摘要:

RSC JOURNALS GO Electronic n FROM 19 From 1 January all 12 of the RSC’s primary journals will be available for subscription via the internet. They will be accessible through the Catchword system which is page- based and retains the integrity and clarity of the printed version in the electronic media. Access to data i s either via the contents pages or by searching for key words within issues (every word in a paper is searchable). Papers can be displayed printed and saved for future reference. THE ROYAL Dalton Transactions SOCI ETY OF Faraday Discussions C H EM I ST RY Journal of Analytical Atomic &- Perkin Transactions 2 Spectrometry && The Analyst Journal of Chemical Research Information Services 1 ChemComm Mendeleev Communications Faraday Transactions Perkin Transactions 1 Analytical Communications Journal of Materials Chemistry KEY FEATURES & BENEFITS Access the most recent work direct from your desktop as soon as i t i s available - while the printed journal may still be on its way to you.Easy and instant access from anywhere in the world Pinpoint the information you want easily and efficiently - the journals are fully searchable Articles of interest can be printed or saved to disk The same high quality research results as in the printed form Full technical support Don’t be lei? behind! Keep up with your contemporaries by subscribing to RSC journals Online TODA) I I I Nnme 1 Address lob Title Organ isa tion I I L D - ~ ~ ~ ~ ~ ~ ~ ~ ~ D D - - J Please return this coupon or write to Jenny McCluskey Sales .ind Promotion Executive at The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge CB4 4WF Alternatively call or fax with your request on (tell 44-(0)1223-420066 (fax) 44-(0)1223-423429 quoting ref E l).{ ROYAL AUSTRALIAN CHEMICAL INSTITUTE AUSTRALIAN ACADEMY OF SCIENCE v XXX COLLOQUIUM SPECTROSCOPICUM INTERNATIONALE World Congress Centre Melbourne Australia September 21st-26th 1997 Participants are invited to submit contributions for presentation on the following topics; Theory Techniques and Instrumentation of :- Atomic Spectroscopy (Emission Absorption Fluorescence) Computer Applications and Chemometrics Electron Spectroscopy Gamma Spectroscopy Laser Spectroscopy Luminescence Spectroscopy Mass Spectrometry (Inorganic and Organic) Methods of Surface Analysis and Depth Profiling UVNisible Spectroscopy NIR Spectroscopy IR Spectroscopy Mossbauer Spectroscopy Nuclear Magnetic Resonance Spectrometry Photoacoustic and Photothermal Spectroscopy Raman Spectroscopy X-Ray Spectroscopy Applications of Spectroscopy to the Analysis of :- Biological and Environmental Samples Food and Agricultural Products Metals Alloys and Geological Materials Industrial Processes and Products Plenary and Invited Speakers To date the following eminent spectroscopists have accepted invitations to present keynote lectures; Freddy Adams Mike Adams Mike Blades John Chalmers Bruce Chase Peter Fredericks Manfred Grasserbauer Mike Gross Mike Guilhaus Peter Hannaford Gary Hieftje Kazuhiro Imai Hiroshi Masuhara Belgium UK Canada UK USA Australia Austria USA Australia Australia USA Japan Japan Andrew Zander Russell McLean Jean-Michel Mermet Caroline Mountford Nicolo Omenetto Mike Ramsey Alfredo Sanz Medel Margaret Sheil Heinz Siesler Richard Snook Yngvar Thomassen Bernhard Welz John Williams Barry Sharp USA Australia France Australia IdY USA Spain UK Australia Germany UK Norway Germany UK In connection with the XXX CSI a number of pre-symposia will be organised the conference will feature an exhibition of the latest spectroscopic instrumentation and associated equipment.Social Programme The scientific programme will be punctuated with memorable :social events and excursions of scientific cultural and tourist interest. The social programme is open to all participants and accompanying persons. sponsors As at August 1995 the following companies have agreed to be major sponsors of XXX CSI 1997; GBC Hewlett-Packard Perkin Elmer and Varian For farther information contact - Secretary Mr P.L. Larkins CSIRO Division of Materials Science & Technology Private Bag 33 Rosebank MDC Clayton VIC 3169 AUSTRALIA Telephone +61 3 95422003 Facsimile +61 3 95441 128 E-mail larkins@rivett.mst.csiro.au Conference Secretariat The Meeting Planners 108 Church Street Hawthorn VIC 31 22 AUSTRALIA Telephone +61 3 98193700 Facsimile +61 3 98195978 Updated information may be obtained from the XXX CSI homepage on the World Wide Web at http://w w w. latro be. edu. au/CSIconf/XXX&I. htm 1 QANTAS has been appointed the sole official carrier to the XXX CSI 1997. When making QANTAS reservations please quote JIF 73Q. The Analyst and JAAS have been appointed as the official journals for publications resulting from CSI ‘97. Authors are encouraged to bring their manuscripts to the conference.

ISSN:0267-9477    

DOI:10.1039/JA99611BP029

出版商:RSC    

年代:1996

数据来源: RSC

摘要:

