection limit was 0.3 pg g-l. Caroli et al. (9212515) have preconcentrated Cd Co Cu and Pb from waters and urine on a column of iminodiacetic acid-ethyl cellulose and found that the performance of this system compared favourably with other resins. Limits of detection were improved by 1-2 orders of magnitude and 12 samples per hour could be analysed. Iodine as I- and 103- has been preconcentrated by factors of 207 and 15 respectively on a membrane disc containing an anion-exchange resin (92/2396). After preconcentration the I- and 103- were oxidized to I2 to enhance analyte158R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 transport to the plasma. Other methods of FI preconcentra- tion have also been reported.Copper has been preconcen- trated from water samples by FI solvent extraction using dithizone-CCI followed by detection by ICP-AES (9212740). Good agreement with the certified value of NIST SRM 1643 water was obtained. Ten-fold preconcentration was achieved yielding a limit of detection of 0.1 ng ml-I. A novel method of preconcentration using Donnan dialysis ion-exchange membranes has been described where enrich- ment factors of up to 100 were obtainable for a 5 min dialysis period (93/C402). Flow injection has also been combined with HG as a means of sample introduction to an ICP-AES system. Gao and Li (931686) used a mixture of KI ascorbic acid and thiourea to eliminate interferences in the on-line FI-HG- ICP-AES determination of As Bi and Sb in geological samples.Limits of detection were 0.2,O. 1 and 0.2 pg g-' for As Bi and Sb respectively and the analysis rate was 60 samples per hour. Standard additions methods have been used with FI techniques. Shen et al. (92/2738) nebulized sample solu- tions continuously and made discrete injections of aqueous calibrants into the sample stream. Recovery for some REEs was 85-1 12% and precision was 4.2% RSD. A program- mable system for dilutions and standard additions has been described (921C3279). As an application Ca Mg and P in digested plant materials were diluted and determined simultaneously. Standard additions were used to determine Al B Cu Fe Mn and Zn in the digests. Good agreement with certified values was obtained. On-line digestion has been reported by Karanassios et al.(92K3346). A sample slurry and acid were pumped into a coil and the flow was stopped. The coil was then sealed and the enclosed sample exposed to microwave radiation for 2 min. The system was reported to provide rapid precise and quantitative digestion of biological and geological samples. A similar procedure has been described by Gluodenis and Tyson (9214636). These workers used an oven and high- pressure conditions for the on-line digestion of cocoa powder. Dickinson et al. (92/CI 959) have used FI to enable direct determination of Cr Fe Mn and Zn in samples such as 30% sodium chloride and 1 mol 1-* ammonium acetate which have a high dissolved solids content. Zhang and Zeng (93/496) studied the matrix effects of sodium chloride on the determination of 11 elements by FI-ICP-AES.Flow injection reduced signal drift and improved the reproduci- bility. The effects of the NaCl varied with r.f. power and it was concluded that the interferences existed in the evapora- tion-atomization-excitation process of the plasma. Discon- tinuous flow analysis and the advantages it offers over continuous flow has been described by Kimber et al. (921C4 195). 2.2.3. Chroma tograph y There has been a large increase in the number of reports using ICP-AES as a detector for chromatography. Howard and Hunt (92/4729) reviewed (14 references) the use of AAS AES and AFS coupled with GC SFC and LC. The problems of interfacing were discussed. Liquid chromato- graphy remains the most popular of the separation tech- niques for coupling with ICP-AES.A chelating resin was used to preconcentrate analytes selectively from matrices such as sea-water whilst background and spectral interfer- ences were reduced (93K238). Porta et al. (9213821) also used a chelating resin (XAD-2 functionalized with 1-(2-thi- azoylazo)-2-naphthoI to preconcentrate Cd Cu Fe Mn Ni and Zn from waters. Limits of detection were 2-40 ng 1-1 and precision was less than 5% RSD. Lanthanides in rock samples have been separated using a cation-exchange resin and ammonium lactate or a-hydroxyisobutyric acid in the mobile phase and detected simultaneously by Sawatari et a/. (931588). In a similar paper the workers determined 15 Nanthanides in less than 40 min per run and obtained detection limits of 0.4-30 ppb (921C3559). Chromium Mn Mo and Ni have been determined in steel samples with results close to the certified values for all except Cr (93/434).The REE were determined in terbium and terbium oxide using a reversed-phase column and an eluent of 2-hydroxyisobutyric acid with recoveries in the range 85-1 00% (9213045). Watkins and Nolan (9213852) deter- mined Hf Sc and Y in geological samples using a cation- exchange column. Limits of detection were 0.2 0.1 and 0.2 eg g-l,. respectively. Boron has been determined in iron and iron disilicide by Yamada et a/. (92/44 17) using an anion- exchange column. Good agreement with certified values was obtained and the limit of detection was 0.05 pg g-' in the iron sample. Metallothioneins have been separated successfully and characterized in biological (9318 52) and marine samples (9212556).Liquid or ion chromatography has been used extensively for speciation studies. Carney et a/. (931C340) used HPLC-ICP-AES to separate butyltin trichloride from tin tetrachloride. Derivatization was not necessary and as an application industrial air samples were monitored. Vanadi- um(v) and VIv species have been determined and precon- centrated from natural waters using a two column system (921260 1 ). Immobilized silica gel bonded with ethylenedi- amine was used to separate Vv and silica gel bonded with ethylenediaminetriacetate was used to collect both Vv and VIv. Recoveries of 9 1-105% and enrichment factors of 40 were obtained. Sulfur speciation has been achieved by Shan et al. (92/C4 124). For the determination of total S in soils a digestion using HN03-HClO under pressure was rec- ommended. The speciation consisted of a sequential extrac- tion procedure in which water soluble adsorbed dilute HCl volatile and soluble pyrite HI reducible ester and carbon- bonded S were determined.Sulfur speciation has also been reported by Halmos and Borszeki (921C4230). Arsenic speciation has again been reported by Rauret et al. (92/2007). Arsenic(rIr) methylarsonic acid dimethylarsinic acid and AsV were eluted from an anion-exchange column using a phosphate mobile phase. The eluate passed into a hydride generator and the hydrides evolved were deter- mined by ICP-AES. Limits of detection were 3.5 3.8 21.3 and 9.2 pg l - l respectively. Recoveries were close to 100% for all but As1[' which was 83.5%.Wiederin (921C3470) separated and quantified various inorganic forms of As Cr and Se using a microcolumn and a direct injection nebulizer. Detection limits were reported to be in the low- ppb range. An ultrasonic nebulizer and various tetraalky- lammonium salts as ion-pairing reagents have been used for the speciation of the same analytes (9212839). Again detection limits were in the low-ppb range. The interface between a microcolumn used for speciation and an ICP- AES detector has been studied by Jinno (921C3465). It was concluded that the column should be coupled directly to the torch to achieve maximum sensitivity and repeatability and to avoid dilution effects produced by the spray chamber. A similar interface was found to be oecessary for coupling SFC with ICP-AES.Laborda et a/. (9211989) also made a comparison of interfaces for speciation purposes. A ther- mospray nebulizer was found to have three times the sensitivity and to be three times more tolerant of organic solvents than a cross-flow nebulizer. Initial results for the speciation of Se as (CH3)3Se+ Se03*- and Se0,2- were promising. The ICP is less commonly used as a detector for other chromatographic techniques. Kato et al. (9213820) have determined methylmercury species by capillary column GC using an axially viewed ICP-AES system with an echelleJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 159R monochromator as a detector. The methylmercury species were converted to the iodide form and separated on a chemical bonded fused silica capillary column coated with methylsilicone.The detection limit was 3 pg and the linear range covered 3 orders of magnitude. Gas chroma- tography-ICP-AES has also been used to study the uptake of 17 elements from sea-water by oysters (921C3573). Size exclusion chromatography has been used successfully to study Fe concentrations as a function of molecular size in bitumens (9311142). A thorough review of packed micro- column SFC coupled with ICP-AES has been presented by Jinno (931610). The problems in the coupling of these two techniques were discussed and overcome. 2.2.4. Electrothermal vaporization A review containing 54 references on the analysis of biological materials by ICP and MIP using thermal vapori- zation as a means of sample introduction has been presented by Matusiewicz (92/4284).Huang et al. (93/68 1) have studied the vaporization mechanisms of analytes of different volatilities. Effects such as vaporizing current and the volume and geometry of the atomizer were studied. Matousek and Mermet (921C3401) have used ETV to determine the effects on the plasma of hydrogen that does not originate from water. Huang et al. (92/2735) studied the effects of transport efficiency between the vaporizer and the ICP. Parameters such as tube material length temperature and diameter were all studied. In a similar paper the mechanism of analyte condensation in the transport pro- cess was explored (93/ 1 123) and non-rare earth impurities in lanthanum oxide were enriched by diethyldithiocarba- mate-CC1 extraction and determined by this technique.The same authors also developed a device that prevented sample expansion between the vaporizer and the ICP (921C4128). As a result increased signal intensity was achieved. The authors also concluded that platform vapori- zation was not suitable for ETV-ICP-AES. The use of halogen-containing compounds to vaporize analytes into an ICP is still receiving a lot of attention with solid liquid and gaseous reagents all being used extensively. The most common solid fluorinating agent used is PTFE. Huang et al. (9212486) used a PTFE slurry to aid the vaporization of carbide forming analytes such as the REE. Detection limits were two orders of magnitude better when fluorination was used and memory effects were negligible. Hu et al. (9211807 9212019 9212615) have produced several papers in this field.Chromium in serum with a detection limit of 1.4 ng ml-l (92/1807) B in plant leaves by a standard additions method with no interferences from Ca K Mg or Na (9212019) and Mo in food slurries with validation by the use of CRMs (92/2615) have been determined. Both solid and gaseous halocarbons have been used by Jian et al. (921C33 18) to volatilize away the matrix. The system used a modified ETV-ICP-AES system that enabled both solid and liquid samples to be analysed. Two types of interface were compared by Kantor (92/4622) using cadmium as the best analyte. Matousek and Wu (921C 1944) have used CC14 and CF3CH20H to volatilize V and W. Memory effects were completely eliminated and the limits of detection were improved over the use of argon-chlorine mixtures. Tungsten filaments continue to be used as electrothermal vaporizers.Fujimoto et al. (921C3584 and 93/592) com- pared direct sample insertion (DSI) using Freon-assisted volatilization with ETV. It was found that DSI was more resistant to oxidative attack but that ETV gave better detection limits. Graphite cup DSI devices have been used successfully by Abdullah et al. (92/C4 199) who managed to obtain superior LODs and precision than with conventional nebulization. Preconcentration of analytes from sea-water and analysis of both solid and liquid matrices was also achieved. Umemoto and Kubota (9211998) compared DSI with normal nebuli- zation. The DSI plasma was found to have a different structure yield a slightly reduced linear range and an electron density 4.5 times lower than when conventional nebulization was used.Background intensities were found to be inversely proportional to the thickness of the graphite cup with a cup of wall thickness 0.5 mm producing an intensity 1.7 times lower than conventional nebulization. Umemoto and Haraguchi (921C3591) used DSI to deter- mine Cu and Fe in lead and zinc metals. Detection limits were 5 ppb for Cu and 20 ppb for Fe in a 2 mg sample. Results for the analysis of CRMs were in good agreement with certificate values. Bir and Rybarczyk (92/C3301) have described a FAPES system constructed from commercially available compo- nents. The performance in terms of detection limits and interferences were discussed. Liang et al. (92/C38 14) have again reported a graphite furnace plasma source for atomic spectrometry with the developments anticipated previ- ously (see J.Anal. At. Spectrom. 1992 7 165R) described. The salt-induced matrix effects in a niobium carbide coated ETV-ICP-AES has been reported by Soman and Gilbert (92lC3293). Transport efficiency was found to be affected by a sea-water matrix. Numerous applications of ETV-ICP-AES have been reported. Mikasa et al. (92/C3609 and 92/4722) determined B in silicon and silica. After dissolution of the sample B was extracted into toluene as the tetrafluoroborate ion associated with Ethyl Violet. The B was then determined by ETV-ICP-AES giving a detection limit of 1 ng ml-I. Another interesting way of determining B in pure iron was described by Yoshikawa and Funabiki (93/C50).They reacted B with methanol and sulfuric acid in a pyrolytic carbon coated tube and determined the evolved methyl borate. Wear metals in lubricating oils have been deter- mined and the results compared with those obtained by rotrode emission spectroscopy (92K33 1 5). Plutonium in urine (931C30) and Cu in pure iron reference materials have also been determined (9213260). In this latter paper 25 analytes were measured simultaneously but precision was poor. This was attributed to the optimum heating pro- gramme being different for each analyte. A method of preconcentration by repeated injection and desolvation has been described by Zhang et al. (931697). Cadmium Pb and Zn have been determined in botanical samples using pelletized solids (92/2404 and 93/C398).The sample was mixed with graphite and pressed into a pellet. The pellet was then heated resistively and the vapour swept to the plasma by a flow of Ar. Detection limits were I 0.6 and 3 ppb for Cd Pb and Zn respectively. 2.2.5. Solid Sampling Procedures Dean (9211460) provided the sole general review of solid sample introduction devices along with those for liquid and gaseous introduction (22 references). Van Loon et al. (921C4126) appraised direct injection techniques such as probe ETV and slurry nebulization for different types of geological industrial and biological test material. Their important conclusion was not surprisingly that no one method was suitable for all sample types. Zaray et al. (92/2507) observed that when comparing direct and indi- rect analysis of trace elements in pure alumina the most suitable solid sampling method depended on the physical properties of the Al,03 such as the mean grain size.Chenery (92/C4080) when reviewing his work on small scale solid sample introduction stressed the importance of consider- ing absolute instrumental detection limits rather than the more conventional concentration based limits.160R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 A small but significant increase of activity in laser ablation for ICP-AES has occurred this year but few new workers appear to be entering the field. Perhaps this will change if the explosion of interest in LA for ICP-MS crosses back to ICP-AES. Unfortunately the cost of an LA system is still relatively high when compared with the cost of an ICP-AES.The use of LA was reviewed ( I 1 references) by Sneddon (92/4472) while Monke-Blankenburg reviewed her own extensive work (921C4107). In this field funda- mental and methodological work is of great importance. Thus Chan and Russo (9212785) monitored the laser- material interaction using spatial and temporal ICP-AES response. Observations on the effect of laser power density condition of sample surface pressure pulses and sample transport were all reported. This work was further devel- oped (931C352) by comparing the effect of the power density of the laser pulse using excimer and Nd:YAG lasers of similar wavelength but different pulse lengths (20 ns and 30 ps respectively). The results were assessed in terms of mass of material ablated and elemental ratios from test materials as measured by the ICP-AES. Mermet et al.(93/C92 1) have investigated the effects of laser parameters such as wavelength (Nd:YAG 1064 532 266 nm and excimer 308 nm) mode (normal and Q-switched) energy density and spot size. Both the amount of material ablated and the ICP-AES response were investigated. The influence of target type (metals and glasses) surface state and transmittance was also observed. They concluded the current lack of understanding does not preclude the use of LA because of its successful performance. Greenhill (9113404) also varied the wavelength of a laser system using harmonic generating crystals from the near-IR to the UV to optimize ablation of various test materials including ores aluminium alloys and carbon based samples.Monke- Blankenburg (92/C3353) reported that transient ICP-AES signals from single shot LA can be described in time by mathematics analogous to FI. Results from models were compared with those found experimentally and new methods of quantification were evaluated. Furuta (92/2634) when analysing pond sediment powder pellets described the effects of transport tubing on emission. It was observed not surprisingly that a 30% variation in response could be reduced to 4% by the use of an Fe internal standard and translation of the sample. Various new analytical methodologies have been pro- posed. When the ablation cell is remote from the ICP-AES by several metres a loss of test material is observed. Lui and Horlick (921C3373) tried to resolve the problem by three alternative methods placing the sample immediately below the ICP torch; placing the sample in the ICP torch on a graphite rod; and ablating material remotely onto a graphite ring and subsequently introducing this into the torch.Iada et al. (9212406) have ablated material under water such that all the material was captured. This slurry was then either nebulized directly or first dissolved. This methodology also allowed filtration of material for observa- tion by SEM. Lin et al. (921 1790) have used a continuous CO laser to ablate totally small samples of test material thus overcoming any matrix effects from phase separation. A detection limit of 1 ppm of Yb was obtained in pressed powder pellets of REE ores and graphite binder.This laser was also used for the ablation of liquid droplets and detection limits twenty times better than solution nebuliza- tion were obtained for Ag Cd and Yb on 20 pl samples. Jowitt and Whiteside (931 1 106) described the analysis of molten steel by observing the real-time emission of the ablation microplasma or by carrier gas transport of the ablated material to an ICP-AES instrument. Applications of LA sampling have continued to be dominated by geochemistry. Li and Duan (9213946) ana- lysed ion-exchange paper on which REE from rocks had been deposited. Thompson et al. (93K38) investigated the ferro-manganese oxide coatings on stream pebbles and trace elements concentrations delineated known copper and gold deposits in North Wales. Ramsey et al.(9311000) have now validated their analyses of large fluid inclusions (> 30 pm) in topaz and halite. Calibration was performed by using sensitivities obtained from aqueous nebulization. Validation was by comparison with qualitative SEM semi-quantitative crushed leach ICP-AES and quantitative synchrotron XRF. Monke-Blankenburg and Gunther (92/3849) used their solid-liquid method of calibration and a Ti internal standard for the determination of La in pseudo-brookite. Fomenkov (921C3376) choose to analyse trace elements in LiF crystals by LA in preference to nebulization because of the low solubility of some fluorides. Slurry nebulization although an established technique for the introduction of solid samples in ICP-AES failed to make a significant impact in the literature.This is partially explained in a review of the advantages and disadvantages of the technique by Jarvis (92/3848) who suggested the major problem is poorer precision compared with solution nebulization. Quantification of the problems was provided by Laird et al. (9114036) (see also Ebdon,L. and Collier AX. Spectrochim. Acta Part B 1988 43 355) who centrifuged suspension of clays into different size fractions. These size fractions were either nebulized directly or after dissolution. Recoveries from 2- 100% were observed depending on size fraction and ICP parameters. For size fractions less than 2 pm recoveries better than 90% were obtained and these fractions also gave reproducible analy- ses. Larger size fractions gave poor recoveries. Both particle size and composition limited the quantitative analysis of Ti02 and A1203 carried out by Broekaert (9212494 and 93/C376).Solutions to the problems of slurry nebulization will only be found after fundamental studies such as that of Ebdon and Foulkes (92/2499). They measured the rotation temperature T of the ICP using the zero-zero vibrational band of the OH radical while introducing aqueous solu- tions humidified argon and aqueous slurries of A1203 or BN. The measured temperatures varied between 2200-3600 K depending on ICP parameters. Somewhat surprisingly no significant decrease in T,o was observed when solutions or slurries up to 1% by mass were intro- duced. Isozaki (931565) optimized the ICP-AES conditions for the determination of Fe in silicon nitride. Ohls et al.(921C3292) have used activated carbon and a complexing agent to separate trace elements from a matrix. This material was then dried and milled before nebulization. Calibration standards were produced by the same method. Both Carrion et al. (9212642) and Liu and Li (921C4146) analysed bio-materials for trace elements by slurry nebuli- zation using aqueous calibration the former validated their work with reference materials. Gomez-Coedo et al. (92138 19) compared spark source (SS)-ICP-AES with aqueous nebulization-ICP-AES and SS- AES for the analysis of low-alloy steel reference materials. The objective criteria studied included detection limit S/B and repeat ability. Spark sou rce-I CP-A ES was subsequently used for the analysis of ferro-vanadium (9214627). The test material was diluted with pure iron to avoid fracturing and Al Cu Si and V were determined with Fe used as an internal standard to improve precision. Reference materials were used to validate accuracy.Fengdi and Mingjun (931C969) also evaluated this technique using reference steels. Interference corrections were calculated by ablating high-purity metals. The advantage of the speed of the method over aqueous nebulization was discussed. Vujicic and Steffan (9212 1 14 and 931525) analysed conducting solids directly by spark ablation and also non-conducting geological materials by placing them in a graphite cup or briquetting them with graphite and wax (for strength).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 161R Oxygen (10%) was mixed with the outer gas and the background equivalent concentrations observed were better than those from aqueous nebulization.A cyclone chamber placed between the SS and the ICP improved repeatability and reduced deposition in the torch. Novel SS procedures have included (93/1254) a spark discharge to molten steel to produce ultra-fine particles for analysis. The discharge plasma observation height and particle content of the carrier gas were studied with respect to the precision of the analysis. Lin and Xu (9212240) loaded powder into a graphite electrode and then arced this directly in the plasma. This appeared to give better S/B than direct powder introduction. Elias-Eljuri et al. (921C3370) determined P in bronze by using an r.f. spark under water and then nebulizing the dispersion.This allowed aqueous calibration and the method was validated with reference materials. Direct sample insertion continued to receive some inter- est despite known matrix effects associated with the differential atomization efficiencies of elements. Umemoto et al. (9211998) compared the spectral characteristics of a plasma with aqueous nebulization and alternatively graph- ite cup insertion. Key features noted included a lower electron number density and lower background intensities for direct sample insertion. The intensity ratio of ion to atom lines was observed to change for some elements and this was attributed to cup position. They went on to insert cups containing pieces of lead and zinc metal into the plasma (93/805). Matrix evaporation occurred before atomization of the Cu and Fe analytes.Time-resolved integration allowed minimization of matrix eflects and interferences. Calibration was performed using standard solutions; the method was validated using reference materials and the RSD of the method was 5-20%. To overcome some of the problems of this method Blain and Salin (931534 93/C2 12) investigated probe design. Sedi- ment reference materials (MESS-1 and PACS-1 from the National Research Council of Canada) were inserted for analysis. The use of internal standards and standard additions allowed accurate calibration for elements of high and intermediate volatility (Cd Cu Hg Mn Pb and Zn) and sub-ppm detection limits for these elements were obtained. Roberts and Snook (93/C81) have made initial studies on the determination of Mn in terephthalic acid resulting in linear calibrations of peak area versus sample mass and RSDs of 6-10%.Direct powder insertion research has been led by Guevre- mont and De Silva (9211 99 1,92/2786,93/538 92/C332 l) starting with the premise that errors can occur in direct powder introduction if there is a size bias in either the introduction system or in the efficiency of vaporization/ excitation in the ICP. The magnitude of the bias from a fluidized bed system was then estimated by labelling two sizes of silica particles with different elements. The chemi- cal labels on the particles from the carrier stream were then removed by acid extraction. A 50+ 50 mixture of 2 I and 34 pm particles became a 65+35 mix after transport (921 199 1).Subsequently dry Chelex resin was introduced containing spikes of elements from I 1 to 1470 ppm. Element ratios gave precisions of ( 5 % . However when the Chelex resin was mixed with a complex test materials i.e. geological reference materials the precision of element ratios degraded to between 2 and 16% (92/2786,92/C332 1). Finally a new device for introducing powders was de- scribed (93/538). Lin ef al. (93/675) increased elemental response and excitation temperature in the plasma when directly introducing powders by applying an auxiliary arc discharge to the plasma thus moving the optimum observa- tion zone higher into the plasma. Liu devised a new method of directly introducing powder particles (92/C4 1 32) by vibrating the carrier gas. The carrier gas was driven by a diaphragm allowing variation of the hydrodynamic field- induced forces and therefore sufficient control of the rate of particle introduction and residence time in the plasma to optimize the analytical conditions.Meyer (92/C3360) sub- sampled the gas stream from a commercial spray drier used to make fine powders and introduced this stream directly into an ICP-AES system and thus avoided the time- consuming process of redissolving the powders when determining metals. 2.2.6. Chemical vapour generation Not surprisingly research into chemical vapour generation as a means of sample introduction into an ICP has focused mainly on the hydride forming elements. There have been several reviews in this area. Zhang et al. (92/2257) have reviewed (55 references) chemical interferences in HG. Several mechanisms were proposed and discussed.The applications of HG techniques to ICP-AES have been reviewed (4 1 references) by Nakahara (92/3889). A critical survey of HG techniques in atomic spectrometry containing 134 references has been presented by Campbell (93/641). A hydride generator made in-house using a peristaltic pump was described by Brooks (92/163 I). Although no gas-liquid separator was required and the response for Se was linear up to 1000 ,ug I - I boron contamination of the torch was problematic. The use of both continuous and discrete hydride generators was described by Steffan and Vujicic (92/209 1). The advantages of using HG as a means of sample introduction were discussed. Several papers have described the presentation of hydrides directly to the nebulizer of an ICP without the need for a normal gas-liquid separator.Li et al. (93/C240) used on-line reduction followed by HG to determine As Sb and Se. The procedure was relatively interference free although copper in excess of 40 pg ml-1 was problematic. Certified reference materials were used to validate the technique. Noelte (92/2644) evaluated the effects of parameters such as pH stoichiometry reaction time and sample introduction into the plasma on the hydride-forming elements and Hg signal intensity. Arsenic Bi Sb Se and Sn have been determined in biological and environmental CRMs with good agree- ment with the certified values (92/2003). Arsenic has been determined in a variety of samples with a detection limit of 4 pg kg-' and recoveries of 99-104% (92/1764). Arsenic and Se levels in mussel and shrimp CRMs (93/680) and As Se and Sb in waters (93/769) have also been determined.Ozaki (92/C3319) determined As Bi and Sb in steels and nickel alloys using high concentrations of HCl and Fell1 to overcome the interference of nickel. Matrix interferences have been eliminated in the determination of Bi in waste samples by the use of a chelating resin to remove ions of Fe and Cu (92/4732). Qiu et al. (92/C4131) noted that the hydrides of the different elements were formed at slightly different times in the same solution. An alternative method of chemical vapour generation has been reported by Kantor and Zaray (92lC4214) in which two versions of halogenation-vaporization were described.The first used a graphite furnace and CCl at 1800 "C to distil trace constituents from samples such as alumina silicon carbide and silicon nitride into an ICP. The second version utilized a laboratory constructed quartz furnace equipped with either a condensation or chemical absorp- tion device. In this version a cold finger condenser was used if the analyte was more volatile than the matrix or an absorption bottle was used if the matrix was more volatile than the analyte. Sulfur has been determined in gallium phosphide crystal (92jC3767). After dissolution of the crystal the S content was determined by reducing sulfate to H2S quantitatively using NaI-HI-H,PO at 130 "C. Sodium sulfate was used to calibrate the procedure. Sulfur contents of 2-10 pg g-' in162R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL.8 gallium phosphide was determined with a precision of 1-3% The results obtained were in good agreement with those obtained by GDMS. 2.3. Instrumentation 2.3.1. Torch and generator design This has been a relatively quiet area during this review period. A review with seven references discussing the advantages of self-oscillating ICP generators has been presented by Fono et al. (92/2542). A new ICP with a ‘direct serial coupled’ r.f. generator has been developed (93K288) and has been found to be both more efficient and more stable than previous designs. This has the advantage that organic solvents can be run more easily. Data were presented for Pb and S in gasoline andLODs for wear metals in oils diluted with a variety of organic solvents were also given.Ishii et al. (92/198 I ) have modified a 27.1 MHz generator to produce one capable of forming He ICPs at 6.8 27.1 and 40.7 MHz at powers of up to 2.5 kW. Detection limits for Br C1 I and S spectroscopic temperatures and electron number densities were measured. The results were compared with those obtained from a 27.1 MHz Ar ICP operating at 1.1 kW. In addition a reduced pressure He ICP operating at 27.1 MHz was investigated and its perform- ance compared with the atmospheric pressure ICP. Gamage et al. (93/C992) have described a new solid state generator which has a novel method of power control. This has been used with an axially viewed ICP and a Paschen Runge polychromator to show that gas flows nebulizer spray chamber drain and sample presentation have less effect on precision than they do in a radially viewed ICP.Chan and Geil (92K3287) described the development and performance of a high solid sample torch which when used in conjunction with a USN produced encouraging preliminary results for continuous determinations of trace metals in matrices such as sea-water brackish water and beverages. A comparison of torch designs has been made by Atherton et al. (92K4203). A new all glass demountable torch was compared with a fixed and a fixed-base demoun- table torch. A variety of samples including those contain- ing high solids were analysed. Nygaard et al. (92K3328 92/C3799) used an axially viewed ICP operating with low gas flows and at 40 MHz to obtain better detection limits and precision compared with a radially viewed ICP.In addition interferences and linearity were un-affected by the end-on viewing. Intra-alkali interferences were also exam- ined and methods for minimizing them studied. 2.3.2. Spectrometers A review (62 references) of ICP instrumentation including charge transfer detectors Cchelle grating and Fourier transform spectrometers sample treatment and introduc- tion devices and expert systems has been presented by Wang et al. (92/1712). Kolizynski et al. (92/2461) have reviewed (27 references) detection by charge injection devices (CID). The advantages of such systems are dis- cussed. The wavelength positioning accuracy of a sequential ICP-AES has been determined by Grosser and Collins (92/2052).The long-term thermal errors were found to be only a few picometres and short term instability had no significant effect on the wavelength. An improved wave- length Cali brat ion algorithm was described. A lot of interest has focused on photodiode array (PDA) spectrometers. An on-line intelligent background correction system for ICP-AES using a laboratory-made PDA spectro- meter has again been described by Huang et al. (92K3585 931593). The system enabled acquisition of data with concurrent background correction. In a related paper (93/507) the same workers presented data for LODs which ranged from 0.002-0.1 mg 1-1 for a variety of analytes. Chang (92/C4 108) found that a PDA spectrometer made in- house gave LODs slightly inferior to those obtained using a PMT.Brushwyler et al. (92/1622) have characterized a PDA spectrometer which uses a series of dispersion gratings and an optical mask to block unwanted parts of the spectrum thereby optimizing resolution. Limits of detec- tion were reported to be comparable with those obtained using a PMT. Interferences were minimal but scattered light was problematic. McGeorge et al. (92/C3796) have described improvements to a commercial PDA echelle spectrometer. The design was said to be versatile and can easily be re-configured for specific tasks. The spectral range was improved to include analytes such as K Li and Na. In a related paper (92/C3320) hydride-forming elements were determined using the same system. The low noise characteristics excellent quantum effici- ency large number of pixels and large dynamic range of a CCD has been used by Bilhorn (9212697).The system was an improved design which was described as ‘anti-bloom- ing’ i.e. saturated areas of the detector do not spill charge to adjacent areas. The custom built spectrometer was based on an Cchelle grating with a CaF prism that operates from 180 to 700 nm. Pomeroy et al. (92/C3811) used this system to resolve the As 228.812 nm and the Cd 228.812 nm lines. Barnard et al. (92/C3706 92/C3793) described a new solid state detector which reportedly provides the same flexibility and data acquisition rate of PDA and CCD spectrometers but with the same photometric performance as a PMT. An echelle spectrometer made from materials that elimi- nate thermal expansion effects has been described by Cassagne et al.(92X3104). Closely spaced lines such as B/Fe Cd/As and P/Cu were resolved and the performance compared with a larger 1 m focal length Paschen Runge spectrometer. Cassagne et al. (92/C4 18 1) described the structure and performance of an echelle spectrometer with a novel multiplexing of detectors as well as an axially viewed ICP source. An automated echelle cross-prism spectrometer was described by Gower et al. (92K3783 see also 93/C40). Performance in terms of BEC detection limits and stability were reported. A discussion of Czerny- Turner monochro- mators and a theoretical study was presented by Wuensch et al. (92/2787). The use ofjfibre optics has gained some attention. Fibre optics have been placed between the ICP source and the entrance slit of the spectrometer (92K4182).The fibre optic can be several metres long and therefore enable the spectrometer to be placed away from the source. An enclosed ICP-AES system for toxic or radioactive samples that can also utilize fibre optics has been described by Marty et al. (921C3330). The novel optics of this instrument allowed coupling to between one and three spectrometers. A spectrometer with fibre optic coupling between the poly- chromator and the PMTs has been described by Quillfeldt and Notzdd (92K3481). One hundred and thirty two optical fibres for 70 elements were positioned to 12 PMTs. Two papers (92lC4133 92X4186) described a new mechanism for wavelength scanning in sequential ICP-AES spectrometers. A harmonic drive mechanism was claimed to have a much improved performance because it provides very fast rotation very good positional repeatability no backlash long operating life and continuous spectrum access.A sequential ICP-AES instrument has been developed (92/C3566) which incorporates a double monochromator and several diffraction gratings thus enabling shorter run times and simultaneous background correction. High resolution spectrometers and the parameters influencing instrumental broadening and the consequences for the optimization of S/B have been reported by Mermet et al.JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY. JUNE 1993 VOL. 8 163R (9211673). High-resolution ICP-AES has also been used to determine REE resolve the three isotopes of U and to analyse various steels and geological matrices (92/C362 7).2.3.3. Instrument Control and Chemometrics Automated analysis received surprisingly little attention in the literature and this is unfortunate in times when the analyst must in most cases strive to be as cost effective as possible. Shields and Peipmeier (9212837) have used a PC to control a mirror that images light from anywhere in a plasma source onto a high resolution echelle spectrometer. This allowed characterization of the source but would also allow optimization of the observation point for different spectral lines. Agnes and Horlick (92/C3297) integrated an automated robotic sample preparation system an ICP source where all the usual parameters including generator frequency were programmable and a direct reading spectro- meter. This system allowed not only variable analytical strategies based on results but also automated optimization for a given matrix.Borsier (92K3296) only considered automated sample preparation for ICP-AES describing a dedicated system based on conveyor belts. It was suggested that a more modern flexible system would be based on robots. The most common method of optimizing ICP-AES after that of a simple univariate search is the use of sequential simplex optimization and this method was extensively reviewed (82 references) by Golightly and Leary (92/3890). A new computer program for the modified simplex approach has also been published by Moore and Bohmer (9211 835). Brenner and Le Marchand (92K3339) suggested that simplex optimization can only provide minimal improvement with complex matrices and in this situation LODs are mainly dependent on spectrometer resolution.Automatic control of the spectrometer entrance and exit slits allowed them to maximize line emission intensity and minimize the effect of interferences when using a scanning ICP-AES. An example of the determination of trace elements in tungsten was given. Matherny and Eckschlager (93/1122) assessed the efficiency of individual optimization steps using information theory with simulated data. Tyler and Shkolnik (92K3336 92K3630) considered the effect of optimizing to different analytical criteria i.e. a set of analytical conditions that improved precision at high levels or improved peak location at low levels. They suggested that in sequential ICP-AES the importance of peak location is underestimated and therefore optimization for peak response might be better than optimization of SIB.Bauer et al. (92/ 1993,92/2006) have performed multivar- iate calibrations and estimated a ‘real’ LOD derived from error propagation theory. Contributions from calibration error were included in the calculations. Interconnections between derived error in concentration and selectivity were found theoretically. However investigations into different definitions of selectivity revealed only limited correlation to errors in concentration. Carre and Mermet (921C3335) also investigated the problems of errors in calibration. They considered the measurement of a concentration in an unknown test material as a two part process. Calibration where a series of standards are used with regression anlaysis to produce a calibration graph followed by counter calibra- tion where the graph is used to calculate concentrations in unknown samples.They observed that both parts contain errors and confidence bands were used to test the adequacy of curve fitting and to evaluate the consequence for measured concentrations. Wegscheider et al. (92K3549) compared multivariate calibration with least squares and Kalman filtering. Both approaches were shown to yield improved detection limits because of the averaging advan- tage of measuring at several wavelengths and because explicit modelling of background was better than discrete measurement. Chen (92IC4130) has proposed a new itera- tive technique known as analyte standard additions that minimizes the effect of matrix and background by giving a better estimate of the ‘true’ background. Starn et al.(92/C3713) have suggested a practical method of on-line calibration and standard additions by the use of a computer controlled HPLC pump. This type of approach where samples and standards are modified chemically within an analysis run could offer a great deal in the future particularly now that advanced computer control and data processing are available. Drift correction is normally performed on both a high- and low-response value. Gueldner (92/ 1878) suggested that rather than using test solutions this process can be performed by using the spectral background and the photo- multiplier dark current as the two points. Data suggested that the applicability of this method depends on spectro- meter properties and favours certain elements.Fredeen and Ivaldi (92/C3758) and Krushevska et al. (92K3337) have both successfully used Myers- Tracy signal compensation but it was noted that ionic lines close in energy sum to that of the internal standard were those best corrected. Mermet (92/C3295) considered the long-term stability limitations of ICP-AES. No commercial software can monitor the ICP parameters that can cause drift and therefore test elements must be used for drift diagnostics. These can be used as internal standards if carefully chosen or might be used as part of a feedback network. Quality assurance and quality control (QA/QC) are two phrases that will be increasingly familiar to analysts working in a more commercial environment.Olsen and Holst (92/4579) described the calculation of a ‘method evaluation function’ (MEF) and they defined this function as the expected value of an analysis as a function of the ‘true’ content of the analyte in the test materials. This generalized function also provides additional information intended to help write tight QA/QC protocols something that is likely to become an increasing demand on the analyst. The determination of trace elements in cellulose filters was given as an example specific to ICP-AES. Borszeki et al. (92/4577) grouped lead alloy samples from ‘good’ and ‘bad’ manufactured products. Linear discrimi- nate analysis of ICP-AES elemental determinations was able to make the classification accurately and was consi- dered to be useful for quality control.Shaw (93/C21) described software to implement a QC protocol for a scanning ICP-AES instrument. The checks it makes are switchable and have user set limits. It also allows remedial actions. These are useful features that many manufacturers could consider for their future software. ArtiJicial intelligence (AI) expert systems and neural networks are an area of chemometrics that is gradually developing with most information currently only appear- ing in conference abstracts. Ugolev and Sokolova (93/1264) have suggested that chemometricians can learn much from many branches of science particularly the ‘hot areas’ of computer science. These techniques could be used to solve problems when there is a degree of uncertainty in experi- mental information.They described new aspects of chemo- metrics with examples obtained when analysing biological material for Cu. Pomeroy et al. (92/2054 and 93/C300) have demonstrated that the large amount of information that array devices in spectrometers provide has allowed the development of expert systems to use this data for ‘on the fly’ matrix-dependent line selection. However such a strat- egy needs a large database of lines and the use of fundamental spectroscopic principles. An example of using such an expert system for environmental monitoring of chemical waste was given. The choice of line selection prior to analysis led Chen el al. (92K4134) to produce a database164R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 that could intelligently associate spectroscopic analysis literature information and acquired knowledge.The pres- ence or absence of an element in ICP-AES spectra should be a simple matter of looking for prominent lines. However in real matrices this is complicated by interferences and statistical error. Wegscheider et al. (921C42 17 921C3306) have used fuzzy logic to make decisions of this nature on a neural network by using Bayes like probabilities. The system worked satisfactorily for trace elements in a tung- sten matrix. Nikdel (921C3307) had previously character- ized the trace element content of orange juice from around the world and a pattern recognition program ‘ARTHUR’ had been used to classify orange juice based on this training set. However this program had no learning ability.In contrast a neural network subsequently tried could learn. The network proved to be both very fast and have a better success rate. Salin et al. (92/C3304) have been developing an expert system to automatically run an ICP-AES instru- ment and they have now evaluated what the system provides as opposed to what the analyst appears to need. Spectral manipulation has provided many reports in the last year because with the wide availability of low cost scanning monochromator systems and powerful personal computers the use of chemometric techniques to manipu- late spectra particularly to correct interferences is much easier than in the past. In a series of papers Yang et al. (9211983 9212718 931698) have developed a numerical derivative technique. This was first evaluated with respect to improving selectivity and they defined a measure of this as the ‘interferent equivalent concentration (IEC)’.Factors that affect derivative spectra such as line shape were discussed in terms of the IEC (921 1983). Noise on raw data also hampered derivative calculations and smoothing and spectral step size criteria were investigated to minimize the IEC (92127 18). They concluded that derivative spectros- copic methods improved SIB by 1-2 orders of magnitude. However this was not accompanied by an improvement in detection limits in simple spectra but when spectral interference occurs the higher resolution can avoid deter- ioration of detection limits (931698). The method was tested on the determination of trace elements in the difficult Y20J matrix and found to give more reliable results than conventional off-peak/on-peak correction methods.Sun et al. (9212246) returned to first principles to solve the problems of spectral interference describing the philosophy behind their computer simulation of ICP-AES spectra and spectral interferences. Formulae for the calcula- tion of spectral linewidths were then proposed for the simulation. An example of the determination of V in an iron matrix was used to test the simulation against real spectra (931487). A modified model was also used to describe line profiles. Voigt profiles were decomposed into Gaussian and Lorentzian components. By comparing simu- lated and real line profiles they determined that the instrumental profile (as opposed to the natural line profile) of a medium resolution spectrometer was approximately Gaussian (921C4118). This modified model was then used to simulate the interference of iron on the Cr 283.6 nm line and the result compared with experimental spectra.Both were unable to resolve the interference but importantly the model was able to predicate spectrometer parameters that could (921C4119). Boumans (9315 16) has also produced a simulation of ICP-AES spectra from fundamental prin- ciples and a database of information on 350 prominent lines of 65 elements. The database of the computer program was designed to be customized by the user. The Kalman filter has been of particular interest as a means of correcting for spectral interferences. Van Veen and De Loos-Vollebregt (9211818) discussed its use and concluded that a spectral characterization should be performed prior to filtering but that it would give only a 1-3-fold improvement in detection limit and it would not correct for non-spectroscopic matrix effects.Karpate (921C4242) compared single element evaluation multivari- ate calibration and Kalman filtering for the determination of trace elements in bauxite and suggested that Kalman filtering gave more reliable results when determining trace elements in the presence of spectral interferences. Ma et al. (921C4 I 16) also evaluated the use of the Kalman filter for a number of complex matrices. Zhang et al. (921C4 136) have used factor analysis to correct for spectral interferences. This required both test spectra and a number of pure spectra to allow a single decomposition.Tests on real data suggested that errors could be due to non-linear combina- tions of pure spectra. A large amount of research into spectral characteristics to aid quantification is being reported only at conferences. Perhaps this suggests that these methods are not yet robust and routine. Improved methods of peak fitting and smooth- ing have been reported (921C3596 93/C2 14 931C298 931C43 1 931C699). A better estimation of background (natural and spectral interference) and its subtraction have been discussed ( 9 2 ~ 4 1 1 6 92/C4 1 20 9 2 ~ 4 1 2 I 92K4 123) 931C80 931C952). Specifically Caughlin and Blok (921C3280) have addressed the problem of FI for complex matrices where accurate background correction is difficult because of the constantly changing signal.They considered two instrumental approaches to background correction. The use of photodiode arrays allows simulta- neous acquisition of peak and background or alternatively high speed data acquisition that allowed accurate on1off peak correction during the period of the changing FI signal. 