Journal of Analytical Atomic Spectrometry JAAS Editorial Board Chairman B. L. Sharp (Loughborough UK) H. Crews (Norwich UK) A. T. Ellis (Abingdon UK) S. J. Haswell (Hull UK) S. J. Hill (Plymouth UK) B. P. Holliday (Cambridge UK) R. C. Hutton (Cheshire UK) D. Littlejohn (Glasgow U K I A. Sanz-Medel (Oviedo Spain) P. D. P. Taylor (Geel Belgirm) JAAS Advisory Board F. C. Adams (Antwerp Belgium) R. M. Barnes (Amherst MA USA) L. Bezur (Budapest Hungary) M. W. Blades (Vancouver Canada) R. F. Browner (Atlanta GA USA) J. L. Burguera (Merida Venezuela) S. Caroli (Rome Italy) J. A. Caruso (Cincinnati OH USA) A. J. Curtius (Florianopolis Brazil) J. B. Dawson (Leeds UK) M. T. C. de Loos-Vollebregt (Delft The Netherlands) 0. F. X. Donard (Talence France) L. Ebdon (Plymouth UK) M. S. Epstein (Gaithersburg MD USA) Fang Zhao-tun (Shenyang China) W.Frech (UmeH Sweden) A. K. Gilmutdinov (Kazan Russia) G. M. Hieftje (Bloomington IN USA) R. S. Houk (Ames / A USA) R. Klockenkamper (Dortmund Germany) B. V. L'vov (St. Petersburg Russia) R. K. Marcus (Clemson SC USA) J. M. Merrnet (Villeurbanne France) T. Nakahara (Osaka Japan) Ni Zhe-ming (Beuing China) J. W. Olesik (ColumBus OH USA) N. Omenetto (Ispra Italy) C. J. Park (Taejon Korea) P. J. Potts (Milton Keynes UK) R. E. Sturgeon (Ottawa Canada) V. Sychra (Prague Czech Republic) S. Tanner (Concord Canada) P. Van Espen (Antwerp Belgium) R. Van Grieken (Antwerp Belgium) B. Welz (Uberlingen. Germany) Atomic Spectrometry Updates Editorial Board Chairman *A. T. Ellis (Abingdon UK) J. A. Armstrong (Edinburgh UK) *J.R. Bacon (Aberdeen UK) R. M. Barnes (Amherst MA USA) S. Branch (High Wycombe UK) R. Bye (Oslo Norway) J. Carroll (Middlesbrough UK) M. R. Cave (Keyworth UK) S. R. N. Chenery (Keyworth UK) +J. M. Cook (Keyworth UK) J. S. Crain (Argonne IL USA) *M. S. Cresser (Aberdeen UK) H. M. Crews (Norwich UK) J. S. Crighton (Sunbury-on-Thames UK) *J. 8. Dawson (Leeds UK) J. R. Dean (Newcastle upon Tyne UK) *E. H. Evans (Plymouth UK) J. Fazakas (Budapest Hungary) A. Fisher (Plymouth UK) L. M. Garden (Middlesbrough UK) +J. M. Gordon (Cambridge UK) D. J. Halls (Glasgow UK) *S. J. Hill (Plymouth UK) *B. Holliday (Cambridge UK) K. W. Jackson (Albany NY USA) R. Jowitt (Middlesbrough UK ) K. Kitagawa (Nagoya Japan) J. Kubova (Bratislava Slovak Republic) *J. Marshall (Middlesbrough UK) H.Matusiewicz (Poznan Poland) A. W. McMahon (Manchester UK) R. G. Michel (Storrs CT USA) *D. L. Miles (Keyworth UK T. Nakahara (Osaka Japarr) Ni Zhe-ming (Beijing China) L. M. W. Owen (Norwich UK) P. J. Potts (Milton Keynes UK) W. J. Price (Budleigh Salterton UK) C. J. Rademeyer (Pretoria South Africa) A. Sanz-Medel (Oviedo Spain) *B. L. Sharp (Loughborough UK) 1. L. Shuttler (Uberlingen Germany) M. Sperling (Uberlingen G'ermany) R. Stephens (Halifax Canada) C. Streli (Vienna Austria) J. Stupar (Ljubljana Slovenia) R. E. Sturgeon (Ottawa Canada) *A. Taylor (Guildford UK) G. C. Turk (Gaithersburg MD USA) J. F. Tyson (Amherst MA USA) P. J. Watkins (London UK) M. White (Ispra Italy) J. G. Williams (Egham UK) P. Wobrauschek (Vienna Austria) *Members of the ASU Executive Committee Managing Editor JAAS Brenda Holliday The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge CB4 4WF UK.Telephone + 44 (0) 1223 420066. Fax + 44 (0) 1223 420247. E-mail RSCl @RSC.ORG (Internet) Deputy Editor Sarah Williams Production Manager Janice Gordon Production Editor Caroline Seeley Technical Editors Ziva Whitelock Roger Young Editorial Secretaries Lesley Turney Claire Harris Frances Thompson American Associate Editor JAAS Dr. J. M. Harnly US Department of Agriculture Beltsville Human Nutrition Research Center Beltsville MD 20705 USA. Telephone + 1 301 -504-856'3 Fax +1 301 504 8314 E-mail harnly@bhnrc.usda.g80v Asia-Pacific Associate Editor JAAS Prof. N. Furuta Department of Applied Chemistry Faculty of Science and Engineering Chuo University 1-1 3-27 Kasuga Bunkyo-ku Tokyo 112 Japan.Telephone 81 -3-381 7-1 906. Fax 81 -3-381 7-1 895. E-mail nfuruta@apchern.chem.chuo-u.ac.jp Advertisements Advertisement Department The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge UK CB4 4WF. Telephone + 44 (0) 1223 432243. Fax + 44 (0) 1223 42601 7. Information for Authors Full details of how to submit materials for publi- cation in JAAS are given in the Instructions to Authors in Issue 1. Separate copies are available on request. The Journal of Analytical Atomic Spectrometry (JAAS) is an international journal for the publi- cation of original research papers communi- cations and letters concerned with the development and analytical application of atomic spectrometric techniques.The journal is pub- lished twelve times a year including comprehen- sive reviews of specific topics of interest to practising atomic spectroscopists and incorpor- ates the literature reviews which were previously published in Annual Reports on Analytical Atomic Spectroscopy (ARMS). Manuscripts intended for publication must describe original work related to atomic spectro- metric analysis. Papers on all aspects of the sub- ject will be accepted including fundamental studies novel instrument developments and prac- tical analytical applications. As well as AAS AES and AFS papers will be welcomed on atomic mass spectrometry X-ray fluorescence/emission spectrometry and secondary emission spec- trometry. Papers describing the measurement of molecular species where these relate to the characterization of sources normally used for the production of atoms or are concerned for example with indirect methods of analysis will also be acceptable for publication.Papers describing the development and applications of hybrid techniques (e.g. GC-coupled AAS and HPLC-ICP) will be particularly welcome. Manuscripts on other subjects of direct interest to atomic spectroscopists including sample prep- aration and dissolution and analyte pre-concen- tration procedures as well as the statistical interpretation and use of atomic spectrometric data will also be acceptable for publication. There is no page charge. The following types of papers will be considered. Full papers describing original work. Communications which must be on an urgent matter and be of obvious scientific importance.Communications receive priority and are usually published within 2-3 months of receipt. They are intended for brief descriptions of work that has progressed to a stage at which it is likely to be valuable to workers faced with similar problems. Reviews which must be a critical evaluation of the existing state of knowledge on a particular facet of analytical spectrometry. Every paper (except Communications) will be submitted to at least two referees by whose advice the Editorial Board of JAAS will be guided as to its acceptance or rejection. Papers that are accepted must not be published elsewhere except by permission. Submission of a manuscript will be regarded as an undertaking that the same material is not being considered for publication by another journal.Manuscripts (three copies typed in double spacing) should be sent to Brenda Holliday Managing Editor JAAS Dr. J. M. Harnly US Associate Editor JAAS or Prof. N. Furuta Asia- Pacific Associate Editor JAAS. All queries relating to the presentation and sub- mission of papers and any correspondence regarding accepted papers and proofs should be directed to the Editor or Associate Editors (addresses as above). Members of the JAAS Editorial Board (who may be contacted directly or via the Editorial Off ice) would welcome comments suggestions and advice on general policy matters concerning JAAS. Fifty reprints are supplied free of charge. Journal of Analytical Atomic Spectrometry (JAAS) (ISSN 0267-9477) is published morithly by The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge CB4 4WF UK. All orders accompanied with payment should be sent directly to The Royal Society of Chemistry Turpin Distribution Services Ltd.Blackhorse Road Letchworth Herts. SG6 lHN UK Tel. +44 (0) 1462 672555; Telex 825372 Turpin G; Fax +44 (0) 1462 480947. Turpin Distribution Services Ltd. is wholly owned by The Royal Society of Chemistry. 1996 Annual subscription rate EEA f599.00 USA $1136.00 Rest of World f614.00. Customers should make payments by cheque in sterling payable on a UK clearing bank or in US dollars payable on a US clearing bank. Air freight and mailing in the USA by Publications Expediting Inc. 200 Meacham Avenue Elmont NY 11003.USA Postmaster send address changes to Journal of Analytical Atomic Spectrometry (JAAS) Publications Expediting Inc. 200 Meacham Avenue Elmont NY 11003. Postage paid at Jamaica NY 11 431. All other despatches outside the UK by Bulk Airmail within Europe Accelerated Surface Post outside Europe. PRINTED IN THE UK. @The Royal Society of Chemistry 1996. All rights reserved. No part of this publicatiori may be reproduced stored in a retrieval system or transmitted in any form or by any means electronic mechanical photographic recording or otherwise without the prior permission of the publishers.Journal of Analytical Atomic Spectrometry JAAS Editorial Board Chairman B. L. Sharp (Loughborough U K ) H. Crews (Norwich U K ) A. T. Ellis (Abingdon UK) S. J.Haswell (Hull U K ) S. J. Hill (Plymouth. U K ) B. P. Holliday (Cambridge. U K ) R. C. Hutton (Cheshire UK) D. Littlejohn (Glasgow U K ) A. Sanz-Medel (Oviedo Spain) P. D. P. Taylor (Gee/ Belgium) JAAS Advisory Board F. C. Adams (Antwerp. Belgium) R. M. Barnes (Amherst. MA USA) L. Bezur (Budapest. Hungary) M. W. Blades (Vancouver. Canada) R. F. Browner (Atlanta GA USA) J. L. Burguera (Merida Venezuela) S. Carol1 (Rome. Italy) J. A. Caruso (Cincinnati. OH. USA) A. J. Curtius (Florianopolis Brazil) J. B. Dawson (Leeds. UK) M. T. C. de Loos-Vollebregt (Delft The Netherlands) 0. F. X. Donard (Talence. France) L. Ebdon (Plymouth UK) M. S. Epstein (Gaithersburg. MD USA) Fang Zhao-lun (Shenyang China) W. Frech (UmeB. Sweden) A. K. Gtlmutdinov (Kazan. Russia) G. M. Hieftje (Bloomington IN USA) R.S. Houk (Ames. /A USA) R. Klockenkamper (Dortmund Germany) B. V. L'vov (St. Petersburg Russia) R. K. Marcus (Clemson SC USA) J. M. Mermet (Villeurbanne France) T. Nakahara (Osaka Japan) Ni Zhe-ming (Beijing China) J. W. Olesik (Columbus OH USA) N. Omenetto (lspra Italy) C. J. Park (Taejon Korea) P. J. Potts (Milton Keynes U K ) R. E. Sturgeon (Ottawa Canada) V. Sychra (Prague Czech Republic) S. Tanner (Concord Canada) P. Van Espen (Antwerp Belgium) R. Van Grieken (Antwerp Belgium) B. Welz (Uberlingen Germany) Atomic Spectrometry Updates Editorial Board Chairman *A. T. Ellis (Abingdon U K ) J. A. Armstrong (Edinburgh U K ) *J. R. Bacon (Aberdeen. UK) R. M. Barnes (Amherst. MA USA) S. Branch (High Wycombe. UK) R. Bye (Oslo Norway) J. Carroll (Middlesbrough U K ) M.R. Cave (Keyworth U K ) S. R. N. Chenery (Keyworth. U K ) *J. M. Cook (Keyworth. U K ) J. S. Crain (Argonne. IL USA) *M. S. Cresser (Aberdeen UK) H. M. Crews (Norwich U K ) J. S. Crighton (Sunbury-on-Thames. U K ) *J. B. Dawson (Leeds U K ) J. R. Dean (Newcastle upon Tyne UK) *E. H. Evans (Plymouth. U K ) J. Fazakas (Budapest Hungary) A. Fisher (Plymouth U K ) L. M. Garden (Middlesbrough U K ) *J. M. Gordon (Cambridge. UK) D. J. Halls (Glasgow. U K ) * S . J. Hill (Plymouth. U K ) *B. Holliday (Cambridge UK) K. W. Jackson (Albany NY USA) R. Jowitt (Middlesbrough UK) K. Kitagawa (Nagoya Japan) J. Kubova (Bratislava Slovak Republic) *J. Marshall (Middlesbrough U K ) H. Matusiewicz (Poznan Poland) A. W. McMahon (Manchester U K ) R. G. Michel (Storrs CT USA) *D.L. Miles (Keyworth U K ) T. Nakahara (Osaka Japan) Ni Zhe-ming (Beijing China) L. M. W. Owen (Norwich U K ) P. J. Potts (Milton Keynes U K ) W. J. Price (Budleigh Salterton UK) C. J. Rademeyer (Pretoria. South Africa) A. Sanz-Medel (Oviedo Spain) *B. L. Sharp (Loughborough UK) I. L. Shuttler (,Uberlingen Germany) M. Sperling (Uberlingen Germany) R. Stephens (Halifax Canada) C. Streli (Vienna Austria) J. Stupar (Ljubljana Slovenia) R. E. Sturgeon (Ottawa Canada) *A. Taylor (Guildford U K ) G. C. Turk (Gaithersburg MD USA) J. F. Tyson (Amherst MA USA) P. J. Watkins (London. U K ) M. White (lspra ltaly) J. G. Williams (Egham UK) P. Wobrauschek (Vienna Austria) *Members of the ASU Executive Committee Managing Editor JAAS Brenda Holliday The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge CB4 4WF UK.Telephone + 44 (0) 1223 420066. Fax + 44 (0) 1223 420247. E-mail RSC1 @RSC.ORG (Internet) American Associate Editor JAAS Dr. J. M. Harnly US Department of Agriculture Beltsville Human Nutrition Research Center Beltsville MD 20705 USA. Telephone + 1 301 -504-8569 Fax +1 301 504 8314 E-mail harnlv@bhnrc.usda.gov Deputy Editor Sarah Wilcams ' Production Manager Janice Gordon Production Editor Caroline Seeley Technical Editors Ziva Whitelock Roger Young Editorial Secretaries Lesley Turney Claire Harris Frances Thompson Asia-Pacific Associate Editor JAAS Prof. N. Furuta Department of Applied Chemistry Faculty of Science and Engineering Chuo University 1-1 3-27 Kasuga Bunkyo-ku Tokyo 112 Japan.Telephone 81 -3-381 7-1 906. Fax 81 -3-381 7-1 895. E-mail nfuruta@apchem.chem.chuo-tJ.ac.jp Advertisements Advertisement Department The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge UK CB4 4WF. Telephone +44 (0) 1223 432243. Fax +44 (0) 1223 426017. Information for Authors Full details of how to submit materials for publi- cation in JAAS are given in the Instructions to Authors in Issue 1. Separate copies are available on request. The Journal of Analytical Atomic Spectrometry (JAAS) is an international journal for the publi- cation of original research papers communi- cations and letters concerned with the development and analytical application of atomic spectrometric techniques. The journal is pub- lished twelve times a year including comprehen- sive reviews of specific topics of interest to practising atomic spectroscopists and incorpor- ates the literature reviews which were previously published in Annual Reports on Analytical Atomic Spectroscopy (ARAAS).Manuscripts intended for publication must describe original work related to atomic spectro- metric analysis. Papers on all aspects of the sub- ject will be accepted including fundamental studies novel instrument developments and prac- tical analytical applications. As well as AAS AES and AFS papers will be welcomed on atomic mass spectrometry X-ray fluorescence/emission spectrometry and secondary emission spec- trometry. Papers describing the measurement of molecular species where these relate to the characterization of sources normally used for the production of atoms or are concerned for example with indirect methods of analysis will also be acceptable for publication.Papers describing the development and applications of hybrid techniques (e.g. GC-coupled AAS and HPLC-ICP) will be particularly welcome. Manuscripts on other subjects of direct interest to atomic spectroscopists including sample prep- aration and dissolution and analyte pre-concen- tration procedures as well as the statistical interpretation and use of atomic spectrometric data will also be acceptable for publication. There is no page charge. The following types of papers will be considered. f u l l papers describing original work. Communications which must be on an urgent matter and be of obvious scientific importance.Communications receive priority and are usually published within 2-3 months of receipt. They are intended for brief descriptions of work that has progressed to a stage at which it is likely to be valuable to workers faced with similar problems. Reviews which must be a critical evaluation of the existing state of knowledge on a particular facet of analytical spectrometry. Every paper (except Communications) will be submitted to at least two referees by whose advice the Editorial Board of JAAS will be guided as to its acceptance or rejection. Papers that are accepted must not be published elsewhere except by permission. Submission of a manuscript will be regarded as an undertaking that the same material is not being considered for publication by another journal.Manuscripts (three copies typed in double spacing) should be sent to Brenda Holliday Managing Editor JAAS Dr. J. M. Harnly US Associate Editor JAAS or Prof. N. Furuta Asia- Pacific Associate Editor JAAS. All queries relating to the presentation and sub- mission of papers and any correspondence regarding accepted papers and proofs should be directed to the Editor or Associate Editors (addresses as above). Members of the JAAS Editorial Board (who may be contacted directly or via the Editorial Office) would welcome comments suggestions and advice on general policy matters concerning JAAS. Fifty reprints are supplied free of charge. Journal of Analytical Atomic Spectrometry (JAAS) (ISSN 0267-9477) is published monthly by The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge CB4 4WF UK.All orders accompanied with payment should be sent directly to The Royal Society of Chemistry Turpin Distribution Services Ltd. Blackhorse Road Letchworth Herts. SG6 lHN UK Tel. +44 (0) 1462 672555; Telex 825372 Turpin G; Fax +44 (0) 1462 480947. Turpin Distribution Services Ltd. is wholly owned by The Royal Society of Chemistry. 1996 Annual subscription rate EEA f599.00 USA $1136.00 Rest of World f614.00. Customers should make payments by cheque in sterling payable on a UK clearing bank or in US dollars payable on a US clearing bank. Air freight and mailing in the USA by Publications Expediting Inc. 200 Meacham Avenue Elmont NY 11003. USA Postmaster send address changes to Journal of Analytical Atomic Spectrometry (JAAS) Publications Expediting Inc. 200 Meacham Avenue Elmont NY 11 003. Postage paid at Jamaica NY 11 431. All other despatches outside the UK by Bulk Airmail within Europe Accelerated Surface Post outside Europe. PRINTED IN THE UK. @The Royal Society of Chemistry 1996. All rights reserved. No part of this publication may be reproduced stored in a retrieval system or transmitted in any form or by any means electronic mechanical photographic recording or otherwise without the prior permission of the publishers.

ISSN:0267-9477    

DOI:10.1039/JA99611FX053

出版商:RSC    

年代:1996

数据来源: RSC

摘要:

FOREWORD Elemental Speciation Special Issue Elemental speciation (most often metal speciation) is becoming a more often required and more thoroughly researched area of trace element analysis than ever before. With the realization that the differences between metal toxicity and metal essentiality are attributable to the particular elemental species whether differing in oxidation state organometallic nature or biomolecular association the push for more species selective determinations is ever increasing Over the past decade there has been a marked advance in species separations through chromatography coupled with ultra- trace spectrometric methods of detection. This J. Anal. At. Spectrom. special issue is devoted to a series of research manuscripts focussing on various aspects of metal speciation studies from sample preparation to future instrumentation to pertinent applications directed towards today’s real problems.Applications involving various chromatographic types atomic spectrometric detection and electrospray mass spectrometry are featured. Importantly the less familiar reader will find the introductions of a tutorial style to help make the transition to the field. The manuscripts begin with a focus on one of the important considerations for metal speciation studies; sample preparation. Clearly as we move to species selective determinations the attention necessary to preserving the integrity of the species in the original samples will ever increase in importance. Supercritical fluid extractions may emerge as one facet of this many faceted sample preparation problem.In this paper a wide-ranging series of modifiers to supercritical fluid carbon dioxide are evaluated as well as differing cartridges and temperatures to ascertain the best experimental parameters for the highest efficiency separation. seemingly unending quest for better sample introduction methods. A novel nebulizer the oscillating capillary nebulizer OCN is described for use in speciation studies. It is described for use with micro flows to macro flows and shows excellent sensitivity when coupled to a micro-LC column. The nebulizer is highly efficient and of very simple design. Following this new nebulizer design is a thorough study comparing several spray chambers Following this we turn to the considering both their design and performance characteristics.Liquid chromatographic methods with ICP-MS detection are employed for evaluating the spray chambers. The low internal volume cyclone spray chamber gives the best performance in this study. A new departure for elemental speciation studies is suggested in the following manuscript whereby ultra- trace level determinations are coupled with a means of obtaining structural information through the use of low- pressure and low-power ICPs. These ‘analyte tunable’ plasmas may one day have the potential to fill the void created by the lack of standard reference materials for all the elemental species in the complex environmental and biological samples we now must deal with sometimes less effectively than we would hope to. We next move to the speciation of inorganic selenium and selenoaminoacids by utilizing LC with focused microwave digestion coupled to hydride generation detection.These authors use atomic absorption plasma emission and plasma mass spectrometry as detection methods. They suggest that more reliable speciation information in real samples can be generated by utilizing two or more atomic detectors coupled to the same separation scheme. focus on organoselenium speciation. LC-ICP-MS is used to separate and quantify a series of these selenium species. Good precision with detection limits less than one ppb is obtained although further research is necessary to separate all of the selenium compounds including the inorganic species with the same separation. Selenium is again a focus element in its speciation in in vitro gastro-intestinal extracts of cooked cod.Helen and her old band ‘The Cruisers’ utilize LC-ICP-MS plus electrospray MS. The study is part of a continuing investigation of selenium bioavailability from the human diet. A relatively large amount of the total selenium was not identifiable by the use of standards. Hence the electrospray MS was employed in both positive- and negative-ion modes to assist with identification. In a manuscript illustrating separation of various metallothionein isoforms size exclusion and ion- exchange HPLC are coupled to a In the next manuscript we also see a quartz T-tube interface utilizing atomic absorption detection. With this interface sub-ng detection levels were obtained for flow injections into aqueous carrier streams.Several fractions were collected between two and eight minutes for the Ag Cd Cu or Zn bound species. The authors illustrate the various metal responses to the different fractions separated. With atomic absorption as the detection base but with filtration methods or chemical reactivity to Chelex some metal species in river surface water rain and snow are characterized by size and molecular weight in the next presentation. Kinetic studies in this manuscript are a departure from the others presented in this special issue. While different from chromatographic/ atomic spectrometric methods they present an interesting and viable alternative to elemental speciation studies as the authors nicely illustrate. The next two manuscripts have electrospray or ionspray MS as their common basis. In the first manuscript chromium is studied extensively.The authors show that electrospray MS can provide useful information on chromium species in solution samples. Various forms of both oxidation states are observed directly. The less common species of both oxidation states such as the polyanion trichromate are discussed. In the next paper ionspray tandem MS is coupled to HPLC for speciation of organoarsenic compounds. Qualitative verification with molecular mode detection was used to verify speciation studies by HPLC coupled with ICP-MS detection. Both manuscripts show the potential for electrospray/ionspray sources involving elemental speciation analysis independently or as a complement to Elemental speciation techniques usually involve a succession of steps including extraction possible derivatization separation and detection.It is critical that the individual species integrity remains unchanged through this stepwise process. The Standards Measurements and Design Program of the European Commission has organized a series of interlaboratory studies to evaluate the different steps. The progress in this important direction is highlighted in the last paper of this issue. This work discusses errors in the various steps of the analysis. In summary this special issue ICP-MS. 54N Journal of Analytical Atomic Spectrometry December 1996 Vol. 11presents a wide range of state-of-the-art research in elemental speciation internationa! reputation and library. spanning many important aspects of this analytical subdiscipline with contributions by leading experts of recognition. The guest editors and the editorial staf'f believe it will become an important addition to your research Joseph A. Caruso Steve J. Hill Journal of Analytical Atomic Spectrometry December 1996 Vol. 11 55 N

ISSN:0267-9477    

DOI:10.1039/JA996110054N

出版商:RSC    

年代:1996

数据来源: RSC

摘要:

Ramon M. Barnes Editor Department of Chemistry 701 LGRC Tower University of Massachusetts Box 3451 0 Amherst Massachusetts 01003-451 0 USA Telephone (41 3) 545-2294 fax (41 3) 545-3757 Objective The ICP INFORMATlON 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 related to the development and appli- cations of plasma sources for spectrochemical analysis. Background ICP stands for inductively coupled plasma discharge which during the past 20 years has become the leading spectrochemical excitation source for atomic emission spectroscopy and ion source for inorganic mass spec- trometry. 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- MA TlON NEWSLETTER in 1975.Other plasma sources such as microwave induced plasmas direct current plasma jets and glow discharges also are included in the scope of the ICP lNFORMATlON NEWSLETTER. Scope As the only authoritative monthly journal of its type the ICP lNFORMA TlON NEWSLETTER is read in more than 40 countries by scientists actively applying or planning to use the ICP or other types of plasma spectroscopy. For the novice in the field the ICP lNFORMATION NEWS- LETTER provides a concise and systematic source of information and background material needed for the selec- tion of instrumentation or the development of new method- ology. For the experienced scientist it offers a single- source reference to current developments and literature.Editorial The ICP INFORMATION NEWSLETTER is edited by Dr. Ramon M. Barnes Professor of Chemistry University of Massachusetts 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 discharges since 1968. He also serves as chairman of the Winter Conference on Plasma Spectrochemistry sponsored by the ICPINFOR- MATION NEWSLETTER. Regular Features Original submitted and invited research articles by ICP Complete bibliography of all major ICP publications. Abstracts of all ICP papers presented at major US and First-hand accounts of world-wide ICP developments.Special reports on dcp microwave glow discharge and Calendar and advanced programs of plasma meetings. Technical translations and reprints of critical foreign- Critical reviews of plasma-related books. Conference Activities The ICP lNFORMATlON NEWSLETTER has sponsored nine international meetings on developments in atomic plasma spectrochemical analysis since 1 980 in Orlando Fort Lauderdale San Diego San Juan St. Petersburg and Kailua-Kona. Meeting proceedings have appeared as Developments in Atomic Plasma Spectrochemical Analysis (Wiley) Plasma Spectrochemistry and Plasma Spectrochemistry Il-IV (Pergamon Press) as well as in special issues of Spectrochimica Acta Part B and Journal of Analytical Atomic Spectrometry.The 1998 Winter Con- ference will be held January 5-10 1998. 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 22 runs from June 1996 through May 1997. Back issues 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 information please call (41 3) 545-2294 fax (413) 545-3757 or contact the Editor. Credit cards are accepted. ISSN 0767-6957 and plasma experts. international meetings. other plasmas. language ICP papers. To order complete this section and send it to ICP lnformation Newsletter %Dr.Ramon M. Barnes Department of Chemistry LGRC Tower University of Massachusetts Box 3451 0 Amherst MA 01003-4510 USA. Start a subscription for the following issue D Volume(s)- (June 19- - May 1 9-) or 0 1 9 (January - December). Enclosed Prepayment 0 Check or money order OVISA O Mastercard Account No. (All 13 or 16 digits) 3 Purchase order (No. ) or c3 Send invoice. Date Cardholder Name Expiration date Cardholder Signature Amount Due $ Mail to Name Organization Address City S ta te/Co u n t ry ZIP/Postal code Telephone Telex/f ax e-mail Note For each credit-card transaction a 4.26% service charge will be added reflecting our bank charges. Current subscription rates are $65 (North America) $89 (Europe South America) or $99 (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 we not accepted.Ramon M. Barnes Editor Department of Chemistry 701 LGRC Tower University of Massachusetts Box 3451 0 Amherst Massachusetts 01003-451 0 USA Telephone (41 3) 545-2294 fax (41 3) 545-3757 Objective The ICP INFORMATlON 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 related to the development and appli- cations of plasma sources for spectrochemical analysis.Background ICP stands for inductively coupled plasma discharge which during the past 20 years has become the leading spectrochemical excitation source for atomic emission spectroscopy and ion source for inorganic mass spec- trometry. 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- MA TlON NEWSLETTER in 1975. Other plasma sources such as microwave induced plasmas direct current plasma jets and glow discharges also are included in the scope of the ICP lNFORMATlON NEWSLETTER. Scope As the only authoritative monthly journal of its type the ICP lNFORMA TlON NEWSLETTER is read in more than 40 countries by scientists actively applying or planning to use the ICP or other types of plasma spectroscopy.For the novice in the field the ICP lNFORMATION NEWS- LETTER provides a concise and systematic source of information and background material needed for the selec- tion of instrumentation or the development of new method- ology. For the experienced scientist it offers a single- source reference to current developments and literature. Editorial The ICP INFORMATION NEWSLETTER is edited by Dr. Ramon M. Barnes Professor of Chemistry University of Massachusetts 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 discharges since 1968.He also serves as chairman of the Winter Conference on Plasma Spectrochemistry sponsored by the ICPINFOR- MATION NEWSLETTER. Regular Features Original submitted and invited research articles by ICP Complete bibliography of all major ICP publications. Abstracts of all ICP papers presented at major US and First-hand accounts of world-wide ICP developments. Special reports on dcp microwave glow discharge and Calendar and advanced programs of plasma meetings. Technical translations and reprints of critical foreign- Critical reviews of plasma-related books. Conference Activities The ICP lNFORMATlON NEWSLETTER has sponsored nine international meetings on developments in atomic plasma spectrochemical analysis since 1 980 in Orlando Fort Lauderdale San Diego San Juan St.Petersburg and Kailua-Kona. Meeting proceedings have appeared as Developments in Atomic Plasma Spectrochemical Analysis (Wiley) Plasma Spectrochemistry and Plasma Spectrochemistry Il-IV (Pergamon Press) as well as in special issues of Spectrochimica Acta Part B and Journal of Analytical Atomic Spectrometry. The 1998 Winter Con- ference will be held January 5-10 1998. 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 22 runs from June 1996 through May 1997. Back issues 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 information please call (41 3) 545-2294 fax (413) 545-3757 or contact the Editor.Credit cards are accepted. ISSN 0767-6957 and plasma experts. international meetings. other plasmas. language ICP papers. To order complete this section and send it to ICP lnformation Newsletter %Dr. Ramon M. Barnes Department of Chemistry LGRC Tower University of Massachusetts Box 3451 0 Amherst MA 01003-4510 USA. Start a subscription for the following issue D Volume(s)- (June 19- - May 1 9-) or 0 1 9 (January - December). Enclosed Prepayment 0 Check or money order OVISA O Mastercard Account No. (All 13 or 16 digits) 3 Purchase order (No. ) or c3 Send invoice. Date Cardholder Name Expiration date Cardholder Signature Amount Due $ Mail to Name Organization Address City S ta te/Co u n t ry ZIP/Postal code Telephone Telex/f ax e-mail Note For each credit-card transaction a 4.26% service charge will be added reflecting our bank charges.Current subscription rates are $65 (North America) $89 (Europe South America) or $99 (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 we not accepted.Ramon M. Barnes Editor Department of Chemistry 701 LGRC Tower University of Massachusetts Box 3451 0 Amherst Massachusetts 01003-451 0 USA Telephone (41 3) 545-2294 fax (41 3) 545-3757 Objective The ICP INFORMATlON 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 related to the development and appli- cations of plasma sources for spectrochemical analysis.Background ICP stands for inductively coupled plasma discharge which during the past 20 years has become the leading spectrochemical excitation source for atomic emission spectroscopy and ion source for inorganic mass spec- trometry. 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- MA TlON NEWSLETTER in 1975. Other plasma sources such as microwave induced plasmas direct current plasma jets and glow discharges also are included in the scope of the ICP lNFORMATlON NEWSLETTER.Scope As the only authoritative monthly journal of its type the ICP lNFORMA TlON NEWSLETTER is read in more than 40 countries by scientists actively applying or planning to use the ICP or other types of plasma spectroscopy. For the novice in the field the ICP lNFORMATION NEWS- LETTER provides a concise and systematic source of information and background material needed for the selec- tion of instrumentation or the development of new method- ology. For the experienced scientist it offers a single- source reference to current developments and literature. Editorial The ICP INFORMATION NEWSLETTER is edited by Dr.Ramon M. Barnes Professor of Chemistry University of Massachusetts 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 discharges since 1968. He also serves as chairman of the Winter Conference on Plasma Spectrochemistry sponsored by the ICPINFOR- MATION NEWSLETTER. Regular Features Original submitted and invited research articles by ICP Complete bibliography of all major ICP publications. Abstracts of all ICP papers presented at major US and First-hand accounts of world-wide ICP developments. Special reports on dcp microwave glow discharge and Calendar and advanced programs of plasma meetings.Technical translations and reprints of critical foreign- Critical reviews of plasma-related books. Conference Activities The ICP lNFORMATlON NEWSLETTER has sponsored nine international meetings on developments in atomic plasma spectrochemical analysis since 1 980 in Orlando Fort Lauderdale San Diego San Juan St. Petersburg and Kailua-Kona. Meeting proceedings have appeared as Developments in Atomic Plasma Spectrochemical Analysis (Wiley) Plasma Spectrochemistry and Plasma Spectrochemistry Il-IV (Pergamon Press) as well as in special issues of Spectrochimica Acta Part B and Journal of Analytical Atomic Spectrometry. The 1998 Winter Con- ference will be held January 5-10 1998. 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 22 runs from June 1996 through May 1997. Back issues 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 information please call (41 3) 545-2294 fax (413) 545-3757 or contact the Editor. Credit cards are accepted. ISSN 0767-6957 and plasma experts. international meetings. other plasmas. language ICP papers. To order complete this section and send it to ICP lnformation Newsletter %Dr. Ramon M. Barnes Department of Chemistry LGRC Tower University of Massachusetts Box 3451 0 Amherst MA 01003-4510 USA.Start a subscription for the following issue D Volume(s)- (June 19- - May 1 9-) or 0 1 9 (January - December). Enclosed Prepayment 0 Check or money order OVISA O Mastercard Account No. (All 13 or 16 digits) 3 Purchase order (No. ) or c3 Send invoice. Date Cardholder Name Expiration date Cardholder Signature Amount Due $ Mail to Name Organization Address City S ta te/Co u n t ry ZIP/Postal code Telephone Telex/f ax e-mail Note For each credit-card transaction a 4.26% service charge will be added reflecting our bank charges. Current subscription rates are $65 (North America) $89 (Europe South America) or $99 (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 we not accepted.Ramon M. Barnes Editor Department of Chemistry 701 LGRC Tower University of Massachusetts Box 3451 0 Amherst Massachusetts 01003-451 0 USA Telephone (41 3) 545-2294 fax (41 3) 545-3757 Objective The ICP INFORMATlON 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 related to the development and appli- cations of plasma sources for spectrochemical analysis. Background ICP stands for inductively coupled plasma discharge which during the past 20 years has become the leading spectrochemical excitation source for atomic emission spectroscopy and ion source for inorganic mass spec- trometry.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- MA TlON NEWSLETTER in 1975. Other plasma sources such as microwave induced plasmas direct current plasma jets and glow discharges also are included in the scope of the ICP lNFORMATlON NEWSLETTER. Scope As the only authoritative monthly journal of its type the ICP lNFORMA TlON NEWSLETTER is read in more than 40 countries by scientists actively applying or planning to use the ICP or other types of plasma spectroscopy. For the novice in the field the ICP lNFORMATION NEWS- LETTER provides a concise and systematic source of information and background material needed for the selec- tion of instrumentation or the development of new method- ology. For the experienced scientist it offers a single- source reference to current developments and literature.Editorial The ICP INFORMATION NEWSLETTER is edited by Dr. Ramon M. Barnes Professor of Chemistry University of Massachusetts 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 discharges since 1968. He also serves as chairman of the Winter Conference on Plasma Spectrochemistry sponsored by the ICPINFOR- MATION NEWSLETTER.Regular Features Original submitted and invited research articles by ICP Complete bibliography of all major ICP publications. Abstracts of all ICP papers presented at major US and First-hand accounts of world-wide ICP developments. Special reports on dcp microwave glow discharge and Calendar and advanced programs of plasma meetings. Technical translations and reprints of critical foreign- Critical reviews of plasma-related books. Conference Activities The ICP lNFORMATlON NEWSLETTER has sponsored nine international meetings on developments in atomic plasma spectrochemical analysis since 1 980 in Orlando Fort Lauderdale San Diego San Juan St. Petersburg and Kailua-Kona. Meeting proceedings have appeared as Developments in Atomic Plasma Spectrochemical Analysis (Wiley) Plasma Spectrochemistry and Plasma Spectrochemistry Il-IV (Pergamon Press) as well as in special issues of Spectrochimica Acta Part B and Journal of Analytical Atomic Spectrometry.The 1998 Winter Con- ference will be held January 5-10 1998. 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 22 runs from June 1996 through May 1997. Back issues 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 information please call (41 3) 545-2294 fax (413) 545-3757 or contact the Editor. Credit cards are accepted. ISSN 0767-6957 and plasma experts. international meetings. other plasmas. language ICP papers. To order complete this section and send it to ICP lnformation Newsletter %Dr. Ramon M. Barnes Department of Chemistry LGRC Tower University of Massachusetts Box 3451 0 Amherst MA 01003-4510 USA. Start a subscription for the following issue D Volume(s)- (June 19- - May 1 9-) or 0 1 9 (January - December). Enclosed Prepayment 0 Check or money order OVISA O Mastercard Account No. (All 13 or 16 digits) 3 Purchase order (No. ) or c3 Send invoice. Date Cardholder Name Expiration date Cardholder Signature Amount Due $ Mail to Name Organization Address City S ta te/Co u n t ry ZIP/Postal code Telephone Telex/f ax e-mail Note For each credit-card transaction a 4.26% service charge will be added reflecting our bank charges. Current subscription rates are $65 (North America) $89 (Europe South America) or $99 (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 we not accepted.