3. MICROWAVE-INDUCED PLASMAS Several reviews regarding MIPs have been published most notably those by Uden (9214268 931820) and Bulska (9214620) who give a robust assessment of the development and application of MIPs as element selective detectors for chromatography. Coulombe et al. (931609) reviewed the fundamental aspects of MIPs as did Mermet (9311090) who also discussed other electrically generated plasmas. Other review and summary papers published pertinent to chroma- tographic applications included those by Sullivan (92/4527 93/603) Webster and Carnahan (931602) and by Deruaz and Brazier (93/1248).the spatial emission characteristics of a 450 W atmospheric pressure He MIP. The TMolo cavity with side viewing port was mounted on an x-y stage allowing movement of the plasma with respect to the optical axis of the spectrometer and the authors found that emission maxima for different elements were distributed along the length of the cavity with Ca nearest and Cl furthest from the bottom of the discharge. The authors suggested that excitation mecha- nisms for metals and non-metals differed with C1 I1 emission being excited via a charge transfer mechanism. Wu and Carnahan have described the characteristics of a high-power MIP (931724).Their device referred to as a kilowatt-plus MIP used a re-designed torch and cavity and was reported to give improved plasma energy coupling and excitation characteristics. On a practical level the limit of detection for C1 was improved by two orders of magnitude. 3.1. Fundamental Studies Literature reports in this area appear to be declining in number. Pak and Koirtyohann (9212628) have reported onJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 165R High power MIPS were also discussed by Furuta and Koga (92lC3302 92lC3593) who described an annular nitrogen plasma which tolerates an aqueous aerosol in a similar manner to the ICP. The authors measured an excitation temperature of 5400 K and suggested that LTE conditions prevailed in this plasma.The effects of EIEs were reported by Jin et al. (92/3051). Aqueous samples were introduced via a USN with a desolvation device and the eflects of EIE upon the atomic emission and atomic absorption of a range of analyte elements were studied. The interaction of power gas flow rates and discharge tube diameter were investigated for a range of EIE (Li Na K Rb Cs) and analyte emission and absorption lines. Although detailed observations were reported it is disappointing that the authors did not interpret the data in mechanistic terms. 3.2. Instrumentation Broekaert et al. (92/2489) have published a comparison between a Beenakker cavity and a surfatron device (see J. Anal At Spectrom. 1992 7 169R). The devices were each operated at optimum conditions using electrothermal sam- ple introduction and the authors found that for Cd and Cu the surfatron device gave lower detection limits and a greater linear dynamic range and showed lower interference from EIE.There is however some contradiction of this last point in the text of the paper in that the authors also mention that the calibration curves with sodium present when using the surfatron device were not parallel to those of pure solutions. Duan et al. (92/38 18) have evaluated a 50 W argon MIP as an atomizer for Hg determination using atomic fluores- cence spectrometry. The device was operated using Ar at 600 ml min-I. Mercury vapour was generated following reduction of Hg with 5% SnCI2 solution. Excitation of Hg was by a pulsed HCL and the instrument gave an LOD of 3 ng m1-I.Evaluation of the system indicated that the viewing height was a critical parameter however the assessment of this system would have benefitted from the use of a rigorous multivariate optimization. 3.3. Sample Introduction 3.3.1. Direct nebulization Aerosol desolvation remains a priority for some workers in this field (92/C3322 92/C3680 93/C180 93/C262) how- ever there has been no substantive literature contribution for some time perhaps indicating a decline in research activity. 3.3.2. Electrothermal vaporization Although sample introduction by direct nebulization is declining the popularity of ETV continues because the solvent loading to the plasma in a typical low power cavity is reduced to a level that does not quench the discharge.Matusiewicz and Kurzawa (92/2228) described the determi- nation ofAs and Se with detection limits of 150 and 200 pg respectively. Evans et al. (92/2754) described a novel tantalum tip ETV device suitable for both MIP-AES and MIP-MS. For volatile elements and using MS detection LODs were generally sub-pg and limited by contamination from the materials used to build the device. Electrothermal vaporization sample introduction was also used by Broekaert et al. (9212489) in the comparison of two MIP sources. system. This was achieved using 10 mmol 1-1 potassium persulfate in 5 mol 1-1 sulfuric acid. The limits of detection for the 447.78 470.49 and 734.86 nm Br emission lines were 29.5 7.46 and 18.4 ng ml-l respectively. Sanz-Medel et al. (921C3294) have outlined methods for the determina- tion of halogens by continuous vapour generation. Oxida- tion of Br C1 and I was achieved using NaCIO KMnO and H202 respectively and detection limits of 20 ng ml-1 for I and of 2 ng m1-l for Br cited. If multivariate optimization was used more regularly (92/C3334) effective comparisons could be made between these systems.3.3.4. Direct analysis of solids In an interesting paper Gelhausen and Carnahan (9212395) reported the determination of the elemental ratios of C H Cl and S in coal following direct sample injection into a 500 W MIP operated in a TMolo cavity. Sample was introduced in 1 mg amounts via a stopcock in the carrier gas line. The key criterion the ratio between C and H which is associated with the rank of the coal could be determined with an accuracy of lo% provided measurements were simultaneous and an appropriate solid calibrant was used.It is unfortunate that no data were reported regarding the transport or atomization efficiencies of the system particu- larly as this type of plasma is not normally considered appropriate for ‘difficult’ matrices and that particles of up to 20 mesh size were introduced. The technique was also able to detect S and C1 although quantification was limited by matrix-induced background shifts. 3.4. Chromatography 3.4. I . Instrumentation Platzer et al. (93/527 931608) evaluated a 140W 27 MHz stabilized capacitative plasma in helium at atmospheric pressure. The discharge was contained within a liquid- cooled silica tube with power coupled via two annular electrodes. Detection limits for the device were reported to be in the low pg s-l range.Wu et al. (92/46 19) described a He r.f. plasma for N specific determination using an avalanche photodiode detector the detection limit for N was 57 pg s-l. The ability to perform simultaneous multi-element deter- minations of analytes is a major advantage of a GC-MIP system. This point was made by several workers (92K3303 92lC3468 92/C3723) but is particularly relevant with regard to the determination of empirical formulae. This has been discussed in earlier reviews in this series (see J. Anal. At. Spectrom. 1992 7 170R) and was again dealt with by Huang et al. (92/4369 92/4500) who appear to be perform- ing a detailed assessment of the capabilities of this application. An obvious extension of this work is the application of rigorous statistical methods to the data as by Kosman and Lukco (92/C3762) and this writer expects this to be a major theme in future updates.3.4.2. Gas chromatograph y-micro wa ve-induced plasma applications Organotin compounds have been determined by GC-MIP at levels of 1 pg 1-l (92/1653) and at an absolute detection limit of 6 pg (92/4271) indicating that this technique is capable of achieving low detection levels. Other organome- t a l k species that have attracted attention include organo- lead species (92K3467) and organomercury species (9212909) and Bulska et al. (9214105) have developed a robust method for the speciation of mercury in whole blood. Element specific analysis remains a major theme for GC-MIP.There have been reports regarding the determi- nation of halogens (93/819 92/C3432 93/C/199) for N 3.3.3. Chemical vapour generation Nakahara et al. (92/462 I 921C3587) described the determi- nation ofBr by oxidation of bromide in a continuous flow166R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 and 0 (92/4298 92/C3434 92/C38 13) and for deuterated compounds (92/2526). 3.4.3. Supercrit ical fluid chroma tograp h y Webster and Carnahan (92/2057) have evaluated 250 W and 500 W He MIPS as SFC detectors. The higher power plasma showed a greater tolerance of variation of mobile phase pressure with stable He and C11I emission intensities for varying flow rates. These authors also evaluated the system for Cl and S determinations using C 0 2 and N20 mobile phases (9212972). In the UV S/Ns were degraded because of molecular band interferences for both mobile phases whilst in the near IR molecular bands were problematic for the N 2 0 mobile phase only.4. DIRECT CURRENT PLASMAS An indication of the body of work that has been performed using DCPs was given by Keliher (92/3892) who reviewed the application of the DCP to geochemical analysis (45 references) and Krull(93/822) who reviewed chromatogra- phic couplings to the DCP (76 references). Developments in instrumentation for DCP tend to focus on modification of the plasma source. This frequently involves the addition of more electrodes which in the most recent variation is six. McGuire and Piepmeier (92/4592) have evaluated a six electrode DCP. The plasma consisted of a horizontal a.c. plasma formed between three electrodes at the top of the device and three d.c. arcs formed between the base electrodes and the top electrode.Sample was introduced through the centre of the three arcs A simplex procedure was used to optimize the system gas flows and d.c. current however detection limits for several elements were approximately 100 times worse than those for ICP- AES. Brindle et al. (9214094) described a continuous jlow hydride generation system for the determination of As in water. Sample and NaBH were pumped into the hydride generator in separate flows. An Ar flow rate of 0.4 1 min-' through the base of the separator both mixed the sample and stripped analyte from solution into a 2 1 min-' carrier Ar flow. Also on sample introduction Thompson and Boss 92/C3768) found that small volume samples (40 pl) could be introduced without significant degredation of signal intensity.Solid sample introduction using slurries has been re- ported frequently for the DCP and in this review period there has been a further upsurge in interest. This may be a reflection upon the potential for higher transport efficiency of larger solid materials although this remains a subject for further work as does the assessment of particle atomization. Jerrow et al. (92/383 1) reported the determination of major elements in soils following fine grinding of the material with zirconia beads and confirmed the importance of reducing particle size to the range 2-5 pm in order to achieve high transport efficiency of the sample to the plasma.Yoon and Long (92/3 102) did not appear to show such clear under- standing of the importance of particle size reduction to achieve high transport efficiency however their proposed addition of propane gas to the nebulizer gas flow may be advantageous for the reduction of refractory oxides. A particulary exciting slurry sample introduction applica- tion has been developed by Fairman et al. (93/C26). Elemental data from the analysis of aqueous slurry samples of kaolin along with multi-component linear regression analysis was used to predict the important product quality characteristics of abrasiveness montmorillonite content and viscosity in china clay production. The methodology employed was rapid and was able to predict accurately (98.3% reliability) the variation in sample abrasiveness and has the capability to be employed for on-line process control in a clay extraction plant.The combination of such analytical capability with information based expert systems (9212054) is clearly an area where DCPs could become a valuable tool. Other more conventional applications of DCPs included the determination of Au (92/2518); of Si in urine (93/1096); of REE in ores (92/2230); the analysis of biological materials (92/4285); and the analysis of waste oils used as secondar-v fuels (92/C3678) where the sample might contain varying ratios of solvent and aqueous phases. LOCATION OF REFERENCES The full list of references cited in this Update have been published as follows 9211448-9212589 J. Anal. At. Spectrom.1992 7(4) 173R-2 13R. 9212590-92lC3494 J. Anal. At. Spectrom. 1992 7(5) 247R-277R. 92lC3495-9214073 J. Anal. At. Spectrom. 1992 7(6) 329R-348R. 9214074-9214734 J. Anal. At. Spectrom. 1992 7(8) 389R-411R. 93lC1-93lC997 J. Anal. AI. Specr'rorn. 1993 8( l) 45R-78R. 931998-93lC1354 J. Anal. At. Spwcfrom. 1993 8(3) 137R-149R. 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 9211084. Methods Phys. Rex Sect. B 1990 B51 133. 9211625. Spectrochim. Acta Part B 199 1,46,2 17.9211626.9211219. Anal. Chem. 1990,62,2 158.9211460. Lab. Pract. Spectrochim. Acta Part B 199 1 46 229. 9211627. Spectro- 1990 39 7 1 75. 9211622. Spectrochim. Acta Part B 199 1 chim. Acta Part B 199 1 46 253. 9211628. Spectrochim. 46 85. 9211623. Spectrochim. Acta Part B 1991 46 115. Acta Part B 1991 46 269. 9211629. 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ISSN:0267-9477    

DOI:10.1039/JA993080151R

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

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Rotterdamseweg 137 2628 AL Delft The Netherlands). Jackson K. W. Mahmood T. M. Analysis of carbon slurries by ETAAS after trace metal preconcentration (Wadsworth Center Lab. Res. New York State Dept. Health Sch. Public Health State Univ. New York P.O. Box 509 Albany NY 1220 1-0509 USA). Bonner Denton M. New generation of combined optical emission ICP mass spectrometric instrumenta- tion (Dept. Chem. Univ. Arizona Tucson AZ 85721 USA). Lorber A. Hidden information in ICP-OES multi- channel data (Nucl. Res. Centre Negev P.O. Box 900 1 Beer-Sheva Israel). Ivaldi J. C. Barnard T. Tracy D. Slavin W. Multivariate methods applied to simultaneous emis- sion spectra from the inductively coupled plasma (Perkin-Elmer 761 Main Ave.Norwalk CT 06859- 0293 USA). Scheeline A. Fundamental atomic reference data- where have we come in 5 years? (Sch. Chem. Sci. Univ. Illinois 1209 W. California St. Urbana IL 6 1801 USA). 05405-0125 USA). 93/C1402. 93/C 1403. 93/C 1404. 9 3/C 1 405. 93/C 1406. 93/C1407. 93/C1408. 93/C 1409. 93/C1410. 93/C1411. 93/C 1 4 1 2. 93/C 14 1 3. 93/C 14 14. 93/C 14 1 5 . 93/C 1 4 1 6. 93/G 14 1 7. 93/C 14 18. de Loos-Vollebregt M. T. C. van Veen E. H. Challenge of digital filtering techniques in multi- element ICP-AES (Delft Univ. Technol. Lab. Mater. Sci. Div. At. Spectrom. Rotterdamseweg 137 2628 AL Delft The Netherlands). Boumans P. W. J. M. Multi-element line selection in inductively coupled plasma atomic emission spectro- metry (ICP-AES) (Philips Res.Labs. P.O. Box 80.000 5600 JA Eindhoven The Netherlands). Blades M. W. Hettipathirana T. LeBlanc C. Gill C. New approaches to the analysis of small samples (Univ. British Columbia Dept. Chem. Vancouver British Columbia Canada V6T lZ1). Tyson J. Critical look at the thermodynamic and kinetic features of atom formation for analytical spectrometry (Dept. Chem. Univ. Massachusetts Amherst MA 01003 USA). Salin E. Ren J. M. Skinner C. Blain L. Ugere G. Search for a solid solution (Dept. Chem. McGill Univ. 801 Sherbrooke St. W. Montreal Quebec Canada H3A 2K6). Mermet J. M. Direct analysis of solid samples in inductively coupled plasma spectrochemistry (Lab. Sci. Anal. Univ. Lyon I 69622 Villeurbanne Cedex France). Chakrabarti C. L. Gilmutdinov A. Kh. Gregoire D. C.Hutton J. C. Lamoureux M. M. Mechanism of aluminium atomization in graphite furnace atomic absorption spectrometry (Centre Anal. Environ. Chem. Dept. Chem. Carleton Univ. Ottawa On- tario Canada K1 S 5B6). Katskov D. A. Shtepan A. M. Atomization of Al Ga In and T1 in ETAAS (State Inst. Appl. Chem. Dobroluybova pr. 14 197 198 St. Petersburg Russia). Brown G. N. Styris D. L. Mass spectrometric elucidation of mechanisms that control the electro- thermal atomization of tin (Pacific Northwest Lab. Richland WA 99352 USA). Hutton J. C. Chakrabarti C. L. Gilmutdinov A. Kh. Mrasov. R. Digital imaging and computer simulation of atom formation and dissipation in a graphite furnace for analytical atomic spectrometry (Centre Anal. Envion. Chem. Dept. Chem. Carleton Univ.Ottawa Ontario Canada K1S 5B6). Fonseca R. W. Holcombe A. Surface studies using tube-in-tube electrothermal atomizers (Dept. Chem. Biochem. Univ. Texas Austin TX 78712 USA). Tan H. Meinhard B. A. Meinhard J. E. Recent investigations of Meinhard concentric nebulizers (J E Meinhard Assoc. 1900-5 E. Warner Ave Santa Ana CA 92705 USA). We15 B. Sperling M. Hertzberg J. Marowsky G. Temporally and spatially resolved gas phase tempera- ture measurements in electrothermal atomizers (Dept. Appl. Res. Bodenseewerk Perkin-Elmer GmbH W-7770 Uberlingen Germany). Jackson J. G. Holcombe J. A. Metal-surface reac- tions at elevated temperatures on various surfaces (Dept. Chem. Univ. Texas Austin TX 78712 USA). Wang P. Holcombe J. A. Solid sample speciation using pressure regulated electrothermal atomizer atomic absorption (Dept.Chem. Biochem. Univ. Texas Austin TX 787 12 USA). McKinstry J. L. Goldberg J. M. Characterization of a plasma gun direct solid sampling source for ICP- AES (Univ. Vermont Dept. Chem. Burlington VT Meyer C. A. Goldstone L. C. Arniaud D. Spectro- chemical analysis of difficult samples by ICP-AES using a new high efficiency high solids nebulizer (Battelle 505 King Ave. Columbus OH 43201 USA). 05405-01 25 USA).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 93/C 1 4 1 9. 93/C 1 420. 93/C 142 1. 93/C 1422. 93/C1423. 93/C 1424. 93/C1425. 93/C1426. 93lC1427. 93/C 1428. 93/C 1429. 93/C 1430. 93/C 143 1. 93/C1432. 93/C1433. 93/C1434. 93/CI 435. Thompson L. J. Boss C. B. Analysis of low-volume nebulized samples by inductively coupled plasma atomic emission spectrometry (North Carolina State Univ.Dept. Chem. Raleigh NC 27695-8204 USA). Wiederin D. R. Pinkson T. L. Analysis of small volume hydrofluoric acid samples by direct injection nebulization ICP spectrometry (Cetac Technol. 5600 S. 42nd St. Omaha NE 68107 USA). Narasimhan K. Koropchak J. A. Flow injection Donnan dialysis preconcentration for trace metals analysis by ICP-AES (Dept. Chem. Biochem. South- ern Illinois Univ. Carbondale IL 62901 USA). Etkin B. French J. B. Jong R. Monodisperse dried microparticulate injection (Inst. Aerospace Studies Univ. Toronto 4925 Dufferin St. Downsview On- tario Canada M3H 5T6). Ward A. F. Application of laboratory data manage- ment systems for inorganic environmental analysis (Ward Scientific 2 Ray Ave. Burlington MA 01803 USA).Peart D. B. Taylor H. E. Intelligent data manage- ment system for water quality studies (USGS-WRD 32 15 Marine St. Boulder CO 80303 USA). Yates D. A. Aries R. Interpretation of multi-element analytical data using principal components analysis (Perkin-Elmer 761 Main Ave.. Nonvalk CT 06859- 0293 USA). Borsier M. Brenner I. B. Use of ICP-AES and ICP- MS for multi-element determination in geochemical prospecting (BRGM BB 6009 45060 Orleans France). Zayhowski E. J. Bushly T. J. Gable C. A. Quality control procedures for inductively coupled plasma optical emission spectrometry at the US Geological Survey national water quality laboratory (U.S. Geol. Surv. 5293 Ward Rd. Arvada CO 80002 USA). Jackson K. W.Qiao H. Mechanism of palladium modification for the removal of chloride interference in ETAAS. (Wadsworth Center Lab. Res. New York State Dept. Health Sch. Public Health State Univ. New York P.O. Box 509 Albany NY 12201-0509 USA). Byrne J. P. Chakrabarti C. L. Lamoureux M. M. Ly T. Gregoire D. C. Chemical modification in graphite furnace atomic absorption spectrometry investigated by inductively coupled plasma mass spectrometry (Dept. Appl. Chem. Univ. Technol. Sydney Australia). Eloi C. Robertson J. D. Xu N. Majidi V. Study of matrix modifiers on heated graphite surfaces (Dept. Chem. Univ. Kentucky Lexington KY 40506 USA). Styris D. L. Harris J. A. Redfield D. A. Bulk diffusion induced analyte loss in graphite atomizers (Pacific Northwest Lab. Richland WA 99352 USA).Rayson G. D. Fresquez M. R. Hall K. Pre- treatment time as a parameter for the evaluation of matrix modifiers in ETAAS (Chem. Dept. Box 30001 New Mexico State Univ. Las Cruces NM 88003 USA). Welz B. Stauss P. Mechanism of interferences of hydride-forming elements on the determination of selenium (Dept. Appl. Res. Bodenseewerk Perkin- Elmer GmbH W-7770 Uberlingen Germany). Dulude G. R. Dauzvardis M. J. Karpova S. Real world applications of a multi-element GFAAS (Thermo Jarrell Ash 8E Forge Parkway Franklin MA 02038 USA). Skelly Frame E. M. Anderson D. A. Balz W. E. Comparison of Sn and Au concentrations in films on silicon subtrates by ICP and flame AA spectrometry 93/c 93/c 93/c 436. 437. 438. 93/C 1439. 93/C 1440. 93/C 144 1. 93/C 1442. 93/C 1443. 93/C1444.93/C1445. 93/C 1446. 93/C 1447. 93/C 1448. 93/C 1449. 93/C 1450. 171R (GE Corporate Res. Dev. P.O. Box 8 Bldg. K1 Rm. 2A 18 Schenectady NY 12301 USA). Tummalapalli C. M. Williams J. C. Development of a microanalytical method for the determination of selenium in bovine heart tissue using Zeeman graphite furnace atomic absorption spectrometry (Dept. Chem. Memphis State Univ. Memphis TN 38 152 USA). Koons R. D. Peters C. A Donnelly B. Electrother- mal atomization of solid samples for element concen- tration determinations in individual hairs (Forensic Sci. Res. Training Center FBI Academy Quantico VA 22135 USA). Steele A. W. Petty R. L. USP heavy metals tes- ting-can atomic spectroscopy offer significant advan- tages? (Glaxo 5 Moore Dr. Research Triangle Park NC 27709 USA).Dunn K. Steele A. Garcia T. Kristof J. Hilborn R. Inductively coupled plasma atomic emission determi- nation of the amount of an iron oxide based ink transferred to a pharmaceutical tablet during the manufacturing process (Glaxo 5 Moore Dr. Re- search Triangle Park NC 27709 USA). Taylor G. D. Jr. Determination of trace metals in environmental samples using fast graphite furnace AAS techniques (43 10 E. Anderson Rd. Orlando FL 32812 USA). Hartmann Webster G. Boss C. B. Sensitivity en- hancement of electric field measurements of surface wave plasmas for gas chromatography detection (North Carolina State Univ. Box 8204 Dept Chem. Raleigh NC 27695-8204 USA). Tend J. King F. L. Sample matrix influences on atomization and ionization in glow discharge mass spectrometry (Dept.Chem. West Virginia Univ. Morgantown WV 26505-6045 USA). Pan C. King F. L. Trace element analysis using modulated glow discharges (Dept. Chem. West Virgi- nia Univ. Morgantown WV 26505-6045 USA). Chen G. King F. L. Correlation between plasma observables and polyatomic ions in glow discharge mass spectrometry (Dept. Chem. West Virginia Univ. Morgantown WV 26505-6045 USA). Meadows L. R. Fotia F. King F. L. Tandem mass spectrometry for the characterization of glow dis- charges (Dept. Chem. West Virginia Univ. Morgan- town WV 26505-6045 USA). Patel B. M. Ali A. H. Johnson D. D. Mansfield C. T. Low level determinations of copper and zinc in water and waste water by graphite furnace atomic absorption and inductively coupled plasma atomic emission spectroscopy (Texaco Res.Dev. PA P.O. Box 1608 Port Arthur TX 77641 USA). Moore J. A. Mixon P. D. Bray C. W. Griffin S. T. Williams J. C. Instrumentation for current control in a pulsed hollow cathode discharge (Dept. Elect. Eng. Chem. Memphis State Univ. Memphis TN 38152 USA). Shkolnik J. Nham T. Tyler G. Low ppb measure- ments using a sequential ICP-AES with an ultrasonic nebulizer (Varian 201 Hansen Court Suite 108 Wood Dale IL 60 19 1 USA). Marawi I. Wang J. Caruso A. Hydride trapping on palladium and subsequent determination by electroth- ermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) (Dept. Chem. Mail Location 172 Univ. Cincinnati Cincinnati OH 45221 USA). Calloway C. P. Jr. Jones B. T. Atomic absorption spectroscopy with a flame emission source (Dept.Chem. Wake Forest Univ. Winston-Salem NC 27 109 USA).172R 93lC I45 1. 93fC 1452. 93lC 9 3lC 453. 454. 93lC 1 4 5 5. 93lC 1456. 93f c 1 457. 93lC1458. 93lC1459. 93lC 1460. 93lCI 46 1. 93lC 1462. 93lC1463. 93lC 1464. 93lC1465. 93/C 1466. JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 Soderquist K. D. Material verification of 90-10 platinum-iridium parts by Zn fusion-ICP-AES (Med- tronic Promeon Div. 6700 Shingle Creek Pkwy Brooklyn Center MN 55430 USA). Abraham V. J. Hatheway J. D. Anderson D. A. Skelly Frame E. M. Determination of siloxanes in spent sulfuric acid (GE Corporate Res. Dev. P.O. Box 8 Bldg. K-I Room 2A32 Schenectady NY 1230 I USA). Shepherd M. A. Forster A. R. Kamla G. J. Implementation of a direct injection nebulizer (DIN) for analysis of volatile hydrocarbon samples and analytes (Shell Development P.O. Box 1380 Hous- ton TX 7725 1-1 380 USA).Morrison G. H. Chemical imaging in biology and medicine using ion microscopy (Baker Lab. Chem. Cornell Univ. Ithaca NY 14853-1301 USA). Resto W. Badini R. G. Winefordner J. D. Two step laser enhanced atomic fluorescence of mercury (Dept. Chem. Univ. Florida Gainesville FL 3261 1 USA). Boss C. B. Bray J. Hamilton J. C. Linearization of electrothermal atomic absorption calibration curves (Dept. Chem. North Carolina State Univ. Raleigh Hamilton J. C. Use of PC/absorb to collect atomic absorption data for stray light linearization computa- tions (Hamilton Assoc. Rt. 2 Box 136B Farmville NC 27828 USA). Vaive J. E. Hall G. E. M. Pelchat J.