ISSN:0267-9477    

DOI:10.1039/JA996110X055

出版商:RSC    

年代:1996

数据来源: RSC

摘要:

FUTURE ISSUES WILL INCLUDE- Determination of Arsenobetaine in Manufactured Seafood Products by Liquid Chromatography Microwave- Assisted Oxidation and Hydride Generation Atomic Absorption Spectrometry-R. Montoro Dinoraz Velez N. Ybanez Analysis of Toxic Elements in Liquid Hazardous Waste Using High Resolution Energy Dispersive X-ray Fluorescence Spectrometry-P. A. Russell R. James Application of Inductively Coupled Plasma Atomic Emission Spectrometry in Forensic Sciences-Nonka Daskalova Marko Lalchev Iontcho Ionov Microsecond Pulsed Glow Discharge Time-of-Flight Mass Spectrometry Analytical Advantages-W. W. Harrison W. Hang Cynthia Baker B. W. Smith J. D. Winefordner Reduction in Background Absorption in the Measurement of Cadmium Lead and Selenium in Whole Blood Using Iridium-sputtered Graphite Tubes in Electrothermal Atomic Absorption Spectrometry-Cornelius Rademeyer Bernard Radziuk Natalya Romanova Yngvar Thomassen Paolo Tittarelli Comparison of Suitability of Various Atomic Spectroscopy Techniques for the Determination of Selenium in Human Blood-0.Mestek M. Suchanek Z. Vodickova B. Zemanova T. Zima Evaluation of a Direct Current Arc Charge Injection Device Spectrograph for Direct Analysis of Soils-Cynthia Mahan Use of Flow Injection Cold Vapour Generation and Preconcentration on Coated Graphite Tubes for Mercury Determination in Natural Waters by Electrothermal Atomic Absorption Spectrometry-Pilar Bermejo-Barrera Jorge Moreda-Pineiro Antonio Moreda- Pineiro A. Bermejo-Barrera Viability of ,lnalysis of Variance Applied to the Data Obtained by Atomic Absorption Spectroscopy of the Metal Content in Welding Fumes-M. P.Hernandez-Artiga Dolores Bellido- Milla Andres Jimenez-Jimenez J. L. H. Hidalgo de Cisneros Determination of Vanadium Rhodium and Platinum in Automotive Catalytic Converters Using Inductively Coupled Plasma Mass Spectrometry Spark Ablation-David M. Coleman Oleg V. Borisov Kristine A. Oudsema Roscoe 0. Carter Determination of Platinum Palladium Rhodium and Titanium in Automotive Catalytic Converters Using Inductively Coupled Plasma Mass Spectrometry Liquid Nebulization-David M. Coleman Oleg V. Borisov Kristine A. Oudsema Roscoe 0. Carter Effect of Easily Ionizable Elements on the Mass Transport Efficiency of Solutions and Slurries Used in Plasma Emission Spectrometry-M.Foulkes Karen O’Hanlon Les Ebdon Application of the Slurry Technique for Selenium Determination in Fish Samples by Electrothermal Atomic Absorption Spectrometry-M. A. Z. Arruda Gustavo S. B. Januzzi Francisco J. Krug Improved Signal-to-Noise Ratio in Glow Discharge Ion Trap Mass Spectrometry via Pulsed Discharge Operation-Douglas C. Duckworth David H. Smith Scott A. McLuckey Analysis of Geological Materials for Bismuth Antimony Selenium and Tellurium by Continuous Flow Hydride Generation Inductively Coupled Plasma Mass Spectrometry Part 1 Mutual Hydride Interferences-Gwendy E. M. Hall J. C. Pelchat Journal of Analytical Atomic Spectrometry December 1996 Vol. 1 1 57 NAnalysis of Geological Materials for Bismuth Antimony Selenium and Tellurium by Continuous Flow Hydride Generation Inductively Coupled Plasma Mass Spectrometry; Part 2.Methodology and Results-Gwendy E. M. Hall J. C. Pelchat Quantitative Analysis of Zirconium Oxide by Direct Current Glow Discharge Mass Spectrometry Using a Secondary Cathode-W. Schelles Rene Van Grieken Behaviour of Selenium(1v) in Transversely Heated Graphite Atomizer for Electrothermal Atomic Absorption Spectrometry in the Presence of Platinum Metals as Chemical Modifiers-Viliam Krivan Anatoly B. Vol yns k y Evaluation of Electrothermal Vaporization. I-T-lambda Measurement and Time Resolution Combined With an Axially Viewed Horizontal Inductively Coupled Plasma Using an Echelle Spectrometer With Wavelength Modulation and Second-derivative Detection-Osamu Kujirai Yoshisuke Nakamura Katsuyuki Takahashi Haruno Okochi Determination of Tin in Nickel Based Alloys by Electrothermal Atomizer Laser Excited Atomic Fluorescence Spectromet r y-Rober t G.Mic hel Karl X. Yang Robert Lonardo Zhongwen Liang Alexander I. Yuzefovsky Francis R. Preli Jr. Xiandeng Hou Microbatch Venturi-type System for the Determination of Selenium(1v) by Hydride Generation Atomic Absorption Spectrometry- Ayrton F. Martins Erico M. M. Flores Sergio R. Mortari Determination of Copper Cadmium and Lead in Biological Samples by Electrothermal Vaporization Isotope Dilution Inductively Coupled Plasma Mass Spectrometry-Shiuh-Jen Jiang Cho-Chiang Chang Spatial Characterization of Emission Intensities Temperatures and Electron Number Densities of High Power N,-Microwave Induced Plasma-Naoki Furuta Masaki Ohata Determination of Gold Content of Geogas by Resonance Ionization Mass Spectrometry-W.Y. Ma Q. Hui M. Xue W. X. Ji D. Y. Chen Determination of Total Mercury in Sediments by Microwave-assisted Digestion-Flow Injection-Inductively Coupled Plasma Mass Spectrometry- Agnes Woller Herve Garraud Fabienne Martin Peter Fodor Olivier F. X. Donard Slurry Sampling Graphite Furnace Atomic Absorption Spectrometry Results From the Second Phase on an International Collaborative Study- Nancy J. Miller-Ihli Optimization and Calibration of Laser Ablation Inductively Coupled Plasma Atomic Emission Spectrometry by Measuring Vertical Spatial Intensity Profiles-Xianglei Mao Richard E. Russo Determination of Ytterbium in Digesta and Animal Faeces by Graphite Furnace Atomic Absorption Spectrometry- Joaquim A.Nobrega Eder C. Lima Francisco J. Krug Elisabete A. N. Fernandes COPIES OF CITED ARTICLES The Library and Information Centre (LIC) of the RSC offers a first class Document Delivery Service for items in Chemistry and related subjects. Contact the LIC The Royal Society of Chemistry Burlington House Piccadilly London W 1V OBN. Tel + 44 (0)171 437 8656 - Fax +44 (0)171 287 9798 - E-mail library@rsc.org. This service is only available from the LIC in London and not the RSC in Cambridge. Atomic Spectroscopy Group Study Bursaries The Atomic Spectroscopy Group Analytical Division RSC invites applications from UK scientists working in the field of analytical spectrometry for study bursaries. These typically will have a value not exceeding f500 and are intended to afford applicants the opportunity for professional development. Specific activities for which the study bursary might be considered include attendance at meetings workshops and seminars or support for study visits to other laboratories. Applications should include a statement of the purpose for which the bursary is sought (1 page A4) and a summary of recent work (1 page A4). The submission should be sent to Dr S. J. Hill Chairman A.S.G. Department of Environmental Sciences University of Plymouth Drake Circus Plymouth PL4 8AA at least 2 months before funds are required. 58 N Journal of Analytical Atomic Spectrometry December 1996 Vol. 11

ISSN:0267-9477    

DOI:10.1039/JA996110057N

出版商:RSC    

年代:1996

数据来源: RSC

摘要:

Ramon M. Barnes Editor Department of Chemistry 701 LGRC Tower University of Massachusetts Box 3451 0 Amherst Massachusetts 01 003-451 0 USA Telephone (41 3) 545-2294 fax (41 3) 545-3757 0 b j ec t ive 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 related to the development and appli- cations of plasma sources for spectrochemical analysis. Background ICP stands for inductively coupled plasma discharge which during the past 20 years has become the leading spectrochemical excitation source for atomic emission spectroscopy and ion source for inorganic mass spec- trometry. 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- MA TION NEWSLETTER in 1975.Other plasma sources such as microwave induced plasmas direct current plasma jets and glow discharges also are included in the scope of the ICP INFORMATION NEWSLETTER. Scope As the only authoritative monthly journal of its type the ICPINFORMA TION NEWSLETTER is read in more than 40 countries 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 NEWS- LETTER provides a concise and systematic source of information and background material needed for the selec- tion of instrumentation or the development of new method- ology.For the experienced scientist it offers a single- source reference to current developments and literature. Editorial The ICP INFORMA TION NEWSLETTER is edited by Dr. Ramon M. Barnes Professor of Chemistry University of Massachusetts 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 discharges since 1968. He also serves as chairman of the Winter Conference on Plasma Spectrochemistry sponsored by the ICPINFOR- MATION NEWSLETTER. Regular Features Original submitted and invited research articles by ICP Complete bibliography of all major ICP publications. Abstracts of all ICP papers presented at major US and First-hand accounts of world-wide ICP developments.Special reports on dcp microwave glow discharge and Calendar and advanced programs of plasma meetings. Technical translations and reprints of critical foreign- Critical reviews of plasma-related books. Conference Activities The ICP lNFORMA TION NEWSLETTER has sponsored nine international meetings on developments in atomic plasma spectrochemical analysis since 1 980 in Orlando Fort Lauderdale San Diego San Juan St. Petersburg and Kailua-Kona. Meeting proceedings 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 Part B and Journal of Analytical Atomic Spectrometry.The 1998 Winter Con- ference will be held January 5-1 0 1998. 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 22 runs from June 1996 through May 1997. Back issues beginning with Volume i May 1975 also are available. To begin a subscription complete the form below and submit it with prepayment or purchase information. For additional information please call (41 3) 545-2294 fax (413) 545-3757 or contact the Editor. Credit cards are accepted. lSSN 0767-6957 and plasma experts. international meetings. other plasmas. language ICP papers.To order complete this section and send it to ICP information Newsletter %Dr. Ramon M. Barnes Department of Chemistry LGRC Tower University of Massachusetts Box 34510 Amherst MA 01003-4510 USA. Start a subscription for the following issue DVolume(s)- (June 19- May 19-) or 0 4 9 (January - December). Enclosed a Prepayment Q Check or money order OWSA CI Mastercard Account No. (All 13 or 16 digits) 3 Purchase order (No. ) or 0 Send invoice. Date Cardholder Name Expiration date Cardholder Signature Amount Due $ Mail to Name Organization Address City State/Country ZI P/Postal code Telephone Telexlf ax e-mail Note For each credit-card transaction a 4.26% service charge will be added reflecting our bank charges. Current subscription rates are $65 (North America) $89 (Europe South America) or $99 (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.Journal of Analytical Atomic Spectrometry 111 111111111 111111 111 111111111 111111 THE ROYAL C H EM I ST RY Information Services I I JASPE2 11 (1 2) 53N-58N 11 29-1 234 461 R-522R CONTENTS NEWS PAGES Editorial-Steve J. Hill Guest Editors Foreword-Joseph A. Caruso Steve J. Hill Diary of Conferences and Courses Future Issues 53N 53N 54N 55N 57N PAPERS Trace Metal Speciation via Supercritical Fluid Extraction-Liquid Chromatography-Inductively Coupled Plasma Mass Spectrohetry Nohora P.Vela Joseph A. Caruso Low-flow Interface for Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry Speciation Using an Oscillating Capillary Nebulizer Lanqing Wang Sheldon W. May Richard F. Browner Stanley H. Pollock 1129 1137 Effect of Different Spray Chambers on the Determination of Organotin Compounds by High-performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry Cristina Rivas Les Ebdon Steve J. Hill 1147 Feasibility Study of Low Pressure Inductively Coupled Plasma Mass Spectrometry for Qualitative and Quantitative Speciation Gavin O’Connor Les Ebdon E. Hywel Evans Hong Ding Lisa K. Olson Joseph A. Caruso 1151 Speciation of Inorganic Selenium and Selenoaminoacids by On-line Reversed- phase High-performance Liquid Chromatography-Focused Microwave Digestion-Hydride Generation-atomic Detection J.M. Gonzalez Lafuente M. L. Fernandez Sanchez A. Sanz-Medel 11 63 Speciation of Organic Selenium Compounds by High-performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry in Natural Samples Riansares MuAoz Olivas Olivier F. X. Donard Nicole Gilon Martine Potin-Gautier Investigation of Selenium Speciation in In Vitro Gastrointestinal Extracts of Cooked Cod by High-performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry and Electrospray Mass Spectrometry Helen M. Crews Philip A. Clarke D. John Lewis Linda M. Owen Paul R. Strutt Andres lzquierdo Approaches to the Determination of Metallothionein(s) by High-performance Liquid Chromatography-Quartz Tube Atomic Absorption Spectrometry Yanxi Tan Patrick Ager William D.Marshall Hing Man Chan Speciation of Some Metals in River Surface Water Rain and Snow and the Interactions of These Metals With Selected Soil Matrices J. Y. Lu C. L. Chakrabarti M. H. Back A. L. R. Sekaly D. C. Gregoire W. H. Schroeder 1171 1177 1183 1189 Investigations Into Chromium Speciation by Electrospray Mass Spectrometry Ian 1. Stewart Gary Horlick Arsenic Speciation by Liquid Chromatography Coupled With lonspray Tandem Mass Spectrometry Jay J. Corr Erik H. Larsen 1203 1215 Atomic Spectrometry Hyphenated to Chromatography for Elemental Speciation Performance Assessment Within the Standards Measurements and Testing Programme (Community Bureau of Reference) of the European Union Philippe Quevauviller CUMULATIVE AUTHOR INDEX 1225 1233 AT0 M I C SPECTROMETRY UPDATES Industrial Analysis Metals Chemicals and Advanced Materials- James S. Crighton John Carroll Ben Fairman Janice Haines Mike Hinds 461 R References Typeset printed and bound by The Charlesworth Group Huddersfield England 01484 51 7077 509R 0267-9477(1996112:1-6

ISSN:0267-9477    

DOI:10.1039/JA99611BX059

出版商:RSC    

年代:1996

数据来源: RSC

摘要:

Atomic Spectrometry Update- Industrial Analysis Metals Chemicals and Advanced Materials JAMES S CRIGHTON * BP Chemicals Chertsey Road Sunbury-on-Thames Middlesex L K TW16 7LN JOHN CARROLL ICI Wilton Research Centre P.O. Box 90 Middlesbrough Clevelmd UK TS90 8 J E BEN FAIRMAN Laboratory of the Government Chemist Queens Road Teddington Middlesex U K T W l l OLY JANICE HAINES AEA Technology 551 Harwell Didcot Oxfordshire UK OX11 ORA MIKE HINDS Royal Canadian Mint 320 Sussex Drive Ottawa Ontario Canadti KIA OG8 SUMMARY OF CONTENTS 1. 1.1 1.2. Table 1. 2. 2.1. 2.1.1. 2.1.2. 2.1.3. 2.2. 2.2.1. 2.2.2. 2.3. 2.4. Table 2. 3. 3.1. 3.2. 3.3. 3.4. 3.5. Table 3. Metals Ferrous Metals and Alloys Non-ferrous Metals and Alloys Summary of the Analyses of Metals Chemicals Petroleum and Petroleum Products Crude oil and fractions Fuels Lubricating oils Organic Chemicals and Solvents Chemicals Solvents Inorganic Chemicals and Acids Nuclear Materials Summary of Analyses of Chemicals Advanced Materials Polymeric Materials and Composites Semiconductor Materials Glasses Ceramics and Refractories Catalysts Summary of Analyses of Advanced Materials This Atomic Spectrometry Update is the latest in an annual series appearing under the title ‘Industrial Analysis’. The structure of the review is broadly the same as in previous years. Direct analysis of solid samples continues to be a prime objective for industrial atomic spectrometry and laser sampling techniques (for both MS and AES) are becoming increasingly common especially in the field of metals analysis.More traditional approaches using glow discharge sources are however still undergoing development and are frequentlj applied to the determination of elemental depth profiles.A novel sampling system has even been described which permits elemental mapping over many tens of square centimeters of a sample surface at one time using GD-AES. The development of rf GD sources is beginning to extend the applications of GD-MS and GD-AES to non-conductive samples and may be particularly useful in the field of advanced materials. However * Review Co-ordinator to whom correspondence should be addressed. Atomic Spectrometry Update although seldom reflected in the volume of published literature XRF still often remains the method of choice within industry for direct analysis of solid samples. The capabilities of the technique have recently been extended to include spatially resolved analysis through the development of instruments with microbeam capabilities and of software packages that are capable of carrying out the analysis of small irregularly shaped particles and this is now beginning to be exploited.TXRF continues to become more established within the semiconductor industry for the determination of contaminants on wafer and device surfaces and the applications of the technique have recently been extended to include the analysis of light elements (e.g. Al C F Mg N Na and 0). It has been estimated that there are now over 100 TXRF instruments in use within the semiconductor industry and the possibility of establishing an industry wide IS0 standard method based around the technique has been discussed at a recent conference.XRF is also frequently the method of choice for many process control applications. In the field of catalyst analysis however traditional solid sampling techniques such as SIMS XPS and electron microscopy (usually in combination with XRD) continue to dominate. Rapid multi-element techniques such as ICP-MS are becoming more widely available and the capabilities are being exploited for a diverse range of ‘fingerprinting’ applications (precious metal identification oilsource rock correlations origin of illicit drugs archaeological artefact correlations etc.). The range of elements covered by ICP-MS is being extended to include ‘difficult’ elements (i.e. those which suffer from molecular ion interferences) through the use of novel sample introduction techniques and/or cool plasmas. Reports on the application of high resolution ICP-MS are starting to appear in the literature and it is clear that this technique offers very high potential particularly for applications in the nuclear industry and for the analysis of advanced materials.At the moment however the number of such reports is relatively small due to the limited availability and high cost of the instrumentation. In cases where multi-element capability is not required it is often difficult to justify expensive instrumentation such as that described above and so many workers are developing innovative approaches to improve sensitivity and eliminate interferences with cheaper alternatives such as FAAS and ETAAS. A large proportion of such work has to some extent been stimulated by the commercial availability of robust and automated sample preparation and sample introduction equipment (ultrasonic nebulizers Journal of Analytical Atomic Spectrometry December 1996 Vol.11 (461 R-508R) 461 Rthermosprays direct injection nebulizers on-line matrix separation/preconcentration systems hydride generation/ desolvation systems etc). Direct injection nebulization (DIN) appears to offer particular advantages for ICP-AES and ICP-MS analysis since it allows direct analysis of samples containing volatile analytes (e.g. As Hg and P in organic feedstocks) and when combined with flow injection can allow extremely rapid analysis (up to 240 samples per hour).Every year sees a growing awareness regarding the impact of industrial products and processes on the environment and this is the driving force for much of the research in the field of atomic spectrometry at the current time. Methods for determination of total element concentrations are fairly well established although developments in ICP-AES (e.g. axially viewed plasma ultrasonic nebulization) have meant that this technique may be starting to undergo something of a renaissance as it can now be used for applications which a few years ago would have required the use of a more sensitive technique such as ICP-MS or ETAAS. The extension of the UV wavelength range of some newer ICP-AES instruments to allow determination of chlorine down to ppm levels also increases the attractiveness of the technique for environmental applications.In many cases however determination of total element concentrations in environmental samples is not sufficient since it is well known that toxicity can vary enormously depending on the chemical form of the element. Methods for element speciation are much less well developed than those for total element concentrations and so the former is a very active field of research at the present time. Most of the work reported is concerned with development of methods for extracting and if necessary derivatizing chemical species prior to measurement using a chromatographic system coupled with an atomic spectrometric detector. In view of the complexity of these problems it seems likely that this will remain an active area of research for many years to come.1. METALS The analysis of ferrous metals non-ferrous metals and their alloys by analytical atomic spectrometry is covered in this section. A summary of the analytical methods reported for metals in the time period under review is given in Table 1. 1.1. Ferrous Metals and Alloys A review (60 references) of analytical atomic spectrometric methods involved in the iron and steelmaking industries was published (96/1385) as was a similar review (16 references) comparing spark emission and X-ray fluorescence spectrometry for process control in steelmaking plants (95/4420). A number of papers focusing on laser solid sampling appeared in the literature during this review period. In situ laser sampling for ICP-AES (95/4725) was accomplished by placing a solid steel sample 1 mm below the plasma by a direct system insertion system.The laser directly above the plasma ablated the metal sample directly into the plasma thus minimizing sample loss and produced a very fast transient signal (0.7-1.7 ms compared with 1 s for a conventional laser ablation system). Improvements in sensitivity were reported. A time of flight mass spectrometer was used as a detector in an ICP-MS system to measure the transient Pb signal generated from a laser pulse impinging upon a cast iron standard (96/3017). Pulse to pulse variations were virtually eliminated by ratioing signals from two Zn isotopes that were simultaneously acquired. A 10 ppb limit of detection (LOD) was reported for Pb in iron. A 'nominally' non-destructive sampling method was reported (95/4173) in which the metal/alloy surface was polished with a diamond lapping disk following which the metal transferred onto the disk was analysed by laser ablation (LA) ICP-MS. The determination of trace elements agreed with certified values of steel standards and detection limits varied between 1 and 10 pg g-'.Interest continues in laser-induced plasma atomic emission spectrometry (LIP-AES) or laser-induced breakdown spec- trometry (LIBS). Sulfur in steel was determined by this spectro- metric method (96/2813) with the plasma generated by 7ns pulses of a Q-switched Nd:YAG laser operating at 20 Hz. Wavelengths below 180 nm were used for detection. The mono- chromator was filled with nitrogen to prevent light absorption by oxygen.No noticeable matrix effects were observed. This method was also used for depth profiling studies of coatings on steel (96/1039). Good precision was reported for 2.7-7.2 pm coatings of Zn-Ni and 0.38 to 1.48 pm of Sn. An ultra-thin coating of Cr (20 nm) was also detected on a steel sample. The main advantages of this method appear to be the profiling performance and rapid measurement times (< 60 s). A COz laser was used to induce a shock wave plasma for atomic emission spectrometric determination of Cr and Ni in steels with an iron emission line as an internal standard (95/3837). A high speed steel was vaporized by this more energetic laser (700 mJ at 5 Hz); however W in this steel could not be determined. A number of papers on glow discharge sources were pub- lished.A method of quantitative depth-profile analysis by GD-AES based on matrix independent emission yields was proposed (95/4714). It was tested by profiling an Al-Ni-Cr- steel thin film system. The determined thickness of the Ni-Cr layer of sample was in agreement with the known value. The thickness of the A1 layer was low biased by 1.8 pm and the reasons for this are not known. A study (95/4186) of discharge conditions for in-depth profile analysis of thin films using an Al-Zn coated steel showed that the internal diameter of the anode etching rate with the rf power and the gas pressure were important in optimizing GD-AES measurements. There were a moderate number of research papers involving atomic emission spectrometry. Most of these investigated differ- ent methods of liquid sample pre-treatment prior to presen- tation to the emission source (commonly an ICP).These are conveniently summarized in Table 1. An interesting compari- son was made between ICP-AES and flame heated quartz tube AAS for the determination of selenium in steels with matrix separation by hydride generation (95/4700). Although Se was determined by both methods ICP-AES showed lower detection limits by a factor of 1.5 to 3 depending on the sample type and had reduced matrix interference. Experiments indicated that these are gas phase interferences and are most likely due to the presence of As and Sn hydrides. The determination of boron in steels continued to be a topic of investigation by on-line separation and pre-concentration flowing into a micro- wave plasma emission source (96/2801).In the flow injection system described the sample passed through a strongly acidic cation exchange column and then through a strongly basic anion exchange column. The microwave plasma excitation source was pursued