-C.Determina- tion of rare earth elements (REE) and transition metals in natural waters by chelation preconcentration ICP-MS (Mineral Resources Div. Geol Surv. Canada 601 Booth St. Ottawa Ontario Canada KIA OE8). Su E. G. Michel R. G. Determination of trace and ultratrace chlorine by graphite furnace laser excited molecular fluorescence spectrometry of indium mono- chloride (Dept. Chem. Univ. Connecticut U-60 Storrs CT 06269 USA). Jackman J. A. Applications of SIMS in modern metallurgy (Metals Technol. Lab. Canada Centre Mineral Energy Technol. Energy Mines Resources Canada 568 Booth St. Ottawa Canada K1A OG1). Hutton J. C. Chakrabarti C. L. Gilmutdinov A. Kh. Digital imaging in atomic absorption spectrometry (Centre Anal. Environ. Chem. Dept. Chem. Carleton Univ.Ottawa Ontario Canada K1S 5B6). Smith E. H. Harris W. C. Compositional SIMS quantification using the CsM+ molecular ion method (Digital Equipment Corp. 77 Reed Rd. Hudson MA 01 749 USA). Webster J. D. Analysis of trapped and quenched silicate melt by SIMS application to volcanic erup- tions (Dept. Mineral Sci. American Museum Natural History Central Park West 79 St. New York NY Harnly J. M. Smith C. Characteristic masses and detection limits for graphite furnace AAS with a continuum source and a photodiode array detector (USDA Nutr. Compos. Lab. Bldg. 16 1 BARC-East Beltsville MD 20705 USA). Lampert J. K. Koermer G. S. Deeba M. Levi-Setti R. Chabala J. High resolution SIMS imaging of FCC catalysts (25 Middlesex Tpke Iselin NJ 08830 USA). Harnly J. M. Effect of high intensity source pulsing on detection limits for graphite furnace AAS with a continuum source and photodiode array detection (USDA Nutr.Compos. Lab. Bldg. 16 I BARC-East Beltsville MD 20705 USA). NC 27695-8204 USA). 10024-5 192 USA). 93fC 1467. 93lC 1468. 93lC 1469. 93lC1470. 93lC 147 1. 9 3lC 93/c 93lC 472. 473. 474. 93lC 1475. 93lC1476. 93lC 9 3lC 477. 478. 93lC I 479. 93/C1480. 93lC 148 1. 93lC1482. Fernando R. Ennever F. K. Jones B. T. Simulta- neous determination of cadmium and calcium in urine by continuum source atomic absorption spectrometry (Dept. Chem. Wake Forest Univ. Winston-Salem NC 27109 USA). Scheie A. J. Holcombe J. A Multi-element detec- tion by electrothermal atomization mass spectrometry using second surface trapping (Dept. Chem. Bio- chem.Univ. Texas Austin TX 78712 USA). LaRue R. M. Tyson J. F. Use of recirculating loop flow injection techniques for sample introduction in graphite furnace atomic absorption spectrometry (Dept. Chem. Univ. Massachusetts Amherst MA 01003 USA). Wang M. Yuzefovsky A. I. Michel R. G. Determi- nation of ultra-trace amounts of copper cadmium lead and cobalt in sea-water by graphite furnace atomic absorption and laser excited fluorescence with a flow injection on-line preconcentration system (Dept. Chem. Univ. Connecticut Box U-60 Storrs CT 06269 USA). Azeredo L. C. Sturgeon R. E. On-line separation and preconcentration for electrothermal atomic absorp- tion spectrometry (Dept. Quim. Km 47 Antiga Estr. Rio-SP. Rio de Janeiro Brazil). Harrison W. W. Ratliff P. H.Effects of water vapour on plasma reactions in glow discharge mass spectrometry (GDMS) (Dept. Chem. Univ. Florida Gainesville FL 326 1 1-2046 USA). Sturgeon R. E. Luong V. T. Willie S. N. FAPES a biased approach (Inst. Environ. Chem. Natl. Res. Council Canada Ottawa Canada K1A OR9). Riby P. G. Harnly J. M. Characterization of a helium plasma in hollow anode FANES (USDA Nutr. Compos. Lab. Bldg. 16 1 BARC-East Beltsville MD 20705 USA). Pereiro R. Starn T. K. Hieftje G. M. Determination of non-metals in vapours by gas-sampling glow dis- charge atomic emission spectrometry (Dept. Chem. Indiana Univ. Bloomington IN 47405 USA). Taylor H. E. Garbarino J. R. Measurement of trace elements in large rivers by ICP-MS (USGS-WRD 3215 Marine St. Boulder CO 80303 USA). You J. Marcus R.K. Thermabeam aqueous sample introduction into a hollow cathode discharge (Dept. Chem. Clemson Univ. Clemson SC 29634-1 905 USA). Winchester M. R. Travis J. C. Salit M. L. Glow discharge as an analytical emission source for Fourier transform spectroscopy (Inorganic Anal. Res. Div. Natl. Inst. Stand. Technol. Gaithersburg MD 20899 USA). Caroli S. Senofonte O. Del Monte Tamba M. G. Brenner I. Applicability of low-pressure discharges to the analysis of non-conducting materials (1st. Super. Sanita Viale Regina Elena 299 00161 Rome Italy). Leis F. Application of a microwave-boosted glow discharge lamp to the analysis of non-conducting powders (Inst. Spektrochem. angew Spektrosk. Bun- sen-Kirchhoff-St. 1 1 D-4600 Dortmund 1 Germany). Mitchell J. Shirley J. Caldwell V.Practical appli- cations of quantitative depth profile analysis by glow discharge atomic emission spectrometry (Leco Corpo- ration 3000 Lakeview Ave. St. Joseph MI 49085 USA). McLaren J. W. Azeredo M. A. Lam J. W. H. Berman S. S. On-line method for the analysis of sea- water by inductively coupled plasma mass spectrome- try (Inst. Environ. Chem. Natl. Res. Council Canada Ottawa Canada K 1 A OR6).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL 93/C 1483. 93/C1484. 93/C 1485. 93/C 1486. 9 3/C 1487. 93/C 1488. 93IC1489. 93/C 1 490. 93/C149 1. 93/C 1492. 93/C 1493. 93/C1494. 93/C1495. 93/C 1496. 93/C1497. 93/C1498. 93/C 1499. Zarrabi K. Armano M. Hodge V. Stetzenbach K. Reid H. Characterization of trace metals in ground water in southern Nevada by ICP-MS (Center Envi- ron.Stud. Univ. Nevada Las Vegas NV 89154 USA). Hall G. S. Murphy E. Determination of sources of lead in tap water by ICP-MS (Dept Chem. Rutgers Univ. New Brunswick NJ 08903 USA). Ketterer M. E. Source identification of lead and other metals at mineral processing sites using inductively coupled plasma mass spectrometry (USEPA Natl. Enforcement Investigations Center Box 25227 Bldg. 53 Denver Federal Center Denver CO 80225 USA). Nixon D. E. Kershisnik M. M. Moyer T. P. Ash K. O. Comparison of ICP-MS with Zeeman GFAAS for the assessment of thallium exposure (Metals Lab. Section Clin. Biochem. Mayo Clinic Rochester MN 55905 USA). Chisum M. E. Duncan A. A. Analysis of mercury in vacuum pump oil (Mason Hanger Silas Mason Anal. Chem. Lab. P.O. Box 30020 Amarillo TX 79177 USA).Ducatte G. Long G. L. Performance of an echelle based HE-MIP-AES detector for SFC (Dept. Chem. Virginia Tech. Blacksburg VA 24061 -02 12 USA). Quimby B. D. Sullivan J. J. Atomic emission detection in gas chromatography (Hewlett-Packard P.O. Box 900 Avondale PA 1931 1 USA). Mason P. B. Carnahan J. W. Improved analyte transport efficiency with a moving band interface for LC-MIP (Dept. Chem. Northern Illinois Univ. DeKalb IL 60 I 15 USA). Sullivan J. J. Quimby B. D. Diagnostics and chemical reactions in an atomic emission detector for GC (Hewlett-Packard Box 900 Avondale PA 193 1 1 USA). Uden P. C. Seeley J. A. Slowick J. J. Zeng Y. Exploring the Periodic Table with GC-AED (Dept. Chem. Lederle Grad. Res. Tower A Univ. Massa- chusetts Amherst MA 0 1003 USA).Kosman J. J. Lukco R. G. Application of GC-AED in the petroleum industry (BP Research 4440 War- rensville Center Rd. Cleveland OH 44 128 USA). Chakrabarti C. L. Absalan G. Hutton J. C. Back M. H. Lazik C. Marcus R. K. Parametric evaluation of sputtering in an r.f. atomizer for atomic absorption spectrometry (Dept. Chem. Carleton Univ. Ottawa Ontario Canada K 1 S 5B6). Olivares J. A. Huff A. K. Garcia E. M. Schroeder N. C. Elemental analysis by r.f.-GDMS instrumenta- tion and analytical capabilities (Los Alamos Natl. Lab. Inorg. Nucl. Chem. Div. P.O. Box 1663 Los Alamos NM 87545 USA). Marcus R. K. Harville T. Analytical figures of merit for r.f. glow discharge atomic emission spectrometry (Dept. Chem. Howard L. Hunter Chem. Labs. Clem- son SC 29634-1 905 USA).Hunault P. Nelis T. Baudoin J. L. Chewier M. Passetemps R. Analysis of non-conductive coatings used in various industrial applications (Instruments S.A. Division Jobin-Yvon B. P. 1 1 8 16-18 Rue Du Canal 9 1 165 Longjumeau France). Giglio J. J. Caruso J. A. Evaluation of alternative gases for r.f. glow discharge (Univ. Cincinnati Dept. Chem. Cincinnati OH 45221-01 72 USA). Heintz M. J. Hieftje G. M. Comparison of several magnetically enhanced r.f. glow discharge source configurations (Dept. Chern. Indiana Univ. Bloom- ington IN 47405-4001 USA). 93/C 1500. 93/C I 50 1. 931C1502. 93/C1503. 93/C 1 504. 931C1505. 93/C1506. 93/C1507. 93/C 1 508. 931C1509. 93/C 1 5 10. 93/C1511. 93/C 1 5 I 2. 93/C 1 5 1 3. 93IC1514. 93/C15 15. 93/C 1 5 1 6. 93/C1517.8 173R Drozdick J. Angstadt A. D. Vizzoni J. Steiner R. Hess K. R. Investigations of plasma excitatiodioni- zation mechanisms in low-pressure glow discharge devices (Dept. Chem. Franklin Marshall Coll. Box 3003 Lancaster PA 17604 USA). Marcus R. K. Shick Jr C. R. Characteristics of a new r.f.-GDMS system (Dept. Chem. Howard 1. Hunter Lab. Clemson SC 29634- 1905 USA). Ohorodnik S. K. Harrison W. W. Effects of alterna- tive discharge gases on ion signal profiles in pulsed glow discharge mass spectrometry (Dept. Chem. Univ. Florida Gainesville FL 326 1 1-2046 USA). Duckworth D. C. Barshick C. M. McLuckey S. A. Glish G. L. Sampling radiofrequency powered glow discharges with a quadrupole ion trap (Oak Ridge Natl. Lab. Oak Ridge TN 3783 1-6375 USA). Denoyer E. R. Lu Q.Stroh A. Recent developments in flow injection ICP mass spectrometry (Perkin- Elmer Corporation 76L Main Ave. Norwalk CT Beauchemin D. Payer M. J. Jamieson H. E.,Multi- elemental analysis of soils by flow injection with slurry nebulization and ICP-MS (Queen’s Univ. Dept. Chem. Sci. Kingston Ontario Canada K7L 3N6). Ford M. Hill S. Hutton R. C. Investigations into the use of methane addition to ICP-MS to reduce polyatomic interferences (Univ. Plymouth Drake Circus Plymouth Devon UK PL4 8AA). Reed N. M. Hutton R. C. Kingston A Brown P. Gibson G. Evaluation of a high efficiency nebuliza- tion system coupled to a high resolution ICP-MS instrumsent (Fisons Instruments VG Element Ion Path Rd. Three Winsford Cheshire CW7 3BX). Wallace C. F. Enhancement of some analyte signals by carbon compounds in ICP-MS (Perkin-Elmer 3206 Tower Oaks Blvd.Rockville MD 20852 USA). Nam S.-h. Masamba W. Zhang H. Hsiech C.-m. Montaser A. Recent studies on helium inductively coupled plasma mass spectrometry (Dept. Chem. George Washington Univ. Washington DC 20052 USA). Vollkopf U. Barger W. H. Blum A. Performance evaluation of ICP-MS with sample introduction by ultrasonic nebulization (Bodenseewerk Perkin-El- mer Postfach 10 1 164 D-7770 Uberlingen Germany). Tanner S. D. Experimental studies of ion kinetic energies in ICP-MS (SCIEX 55 Glencameron Rd. Thornhill Ontario Canada L3T 1 P2). Myers D. P. Hieftje G. M. Preliminary character- istics of a plasma source time-of-flight mass spectro- meter (Chem. Dept. Indiana Univ. Bloomington IN 47405 USA).Sparks C. M. Pinkston L. Holcombe J. A. Funda- mental studies of ETV-ICP-MS (Dept. Chem. Bio- chem. Univ. Texas Austin TX 787 12 USA). Liezers M. Godwin F. Gregson D. Brown P. Helium MIP quardrupole MS-some fundamentals (Fisons Instruments VG Elemental Ion Path Road Three Winsford Cheshire UK CW7 3BX). Ivanovic K. A. Coleman D. M. Kunz F. W. Schuetzle D. Application of spark sampling ICP-MS to the quantitative analysis of solids (Wayne State Univ. 171 Chem. Bldg. Detroit MI 48202 USA). Zhao J. Lubman D. M. Trace detection of organic species using an atmospheric pressure r.f. glow dis- charge ionization source (Dept. Chem. Univ. Michi- gan Ann Arbor MI 48 109 USA). Barshick C. M. Duckworth D. C. Smith D. H. Solution residue analysis using glow discharge mass spectrometry (Anal.Chem. Div. Oak Ridge Natl. Lab. Oak Ridge TN 37831-6375 USA). 06859-02 15 USA).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 174R 93/C 1 5 1 8. 93/C 1 5 1 9. 93/c 93lC 520. 521. 93lC 1522. 93lC 1523. 93lC 1524. 93lC 1525. 93lC 93lC 526. 527. 93lC1528. 93lC1529. 93lCI 530. 93lC 93lC 531. 532. Fang D. Madan R. Altasas T. Mathews R. Platinum impurity analysis by GDMS (Mater. Res. Corp. Anal. Lab. 560 Route 303 Orangeburg NY 10962 USA). Fang D. Seegopaul P. Evaluation of sample prepara- tion procedures for W-TI sputtering target materials for the determination of alkali elements by GDMS (Mater. Res. Corp. Anal. Lab. 560 Route 303 Orangeburg NY 10962 USA). Yuzefovsky A. I. Michel R. G. Role of barium as a matrix modifier in the formation of magnesium monofluoride as determined by laser excited molecu- lar fluorescence spectrometry in a graphite tube fur- nace (Dept.Chem. Univ. Connecticut Box U-60 Storrs CT 06269 USA). Ruzicka J. Enhancement of atomic spectroscopies by flow injection analysis (Dept. Chem. BG-1 0 Univ. Washington Seattle WA 98 195 USA). Tyson J. F. Overcoming kinetic limitations of the flow injection atomic spectrometry combination (Dept. Chem. Univ. Massachusetts Amherst MA 01003 USA). Denoyer E. R. Beres S. A. Fast transient ICP-MS how many ions are enough? (Perkin-Elmer 761 Main Ave. Norwalk CT 06859-021 5 USA). Welz B. Sperling M. Sun X. On-line preconcentra- tion of trace elements in biological materials for determination by atomic absorption spectrometry (Dept. Appl.Res. Bodenseewerk Perkin-Elmer GmbH P.O. Box 101 164 W-7770 Uberlingen Ger- many). Beauchemin D. Li Z.-b. Denoyer E. R. Evaluation of on-line preconcentration techniques for ICP-MS (Queen’s Univ. Dept. Chem. Kingston Ontario Canada K7L 3N6). Amarasiriwardena C. J. Durrant S. F. Bakowska E. G. Israel Y. Barnes R. M. Determination of barium in sea-water by flow injection sample-to-standard additions method and inductively coupled plasma mass spectrometry (Dept. Chem. Lederle Grad. Res. Center Univ. Massachusetts Amherst MA 0 1003- 0035 USA). Feuerstein M. Schlemmer G. Improving detection limits by an order of magnitude by coupling hydride generation flow injection techniques with electrother- mal atomization (Bodenseewerk. Perkin-Elmer GmbH P.O. Box 101 164 W-7770 Uberlingen Ger- many).Koropchak J. A Allen L. B. Davis J. M. Dispersion of discrete samples in aerosol form fundamental studies (Dept. Chem. Biochem. Southern Illinois Univ. Carbondale IL 6290 I USA). Debrah E. Tyson J. F. Hinds M. W. Closed loop recirculating manifold for matrix isolation in flow injection flame atomic absorption spectrometry (Chem. Dept. Lederle Grad. Res. Center Univ. Massachusetts Amherst MA 01003 USA). Shum S. C. K. Pang H.-m. Houk R. S. Elemental speciation by inductively coupled plasma mass spec- trometry with direct injection nebulization (Iowa State Univ. Ames Lab. USDOE Ames I A 5001 I USA). Michel R. G. Laser excited atomic fluorescence in graphite furnaces for metals and non-metals (Dept. Chem. Univ. Connecticut 2 15 Glenbrook Rd.Storrs CT 06269-3060 USA). Castillano T. M. Giglio J. J. Caruso J. A. Evans E. H. Low pressure inductively coupled plasma mass spectrometry as a detector for gas chromatography (Univ. Cincinnati Dept. Chem. Cincinnati OH 4522 1-0 172 USA). 93lC1533. 03lC1534. ‘33lC1535. 93lC1536. 93lC 1537. 93lC 1538. 93lC 93/c 93lC 93lC 93lC 93lC 539. 540. 541. 542. 543. 544. 93lC1545. 93lC 93lC 546. 547. Vela N. P. Caruso J. A. Supercritical fluid extraction followed by inductively coupled plasma mass spectro- metry for the analysis of organometallics (Dept. Chem. Univ. Cincinnati Cincinnati OH 4522 I - 01 72 USA). Petrucci G . A. Badini R. G. Imbroisi D. Smith B. W. Winefordner J. D. Resonance detection of pho- tons (Univ. Florida Dept. Chem. Gainesville FL Robie D. J. Simeonsson J.B. Smith B. W. Winefordner J. D. Collisional coupling rates of copper and silver in an ICP and an air-acetylene flame using fluorescence dip spectroscopy (Univ. Florida Dept. Chem. Gainsville FL 3261 1-2046 USA). Ayala N. L. Barber T. E. Winefordner J. D. Resonance line lasers as excitation sources for atomic spectrometry (United States Dept. Agric. Agri. Res. Serv. North Atlantic Area Eastern Regional Res. Center 600 E. Mermaid Lane Philadelphia PA 191 18 USA). Lipert R. J. Lee S. C. Edelson M. C. High- resolution spectroscopy of atomic vapours using diode lasers (Ames Lab. USDOE Iowa State Univ. Ames IA 5001 1 USA). Lee S. C. Lipert R. J. Edelson M. C. First observation of actinide elements by optogalvanic spectroscopy using a diode laser source (Ames Lab.USDOE Iowa State Univ. Ames IA 5001 1 USA). Cheam V. Lechner J. Sekerka I. Desrosiers R. LEAFS development for direct analysis of environ- mental samples (Natl. Water Res. Inst. Res. Appl. Branch P.O. Box 5050 Burlington Ontario Canada L7R 4A6). Hanna C. P. Tyson J. F. McIntosh S. Determina- tion of total mercury in environmental clinical and waste eMuent samples by flow injection cold vapour atomic absorption spectrometry (Dept. Chem. Univ. Massachusetts Amherst MA 01 003 USA). Anderson B. R. Holcombe J. A. Use of yeast metallothionein in trace metal analysis (Dept. Chem. Biochem. Univ. Texas Austin TX 78712 USA). Cleland S. L. Vela N. P. Caruso J. A. Determina- tion of trace metals by plasma spectrometric detection with supercritical fluid extraction (Univ. Cincinnati Dept. Chem.Mail Location 172 Cincinnati OH 4522 I USA). Wells-Sendler S. Foust R. D. Jr. Trace metal analysis of mixed phase (water-sediment) samples (Chem. Dept. Northern Arizona Univ. Flagstaff AZ 8601 1 USA). Lian L. Horvat M. Bloom N. S. Improved method for the determination of mercury speciation by aque- ous phase ethylation and carbotrap preconcentration followed by isothermal gas chromatography with cold vapour atomic fluorescence spectrometric (CVAFS) detection (Brooks Rand 3950 Sixth Av. Northwest Seattle WA 98 107 USA). Barnes B. S. Kaine L. A. Sheppard B. S. Votel M. P. Wolnik K. A. Sample pre-treatment and mi- crowave digestion of biological samples for analysis by inductively coupled plasma spectrometry (US Food Drug Admin. Natl. Forensic Chem.Center 1141 Central Pkwy Cincinnati OH 45202 USA). Engelhart W. G. Optimization of microwave acid digestion procedures for organic sample matrices using a dual pressure and microwave immune fibre optic temperature control system (CEM 3 100 Smith Farm Rd. Matthews NC 28105 USA). Wang J. Olson L. K. Caruso A Preliminary investigation of capillary electrophoresis with ICP-MS for trace element determination (Dept. Chem. Univ. 326 I 1-2046 USA).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993. VO1 93lC1548. 93/C1549. 931C 1550. 93/C 155 1. 931C1552. 93/C1553. 93/C1554. 93/C1555. 93lC1556. 93lC1557. 9 3 x 1 558. 93lC1559. 931C 1 560. 931C 1 56 1. 931C 1 562. 931C 1563. 931C1564. 93/C1565. Cincinnati ML 172 Cincinnati OH 4522 1-0 172 USA). Subramanian K. S.Inskip M. J. Connor J. W. Bone lead analysis development of sampling and analytical methodology for milligram samples (Environ. Health Centre Health Welfare Canada Tunney’s Pasture Ottawa Ontario Canada K 1 A OL2). Beyer J. O. von Nehring Q. G. Net weight dispen- ser-a device for rapid and very precise sample and standard preparation (Dow Chemical USA Anal. Sci. 1897A Bldg. Midland MI 48667 USA). Cai M.-x. Montaser A. Mostaghimi J. Modelling and simulation of helium ICPs torch design (Dept. Chem. George Washington Univ. Washington DC 20052 USA). Dziewatkoski M. P. Boss C. B. Molecular decompo- sition processes in microwave plasmas (Dept. Chem. North Carolina State Univ. Raleigh NC 27695-8204 USA). Alvarado J. S. Brandi P. G. Carnahan J. W. Mechanistic and analytical examinations of MIPS in the 100 to 200 nm spectral region (Dept.Chem. Northern Illinois Univ. DeKalb IL 601 15 USA). Blades M. W. Hettipathirana T. LeBlanc C. Gill C. Characteristics of radiofrequency capacitive dis- charges in helium (Univ. British Columbia Dept. Chem. Vancouver British Columbia Canada V6T 1Z1). McCleary K. A Long G. L. Influence of water on a helium MIP (Dept. Chem. Virginia Tech Blacksburg VA 2406 1-02 12 USA). Goode S. R. Emily J. Development and characteri- zation of an annular microwave-induced plasma (Dept. Chem. Univ. South Carolina Columbia SC 29208 USA). Majidi V. Joseph M. R. Emission characteristics of laser induced plasmas in helium (Dept. Chem. Univ. Kentucky Lexington KY 40506 USA). Heise T. W. Yeung E. S. Fluorescence imaging of gas-phase molecules produced by matrix-assisted laser desorption (Dept.Chem. Ames Lab. USDOE Iowa State Univ. Ames IA 500 1 I USA). Cremers D. A. Kane K. Y. Rapid field-based detection of lead in paint using the laser spark (MSJ567 Los Alamos Natl. Lab. Los Alamos NM 87545 USA). Owens M. D. Majidi V. Laser plasma sampling for elemental mass spectrometry (Chem. Dept. Univ. Kentucky Lexington KY 40506 USA). Vertes A. Hydrodynamic modelling of laser-solid interaction what can we learn from it? (George Washington Univ. Washington DC 20052 USA). Goldberg J. M. Dorman F. O’Brien E. Theta pinch re-excitation of a laser plasma (Univ. Vermont Dept. Chem. Burlington VT 05405-01 25 USA). Ridge J. R. Crouch S. R. Investigation of a carbon rod atomization system for laser breakdown spectro- scopy (Dept.Chem. Michigan State Univ. East Lansing MI 48224 USA). Joseph M. R. Majidi V. Laser plasma excittion of electro t hermall y a tom ized species (Dept . Chem. Univ. Kentucky Lexington KY 40506 USA). Mauchien P. Briand A. Lacour J. L. Andre N. Semerok A. Solid sample analysis by optical emission spectroscopy in laser produced plasma (DPE/ SPENSPS Ce Fonenay Aux Roses BP6 92265 Fon- tenay Aux Roses Cedex France). Lee Y.-i Sneddon J. Kim G.-h. Teng Y.-y. Gas breakdown behaviour in an excimer laser-ablated 93/C 1566. 93/C1567. 93/C1568. 931C1569. 93/C 1 570. 93/C1571. 93/CI 572. 93/C1573. 93/C1574. 93/C 1575. 93/C 1576. 93/C1577. 93/CI 578. 931C 1579. 93lC1580. 93/C158 1. 8 175R plasma (Dept. Chem. Univ Massachusetts Lowell MA 0 1854 USA).Koskelo A Cremers D. Rapid analysis of metal particles on filters by laser ablation inductively coup- led plasma spectroscopy (MS-J567 Los Alamos Natl. Lab. Los Alamos NM 87545 USA). Ediger R. D. Challenge of the successful ETV-ICP- MS analysis (Perkin-Elmer 76 1 Main Ave. Norwalk Pinkston T. L. Sparks C. Multi-element determina- tion of trace contaminants in tetramethyl ammonium hydroxide by inductively coupled plasma mass spec- trometry (SEMATECH 2706 Montopolis Dr. Aus- tin TX 78741 USA). De Carlo E. H. Pruszkowski E. Determination of alkaline earth and rare earth elements in marine ferromanganese deposits (Dept. Oceanogr. 1000 Pope Rd. Univ. Hawaii Honolulu HI 96822 USA). Van Hoven R. L. Doughten M. W. Nam S.-h. Dorrzapf A. F. Montaser A Determination of Pt Pd Rh and Ir in geological materials by direct solid sampling of fire assay beads using spark ablation ICP- MS (George Washington Univ. Dept.Chem. Wash- ington DC 22052 USA). Fredeen K. J. Yates D. A. Use of principal compo- nents analysis with laser sampling ICP-MS (Perkin- Elmer 761 Main Ave. Norwalk CT 06859-0215 USA). Shrader D. E. Flajnik C. Moffett J. Howarth H. Development of a universal spray chamber design for flame atomic absorption spectrometry (FAAS) (Var- ian 201 Hansen Court Suite 108 Wood Dale IL 60191 USA). Sneddon J. Farah K. S. Pascucci P.R. Multi-element atomic absorption spectrometry (Dept. Chem. Univ. Massachusetts Lowell MA 01 854 USA). Dulude G. R. Karpova S. Pfeil D. O. Multi-element determinations by continuous flow hydride genera- tion (Thermo Jarrell Ash 8E Forge Pkwy Franklin MA 02038 USA).Franz S. F. Anderson D. P. Malte X. Real-time internal standardization for trace and major elemental determination in lubricating oil by ICP-AES (Lukas Spectro 160 Ayer Rd. Littleton MA 01460 USA). Delles F. Knowles M. Intelligent system for automa- tion of quality assurance and control procedures in graphite furnace atomic absorption spectrometry (GFAAS) (Varian 201 Hansen Court Suite 108 Wood Dale IL 60 19 1 USA). Seeley L. Charge injection device (CID) versus photographic emulsion d.c. arc atomic emission spec- trographic analysis of environmental samples for trace levels of toxic elements (U.S. Geol. Survey Natl. Res. Program Water Resource Division P.O. Box 25046 MS 404 Denver CO 80225 USA). Caruso J.A. Helium sources for plasma spectrome- try (Dept. Chem. Univ. Cincinnati Cincinnati OH 45221 USA). Koons R. D. Merrill R. A. Peters C. A. Forensic comparison of household aluminium foils using ICP- AES (Forensic Sci. Res. Training Center FBI Acad. Quantico VA 22135 USA). Liu H.-y Montaser A. Food analysis by inductively coupled plasma atomic emission spectrometry with a low-cost ultrasonic nebulizer (Dept. Chem. George Washington Univ. Washington DC 20052 USA). Farnsworth P. B. Wu M. Lee M. Lee E. Prince J. Time-of-flight mass spectrometry with atmospheric- pressure plasma ion sources (Dept. Chem. Brigham Young Univ. Provo UT 84602 USA). CT 06859-02 15 USA).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 176R 93lC 1582. 93lC1583. 93lC 93lC 9 3lC 584.585. 586. 93lC1587. 93lCl588. 93lCl589. 93lC 1590. 93lC 93lC 93/c 93lC 9 3lC 93lC 93lC 591. 592. 593. 594. 595. 596. 597. 931 1598. Hall G. S. Wu X. Williams E. T. Multi-elemental analysis of three rings by ICP-MS (Dept. Chem. Rutgers Univ. New Brunswick NJ 08903 USA). Hodge V. F. Laing G. A. Determination of radium- 226 in drinking water by ICP-MS (Univ. Nevada Las Vegas Las Vegas NV 89 154 USA). De Silva N. Guevremont R. Direct powder introduc- tion-inductively coupled plasma emission spectro- metry with a photodiode array spectrometer (Mineral Resources Div. Geol. Survey Canada 610 Booth St. Ottawa Ontario Canada K1 A OE8). Beavis R. C. Experimental parameters in LDMS ion sources (Dept. Phys. Memorial Univ. Newfound- land St. John’s Newfoundland Canada A1 B 3x7). Gluodenis T.J. Jr. Tyson J. F. Determination of trace metals in solid samples via on-line digestion flame atomic absorption spectrometry (Chem. Dept. Univ. Massachusetts Amherst MA 0 1003 USA). Spragg R. Aries R. Lidiard D. Role of diagnostic tools in multivariate calibration (Perkin-Elmer Post Office Lane Beaconsfield Buckinghamshire UK HP9 IQA). Anderson D. A. Skelly Frame E. M. Comparison of direct analysis of solid polymers by graphite furnace AAS with microwave digestion and conventional ashing (GE Corporate Res. Dev. P.O. Box 8 Bldg. K- 1 Room 2A32 Schenectady NY 1230 1 USA). Bradshaw D. K. Analysis of paint chips using slurry sample introduction for graphite furnace AAS (Per- kin-Elmer 400 Technology Park Lake Mary FL 32746 USA). Wu M. Hieftje G.M. Effect of desolvation on the easily ionized element interference in ICP spectrome- try (Dept. Chem. Indiana Univ. Bloomington IN 47405 USA). Ogilvie C. Hemming C. Farnsworth P. B. Charge transfer in the ICP a survey of the transition metals (Dept. Chem. Brigham Young Univ. Provo UT 84602 USA). Olesik J. W. Hobbs S. E. Aerosol desolvation and particle vaporization in ICPs (Lab. Plasma Spectro- chem. Laser Spectrosc. Mass Spectrom Dept. Geol. Sci. Ohio State Univ. 1090 Carmack Rd. Columbus OH 43210 USA). Sesi N. N. Hanselman D. S. Huang M. Hieftje G. M. Effects of EIEs and non-EIEs on the fundamental parameters of the inductively coupled plasma (Dept. Chem. Indiana Univ. Bloomington IN 47405 USA). Weston J. M. Shick C. S. Marcus R. K. Data acquisition and evaluation by a computer controlled Langmuir probe system (Howard L.Hunter Chem. Labs. Clemson Univ. Clemson SC29634- 1905 USA). Letokhov V. S. Laser spectroscopy and its applica- tions in analytical chemistry (Inst. Spectrosc. Russian Acad. Sci. Troitsk Moscow Region 142092 Russia). Marshall J. Carroll J. Franks J. Paterson D. S. Semi-quantitative analysis by ICP-MS using an expert system (ICI Materials Wilton Res. Centre P.O. Box 90 Wilton Middlesbrough Cleveland UK TS6 8JE). Benzing R. Parry S. J. Bennett B. A. Problems of standardization and validation in multi-elemental trace analysis of air filters plastis carbon and boron (Centre Anal. Res. Environ. Imperial Coll. Sci. Technol. Med. Buckhurst Rd. Ascot Berkshire UK SL5 7TE). Taddia M. Bois M. Poluzzi V.Determination of tin in indium phosphide by electrothermal atomic absorp- tion spectrometry and inductively coupled plasma mass spectrometry (G. Ciamician Dept. Chem. Univ. Bologna Via Selmi 2 1-40 126 Bologna Italy). 93lC1599. 93lC 1600. 93lC160 1. 93lC 1602. 93lC 1603. 93lC 1604. 93lC 1605. 93lC 1606. 93lC1607. 93lC 1608. 93lC 1609. 93lC 16 10. 93lC1611. 93lC16 12. 93lC 1 6 1 3. 93/C 16 14. 93/C 16 15. Bermejo Barrera P. Soto Ferreiro R. Aboal Somoza M. Dominguez Gonzalez R. Bermejo Barrera A. Comparative study between palladium-magnesium nitrate as a chemical modifier and graphite tubes coated with zirconium in electrothermal atomic ab- sorption spectrometry (Anal. Chem. Nutr. Bromatol. Dept. Fac. Chem. 15706 Santiago de Compostela Spain). O’Gram S. J. Dean J.R. Glow discharge sources for advanced materials (Dept. Chem. Life Sci. Univ. Northumbria Newcastle Ellison Bldg. Ellison Place Newcastle upon Tyne NE1 8ST). Falk H. Instrumental and applicational peculiarities of atomic spectrometry below 200 nm (Spectro Anal. Instrum. Gesellsch. Anal. Chem. Boschstr. 10 D- 4 190 Kleve Germany). Thompson M. Flint C. D. Brown P. R. Zochowski S. W. Laser ablation of metals and refractories what really happens? (Birkbeck Coll. Gordon Hse. 29 Gordon Sq. London UK WCI H OPP). McNeill R. Barnard C. L. R. Signal modulation and data acquisition in atomic spectrometry (Dept. Phys. Sci. Glasgow Poly. Cowcaddens Rd. Glasgow UK G4 OBA). Stockwell P. B. Ebdon L. C. Hill S. J. Corns W. T. Automated determination of arsine stibine and other hydrides using a new atomic fluorescence detector (P S Analytical Arthur House B4 Chaucer Business Park Watery Lane Kemsing Sevenoaks Kent UK TN I5 6QY).Jin Q.-h. Duan Y. Li Y. Liu X. Du X. Liu M. Shi W. Some further observations on development of microwave plasma torch (MPT) spectrometry (Dept. Chem. Jilin Univ. Changchun 130023 China). Thompson M. Analytical data and robust statistics a true marriage of great convenience (Dept. Chem. Birkbeck Coll. Gordon Hse. 29 Gordon Sq. London UK WClH OPP). Penninckx W. Smeyers-Verbeke J. Massart D. L. Spanjers L. G. C. W. Maris F. Knowledge-based systems for method selection in atomic absorption analysis of Farmaca (Vrije Univ. Brussel Laarbeek- laan 103 1090 Brussels Belgium). De Bievre P. Isotope dilution mass spectrometry as a primary method of analysis (Central Bureau Nucl. Meas.Comm. Europ. Commun. B-2400 Geel Bel- gium). Walker R. F. Measurement traceability and authenti- cation (Lab. Gov. Chemist Queen’s Road Tedding- ton Middlesex UK TWl I OLY). Wagstaffe P. J. Certified reference materials and the BCR programme (BCR Prog. Comm. Europ. Com- mun. 200 rue de la Loi B-1049 Brussels Belgium). Williams A. Ellison S. Measurement uncertainty in chemical analysis (Lab. Gov. Chemist Queen’s Rd. Teddington Middlesex UK TW 1 1 OLY). Squirrell D. C. M. Critical appraisal of instrumenta- tion-a guide to selection of equipment (RSC Anal. Div. Anal. Methods Committee Instrumental Criteria Sub-committee Burlington House Picca- dilly London UK W 1 V OBN). Haswell S. J. Total reflection X-ray tluorescence- coming of age in a simultaneous trace multi-analysis world (Sch.Chem. Univ. Hull Hull UK HU6 7RX). Campbell M. Zheng R. Singhal R. Ledingham K. W. D. Novel ablation chamber for laser ionization spectroscopy measurements (Dept. Phys. Sci. Glas- gow Poly. Gweaddens Rd. Glasgow UK G4 OBA). Savage I. F. Haswell S. J. Preparation of biological samples by microwave dry ashing for TXRF analysisJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 177R 931C 1 6 1 6. 931c 9 31C 931c 931c 931c 617. 618. 619. 620. 621. 931C1622. 931C 1623. 931C1624. 931C 1625. 931C 1626. 931C 1627 931C 1628. 931C 1629. 931C 1 630. of volatile elements (Sch. Chem. Univ. Hull Hull UK HU6 7RX). Reid H. J. Edmonds T. E. Greenfield S. Microwave digestion of ‘difficult’ samples (Dept.Chem. Lough- borough Univ. Technol. Loughborough Leicester- shire UK LEI 1 3TU). Davidson C. M. Littlejohn D. Thomas R. P. Overnell J. Determination of the distributions of redox-sensitive elements in inshore marine sediments (Dept. Pure Appl. Chem. Univ. Strathclyde 295 Cathedral St. Glasgow UK G 1 1 XL). Baluja-Santos C. Gonzalez-Portal A H ydride gener- ation atomic spectrometry in the work environment (Dept. Anal. Chem. Nutr. Bromatol. Fac. Chem. 15706 Santiago de Compostela Spain). Prudnikov E. D. Elgersma J. W. Smit H. C. Errors and detection limits in inductively coupled plasma spectrometry (State Univ. St. Petersburg 199034 Russia). Prudnikov E. D. Elgersma J. W. Smit H. C. Pulse nebulization method in inductively coupled plasma spectrometry (State Univ.St. Petersburg 199034 Russia). Kargosha K. Taimoory A. Study on flame atomic emission spectrometry with new way of sample intro- duction (Chem. Chem. Eng. Res. Centre Iran Teh- ran P.O. Box 14335-186 Iran). Kargosha K. Shivapoor Z. Graphite furnace AAS determination of lead in human serum using ramp heating programme (Chem. Chem. Eng. Res. Centre Iran Tehran P.O. Box 14335-186 Iran). Bagur G. Gizquez D. Sanchez M. Martin A. M. Dept. Anal. Chem. Fac. Sci. Univ. Granada 18071 Granada Spain). WyciSlik A Routine determination of major alloying elements in metallurgical samples by atomic absorp- tion spectrometry (Silesian Tech. Univ. Dept. Metallurgy Graniczna 16 40-01 7 Katowice Poland). Thompson M. Coles B. Hale M. Sampling theory preconcentration laser ablation atomic spectrometry chemometrics hostile environments and man’s lust for gold (Birkbeck Coil.Gordon Hse. 29 Gordon Sq. London UK WClH OPP). O’Gram S. J. Dean J. R. Franks J. Marshall J. Sample preparation techniques for glow discharge atomic spectroscopy (Dept. Chem. Life Sci. Univ. Northumbria Newcastle Ellison Bldg Ellison Place Newcastle upon Tyne UK NEl 8ST). Benito S. Vicente J. Speciation of organotin com- pounds by high-performance liquid chromatography using an inductively coupled plasma mass spectro- meter as a detector (Environ. Inst. TP 460 JRC Ispra 2 1020 Italy). Zaranyika M. F. Mazuru M. E. Mutual spectroche- mica1 interference effects between strontium and sodium and strontium and potassium in air-acetylene flame (Chem. Dept. Univ.Zimbabwe P.O. Box MP 167 Mount Pleasant Harare Zimbabwe). McLeod C. W. Jansen A. Crighton J. Trace element analysis of oils by laser ablation inductively coupled plasma spectrometry (Chem. Anal. Res. Centre Sheffield Hallam Univ. Sheffield UK SW IWB). Bermejo Barrera P. Aboal Somoza M. Soto Ferreiro R. Bermejo Martinez F. Palladium-magnesium ni- trate as a chemical modifier for the determination of lead in mussel slurries by electrothermal atomic absorption spectrometry (Anal. Chem. Nutr. Broma- tol. Dept. Fac. Chem. 15706 Santiago de Compos- tela Spain). 931C 163 I . 931C 1632. 93lC1633. 931C1634. 931C 1 635. 931C 1636. 931C1637. 931 1638. 931 1639. 9 31 9 31 931 931 640. 641. 642. 643. Przepiera A. Wisniewski M. Jablonski M. Deter- mination of trace elements content in titanium diox- ide pigments by wavelength-dispersive X-ray fluores- cence spectrometry and inductively coupled plasma methods (Appl.Inorg. Chem. Centre Polish Acad. Sci. Kuinicka 1 72-010 Police Poland). Yaman M. Giiqer S. Determination of vanadium in urine and animal tissues by atomic absorption spectro- metry (Dept. Chem. Fac. Arts Sci. Univ. Firat Elazig Turkey). Alimonti A. Petrucci F. Caroli S. Lastity A. Determination of ultratrace elements in fresh and sea- waters by combined preconcentration-inductively coupled plasma atomic emission spectrometric methods (1st. Super. Sanita Viale Regina Elena 299 001 61 Rome Italy). Bermejo Barrera P. Beceiro Gonzalez E. Bermejo Barrera A. Barciela Garcia J. Barciela Alonso C. Separation of chromium(rI1) and chromium(vr) using complexation of chromium(II1) with 8-hydroxyqui- nolin and determination of both species in mineral waters by electrothermal atomic absorption spectro- metry (Anal. Chem.Nutr. Bromatol. Dept. Fac. Chem. 15706 Santiago de Compostela Spain). Bermejo Barrera P. Beceiro Gonzalez E. Pita Calvo C Bermejo Martinez F. Determinatin of molyb- denum in water by electrothermal atomic absorption spectrometry with different matrix modifiers and study of preconcentration on the graphite tube (Anal. Chem. Nutr. Bromatol. Dept. Fac. Chem. 15706 Santiago de Compostela Spain). Bermejo Barrera P. Pita Calvo C. Beceiro Gonzalez E. Bermejo Barrera A. Comparative study of the effectiveness of palladium-magnesium nitrate and palladium-hydrochloride hydroxylamine as matrix modifiers for the determination of molybdenum in biological fluids by electrothermal atomic absorption spectrometry (Anal.Chem. Nutr. Bromatol. Dept. Fac. Chem. 15706 Santiago de Compostela Spain). Yaman M. Kokqam I. Determination of trace elements in hair of epileptic patients (Firat Univ. Sci. Arts Fac. Dept. Chem. Elazig Turkey). Hanna C. P. Tyson J. F. Offley S. G. 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Bloomington IN 470405 USA). Carre M. Poussel E. Mermet J.-M. Drift diagnos- tics in inductively coupled plasma atomic emission spectrometry.Plenary Lecture J. Anal. At. Spectrom. 1992 7 791. (Lab. Sci. Anal. Univ. Lyon I 69622 Villeurbanne Cedex France). Luan S. Pang H.-m. Shum S. C. K. Houk R. S. Noise characteristics of aerosols produced by induc- tively coupled plasma nebulizers J. Anal. At. Spec- from. 1992 7 799. (Ames Lab. US Dept. Energy Dept. Chem. Iowa State Univ. Ames IA 5001 1 USA). Castillano T. M. Vela N. P. Caruso J. A. Story W. C. Evaluation of an ultrasonic nebulizer for sample introduction in inductively coupled plasma atomic emission spectrometry J. Anal. At. Spectrom. 1992 7 807. (Dept. Chem. Univ. Cincinnati Cincin- nati OH 4522 1-0 172 USA).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 192R 9312043. 9312044. 9 312045. 93 93 2046.2047. 9 312048. 9312049. 9312050. 931205 1. 9312052. 9312053. 9312054. Tarr M. A. Zhu G.-x. Browner R. F. Transport effects with dribble and jet ultrasonic nebulizers J. Anal. At. Spectrom. 1992 7 813. (Sch. Chem. Bio- chem. Georgia Inst. Technol. Atlanta GA 30332- 0400 USA). Brenner I. B. Bremier P. Lemarchand A. Perform- ance characteristics of an ultrasonic nebulizer coupled to a 40.68 MHz inductively coupled plasma atomic emission spectrometer J. Anal. At. Spectrom. I992,7 819. (Geol. Survey Israel 30 Malkhe Israel St. Jerusalem 9550 1 Israel). Jahl M. J. Barnes R. M. Sealed inductively coupled plasma atomic emission spectrometry. Part 3. Optim- ization of experimental variables J. Anal. At. Spec- trom. 1992 7 825. (Dept. Chem. Lederle Grad. Res Center Univ.Massachusetts Amherst MA 0 1003- 0035 USA). Jahl M. J. Barnes R. M. Analysis of silane with a sealed inductively coupled plasma discharge J. Anal. At. Spectrom. 1992 7 833. (Dept. Chem. Lederle Grad. Res. Center Univ. Massachusetts Amherst Jacksier T. Barnes R. M. Qualitative analysis of arsine by sealed inductively coupled plasma atomic emission spectrometry J. Anal. At. Spectrom. 1992,7 839. (Dept. Chem. Lederle Grad. Res. Center Univ. Massachusetts Amherst MA 01 003-0035 USA). Krushevska A. Barnes R. M. Amarasiriwaradena C. J. Foner H. Martines L. Determination of the residual carbon content by inductively coupled plasma atomic emission spectrometry after decomposition of biological samples J. Anal. At. Spectrom. 1992 7 845. (Dept. Chem. Univ. Massachusetts Lederle Grad.Res. Center Towers Amherst MA 01003-0035 USA). Krushevska A. Barnes R. M. Amarasiriwaradena C. J. Foner H. Martines L. Comparison of sample decomposition procedures for the determination of zinc in milk by inductively coupled plasma atomic emission spectrometry J. Anal. At. Spectrom. I992,7 85 1. (Univ. Massachusetts Dept. Chem. Lederle Grad. Res. Center Amherst MA 0 1003-0035 USA). Caroli S. Alimonti A. Delle Femmine P. Petrucci F. Senofonte O. Violante N. Menditto A. Morisi G. Menotti Z. Falconieri P. Role of inductively coupled plasma atomic emission spectrometry in the assessment of reference value for trace elements in biological matrices J. Anal. At. Spectrom. 1992 7 859. (Dept. Appl. Toxicol. 1st. Superiore Sanita Viale Regina Elena 299 00 16 1 Rome Italy).Freire dos Reis B. Fernanda Gine M. Krug F. J. Bergamin Filho H. Multipurpose flow injection sys- tem. Part 1. Programmable dilutions and standard additions for plant digests analysis by inductively coupled plasma atomic emission spectrometry J. Anal. At. Spectrom. 1992 7 865. (Cent. Energ. Nucl. Agric. Univ. SBo Paulo Av. Centenario 303 C. Postal 96 13400 Piracicaba SP Brazil). Fariiias J. C. Barba M. F. Determination of macro- constituents in advanced ceramic materials by induc- tively coupled plasma atomic emission spectrometry J. Anal At. Spectrom. 1992 7 869. (Lab. Anal. Quim. Inst. Cerhm. Vidrio (CSIC) 28500 Arganda del Rey Madrid Spain). Fariiias J. C. Barba M. F. Determination of impuri- ties in lead zirconate-titanate electroceramics by inductively coupled plasma atomic emission spectro- metry J.Anal. At. Spectrom. 1992,7,877. (Lab. Anal. Quim. Inst. Ceram. Vidrio (CSIC) 28500 Arganda del Rey Madrid Spain). Perry B. J. Van Loon J. C. Speller D. V. Dry- chlorination inductively coupled plasma mass spectro- metric method for the determination of platinum MA 01 003-0035 USA). 9 31205 5. 9 3/20 5 6. *9 31 20 5 7. 9312058. 9312059. 9312060. 931206 1. 9312062. 9312063. 9312064. 9 31206 5. group elements in rocks J. Anal. At. Spectrom. 1992,7 883. (Dept. Geol. Univ. Toronto Canada M5S 3B1). Akatsuka K. McLaren J. W. Lam J. W. Berman S. S. Determination of iron and ten other trace elements in the open ocean sea-water reference ma- terial NASS-3 by inductively coupled plasma mass spectrometry J. Anal. At.Spectrom. 1992 7 889. (Inst. Environ. Chem. Natl. Res. Council Canada Ottawa Canada KIA OR6). Hill S. J. Hartley J. Ebdon Kl. Determination of impurities in organometallic compounds dissolved in diethyl ether by flow injection inductively coupled plasma mass spectrometry J. Anal. At. Spectrom. 1992,7 895. (Plymouth Anal. Chem. Res. Unit Dept. Environ. Sci. Univ. Plymouth Drake Circus Plymouth Devon UK PL4 8AA). Marawi I. Bielski B. A. Caruso J. A. Meeks F. R. Measurements of inductively coupled plasma temper- atures comparison of N,+ rotational temperatures with optical pyrometry J. Anal. At. Spectrom. 1992,7 899. (Dept. Chem. Univ. Cincinnati Cincinnati OH Chen Z.-x. Longerich H. P. Fryer B. J. Recycling nebulization system with a disposable spray chamber for analysis of sub-milligram samples of geological materials using inductively coupled plasma mass spectrometry J.Anal. At. Spectrom. 1992 7 905. (Dept. Earth Sci. Centre Earth Res. Res. Memorial Univ. Newfoundland St. John’s Newfoundland Canada A l B 3x5). Amarasiriwardena C. J. Krushevska A. Foner H. Argentine M. D. Barnes R. M. Sample preparation for inductively coupled plasma mass spectrometric determination of the zinc-70 to zinc-68 isotope ratio in biological samples J. Anal. At. Spectrom. 1992 7 9 15. (Dept. Chem. Lederle Grad. Res. Center Univ. Massachusetts Amherst MA 0 1003-0035 USA). Riglet C. Provitina O. Dautheribes J.-L. Revy D. Determination of traces of neptunium-237 in enriched uranium solutions using inductively coupled plasma mass spectrometry J.Anal. At. Spectrom. 1992 7 923. (Commiss. Energ. Atom. Centre d’Etudes Cadarache DSDISEPISAED 1 3 108 Saint-Paul-les- Durance Cedex France). Wang J.-s. Evans E. H. Caruso J. A. Addition of molecular gases to argon gas flows for the reduction of polyatomic-ion interferences in inductively coupled plasma mass spectrometry J. Anal. At. Spectrom. 1992 7 929. (Dept. Chem. Univ. Cincinnati ML 172 Cincinnati OH 4522 1-0 172 USA). Craig J. M. Beauchemin D. Reduction of the effects of concomitant elements in inductively coupled plasma mass spectrometry by adding nitrogen to the plasma gas J. Anal. At. Spectrom. 1992,7,937. (Dept. Chem. Queen’s Univ. Kingston Ontario Canada K7L 3N6). Raith A. Vieth W. Huneke J. C. Hutton R. C. Quadrupole versus magnetic sector glow discharge mass spectrometry comparison of quantitative analyt- ical capabilities J.Anal. At. Spectrom. 1992 7 943. (Charles Evans Assoc. 30 1 Chesapeake Dr. Redwood City CA 94063 USA). Jakubowski N. Stuewer D. Application of glow discharge mass spectrometry with low mass resolution for in-depth analysis of technical surface layers J. Anal. At. Spectrom. I992,7 95 1. (Inst. Spektrochem. angew. Spektrosk. Postfach 10 13 52 W-4600 Dort- mund 1 Germany). Fang D. Seegopaul P. Sample preparation of high- purity titanium for analysis by glow discharge mass spectrometry J. Anal. At. Spectrom. 1992 7 959. (Mater. Res. Corp. 560 Route 303 Orangeburg NY 10962 USA). 45221-0172 USA).JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY. JUNE 1993. VOL. 8 193R 9312066. 931206 7. 9312068. 9312069. 9312070.931207 1. 9312072. 9312073. 9312074. 931207 5. 9312076. 9312077. Peters G. R. Beauchemin D. Versatile interface for gas chromatographic detection or solution nebuliza- tion analysis by inductively coupled plasma mass spectrometry preliminary results J. Anal. At. Spec- trom. 1992 7 965. (Dept. Chem. Queen’s Univ. Kingston Ontario Canada K7L 3N6). Vela N. P. Caruso J. A. Determination of tri- and tetra-organotin compounds by supercritical fluid chro- matography with inductively coupled plasma mass spectrometric detection J. Anal. At. Spectrom. 1992 7 97 1. (Dept. Chem. Univ. Cincinnati Cincinnati Seeley J. A. Zeng Y. Uden P. C. Eglinton T. I. Ericson I. Pyrolysis-gas chromatographic atomic emission detection for sediments coals and othr petrochemical precursors J.Anal. At. Spectrom. 1992,7 979. (Dept. Chem. Lederle Grad. Res. Tower A Univ. Massachusetts Amherst MA 01 003 USA). Jhbinski R. Adams F. C. Ultratrace speciation analysis of organolead in water by gas chromatogra- phy-atomic emission spectrometry after in-liner pre- concentration J. Anal. At. Spectrom. 1992 7 987. (Dept. Chem. Univ. Antwerp (UIA) Universiteit- splein 1 B-26 10 Wilrijk Belgium). Olson L. K. Caruso J. A Determination of halogen- ated compounds with supercritical fluid chromatogra- phy-microwave-induced plasma mass spectrometry J. Anal. At. Spectrom. 1992 7 993. (Dept. Chem. Univ. Cincinnati Cincinnati OH 4522 1 USA). Kovacic N. Ramus T. L. Application of a mi- crowave-induced plasma atomic emission detector for quantification of halogenated compounds by gas chro- matography J.Anal. At. Spectrom. 1992 7 999. (Dow Chemical Comp. P.O. Box 1398 Pittsburg CA 94565 USA). Caetano M. Golding R. E. Key E. A. Factorial analysis and response surface of a gas chromatography microwave-induced plasma system for the determina- tion of halogenated compounds J. Anal. At. Spec- trom. 1992 7 1007. (Cent. Quim. Anal. Escuela Quim. Fac. Cienc. Univ. Central Venezuela P.O. Box 47 102 Caracas 104 1-A Venezuela). Argentine M. D. Barnes R. M. Comparison of stripline source and enhanced beenakker microwave cavity designs for atomic emission spectrometry J. Anal. At. Spectrom. 1992,7 1013. (Lederle Grad. Res. Center Dept. Chem. Univ. Massachusetts Amherst Liang Z.-w. Lonardo R. F. Takahashi J. Michel R. G. Preli F.R. Jr. Laser-excited fluorescence spectrometry of phosphorus monoxide and phospho- rus in an electrothermal atomizer determination of phosphorus in plant and biological reference materials and in nickel alloys J. Anal. At. Spectrom. 1992 7 1019. (Dept. Chem. Univ. Connecticut 215 Glen- brook Rd. U-60 Storrs CT 06269-3060 USA). Lorenzen C. J. Carlhoff C. Hahn U. Jogwich M. Applications of laser-induced emission spectral analy- sis for industrial process and quality control J. Anal. At. Spectrom. 1992 7 1029. (Krupp Forschungsinst. GmbH Postfach LO 22 52 D-4300 Essen 1 Ger- many). Hettipathirana T. D. Blades M.W. Temporal emis- sion and absorption characteristics of silver lead and manganese in furnace atomization plasma excitation spectrometry J. Anal. At. Spectrom.1992 7 1039. (Dept. Chem. Univ. British Columbia 2036 Main Mall Vancouver British Columbia Canada V6T lZl). Gilmutdinov A. Kh. Chakrabarti C. L. Hutton J. C. Three-dimensional distributions of oxygen in graphite and metal tube atomizers for analytical atomic spec- trometry J. Anal. At. Spectrom. 1992 7 1047. OH 4522 1-0 172 USA). MA 01003-0035 USA). 9312078. 9312079. 9312080. 931208 1. 9 312082. 9312083. 9312084. 9312085. 9312086. 9312087. 9312088. 9312089. (Centre Anal. Environ. Chem. Dept. Chem. Carleton Univ. Ottawa Ontario Canada KIS 5B6). Iwamoto E. Ohlsson K. E. Baxter D. C. Frech W. Spatially resolved spectroscopic measurements of CN C2 and Al in graphite tube electrothermal atomizers under various operating conditions J. Anal. At. Spectrom. 1992 7 1063.(Dept. Anal. Chem. Univ. Umei S-901 87 Umei Sweden). Mile B. Rowlands C. C. Jones A. V. Single calibration method for the determination of lead in nickel alloys and steels by electrothermal atomic absorption spectrometry J. Anal. At. Spectrom. 1992 7 1069. (Sch. Chem. Appl. Chem. Univ. Wales Coll. Cardiff Cardiff UK CFl 3TB). Belarra M. A. Lavilla I. Anzano J. M. Castillo J. R. Rapid determination of lead by analysis of solid samples using graphite furnace atomic absorption spectrometry J. Anal. At. Spectrom. 1992 7 1075. (Dept. Anal. Chem. Univ. Zaragoza 50009-Zaragoza Spain). Marchante Gayon J. M. Sanz-Medel A. Fellows C. Rock P. Determination of cadmium in human urine using electrothermal atomic absorption spectrometry with probe atomization and deuterium background correction J.Anal. At. Spectrom. 1992 7 1079. (Dept. Phys. Anal. Chem. Fac. Chem. Univ. Oviedo Julian Claveria sln 33006 Oviedo Spain). Carbonell V. Morales-Rubio A. Salvador A. de la Guardia M. Burguera J. L. Burguera M. Atomic absorption spectrometric analysis of solids with on- line microwave-assisted digestion J. Anal. At. Spec- trom. 1992 7 1085. (Univ. Valencia Dept. Quim. Anal. clDr. Moliner 50 46 100 Burjassot Valencia Spain). Long G. L. Bolton J. S. Influence of propane on the atomic emission and atomic absorption signals in an inductively coupled argon plasma J. Anal. At. Spec- trom. 1992,7 1091. (Dept. Chem. Virginia Polytech. Inst. State Univ. Blacksburg VA 2406 1-02 12 USA). Thompson M. Flint C. D. Chenery S. Knight K. Time resolved system for the analysis of particles in the inductively coupled plasma-preliminary studies J.Anal. At. Spectrom. 1992 7 1099. (Dept. Chem. Birkbeck Coll. Gordon House 29 Gordon Sq. Lon- don UK WClH OPP). Gomes A.-M. Bacri J. Sarrette J.-P. Salon J. Measurement of heavy particle temperature in a radiofrequency air discharge at atmospheric pressure from the numerical simulation of the NO y System J. Anal. At. Spectrom. 1992 7 1103. (Centre Phys. At. Unite Assoc. CNRS No. 277 Univ. Paul Sabatier 1 18 Route Narbonne 3 1062 Toulouse Cedex France). Ebdon L. Goodall P. Slurry atomization using hydrogen-modified inductively coupled plasmas J. Anal. At. Spectrom. 1992 7 1 1 1 1 . (Plymouth Anal. Chem. Res. Unit Dept. Environ. Sci. Univ. Ply- mouth Drake Circus Plymouth UK PL4 8AA). Jerrow M. Marr 1. L. Cresser M. S. Significance of generation of cation-exchange surfaces by grinding to slurry nebulization J.Anal. At. Spectrom. 1992 7 2087. (Dept. Chem. Meston Bldg. Univ. Aberdeen Old Aberdeen UK AB9 2UE). Mierzwa J. Zyrnicki W. Study of matrix effects on rare earth elements in hollow cathode discharges J. Anal. At. Spectrom. 1992 7 1121. (Central Lab. M. Curie-SModowska Univ. 20-03 1 Lublin Poland). Ketterer M. E. Assessment of overall accuracy of lead isotope ratios determined by inductively coupled plasma mass spectrometry using batch quality control and the Youden two-sample method J. Anal. At. Spectrom. 1992 7 1 125. (United States Environ. Protection Agency Natl. Enforcement Investig. Cen-194R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 93/2090. ter Box 25227 Bldg. 53 Denver Federal Center Denver CO 80225 USA).Pretty J. R. Blubaugh E. A. Evans E. H. Caruso J. A. Davidson T. M. Determination of copper and cadmium using an on-line anodic stripping voltamme- try flow cell with detection by inductively coupled plasma mass spectrometry J. Anal. At. Spectrum. 1992. 7 . 113 1. (Deot. Chem. Univ. Cincinnati Cin- 9312092. Kim A. W. Foulkes M. E. Ebdon L. Hill S. J. Patience R. L. Barwise A. G. Rowland S. J. Construction of a capillary gas chromatography induc- tively coupled plasma mass spectrometry transfer line and application of the technique to the analysis of alkyllead species in fuel J. Anal. At. Spectrum. 1992 7 1147. (Dept. Environ. Sci. Univ. Plymouth Drake Circus Plymouth Devon UK PL4 8AA). 93/2093. Gray A. L. Stabilization of an inductively coupled cinnati,’OH 4522 1-01 72 USA).Ward N. I. Durrant S. F. Gray A. L. Analysis of plasma for inductively coupled plasma mass spectro- biological standard reference materials by laser abla- metry with a flared torch extension J. Anal. At. tion inductively coupled plasma mass spectrometry J. Spectrum. 1992 7 1 15 1. (NERC ICP-MS Facility Anal. At. Spectrum. 1992 7 1139. (Dept. Chem. Dept. Geology Royal Holloway Bedford New Coll. Univ. Surrey Guildford Surrey UK GU2 5XH). Egham Hill Egham Surrey UK TW20 OEX). 93/2091.

ISSN:0267-9477    

DOI:10.1039/JA993080169R

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 195R 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) 1R 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 S/B 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-i nduced 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 TechnologyJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE '93 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 stamp. 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ISSN:0267-9477    

DOI:10.1039/JA993080195R

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 499 Chromatography Coupled With Inductively Coupled Plasma Atomic Emission Spectrometry and Inductively Coupled Plasma Mass Spectrometry A Review Steve J. Hill Martin J. Bloxham and Paul J. Worsfold Department of Environmental Sciences University of Plymouth Plymouth Devon UK PL4 8AA Summary of Contents Introduction High-performance Liquid Chromatography-Inductively Coupled Plasma 2.1 Environmental Applications 2.2 Clinical Applications 2.3 Industrial Applications 2.4 General Analytical Approaches High-performance Liquid Chromatography-Inductively Coupled Plasma 3.1 Environmental and General Applications 3.2 Clinical and Industrial Applications Atomic Emission Spectrometry Mass Spectrometry Gas Chromatography-Inductively Coupled Plasma Atomic Emission Spectrometry Gas Chromatography-Inductively Coupled Plasma Mass Spectrometry Conclusions Keywords Coupled techniques; high-performance liquid chromatography and gas chromatography; inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry; trace metal speciation; review Introduction The various techniques of analytical atomic spectrometry offer the possibility of detecting a wide range of metals and non-metals although by themselves they only yield infor- mation on total concentrations.Thus with the increasing demand for both qualitative and quantitative information on the form of the metal in a wide range of samples trace metal speciation studies have increasingly coupled the separatory powers of chromatography with the sensitivity and selectivity of atomic spectrometry for detection.The area has received much attention and has been the subject of many papers. Two major reviews covering the direct coupling of gas chromatography (GC)-atomic spectro- metry' and liquid chromatography-atomic spectrometry* were published in the mid- 1980s. Together these reviews covered over 250 papers dating back to 1965 and critically evaluated the various types of coupling then available. However since that time many developments in coupled techniques have been made particularly in response to the need for versatile systems which facilitate the obtain- ment of better detection limits and which lend themselves to routine laboratory operation. One of the major advances in atomic spectrometry since the reviews were published has been the introduction and widespread adoption in many laboratories of commercial inductively coupled plasma mass spectrometry (ICP-MS) systems.Such instru- ments provide significantly lower detection limits than inductively coupled plasma atomic emission spectrometry (ICP-AES) instruments and when coupled with either gas or liquid chromatography offer on-line operation in real time. In addition ICP-MS also offers a multi-element mode which can be used for trace-metal speciation in real samples. This review covers the use of coupled liquid and gas chromatography with both ICP-AES and ICP-MS systems with an emphasis on applications to real samples. Every effort has been made to avoid duplication of material covered in the previous reviews.However some early high- performance liquid chromatography (HPLC) couplings with an ICP-AES system have been included since in many cases the nature of the coupling with an ICP-MS system is essentially the same although the chromato- graphy e.g. mobile phase may have to be modified for use with ICP-MS. Although only a modest number of GC-ICP- AES couplings have been reported the use of capillary GC with ICP-MS offers some exciting potential use for the future. High-performance Liquid Chromatography-Inductively Coupled Plasma Atomic Emission Spectrometry When used as a detector for HPLC the ICP offers good sensitivity a dynamic range of over five orders of magni- tude and multi-element detection capabilities. However conventional HPLC-ICP couplings i.e.direct connection between the end of the HPLC column and the nebulizer can suffer from poor transport efficiency particularly when pneumatic nebulizers are used. Such couplings also demon- strate low tolerance to many of the organic solvents commonly employed in mobile phases for HPLC. Investiga- tions have therefore been performed to characterize the effects of mobile-phase composition and flow rates on HPLC-ICP methods3v4 In addition workers have reported studies on modified nebulizer and spray chamber arrange- ments in an attempt to maximize analytical performance; e.g. the effects of nebulization chamber position using both Meinhardsy6 and fixed cross-flow7,* nebulizers for liquid HPLC-ICP couplings. These studies revealed that for aqueous eluents peak broadening and distortion occurred when the chamber was placed inside the ICP gas box due to extended liquid transport.However when the chamber was500 JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 placed outside the gas box a loss in signal commensurate with aerosol transport over an equivalent distance oc- curred thus emphasizing the importance of keeping the dead volume associated with the coupling to a minimum. More recently a number of other workers have tried ultrasonic nebulizer^,^ thermospray vaporizers8*10J1 and glass-frit nebulizersI2 for sample introduction in HPLC-ICP-AES. In all cases improvements in sample transport efficiency have been reported when compared with pneumatic nebulization particularly for organic sol- vents.The solvent load of the plasma (important in terms of plasma stability) can be decreased by aerosol thermostat- ing,13-15 cooling of the spray chamber,15*16 and application of a c ~ n d e n s e r . l ~ - ~ ~ The amount of solvent introduced into the plasma may also be reduced by employing micro HPLC systems for the separations.20v21 In a brief communication Lawrence et al. ,22 described a total injection microconcen- tric nebulizer that was reported to yield up to 100°/o nebulization and transport efficiency for HPLC-ICP-AES. Later this group under Fassel extended the study and the direct injection nebulizer (DIN) was again used in HPLC-ICP-AES studies,12 although this time the range of organic solvents was extended to include up to 100% methanol acetonitrile isobutyl methyl ketone and pyridine in the HPLC eluent.In addition it was reported that detection limits using HPLC-DIN-ICP-AES for a number of elements were better than those obtained by other workers using HPLC-ICP-AES with other nebulizer ar- rangements. From our own experience the fragility of such devices can be a disadvantage although the recent avail- ability of commercial designs might encourage their more widespread application. In all of the above developments the principal aim has been to minimize band spreading in the interface following separation by the chromatographic column. Various types of HPLC columns have been used including thermal gradient application^.^^ However supercritical fluid chro- matography (SFC) has also been used recently in conjunc- tion with ICP-AES d e t e ~ t i o n .~ ~ - ~ ~ The unique properties of supercritical fluids totally eliminate the need for the nebulizer-spray chamber interface since as the fluid leaves the chromatographic column and restrictor it becomes a gas at atmospheric pressure and will transport essentially 100% of the sample in a readily atomized form. In one of the first papers in this area Fujimoto et reported the interfacing of an ICP to a packed column SFC system and evaluated its performance with ferrocene and its deriva- tives. An ICP coupling to a capillary SFC has also been reported and in this case applied to the separation of organosilicon corn pound^.^^ A short review of this inter- esting area discussing techniques for coupling SFC to ICP-AES has also been prepared by Li,26 although in all reported cases the ICP suffers from the same limitations for elemental speciation in SFC as in other forms of chromatography i.e.poor response for many non-metallic elements. The following tables (Tables 1-4) list the various applica- tions reported for HPLC-ICP-AES. The four categories used for the tables i. e. environmental clinical industrial and general applications are only meant as a guide to aid the reader since many publications describe several appli- cations that might fit one or more of these sections. Publications dealing with development work using labora- tory chemicals as samples are described in Table 4 under general applications. It should also be noted that a surpris- ing number of workers do not give details of the detection limits achieved in their work and this is reflected in the tables.Table 1 HPLC-ICP-AES applications (environmental) Detector ICP all argon plasma 1.05- 1.9 kW FP. HPLC coupled to ICP via Teflon tubing into a cross-flow nebulizer ICP all argon 1.3 kW FP. HPLC coupled to ICP via Teflon tubing into a cross-flow nebulizer All argon ICP HPLC coupled to ICP via Teflon tubing into a cross-flow nebulizer Bausch & Lomb ARL 34000 48 channel. HPLC coupled via PTFE tubing into cross-flow nebulizer PlasmaTherm HFP2500D ICP 1.5 kW FP. HPLC coupled via Teflon capillary tubing into a concentric nebulizer Chromatography Zorbax Cs column (250 x 4.4 mm i.d.). Mobile phase linear gradient of 55Oh ethanol up to 80°h EDTA Anion-exchange column p-bondpak- NH,.Mobile phase oxylate-Mg buffer 30 cm columns packed with 3 types of ion exchanger bondpak-NH,; Nucleosil CH3- 10; and Nucleosil S03H- 10. Mobile phase 0.05 mol 1 - I phosphate buffer Hamilton PRB 1 reversed-phase column. Mobile phase 0.002 mol I-' hexadecyl- trimethylammonium bromide (HTAB) pH 9.6 Various columns C,* ODS Spherisorb; Cs Ultrasphere; C 5 mm; and C LiChrosorb RP-2. Mobile phase various water and alcohol mixtures were studied Sample Detection limits Comments Ref. 3 Separation of Fe 0.7 ng - iron carbonyl and molybdenum carbonyl compounds Mo 0.3 ng Separation and quantitative analysis of orthophosphate diphosphate and triphosphate Separation and quantitative analysis of As compounds in biological sainples Arsenic selenium and phosphorous compounds Demonstration of the suitability to the separation of tetramethyl and tetraethyllead in gasoline of HPLC-ICP Ortho 0.5 p g di 1.0 pg tri 3.0 p g As 2.6 ng As 130 p g I-' ATP and ADP also 28 anal ysed Other detection 29 also employed (HPLC-AA and DCP) 30 TML 42 mg I-' Optimum HPLC 31 TEL 2 12 mg I- conditions C2 LiChrosorb column; butanol- ethanol-water ( I 5 + 35+50) mobile phaseJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL.8 50 1 Table 1-con tin ued Detector Chromatography PlasmaTherm Various reversed- HFP2500D all phase and ion- argon ICP. exchange columns HPLC coupled via Teflon capillary tubing into a cross-flow nebulizer Sample Determination of alkyllead coin pou n ds Detection limits Comments Ref. TML 33 pg s-' Glass frit nebulizer 32 TEL 100 pg s-' incorporated to increase ICP ability to accept organic solvents with high evaporation rates Jarrell-Ash 975 AtornCornp ICP 1.2 kW FP. HPLC coupled via PTFE tubing into a cross- flow nebulizer Either TSK3000SW Fractionation and (600 x 7.5 mm i.d.) or measurement TSK2000SW (500 x of metal 7.5 mm i.d.) size- species at exclusion columns.ambient levels Mobile phase in natural distilled de-ionized waters water Not reported By coupling SEC 33 with ICP it was possible to determine if metal peaks would co-elute with ultraviolet absorbing dissolved organic matter Hydride generation 34 derivitization successfully interfaced with paired ion Plasma 100 all argon ICP Paired ion Trace analysis reversed-phase and speciation C type columns for arsenic (250 x 4.6 mm id.).Mobile phase environmental 0.005 mol I-' paired-ion chromatography (PIC) drinking water reagent (Waters) supplies anions in Not reported reversed-phase HPLC Improved sensitivity and shortened retention time of CrVi was attained by the formation of tetrat h iocyanato- chromate(II1) prior to injection Cr"' 7.5 ng CrVi 22.0 ng 35 All argon ICP Short column packed with a porous polyacrylate- based anion- exchange resin. Mobile phase 5.0 x lo-* mol I-' potassium hydrogenphthalate solution pH 6.5 Ion-exchange preconcent ration column (100 x 1.6 mm) packed with iminodiacetate chelating resin. Mobile phase 0.1 mol I-' sodium citrate Determination of Criil and CrVi as a method for the fractional determination of Cr species in waste waters Determination of cadmium in certified biological reference materials and waste water samples Jarrell-Ash 1.0 kW FP.HPLC coupled via Teflon-PTFE tubing into a conventional nebulizer ICAP-575 ICP Cd2+ 0.05 ng ml-' Ion-exchange 36 preconcentrat ion allowed a 25-fold improvement in sensitivity and detection limits over direct aspiration of the aqueous solution - 37 Bausch and Lomb 34000 1.6 kW FP. HPLC coupled via Teflon tubing into a concentric nebulizer Bausch and Lomb ARL 34000 argon ICP Hamilton PRP-I Detection of column (250 x 4.1 mm). Mobile Phase containing Methanol-0.05 mol I-' surfactants ammonium acetate in waste sulfur waters Sulfur 15 ng Hamilton PRP- I Quantitative reversed-phase determination of column (25 x 4 mm) arsenobetaine in crabs lon-exchange Separation of chromatography lanthanide using cation- series elements exchange columns in marine Fe-Mn (Bio-Rad AGSOW-X8 crusts resin).Mobile phase 1.7-6.0 mol I-' HCI dependent on procedure Nucleosil SB anion- Determination exchange column and speciation (200 mm). of arsenic Mobile phase in aquatic 50 mmol I-' NaH2P04.H20 media buffered to pH 6.75 with Na2HP04-2H20 3 ng methylarsonic acid - 38 Leernan Laboratories Plasmaspec 1 ICP 0.98 kW FP Not reported Major (Fe and Mn) and minor constituents (Al Co Cu Ni Ca Mg) eluted with 1.7-2 mol I-' HCI; the rare earth elements (REE) then eluted from the resin with 4.0 or 6.0 mol I-' HCI 39 PlasmaTherm ICP 1.0 kW FP. HPLC coupled via PTFE tubing to a hydride generation system. The nebulizer was replaced with a gas-liquid separator Jobin-Yvon JY24 ICP HPLC interfaced into a concentric nebulizer 1.3-1.7 kW FP.As"' 3.5 pg I-' of As A gas-liquid 40 MMA 3.8 pg I-' of As DMA 2 I .3 pg I-' of As AsV 9.2 pg 1-' of As separator was used to impede the entrance of the mobile phase into the plasma torch 1 nvest igat ion of organometallics in the marine ecosystem (Zn Cd Cu) Not reported 41 Gel permeation SEC column (TSK G 3000SW). Mobile phase phosphate buffer pH 7.5502 JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 Table l-continued Detector JY 48P 36 channel argon ICP 1 . 1 kW FP. Concentric glass nebulizer PlasmaTherm HFSSOOOd ICP 0.85 kW FP. HPLC coupled via heated transfer line directly into the ICP torch assembly Perkin-Elmer 5500 ICP 1.25 kW FP. Column eflluent line inserted directly into a cross-flow nebulizer All argon ICP-AES Chromatography Ion-exchange 8 PSCX IOpm radial pak LC cartridge. Mobile phase 0.1 mol 1-' NaNO 0.02 mol I-' MgCl SFC fused silica capillary column coated with poly(dimethylsi1oxane).Mobile phase SFC-grade carbon dioxide Waters Z module ion-exchange column containing Bio-Rad Aminex resin. Mobile phase gradient from water to ammonium carbonate Econosphere Cle reversed-phase column (25 cm x 4 mm). Mobile phase stepwise aqueous methanol gradient ( 10-70%) Sample Determination of Y and selected REE in geological samples Evaluation of SFC-ICP-AES as a selective detector for organosilicon compounds Separation of biologically important As species Determinatiori of inorganic lead and several a1 kyllead compounds Detection limits Comments Ref.42 Yttrium 1-2 pg g-I - 5.8 ng of Si injected Sensitive to 60 ng As injected onto the column 74-3 17 ng 43 44 45 2.1 Environmental Applications The majority of publications to date employing HPLC-ICP-AES have described work that can be placed under the broad heading of environmental applications. Of these there is a notable emphasis on the determination of specific organometallic compounds and in particular orga- noarsenic and organolead compounds. However although the detection systems and interface designs are often very similar the nature of the mode of separation is often different. For example Morita et al.29 have described the separation of arsenite arsenate methylarsonic acid (MMA) dimethylarsinic acid (DMA) and arsenobetaine (AsB) with both anion- and cation-exchange chromatograpy with phosphate buffers as mobile phases.The detection limit for As using the As I 193.6 nm line was reported as 2.6 ng s-' (20). The same arsenic species have also been determined by Irgolic et al. ,30 although phenylarsonic acid was determined instead of arsenobetaine and a reversed- phase column was used. Slightly poorer detection limits (= 13 ng) were obtained. A similar variety of chromato- graphic approaches is also found for the determination of organolead compounds with both rever~ed-phase~l and ion- exchange columns being used.32 A wide range of environmental samples have been investigated using HPLC-ICP-AES. These include natural water^;^^^^^ waste water^;^^-^^ marine samples (e.g. crabs,38 marine crusts39 and other marine organism^;^^*^^ petroleum product^;^^*^^ geological samples;42 and certified reference materials.36 The elements determined include As Cd Cr Cu Fe Mn Mo P Pb S Se Si Y and Zn although a number of other elements of environmental interest are discussed in Section 2.4 (Table 4).Details of reported environmental applications of HPLC-ICP-AES are pre- sented in Table 1. 2.2. Clinical Applications This section discusses applications of HPLC-ICP-AES to clinical samples and includes publications that have used the technique to determine trace elements in amino acids blood pharmaceutical products proteins vitamins and other biological matrices. One of the most commonly determined elements in this section is phosphorus. Since the terminal phosphate groups found in nucleotide mole- cules can be separated using anion-exchange chromato- graphy the use of HPLC-ICP-AES provides an attractive means of determining individual monomeric units.The technique also overcomes some of the problems encoun- tered when using more conventional detection techniques such as spectrophotometry since nucleotides tend to be hygroscopic and unstable and in addition require indivi- dual calibration graphs to take account of the unique extinction coefficients associated with each type of nucleo- tide. In one of the first studies in this area Hiene et al.,46 assessed the capabilities of ICP-AES as a selective detector by observing the P I emission at 2 13.6 nm. The nucleotides were separated on an anion-exchange column using acetate buffers and calibrated using a single calibrant of Na2HP04(aq).A detection limit of 750 ng of phosphorus was obtained with an RSD of 4.5%. Anion exchange has also been used for the determination of ribonucleoside-5'- mono- 5'-di and 5'-triphosphates again monitoring the phosphorus emission by ICP-AES.47 Other workers have also employed gel-permeation columns e.g. for the deter- mination of C Co and P in vitamin BI2; cation-exchange columns e.g. in the determination of amino acids (moni- toring the C and S emission); reversed-phase column^;^ and more recently size-exclusion chromatography as in the determination of ferritin in pharmaceutical products.48 Table 2 gives details of these applications together with other published work in this area. 2.3 Industrial Applications Directly coupled HPLC-ICP-AES has also been reported for a number of industrial applications such as the determination of trace elements in petroleum products coal process streams and oil share^,'^^^^-^* the characteriza-JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL.8 503 Table 2 HPLC-ICP-AES applications (clinical) Detector Jobin-Yvon 38 Type I11 ICP 1.27 kW FP. HPLC coupled via Teflon tubing into various nebulizers including a continuous- flow ultrasonic nebulizer Chromatography Various columns Vydac 201TP C18 ( 2 5 0 ~ 4 . 6 mm id.) Partisil 5 ODs3 ( 2 5 0 ~ 4 . 6 mm i.d.); Hamilton PRP- 1 ( 1 5 x 4 mm i.d.). Mobile phase various eluents were used including the ion-pairing reagent tetrabutylammonium phosphate Develosil 100-5 capillary column ( 2 3 0 ~ 0 .3 5 mm id.). Mobile phase toluene and chloroform MicroPak AX- 10 anion-exchange column (300 mm). Mobile phase A 0.007 mol 1-' NaC2H302 pH 4 and B 0.3 mol 1-I NaC2H302 0.3 mol 1-1 NaCl pH 3. Linear gradient from A to B of 5 min Stainless steel anion-exchange columns (500 x 4 mm i.d. 250x4 mm i.d.). column packing. Mobile phase 0.1-0.73 rnol 1-' HCOONH PH 3 Either TSK G4000SW or TSK G 5000PW Superose 6HR 10130 size-exclusion chromatography columns. Mobile phase KH,P04 0.07 mol I-' NaClO 1 rnol ]-I NaN rnol I-' pH 6.8 TSK GEL 3000SW (600 x 2 mm) gel- permeation column. Mobile phase 0.9W NaCl aqueous solution I EX-260-SA-SIL Sample Speciation of ionic compounds containing As Se and Cr Detection limits Comments Se 10-14 mg I-' The analytical As 30-40 mg I-' figures of merit Cr 8-10 mg 1 - I using an ultrasonic nebulizer were comparable to or better than conventional nebulization in terms of organic solvent tolerance sensitivity detection limits and repeatability Ref.9 20 46 Jarrel Ash 500s argon ICP. HPLC coupled via stainless-steel tubing into a cross-flow nebulizer All argon ICP HPLC coupled via PTFE tubing into a Babington principle nebulizer 1.0-3.0 kW FP. Not reported Organornetallic speciation in petroleum and biological samples Micro-column LC using a no spray chamber nebulization system Determination of nucleotides by analysing the total P concentration 750 ng of P A Babington type nebulizer was used to aspirate the high percentage salt solutions with a 6% e ficiency Jarrel-Ash 1.3 kW FP. HPLC coupled via Teflon tubing into a cross-flow nebulizer ICAP-50 ICP Concentration as Column temperature 47 P 0.37-0.56 p g ml-L maintained at 60 "C with a column oven Determination of ribonucleoside 5'-mono- 5'-di- and 5'-triphosphate by analysing the integrated emission intensity of P Jobin-Yvon 38VHR ICP 2.2 kW FP.HPLC coupled via PVC tubing into a concentric nebulizer Analysis of ferritin in pharmaceutical products 48 Fe 1.1 ng Jarrell-Ash AtomComp all argon ICP 1.25 kW FP. HPLC coupled via Teflon tubing into a cross-flow nebulizer Plasma 100 all argon ICP Not reported Vitamin B,* was 49 not recovered completely possibly owing to adsorption onto the stainless-steel tubing Determination of C Co and P in vitamin BI2 and the multi-element analysis of proteins CrlI1 220 mg ml-I CrV1 450 mg ml-1 50 Paired ion reversed-phase C18 type columns (250 x 4.6 mm i.d.).Mobile phase 0.005 moll-' PIC reagent Reversed-phase C18 type column. Mobile phase NaCl or LiCl saturated with tributyl phosphate buffered Nucleosil-NH(CH,) strong anion-exchange column. Initial mobile phase 0.002 rnol I-'- ammonium dihydrogen phosphate (ADP) 0.005 mol I-' ammonium acetate pH 4.6. Second mobile phase 0.08 mol I-' ADPpH 6.9 to pH 3.9-6.0 Qualitative and quantitative analysis of various metal cations or anions Cd Zn Hg As above Not reported 51 Sequential ICP atomic emission spectrometer 1.04 kW FP. HPLC coupled via Teflon tubing into a Fisher cross-flow nebulizer Absolute 52 ng As"' 140 ng SeIV 57 ng AsV 91 ng Se"' 52 Speciation and quantification of arsenate arsenite selenate and selenite504 JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL.8 Table 2-continued Detector Jarrell-Ash 1.2 kW FP. HPLC coupled via small diameter Teflon tubing into a cross-flow nebulizer ICAP-50 ICP ARL 3520 all argon ICP 1.05 kW FP. HPLC coupled via PTFE tubing into a GMK nebulizer Chromatography Stainless-steel column (300 x 4 mm i.d.) packed with a strong cation-exchange resin. Mobile phase gradient elution from 0.2 mol I-' NaH2POf pH 3.2 to 0.2 rnol I- NaH2P0 pH 4.3 TSK G3000SW SEC column. Mobile phase 0.1 rnol I-' HEPES. 0.1 rnol I-' NaCl pH 7.4 Sample Determination of amino acids Study of the distribution of Cu Fe ZR and Co in various biological samples including milk and blood Detection limits Comments Ref. and 1-3 pg ml-l intensity at 193.09 nm.detection limit obtained by S I emission detecting emission intensity at intensities of C and S 180.73 nm respectively 30-50 pg ml-' C I emission 53 Not reported 54 Table 3 HPLC-ICP-AES applications (industrial) Detector Plasma Therm HFS5000D ICP 1.8 kW FP. HPLC coupled via stainless-steel tubing into a direct injection nebulizer R.f. Plasma Products HFP 2500f ICP 1.4 kW FP. HPLC coupled via Teflon tubing into a concentric nebulizer Bausch and Lomb 3580 all argon ICP R.f. Plasma Products HFP 2500F ICP 1.4 kW FP. HPLC coupled via Teflon tubing into a concentric nebulizer AtomComp 975 ICP 1.75 kW FP. HPLC coupled via PTFE tubing into a cross-flow nebulizer ICP all argon Shimadzu V I000 ICP 1.2 kW FP. A hydrofluoric acid-resistant sample introduction system was used ARL 3520 ICP 1.22 kW FP.HPLC coupled via direct connection of HPLC eluent into a concentric nebulizer Jarrell Ash all argon ICP 1.2 kW FP. HPLC coupled via Teflon tubing into a cross-flow nebulizer Sequential ICP-AES Chromatography Panisil 5 ODs-3 CIS reversed-phase column (250 x 4.6 min i.d.). Mobile phase 5 mmol I-' aqueous tetrabutylammonium phosphate used to generate temperature gradient. HPLC column placed inside oven. Carbosphere ODS (150x2 mm) for non-aqueous. Microsorb C ( 100 x 4.6) for aqueous Two analytical sciences SEC UltraGel MXL columns connected in series H-P 57 1 OA GC Size-exclusion chromatography SEC columns 300 x 7.5 mm PL-Gel; and 250 x 9.5 mm GP250. Four mobile phases Column-exchange chromatography columns prepared with tri(2-ethyl hexy1)phosphate (TEHP) or dihexyl-NJVdiethyI- carbamoyl-methylenephosphate (DHDECMP) Anion-exchange column packed with either Dowex 1-X4 or Dowex 2-X8.Mobile phase 2 rnol I-' nitric acid Sulfite ion exclusion column (100 x 7.8 mm) of polystyrenedivinylbenzene with 1096 cross linking. Mobile phase 0.1 % HCI v/v pH I .84 Stainless-steel column (250 x 4 mm) packed with strong cation-exchange resin. Mobile phase 0.4- I .O rnol 1-' ammonium lactate Ion chromatography Sample Various samples including gravimelt process stream materials and crude shale oils Sulfur (aqueous) silicon (non-aqueous) Molecular size distribution of specific elements in petroleum crudes and 650+ (S and Vn) Study of the behaviour of V Ni and S during heavy crude oil conversion processes Detection limits Comments Ref.Relative detection limit Evaluation of the 12 0.74-39 ng ml-' arsenite direction injection 42 ng ml-' nebulizer selenite application of a S 4 ng s-I Si 0.2 ng s-' Application of 23 thermal gradient LC Not reported Not reported 55 56 Molecular size speciation of V and Ni complexes in oil 3.5 ng of Ni 0.5 ng of V Characterization of selected nuclear fuel materials Not reported 57 58 materials Determination of B in iron disilicide and high-purity iron B 0.01 pg ml-I in - solution 0.05 pg g-I in high-purity iron Detection of sulfite with reference to the determination of sulfite in beverages and foods Sulfite as S 0.08 mg ml-I Determination of rare earths elements 0.001-0.3 pg ml-I 15 rare earths determined 59 60 61 Determination of Cr Not reported - 62 Mo Mn and Ni in certified steel samplesJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL.8 505 Table 4 HPLC-ICP-AES applications (analytical) Detector Jarrel-Ash 975 AtomComp ICP 1.2 kW FP. HPLC coupled via Teflon capillary tubing into the ICP nebulizer Chromatography Anion-exchange column ( 100 mm x 2.1 mm i.d.) packed with Aminex A-14 anion-exchange resin. Mobile phase aqueous 0.05 mol I-' (NH4)2SOJ 50 x 4.1 mm i.d. stainless-steel anion-exchange column Sample Evaluation of ICP as a detector for HPLC peaks containing specific elements Detection limits Cu 6.9 ng. Detection limits also determined for 25 other elements Comments ICP compared with AAS for the detection of HPLC peaks composed of H,edta and H,nta (nitrilotriacetic acid) chelates of copper Ref.4 5 8 PlasmaTherm 2500 ICP 1.2 kW FP. HPLC coupled via Teflon capillary interface into a concentric nebulizer Perkin-Elmer Plasma I1 ICP 1.4 kW FP for aqueous solution. 1.9 kW FP for organic solution. HPLC coupled via a thermospray vaporizer into a cross-flow nebulizer Jobin-Yvon 38 Type 111 ICP I .27 kW FP. HPLC coupled via Teflon tubing into various nebulizers including a continuous- flow ultrasonic nebulizer Not reported Examined the properties of the location of pneumatic nebulizer spray chamber systems on transport mechanisms Using a thermospray nebulizer a threefold increase in sensitivity was achieved along with a 33% increase in the methanol Speciation of Se in (CH3hSe+ Se0& and Se042- Waters IC-PAK anionic column (1 50 x 4 min i.d.).Mobile phase ammonium citrate 0.08 mol I-' pH 3.3. A detection limit of 44 pg 1-1 was achieved with 25% methanol in the Se standard solution addition to the plasma Various columns Vydac 201TP CIS (250 x 4.6 mm i.d.) Partisil 5 ODs3 ( 2 5 0 ~ 4 . 6 mm i.d.) Hamilton PRP- 1 (1 50 x 4 mm id.). Mobile phase various eluents were used including the ion- pairing reagent tetrabutylammonium phosphate 1 OOA p-Styragel size-exclusion chromatography column. Mobile phase toluene Speciation of ionic compounds containing As Se and Cr Se 10-14 mg I-' As 30-40 mg I-' Cr 8-10 mg 1-1 The analytical figures of merit using an ultrasonic nebulizer were comparable to or better than conventional nebulization in terms of organic solvent tolerance sensitivity detection limits and repeatability 9 ARL I37000 ICP 1.4 kW FP.HPLC coupled via Teflon or 3 16 stainless-steel tubing into a Pyrex glass nebulizer Determination of organometallic species in synthetic mixtures Detection limits in toluene were found to be comparable to those found in aqueous static operation of Not reported ICP-AES A Pyrex spray chamber to facilitate the interface and to be compatible with volatile solvents was developed 16 Cu-acac Zn-ddtc Cr-ddtc Fe-ddtc Cu-ddtc Co-ddtc 21 Jarrell Ash 500s all argon ICP 1.2-2.0 kW FP Teflon columns either reversed phase (1 20 x 0.5 mm) or normal phase ( 1 50 x 0.5 mm i.d.). Mobile phase methanol-water Ion pairing reversed-p hase (500x 1 mm i.d.) C18 microbore column Mobile phase water Anion-exchange column p-bondpak- Mobile phase oxylate-Mg buffer (HRSM-50-CI 8).NH2. Micro-HPLC coupled to ICP-AES for analysis of organometallics PlasmaTherm argon ICP. HPLC coupled via stainless-steel tubing into a micro- concentric nebulizer ICP all argon 1.3 kW FP. HPLC coupled via Teflon tubing into a cross-flow nebulizer PlasmaTherm ICP 1.0 kW FP. HPLC coupled via PTFE tubing to a hydride generation system. The nebulizer was replaced with a gas-liquid separator Jarrell Ash 500s argon ICP 2.2 kW FP. HPLC coupled via Teflon tubing into a cross-flow nebulizer Reference solution of Mg Mn Cd As Se Hg Sr Co Ba Pb and Cr Absolute detection limit Cr"' 2.2 ng As 13.0 ng 22 Separation and quantitative analysis of orthophosphate diphosphate and triphosphate Ortho- 0.5 pg Di- 1.0 pg Tri- 3.0 p g ATP and ADP also 28 anal ysed Determination of As speciation in aquatic media As"' 3.5 pg 1-' As MMA 3.8 pg I-' As DMA 2 1.3 pg I-' As AsV 9.2 mg 1-' As The use of a gas-liquid separator impedes the entrance of the mobile phase into the plasma torch 40 Nucleosil SB anion- exchange column (200 mm).Mobile phase 50 mmol I-' NaH2P04-H20 buffered to pH 6.75 with Na2HPO4-2H20 Teflon microcolumn (200x 1 mm i.d.) packed with Fine Gel SC220. Mobile phase distilled water Analysis of carbon containing compounds 800 ng of C 63506 JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 Table 4-continued Detector Jarrell-Ash 955 Plasma Atomcomp ICP 0.8-1.2 kW FP. Ion-exchange column coupled via PTFE flow injection manifold into a cross-flow nebulizer Shimadzu ICPQ- 100 ICP 1.3-1.4 kW FP.Ion-exchange column coupled via PTFE flow injection manifold into a concentric nebulizer Instrument Laboratory Model 200 ICP. HPLC coupled via Teflon tubing into an all glass spray chamber Jarrell-Ash 975 AtomComp ICP 1.2 kW FP. HPLC coupled via PTFE tubing into the ICP nebulizer All argon ICP-AES Chromatography Single or parallel preconcentrating ion-exchange columns (20 x 2.3 mm i.d.) packed with Chelex- 100 resin. Mobile phase 2 mol I-' nitric acid Preconcentrat ing ion-exchange microcolumn (20 x 3.2 mm i.d.) packed with Muromac A-1 resin. Mobile phase 2 mol I-' HN03 Two C columns in series (1 50 x 3.9 mm id.). Mobile phase 0.06 mol I-' ammonium acetate 0.005% v/v mercaptoethanol Anion-exchange column (250 x I .6 mm) packed with sub-400 mesh AGI x 4 anion-exchange resin.Mobile phases 0.05 rnol I-' (NH&SO Cation-exchange chromatography. Mobile phase a-hydroxyisobutyric acid or ammonium lactate Sample Ba Be Cd co cu Mn Ni and Pb standards Determination1 Ti V Fe"' and A1 of Cr"' Determination! of inorganic and organomercury compounds Determination. of NTA and EDTA chelates of Cu Zn Ca and Mg Determination of lanthanoids in standard rock samples Detection limits Ba 0.04 pg I-' Be 0.008 pg I-' Cd 0.04 pg I-' Mn 0.04 pg I-' Ni 0.02 pg I-' Pb 2.0 pg 1 - I c o 0.1 pg I-' cu 0.2 pg I-' A1 1.5 pg I-' Cr"' 0.21 pg 1-1 Fell1 0.1 1 pg I-' Ti 0.08 pg I-' V 0. I5 pg I-' 32-62 mg 1-' based on a signal-to- noise ratio of 2:1 Not reported Not reported Comments Ref. F1-ion exchange 64 ICP-AES gave a detection limit 20 times better than for conventionally aspirated systems Signal enhancements 65 of 34- I I3 times better than conventionally aspirated systems were achieved using this system Post-col um n cold 66 vapour generation used to improve detection limits For the species studied the sensitivity of ICP-AES detection was better than or virtually equal to that of UV detection at 254 nm 67 68 - tion of selected nuclear fuel materials,58 impurities in high- purity iron,59 and by monitoring sulfur emission the determination of sulfite in beverages and foods.60 In a study by LaFreniere et a1.,I2 a direct injection nebulizer was used for elemental speciation studies on coal process streams and various oil-based samples.The limits of detection achieved using the HPLC-DIN-ICP-AES system for a range of elements (As Cd Co Cr Cu Ni S Se and Zn) were compared with other coupled techniques.These workers reported that the limits of detection obtained using HPLC-DIN-ICP-AES were either comparable to those obtained by continuous-flow sample introduction into the ICP or inferior by only a factor of four (As) and concluded that this was due to the low dead volume (1.5 pl) associated with the DIN interface which resulted in low or negligible extra-column analyte dispersion. However despite this obvious benefit there have been few subsequent publica- tions in this area possibly reflecting the practical problems associated with this device as discussed above. The chromatography associated with the various indus- trial application has once again been diverse with both anion- and cation-exchange reversed-phase and size- exclusion chromatography all being reported.Table 3 gives details of the columns used for these studies together with an overview of the industrial applications reported to date. 2.4 General Analytical Approaches This section includes publications which do not readily fit into the three categories described in Section 2.1 2.2 and 2.3. Many of these publications report development work and so do not include 'real' samples. This section covers papers describing work using laboratory standards and synthetic mixtures. However many of the approaches described could readily be used in one or more of the application areas discussed above. Once again various types of chromatography have been explored although the interface-detection systems are often evaluated more fully than in some of the applications papers discussed above.Spray chamber construction for example has been investigated with respect to the organic solvents used in HPLC mobile phases16 and in terms of sample transport mechanism^.^ The use of different types of nebulizer such as cross-flow micro-c~ncentric,~~~~~ ultra- sonic9 and thermospray8J0J have also been evaluated. The use of both flow injection technique^^^.^^ and post-column cold vapour g e n e r a t i ~ n ~ ~ . ~ ~ are also included. In some papers two or more of these factors are incorporated into the system used. For example in one of the more recent papers by Elgersma et al.,I1 the performance of a low consumption thermospray nebulizer is described for spe- cific use with micro-HPLC and general use in flow injection with ICP-AES detection.Table 4 gives further details of the publications that fall into this more general section and includes work on the element specific detection of over 20 elements. 3 High-performance Liquid Chromatography- Inductively Coupled Plasma Mass Spectrometry The use of ICP-MS as an element specific detector for HPLC offers both exceptional sensitivity and multi-JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 507 element capability. Although ICP-MS can handle the same 3.1 Environmental and General Applications types of chromatographic eluents as ICP-AES the better sensitivity often eliminates the need for additional tech- niques such as post-column derivatization. In addition the capability of ICP-MS for isotope ratio determinations can also be exploited thus allowing isotope dilution analyses to be used where techniques such as spark source mass spectrometry were used in the past. The use of isotope dilution also saves on the time required to prepare multiple chromatograms from which to obtain calibration graphs and compensates for matrix effects.Finally the ability of HPLC to remove troublesome matrix interferences on-line offers a potential generic advantage for all ICP-MS applications. The coupling of HPLC with the ICP-MS instrument has been investigated by a number of workers. In one of the first papers in this area by Dean et al.,69 the characteristics of HPLC-ICP-MS couplings were investigated using the number of theoretical plates peak tailing rise time and wash-out time as criteria of merit.The HPLC flow rates used in this work were limited to between 0.5 and 1.5 ml min-' in order to remain compatible with the normal range of uptake rates of the cross-flow nebulizer. It was found that the optimum coupling consisted of a short aerosol line with extended liquid transport tubing. More recent papers have tended to adopt a similar approach. As stated above ideally the choice of mobile phase to achieve optimum chromatographic separation should not be compromised. In general although flow rates might be restricted good separations with relatively short retention times have been reported. However problems can arise when using ICP-MS with mobile phases containing certain buffers or high concentrations of organic solvent.For example Heitkemper et aL70 reported that the phosphate buffer system used in their work on the speciation of arsenic in urine caused rapid erosion and clogging of the nickel sampling cone. After about 2 h the nickel sampler became badly pitted and salt deposits started to clog the sampling orifice. In this case a solution was found using an aluminium sampler with a 0.7 mm orifice which tolerated the phosphate buffer solution well. The use of mobile phases with high concentrations of organic solvent can be a bigger problem since they lead to elevated reflected powers even at high forward powers (FP) which can lead to generator cut-out with extended use. Furthermore soot deposits on the faces of the sampler and skimmer cones within the ICP-MS interface region result in elevated noise and decreased signals. These problems can be overcome by introducing oxygen into the nebulizer although the reflected powers can still be greater than 100 W.An alternative approach is to replace the standard torch supplied with most commercial instruments with a low argon flow torch. This approach was employed by Branch et al.,72 who used a Fassel torch design with 1.3 mm jets in the outer and intermediate gas flow and a configuration ratio of 0.82; this contrasts with gas inlets of 6 mm and a configuration ratio of 0.78 in the standard Fassel torch. When operated at a total argon flow of 10.55 1 min-I the reflected power was less than 25 W and no soot deposition was observed on the cones.To reduce the amount of organic solvent from the mobile phase actually reaching the plasma most workers reduce the temperature of the spray ~ h a m b e r ~ ~ . ~ ~ although more efficient desolvation can be achieved by passing the aerosol through a heating chamber priorto the co~lingcondenser.'~~~~ A range of desolvation systems have been described which A number of reports describing off-line preconcentration of trace metals in matrices such as sea-water,sl and the removal of matrix elements by ion exchanges2 using ICP-MS detection were published in the mid 1980s. However the first work to look at the feasibility of using ICP-MS as an on- line multi-element detector for HPLC was published by Thompson and Houk in 1986.83 In the original study ion pair reversed-phase liquid chromatography was used and sample introduction was achieved by ultrasonic nebuliza- tion with aerosol desolvation.The work concentrated on arsenic and selenium species and gave detection limits ofthe order of 0.1 ng. This study also reported on the precision (<2%) and accuracy (=lYo) when using isotope ratio measurements and concluded that HPLC-ICP-MS had considerable potential for speciation studies using stable tracer isotopes. Jiang et al.74 also reported on the removal of various ionization interferences by utilizing chromatogra- phic retention of metal complexes in ICP-MS studies. As with HPLC-ICP-AES various forms of chromato- graphy have also been employed with ICP-MS. Micellar liquid chromatography has been used for example in the speciation of alkyltin corn pound^.^^ Trimethyltin chloride triethyltin bromide and tripropyltin chloride were sepa- rated with a 0.1 mol l-' sodium dodecyl sulphate (SDS) micellar mobile phase and CIS stationary phase.Detection limits reported for the three tin species were 27,5 1 and 1 1 1 pg respectively. Three other tin species were also separated; monomethyltin trichloride dimethyltin dichloride and trimethyltin chloride. In this case a 0.02 mol 1-' SDS mobile phase was used and detection limits of 46 26 and 126 pg respectively where obtained. The maximum SDS concentration for use in this work was shown to be 0.1 mol 1 - I if clogging of the torch and sampling orifice was to be avoided. Other workers have used ion-exchange resins to separate organotins.Branch et al.72 employed a column packed with Partisil (10 pm) for the determination of tributyltin species in waters. This study also presented the results from a 'blind-trial' of water samples spiked with tributyltin and concluded that HPLC-ICP-MS offered a sensitive and accurate method of determining the tributyl- tin ion at normal environmental levels. More recently SFC coupled with ICP-MS has been reported,s4 again for the determination of organotins. In this work separation of tetraalkyltin compounds gave detection limits in the sub-pg range (0.034 pg for tetrabutyltin and 0.047 pg for tetraphe- nyltin). The system used was linear over three orders of magnitude (1-1000 pg) and gave an RSD of better than 5%. Considering the relatively short period of time that ICP- MS has been available in many laboratories there are a surprising number of publications reporting a range of applications of HPLC-ICP-MS. These include mercury speciation in tuna fish,s5 arsenic in various marine reference materials,86-88 tin in natural waters71.72y89+90 and harbour sediment^,^^ metals in soil leachatesg2 and tellurium com- pounds in waste water streams.93 Various applications of HPLC-ICP-MS in marine analytical chemistry have also been reviewed by McLaren et aL9' This publication dis- cusses the speciation of mercury and tin in some detail as well as the application of isotope dilution studies for metal speciation in marine samples.Details of the various environmental applications of coupled HPLC-ICP-MS are presented in Table 5.are capable of removing a large percentage of the organic solvent (up to 80%)prior to its reaching the p l a ~ m a . l ~ * ~ ~ - ~ ~ T h e advantages of such desolvation systems in terms of In terms of clinical and industrial apdications for 3.2 Clinical and Industrial Applications HPLC-ICP-MS are the increase in plasma stability and the availability of detection limits that are comparable to those obtained during aqueous operation. HPLC-ICP-MS arsenic has been one of ihe elements to receive most attention. This reflects both the widespread interest in this element and the problems of determining508 JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 Table 5 HPLC-ICP-MS applications (environmental and analytical) Detector VG PlasmaQuad 1.65 kW FP. HPLC coupled to ICP via Teflon tubing into a standard nebulizer VG PlasmaQuad HPLC coupled to ICP via silicon rubber tubing into a standard nebulizer.Survey scan data acquisition mode SCIEX Elan 250 1.25 kW FP. HPLC emuent from column coupled to ICP-MS via an ultrasonic nebulizer Multiple-ion monitoring mode SCIEX-Elan 250 1.2 kW FP. HPLC coupled to ICP-MS via stainless-steel tubing into an ultrasonic nebulizer. Operating in peak hopping mode VG PlasmaQuad 1.35 kW FP. SFC coupled to ICP-MS via a stainless-steel heated transfer line directly into the ICP injector VG PlasmaQuad 1.3 kW FP. HPLC coupled to ICP via Teflon (FEP) tubing into nebulizer inlet ICP-MS 1.0-1.8 kW FP. ICP-MS ICP-MS ICP-MS ICP-MS Chromatography Spherisorb ion pair ODS-2 column or Adsorbosphere SCX ion-exchange column Partisil STX column ( 2 5 0 ~ 4 .6 mm i.d.). Mobile phase 80 + 20 methanol- water 0.1 mol I-' with respect to ammonium acetate Sample Detection limits Comments Ref. Speciation and detection of organotin compounds ICP-MS Major Sn 71 0.4-1 .O ng Sn ICP-AES at 120 200-1 700 ng Sn isotope measured Monitoring TBT Low flow Standard and 72 in waters torch low flow torches 500 ng ml-' used Standard torch 25 ng ml-I Study of the retention of com lexes of MoS and TiIV in 1% HN03 in distilled water using chromatographic retention c u 2 pg I-' Zn 1 pg I-' Cd 1 fig I-' Hamilton PRP-1 column ( 1 50 x 4.1 mm i.d.). Mobile phase N-methyl- fluorohydroxamic acid de-ionized distilled water with 290 ethanol 74 Near 0.1 ng (as element) for six species of As and Se 83 Econosphere C,8 column (250 x 4.6 mm i.d.).Mobile phase 5% methanol in water 0.005 mol 1 - I PIC-I35 pH 3.0 Elemental speciation of 30 elements particularly As and Se SB-Octyl-50 capillary column housed in a gas chromatograph. Mobile phase bone dry grade carbon dioxide Separation of tetraalkyltin compounds TBT 0.034 pg TPT 0.047 pg 84 Waters PicoTag CI8 column. Mobile phase 0.06 mol I-' ammonium acetate 3% acetonitrile and 0.005% vlv 2-mercaptoethanol Pierce C,* column (300 x 4.6 mm i.d.). Mobile phase 1.0 mmol 1-' sodium dodecyl sulfate 5% methanol 2.5% acetic acid pH 5.3-6.8 Hg speciation in NBS RM-50 Albacore Tuna sample and thimerosal in contact lens solution LC-ICP-MS 0.6-1.2 ng ml-I for three mercury species LC-cold vapour ICP-MS 7-20 ng ml-I for three mercury species ( i ) For post column 85 Hg cold vapour generation spray chamber replaced with glass chamber.(ii) Optimized at m/z 20 I to minimize background at 202 FI-ICP-MS detection 86 Iimi t s were compared. Arsenobetaine 30 pg of As SCIEX Elan 250 1.4 kW FP. HPLC coupled to ICP via Teflon tubing into a standard nebulizer. Single-ion monitoring mode SCIEX Elan 250 1.4 kW FP. HPLC coupled to ICP via Teflon tubing into a standard nebulizer. Multi-element analysis mode Yokogawa PMSl 00 1.3 kW FP. HPLC coupled to ICP via Teflon tubing into a concentric nebulizer ICP-MS ICP-MS ICP-MS Quantification of As species in Dogfish Muscle reference material (DORM-]) Arsenobetaine 300 pg of As Columns either anion pairing anion exchange or cation pairing Determination of As species in DORM- 1 Absolute detection limit 50-300 pg Anion pairing found 87 to be more sensitive to changes in matrix anion exchange more tolerant.Cation pairing more suitable for DMA and AsB in biological samples with high salt content 88 - Asahipak GS220 reversed-phase gel permeation column (500 x 7.6). Intersil ODs-2 reversed-phase column (250 x 4.6) Mobile phase anionic As TRA pairing ion pH 7; cationic As alkylsulfonate pH 3 Separation and Arsenobetaine detection of 15 As natural samples including human urine after eating fish (VIII) and cacodylate compounds from (IV) 20-50 pg Of ASJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 509 Table 5-continued Detector VG PlasmaQuad 1.3 kW FP. HPLC coupled to ICP via Teflon capillary tubing into a standard concentric nebulizer ICP-MS Chromatography Spherisorb ODS-2 column (500 x 4.6 mm id.) Mobile phase prepared by addition of the appropriate modifier to the stock solution and diluted with 3% vlv propanol Octyl-50 capillary column (2.5 x 50 mm i.d.) fitted into a Hewlett-Packard 5890 series I1 GC oven.Mobile phase bone dry grade liquid C02 Strong cation- exchange column Sample Speciation of alkyltin compounds Detection limits TMT-CI 27 pg TPrT-CI 1 I I pg MMT-TCI 46 pg DMT-DCI 26 pg TET-Br 51 pg Comments Ref. Micellar LC applied 89 using 0. I or 0.02 mol I-' SDS micellar mobile phase 90 VG PlasmaQuad 1.35 kW FP. SFC coupled to ICP via insulated copper tubing from the GC oven into the ICP torch ICP-MS Determination of ultra-trace levels of organotin compounds Tetrabutyltin 0.034 pg Tetraphenyltin 0.047 pg 91 SCIEX Elan 500 1.2 kW FP.Fitted with a thermostated nebulizer spray chamber SCIEX Elan 500 1.2 kW FP. HPLC coupled to ICP-MS via 0.5 mm i.d. tubing into the nebulizer SCIEX Elan 500 1.5 kW FP. HPLC coupled to ICP via PTFE tubing into a Meinhard type nebulizer ICP-MS ICP-MS. ICP-MS Determination of tributyltin and dibutyltin in the harbour sediment reference material PACS-I Tributyltin 5 ng g-' Sn Dibutyltin 12 ng g-' Sn Superose- 1 2 size exclusion column. Mobile phase 0.2 mol I-' ammonium acetate pH 3.6-5.2 Determination of organic and inorganic Al Mn Fe .Ni Cu Zn Cd and La in soil leachates Not reported 92 At a higher pH more organic material was dissolved whereas the total metal concentration was usually lower Dionex ion chromatography AG4A + AS4A column.Mobile phase eluent 1 200 mg I-' NaOH eluent 2 500 mg I-' Na2C03 eluent 3 500 mg I-' NaHCO Eluent 4 H20 Hamilton PRP-I or Vydal 201TP. Ion-pairing reagent and mobile phase dependant on compound to be separated Determination of Te compounds in waste water streams Not reported - 93 SCIEX Elan 250 1.25 kW FP. HPLC coupled to ICP via stainless-steel tubing into an ultrasonic nebulizer SCIEX Elan 500 ICP-MS ICP-MS Detection of 0.4-4.0 ng P P and S compounds 7.0 ng S Analyte sensitivity 94 decreases as organic modifier concentration in mobile phase increases Analysis of target and non-target pollutants in aqueous leachates including CI other halogens P and S Not reported Anion-exchange chromatography using SGE 25OGL-SAX columns (250x 2 mm).Mobile phase ammonium acetate buffer and acetonitrile Preliminary data 95 presented on an anion- exchange chromato- graphy particle beam-MS based technique for the detection of the target compound Cchloro- benzene sulfonic acid Spray chamber 96 coded to 8 "C VG PlasmaQuad 1.3 kW FP. HPLC coupled to ICP-MS via Teflon FEP tubing into the nebulizer ICP-MS Waters PicoTag CIS column (isocratic separation). Mobile phase 0.4 mol I-' 2-hydroxy-2-methyl- propanoic acid 0.02 mol I-' octanesulfonic acid (pH 3.8). BakerBond WP CIS column (gradient separation). Mobile phase 0.05-0.4 mol I-' 2- hydroxy-2-methyl propanoic acid Metal free GLT column packed with Intersil ODS-2 (5 pm). Mobile phase 5 or 25% methanol in water with ion-pair reagent Determination of rare earth elements in SRM 1633a Fly Ash Ho 0.4 ng ml-' La 5.0 ng ml-' SCIEX Elan 250 1.3 kW FP.HPLC coupled to ICP-MS via a direct injection nebulizer (DIN) VG PlasmaQuad 1.35 kW FP. HPLC coupled to ICP-MS via Polyplex tubing into a type C-l concentric nebulizer ICP-MS ICP-MS Charged species of Sn and As separated as ion pairs Sn 16-20 pg I-' AS 0.4- I .2 pg I-' The use of DIN 97 improved the detection limit by 1-2 orders of rnagni t ude Asiti 0.063 ng AsV 0.037 ng DMA 0.032 ng MMA 0.080 ng Wescan AnionIR-IC ion-chromatograph y column (250 x 4. I mm). Mobile phase ammonium carbonate and ammonium hydrogen carbonate buffered to pH 7.5 Speciation of As in urine club soda and wine Sensitivity was improved 98 by using an He-Ar mixed- gas ICP as the ionization source510 JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL.8 Table 5-continued Detector All argon HPLC coupled to ICP-MS via a Tefzel transfer line ICP-MS. All argon ICP-MS Chromatography Dionex AS4A anion- exchange column. Mobile phase 6 mmol 1-I ammonium sulfate or 10 pmol I-' HCIO buffered to pH 9 Ion pair reversed-phase chromatography Sample Detection limits Comments Ref. Determination of Cr"' 0.4 pg ml-I This method was 99 hexavalent Cr compared with a method using the same ion- chromatographic separation coupled with colorimetry. Detection limits were comparable for both techniques. Pb speciation in a Inorganic Pb 0.37 ng - lead fuel reference material and a water quality control sample TEL 0.14 ng TPhL 0.17 ng TTEL 3.9 ng 100 arsenic species using more traditional forms of analysis.Whilst hydride generation is well suited to the reducible forms of arsenic species such as arsenobetaine are not suited to this approach and so were often estimated by subtraction once the reducible forms and total arsenic had been determined. The HPLC-ICP-MS method overcomes this problem and allows both the reducible and non- reducible forms of arsenic to be determined with good sensitivity. Heitkemper et aL7O have used this technique to determine arsenic in urine. Four arsenic species were determined arsenic; arsenate; dimethylarsinate; and mono- methylarsonate using an anion-exchange system. The determination of the arsenite (As3+) was however compli- cated by the presence of 40Ar35C1 ions (rnlz=75) resulting from the correlation of chlorine-containing species.In a later work the same group reduced the interference by employing ion chromatography to resolve the chloride from the arsenic compounds.73 A 20-fold dilution of the urine samples was necessary to avoid column overloading from chloride and subsequent argon chloride interference. Re- cently Hill et al.Io1 have shown that the ArCl interference can be eliminated by the addition of nitrogen to the outer and nebulizer gas flows in the presence of 1% m/v chloride. These workers have also shown that the addition of nitrogen aids the determination of selenium and vanadium in the presence of chloride and in addition promotes the reduction of Mo+ and ArO+ interferences and the back- ground response. Several studies in this area have utilized HPLC-ICP-MS for studies of metalloprotein species.Dean et al.69 investi- gated the characteristics of HPLC-ICP-MS couplings for this sort of application using the number of theoretical plates peak tailing rise time and wash-out time as criteria of merit. They found that a short aerosol connection line was optimal and when compared with on-line UV monitor- ing ICP-MS gave a comparable number of theoretical plates. In another study on metalloproteins Mason et a1.Io2 used size-exclusion HPLC coupled with ICP-MS and concluded that the technique had considerable potential for the rapid quantitative analysis of metals associated with cytosolic metal-binding ligands. The greatest limitation encountered was the ability to effectively separate the various metal binding moieties although the workers suggest that this might be overcome using tandam HPLC systems e.g.size exclusion followed by ion exchange. Other studies that can be placed under the general heading of clinical and industrial applications include the determination of lead and other trace element species in blood by size-exclusion chr~matography-ICP-MS,~~~ the determination of cadmium species in kidney,Io4 the deter- mination of gold-based drug metabolites in human the use of reversed-phase chromatography for the separation of zinc species in chicken meat,98 the determina- tion of thiomersal (thimerosal) in biological productsIo6 and in one of the few industrial applications the determi- nation of rare earth impurities.Io7 Details of these applica- tion are presented in Table 6.4 Gas Chromatography-Inductively Coupled Plasma Atomic Emission Spectrometry The first couplings of a gas chromatograph to an ICP were reported in the late 1970s. In one ofthe first studies Windsor and Dentonlll explored the capabilities of ICP-AES for the elemental analysis of organic compounds using an all argon plasma. In this work various organic and organometallic compounds were determined utilizing the simultaneous multi-element capabilities of the coupling. The interface employed for the study used a T-junction which enabled an argon make-up gas to be added to the eluent from the packed column gas chromatograph which was connected to a demountable ICP torch. The optical system incorporated a 0.35 m scanning monochromator and a 1.5 m 0.02 nm resolution multichannel direct-reading spectrometer.In a later report the same group extended their work to derive empirical formulae for a number of organic com- pounds although with limited success. 1 1 * During the same period Sommer and Ohls used a GC-ICP technique employing both all-argon-and nitrogen-cooled plasmas for the determination of tetraalkyllead compounds113 and nickel and zinc diethyldithiocarbamates (ddtc),I14 whilst Fry et a1.II5 investigated a large number of fluorine atom lines for the selective detection of various fluorine-con- taining organic compounds. This latter group of workers also monitored near-infrared oxygen emissions to enable oxygen-specific detect ion.' l 6 Despite this early activity the ICP has never been widely adopted as a GC detector and there have been very few papers on the subject since the early 1980s.This is in contrast to the adoption of ICPs for detection in HPLC monitoring and the use of microwave induced plasmas (MIPS) for GC work.l17 The use of an ICP does offer the advantage of withstanding organic solvents more readily than does an MIP because of its higher gas temperature. In addition oxygen or nitrogen does not have to be added to the plasma to reduce deposits since although deposits can sometimes form on the inside of an extended ICP coolant tube they are formed well above the observation zone. However these advantages are outweighed by the fact that the performance levels for non-metals are much inferior to those using an MIP and so whilst GC-ICP couplings are now very seldom used GC-MIP has seen something of a revival in recent years with the introduction of a second generation of commercial instruments.Table 7 gives details of the various applications that have been published for GC-ICP-AES.JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 51 1 Table 6 HPLC-ICP-MS applications (clinical and industrial) Detector VG PlasmaQuad 1.35 kW FP. HPLC coupled to ICP-MS via PTFE tubing into crossflow nebulizer. Single-ion monitoring mode VG PlasmaQuad HPLC coupled to ICP via Flexon HP tubing into a concentric nebulizer VG PlasmaQuad HPLC coupled to ICP-MS via Polyplex tubing VG PlasmaQuad Ar-ICP-MS 1.35 kW FP. He-ICP-MS 1.55 kW FP. Type C-1 concentric. nebulizer VG PlasmaQuad I .25 kW FP. HPLC coupled to ICP via Teflon capillary tubing into a standard concentric nebulizer ICP-MS ICP-MS 1.5 kW FP.ICP-MS 1.35 kW FP. ICP-MS Chromatography Superose- I2 SEC column capable of separating proteins of relative molecular mass 1000-300000. Mobile phase 0. I2 rnol I-' Tris.HC1 pH 7.5 Weak anion-exchange column ( 2 5 0 ~ 4 . 6 mm i.d.). Mobile phase 30% methanol-15 mmol I-' NH4H,P04-1.5 mmol I-' Wescan anion R-IC column ( 2 5 0 ~ 4 . 1 mm i.d.) Mobile phase 5 m mol I-' phthalic acid Wescan anion R-IC column (250 x 4.1 mm i.d.). Gradient programme using 2% propan- 1-01 and 50 mmol I-' carbonate buffer pH 7.5 Spherogel TSK SW 2000 size- exclusion column (600 x 7.5 mm). Mobile phase 0.06 mol I-' TriseHCI 0.05% NaN pH 7.5 CH3COONHj pH 5.75 Sample Detection limits Study of Not reported metallo-proteins in gel filtration standard and solutions of metallo-thionein and ferritin Comments Physical coupling was studied in detail particularly involving minimum liquid transport and extended aerosol transport and vice versa Determination of As3+ complicated by interference from co-elution of C1-containing species forming ArCI+ ions Ref.69 70 73 108 102 Speciation of As in urine 20-91 pg in aqueous media 36-96 pg in urine A"' 340 pg AsV 420 pg DMA 700 pg Elimination of AgCI+ interference from As speciation in urine samples As"' 4.95 pg I-' AsV 6.0 pg 1-l DMA 1.2 pg I-' MMA 3.6 p g I-' (100 ml injection) As in urine Paper also contains results for As speciation in club soda and wine Separation and elemental analysis of metallo-proteins in biological samples Absolute 240-350 pg of protein (calculated from the peak areas of the Cd signal) The techniques' versatility has been demonstrated by quantitative multi- element analysis of cytosolic metal-binding proteins separated from a species of polychaete worm SCIEX Elan 250 HPLC coupled to ICP via PTFE tubing into a cross-flow nebulizer VG PlasmaQuad 1.3 kW FP.HPLC coupled to ICP via Teflon tubing into a cross-flow nebulizer. Single-ion monitoring mode SCIEX Elan 250 1.3 kW FP. HPLC coupled to ICP via PTFE tubing into a concentric nebulizer. Multi-element mode VG PlasmaQuad PQ2 Turbo Plus HPLC coupled to ICP-MS via a V7 manual valve into a de Galan nebulizer ICP-MS 1.3 kW FP. ICP-MS ICP-MS ICP-MS 1.35 kW FP. TSK G 3000 SW size-exclusion column (300 x 7 mm).Mobile phase 0.1 rnol 1-' Tris.HC1 pH 7.2 Superose- I 2 SEC column. Mobile phase 0. I 2 rnol I-' Tris.HC1 pH 7.5 Determination of lead and other trace element species in blood Pb in protein fraction 0.15-0.05 pg I-' 103 104 Investigation of Cd speciation in kidney Not reported 105 ( a ) Altech WAX300 anion-exchange column. Mobile phase 15 min gradient from 20-200 mmol I-' Tris buffer (b) TSK 250 SEC column. Mobile phase aqueous 25 mmol I-' Tris buffer Both size- exclusion and reversed-phase chromatography Determination of Au drug metabolites in human blood Cu 3.0 pg Cd 7.0 pg Zn 8.0 pg Au 10.0 pg 98 Size exclusion chromatography was used to separate known proteins. Reversed-phase chromato- graphy was used to separate Zn-containing species in chicken meat Determination of thimerosal and biological products Determination of rare earth elements as Not reported VG PlasmaQuad Procedure as per ref.82 Yokogawa PMS2OO HPLC coupled to ICP via PTFE tubing into a Meinhard concentric nebulizer ICP-MS. ICP-MS 1.4 kW FP. Waters PicoTag C column Procedure as per ref. 82 Yokogawa Excelpak ICS-C35 ( 1 50 x 4.6 mm) and ion-chromatography columns. Mobile phase either lactic acid or hydroxyisobutyric acid. Both adjusted to pH 4.3 Gel permeation liquid chromatography ICS-CI 5 (125 x 4.9) Not reported Spray chamber cooled to 8 "C 106 107 1.0-5.0 pg ml-' for 14 rare earth elements impurities in other rare earth materials 109 110 All argon ICP-MS Determination of Fe- containing proteins Ferritin 0.01 pg Haemoglobin 1 .O pg Myoglobin 0.7 pg Cytochrome c 0.4 pg MePb 0.2 pg Pb EtPb 0.2 pg Pb MeHg 18 pg Hg Speciation of Hg and Pb compounds in human urine SCIEX Elan 250 HPLC coupled to ICP via a narrow bore Polysil tubing into a direct injection nebulizer (DIN) ICP-MS 1.4 kW FP.PEEK micro-bore column packed with reversed-phase Ct8 material. Mobile phase ammoniun salts of S5 S7 and S12512 JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 Table 7 GC-ICP-MS/AES applications Detector All argon ICP. GC coupled via stainless-steel tubing into a demountable ICP torch Jarrell-Ash 0.8 kW FP. GC coupled to ICP via stainless- steel tubing into the sample tube of the plasma torch PlasmaTherm 250 ICP 1.5 kW FP. GC coupled to ICP via heated stainless-steel tubing PlasmaTherm 2500 ICP 1.75 kW FP. GC coupled to ICP via heated stainless-steel tubing 66-100 ICP Chromatography 6 ft x 118 in 0.d. column packed with 8% Carbowax I540 on 80/100 mesh firebrick Sample Detection limits Comments Ref.Simultaneous multi-elemen t analysis of GC emuents Br 2 x lo5 ng - C 12.0 ng CI 7 x lo3 ng Fe 5.9 ng Pb 33.0 ng 1 1 1 I12 6 ftx3.175 mm 0.d. column packed with 8% carbowax 1540 on 801 I00 mesh firebrick Determination of Not reported the elemental compositions and empirical formulae of hydrocarbons and halogens 6 ft x 1/8 in capillary column packed with Amine 220. Carrier gas argon Determination of F F 1 mg I I5 Selective quantitative determination of 0 in volatile liquid mixtures 0 650 ng The detection limit 1 16 for the GC-ICP system was considerably worse than for direct gas sampling loops (20 ng) owing to band spreading on the GC column - 1 I8 122 x 0.46 mm capillary column packed with 10% Carbowax on 80-100 mesh Chromosorb P.Carrier gas argon PlasmaTherm 2500 all argon ICP 1.85 kW FP. Heated transfer line connecting GC to ICP-AES 4 ft x 1/8 in nickel tube column packed with 80-100 mesh Chromosorb WHP. Stationary phase 20% amine 220. Carrier gas argon 3.5 f t x 3 mm i.d. column packed with chromosorb 102 Detection 01' N- containing compounds N 0.25 ,ug All argon plasma ICP 1 kW FP Ge As Sn Sb hydrides generated cold trapped and passed through plasma Determination of volatile organometallic species in complex mixtures such as the products of coal conversion Detection of S compounds in fossil fuels Ge 4 ng As 50 ng Sb 50 ng 119 A number of organoselenium compounds were observed in the gasification by-products of a spiked coal sample 120 PIasmaTherm HFP2500 ICP 1.5 kW FP.GC coupled via glass lined stainless-steel capillary tubing directly into the plasma torch R.f. plasma detector consisting of a helium r.f. plasma doped with a small amount of oxygen in a I mm i.d. quartz tube. GC coupled directly to the system Daini Seikosha GC coupled to ICP via PTFE tubing heated with a tape heater to 150 "C ICP-AES 0.5- I. 1 kW FP. I .8 m x 2 mm i.d. borosilicate column packed with 5% OV-I01 on Chrom W-HP 80- 100 mesh. Carrier gas argon Pb 6 Pg Sn 25 pg Fe 15pg Se 100 pg Si 40 pg Cr 60 pg c 75 Pg 200 ,um i d . fused silica column coated with methyl or biphenyl polysiloxane. Carrier gas oxygen S 0.5 pg s-I Detection limits 121 selectivity and linearity were all considerably better than those achieved using flame photometric detection Fused silica capillary column coated with methylsilicone. Carrier gas helium.Flow rate 7.5 ml min-I 25 mx0.32 mm high-temperature column packed with a siloxane carborane stationary phase. Carrier gas helium Determination of Methylmercury Methylmercury species 122 methylmercury species as Hg 3 pg were converted into the iodide form VG PlasmaQuad 2 GC coupled to ICP via heated transfer line with an aluminium core through which the capillary is passed All argon plasma ICP-MS 1.35 kW FP. GC connected to ICP via glass lined stainless-steel tubing ICP-MS 1.5 kW FP. Analysis of al kyllead species in fuel TEL 0.7 pg s-I This method is also 123 applicable to the analysis of relatively non-volatile organometallics Molecular sieve adsorbent column.Stationary phase 10% didecyl phthalate-10% carbowax 20 mol I-' Carrier gas argon Multi-element Range 0.001-400 ng s-' - analysis and isotope ratio determinations in individual organic compounds 124JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY JUNE 1993 VOL. 8 513 Table 7-continued Detector Chromatography SCIEX Elan Column 3Oh OV-I on ICP-MS 1.25 or 1.5 kW FP. Chromosorb W. Carrier gas GC coupled to ICP via heated argon 8 ml min-’ and stainless-steel oxygen 2 ml min-‘ tubing (0.5 m) All argon axially viewed ICP-AES Fused silica capillary column coated with methylsilicone Sample Detection limits Comments Ref. Separation and determina- Me,SnPe 6 ng Limits of detection 126 tion of pentylated Sn MelSnPe 16 ng achieved in this compounds MeSnPe3 10 ng preliminary work were worse by over 2 orders of magnitude than electrothermal atomic bsorption detection Determination of Methylmercury - I27 methylmercury 3 Pg as Hg species in air 5 Gas Chromatography-Inductively Coupled Plasma Mass Spectrometry The analytical capabilities of using a mass spectrometer to monitor ionic species from an ICP have been well known since the mid- 1980s.Now that many laboratories have ICP- MS available it is perhaps not surprising that once again workers are starting to re-evaluate the elemental analysis of individual compounds eluting from a gas chromatograph using this state-of-the-art detection system. One of the first papers to report a GC-ICP-MS coupling was by Chong and Houk in 1987.124 In this work a GC with a packed column was interfaced to an ICP-MS in order to yield atomic mass spectra of a number of organic compounds.The detection limits obtained were in the range 0.001-500 ng s-l depending on the ionization energy of the element and its abundance in the background spectrum. This study also exploited the possibility of isotope ratio work using ICP- MS although the precision reported was not adequate to study the effects of isotopic fractionation by natural physiochemical processes such as those occurring in geo- logical samples food products and biological tissues. To date however little work has been published on GC-ICP-MS although a number of research groups have recently reported developments using capillary GC-ICP- MS at conferences.Capillary GC provides good efficiency and rapid separation but the mass loading that is possible without overloading the column and hence degrading resolution can restrict detection limits. The most recently published work in this area123 described the construction of a capillary GC-ICP-MS interface and its application to the speciation of alkylleads in fuel. However the technique lends itself to the determination of a range of organometal- lic compounds and Kim et a1.12’ have successfully used the interface for a retention index window (volatility range) in excess of 3400 (C34). Published applications of GC-ICP-MS are presented in Table 7. 6 Conclusions It is clear that with the growing demand for species-specific information on many elements present in a wide range of matrices many laboratories have adopted the approach of coupling the separatory powers of chromatography with the element-specific detection offered by atomic spectroscopy. The reluctance of many laboratory managers in the past to bring together the necessary equipment often traditionally sited in different sections of the laboratory has been overcome by the wealth of evidence that is now available to support the use of directly coupled techniques to obtained unequivocal information for speciation studies.The use of plasmas to monitor not only metal emission lines but also carbon lines could providing non-carbon containing elu- ents are used offer a universal HPLC detector. Many of the early problems associated with the use of ICP-AES as the detector have now been alleviated although for many environmental samples detection limits are still a problem.The use of ICP-MS however not only provides a means of obtaining significantly lower detection limits but also provides the facility for isotope dilution studies and by utilizing the simultaneous multi-element capabilities gives a truly versatile detection system. Most of the interface systems currently in use are relatively cheap and easy to construct require few (if any) modifications to existing instrumentation have short in- stallation times and can be readily demounted when not in use. 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ISSN:0267-9477    

DOI:10.1039/JA9930800499

出版商:RSC    

年代:1993

数据来源: RSC