because of its lower cost (compared with ICP) but since it suffers from matrix interferences the described sample pre-treatment was necessary. The accuracy of the method was verified with certified materials and the precision varied from 3.6 to 4.7% RSD for B concentrations ranging from 12 to 100 pg g-'. ICP-MS is becoming an increasingly common method for the determination of trace elements in high purity iron and steels. However molecular ion interferences originating from matrix elements can be troublesome.Mass spectral interferences (above 69 m/z) from matrix components in high purity iron and low and high alloy steels (eg. Cr Fey Mn Mo Ni and W) in combination with different acids have been experimen- tally determined (96/2436). It was recommended that prior knowledge of the material before analysis would aid in antici- pating potential interferences. A direct flow injection manifold 462 R Journal of Analytical Atomic Spectrometry December 19!?6 Vol. 1 1Table 1 SUMMARY OF THE ANALYSES OF METALS Technique; atomization; analyte form* Element Matrix Sample treatment/comments Reference Ag Au-Ag jewellery alloys XRF;-;S No sample pretreatment reported. Determination range was 1-99.99% m/m Samples (1 g) dissolved in 25 ml HF-HN0,-H20 (1 1 l) diluted to 100 ml with water and then 10 ml of solution mixed with 10 ml 50% HNO and diluted to 100 ml.Resulting solutions (0.5 ml) mixed with 0.5 ml of 0.6% ammonium dihydrogenphosphate-0.5% Ni solution prior to analysis using ETAAS. (Detection limit 0.06 pg I-') Copper (0.3 g) dissolved in 15 ml HCl-HNO (4 1 ) then diluted to 50 ml with water. Detection limit was 0.017 pg ml-' and precision 2.7-6.3% (RSD) Samples (1 or 2 g) dissolved in 20 or 40 ml of HC1 boiled with H202 (1 or 2 ml) then diluted to 100 ml with water. N,O-C,H flame used. Limits of interfering components quoted Sample solutions adjusted to pH 3.8 and shaken with 5 ml 0.16% N-nitrophenylhydroxylamine-lead in benzene for 1 min. A1 determined indirectly by measurement of Pb in aqueous phase which was displaced by Al.Linear calibration up to 5 pg ml - ' . (RSD < 2.6%; LOD 0.0048 pg ml - ') Most of the cadmium distilled off at 360°C under vacuum. Residue dissolved in 0.2 ml of 50% HNO and diluted to 2 ml with water. Pd nitrate matrix modifer added if As concentration <0.01 pg ml-'. (Detection limit 4 ng g-'; RSD 0.34 at 5 pg g-') 9513504 9514696 As for P Interferences from nickel and cobalt removed by adding DTPA. Solution made alkaline with NaOH and filtered to remove copper hydroxide. Tetrahydroborate was added and resulting solution mixed with HC1 in continuous-flow hydride generation system As for Ag Steel dissolved in aqua regia within high pressure microwave vessels. Be added as internal standard. Discrete volume (220 pl) introduced using flow injection system.(Detection limit 0.2 pg g-' and RSD < 1.5% for 100 ng B in 0.5% Fe) Dissolved samples treated to form ionic complex Cu( phenyl),2f-B-phenylhydroxyacetic acid. Complex extracted into MIBK and B content determined indirectly by measuring Cu concentration in solution Aliquot of dissolved sample passed through two on-line anion exchange columns (one strongly acidic and the other strongly basic) in series to remove interferences. RSD was 4.2% at 0.2 mg I-' and detection limits were 0.0055 mg 1-' at 45 samples h-' and 0.0018 mg I-' at 20 samples h-' Ag Nickel-based alloys and AA;ETA;L steels Ag Copper A1 Zinc and zinc alloys AA;F;L AA;F;L 961389 9513421 A1 Copper alloys AA;F;L 961358 As Cadmium A A;ETA;L 951343 1 As Caesium As Nickel alloys and copper metal AA;F;L AA or AE;F;I 951440 1 9612 8 8 3 Au Au-Ag jewellery alloys B Steels XRF;-;S MS;ICP;L 9513504 9513557 Steel 9513785 B AA;F;L B Steels AE;MIP;L 9612801 B Cobal t-based alloys AA;ETA;L 9612975 Samples (30 mg) mixed with 2.5-3.0 ml aqua regia at room temperature for 1 h; heated in a water-bath (70 "C) mixed with 0.2% HNO and diluted to 20 ml.A 5 ml aliquot was mixed with 1.5 ml 20 g 1-' Ni and diluted to 10 ml. 10 pl aliquot plus 20 p1 2000 mg 1- ' Zr injected into atomizer. (RSD 3.3%) Alloy samples (100-300 mg) dissolved in 6 mol I - ' HCl and then diluted to 50ml with water. Aliquots of 10 pl were mixed with 10 p1 of a o-phenanthroline solution dried at 110 "C loaded into tungsten boat furnace and 15 p1 0.9 mol 1-' ethylmagnesium bromide in THF added prior to vaporization into ICP.(LOD 1.1 pg) Comparison between flame and hydride generation with and without a slotted tube atom trap Samples (1 g) dissolved in 25 ml HF-HN03-H20 (1 1 1) and diluted to 100 ml. Aliquots (0.5 ml) mixed with 0.1 ml Ni-Hf solution ( 15 2 m/v) and 0.15 ml 25% tartaric acid. (Detection limit 1 Pgl-') Be Aluminium-based alloys AE;ICP;L 961302 Bi Copper-based alloys AA;F;L AA;ETA;L 9514261 9514696 Bi Nickel-based alloys and steels Journal of Analytical Atomic Spectrometry December 1996 Vol. 11 463RTable 1 (continued) Element Matrix Bi Zinc metal Cd Cobalt Cd Zinc and zinc alloys c o Steels c o Zircalo y Cr Aluminium c u c u c u Ge Zinc and zinc alloys Zinc and zinc alloys Tungsten alloys Low-alloy steel Zinc and zinc alloys Technique; atomization; analyte form* Sample treatment/comments Reference AA;ETA;L AA;F;L 9513386 95 13425 AA;F;L MS;ICP;S AE;ICP;L 9611280 9612352 9611433 MS;ICP;L Sample dissolved in 7 mol 1-' HN03 and evaporated to near dryness.Residue re-dissolved in 0.5 mol 1-' HNO and injected into a carrier stream of 0.1 moll-' KI onto anion-exchange mini-column. Analytes eluted with 2 mol 1-' HNO directly into ICP-MS. Calibration linear to 10 ng ml-' and detection limit 0.014 ng ml-' Sample (0.1 g) dissolved by heating with 10 ml 50% HNO and diluted. A 20 pl aliquot injected into the atomizer dried and atomized (without pyrolysis). Precision varied between 1 and 7% Samples (1 g) dissolved in boiling H2S04-HN03 cooled mixed with 10 ml urea (10 g 1-') diluted to 100 ml and mixed with 3 ml NaI solution (750 g 1-I).Resulting solution extracted with 25 ml tri-n-octylamine (10 ml 1-') in n-butyl acetate and analysed by AAS. (Concentration range 0.0001-0.02 m/m Cd) Sample solution (500 pl) injected into flow injection manifold and mixed with an acetylacetone-buffer solution at 1.5 ml min-'. Precipitated Co-acetylacetone was collected on in-line filter and dissolved with 80 pl MIBK and passed directly to the spectrometer. Precision was 2.5% (RSD) for concentrations < 25 ng ml-' Pulsed Nd YAG laser (1064 nm) operated at 150 mJ with sampling depth of 12 mm for LA-ICP-MS. Good agreement reported for analysis of reference materials. (RSD 1.5%) .Aliquots (10 pl) of dissolved sample and 10 pl of 8-hydroxyquinolinate (0.10 mol 1- ') mixed dried in a tungsten cuvette and loaded into a tungsten boat furnace.Sample vaporized at 950 "C into ICP torch. Results agreed with certified Cr concentrations for standard reference samples. (RSD 4.6% for 2.5 ng Cr) ;Samples (2 g) boiled in 35 ml H2S04-HN03 cooled mixed with 10ml l o g 1-' urea diluted to 100ml and mixed with 3 ml NaI (750 g 1-I). Cu was extracted using 15 ml tri-n-octylamine (10 ml 1-') in n-butyl acetate. Concentration range was 0.0001-0.0025% m/m Cu. Results from inter-laboratory comparison given diluted to 100 ml with water. Analysis followed further 10 fold dilution with water. Applicable to concentration range 0.25-1.25% m/m Cu. Results from inter-laboratory comparison given !Samples (3 g) dissolved in 10 ml of 50% HCl and Co internal standard added.Solution was decanted from undissolved tungsten powder which was then washed with water. The solutions and washes were combined and diluted to 25 ml. Aliquots of 400 pl absorbed on a piece of filter-paper dried and analysed by XRF. Samples (0.2 g) dissolved in 5 ml aqua regia diluted to 100ml with 1 mol 1-' HNOJ and filtered. A 1 ml aliquot was injected into hydride generator (1% NaBH and a carrier of H3P04 and L- cysteine). Volatile Ge hydride was collected in situ on heated Zr coated graphite tube or platform. (RSD 2% at 1 pg 1-I; LOD 9-18 pg) Samples (0.5 g) dissolved in 20 ml HC1 and 1 ml H202 then diluted to 200 ml with water and analysed by AAS at 285.2 nm using an N,O-C2H2 flame. Method is applicable to Mg concentrations of 0.002-0.1% and can tolerate up 5% A1 content.Results from an inter-laboratory comparison presented 9611309 Samples (1 g) boiled in 60 ml 50% HN03 and AA;F;L 95 13422 AA;F;L XRF;-;L 9513423 9612926 A A;ETA; L 96/29 1 AA;F;L 9513420 464R Journal of Analytical Atomic Spectrometry December 1996 Vol. 1 1Table 1 (continued) Technique; atomization; analyte form* Element Matrix Sample t reatmen tlcommen ts Reference Mn Copper alloys AA;F;L Chips millings or turnings (0.75 g) dissolved in 10 ml HN03 and 0.5 ml HF mixed with 10 ml H3BO3 (30 g 1-') and diluted to volume with water. Mn in resulting solutions determined by AAS at 279.48 and at 403.08 nm for Mn < 3% and Mn > 3% respectively. Results from inter-laboratory comparison given 9513427 As for Co. Precision was 7% (RSD) Comparison of results from 6 laboratories Alloy chips 0.5 g (or 1.0 g) wetted with 10 ml (or 20 ml) water then 40 ml (or 20 ml) of 50% HC1 added.Dissolution began cold then 10 (or 5 ) drops conc. HNO added and solution boiled for 1-2 min. After cooling samples were made up to 100 ml. Standard additions used to verify Ni concentrations None Cs'primary ion beam used for the local quantification of surface oxygen Sample reacted with ethanol treated with 50% H2S04 and evaporated to near dryness. Residue dissolved in water and mixed with 2 mol 1- ' H2S04-0.2 mol 1-' Na2Mo04-0.1 mmol 1-' malachite green and diethyl ether. Total P and As were determined by measuring the Mo in organic phase. P alone determined by including 2 mmol 1-' Na2S20 As for Cd. Determination by AAS with 283.3 and 217.0 nm for 0.0001-0.005% and 0.005-0.03% Pb respectively Copper alloys dissolved in HNO and HF and mixed with H$O3.Solution diluted to volume with water and analysed by AAS at 217.0 and 283.3 nm for 0.0001-0.005% and 0.005-0.03Y0 Pb respectively. Results from inter-laboratory comparison given HN03-HF-HC104. Residue (containing Pb) dissolved in 5 ml 50% HNO and diluted to volume with water. Precision and recoveries were 2.6% (RSD) and 101-106% respectively Aluminium matrix dissolved with As for Ag Iron matrix was removed by solvent extraction with 4-methylpentan-2-one. Samples analysed using ETV-ICP-MS with calibration using isotope dilution. RSD was 10% at 2 pg g-' and detection limit 0.05 pg g-' Samples cut to fit into sample chamber (filled with N2).RSD 5% for S concentration >0.05% Dissolved samples treated with 0.1 YO L-cysteine in 0.5 mol 1-' HCl to convert Sb" to Sb"'. Discreet samples injected into continuous flow hydride generation system with detection by AFS. Calibration was linear to 1 pg ml-' and detection limit was 22 pg ml-' Large excess of copper acted as matrix modifier for determination of Sb Selenium hydride generated from dissolved sample and preconcentrated within a palladium coated graphite tube. Precision was 5.4-6.1 YO (RSD) and recoveries 97-1 10% concentrations (up to 8000 mg 1-') of Ni2+ and Co2+ masked by EDTA or DTPA. Tartarate was an effective masking agent for up to 5000 mg 1-' for Fe3+ and Cr3+. (Detection limits 0.1 pg g-' for nickel and 0.3 pg g-' for steel) Comparison between between AA and ICP-AES for determination of Se using hydride generation.The detection limit was lower by 1.5-3 times when ICP-AES was used Analysis using hydride generation with high AA or AE;F or 1CP;L Mo N Ni Zircalo y Steels Magnesium alloy MS;ICP;S AA;F;L AE;-;S 9612352 9611099 9513428 0 0 Steel Titanium XRF;-;S S1MS;S 961624 96/23 16 P Caesium AA;F;L 9514401 Pb Pb Zinc and zinc alloys Copper alloys AA;F;L AA;F;L 9513424 9513426 Pb Aluminium AA;ETA;L 9514561 Pt S Au-Ag jewellery alloys S tee1 XRF;-;S MS;ICP;L 9513504 9612805 S Sb AE;laser;S AF;F;L 96/28 13 961274 Sb Se Copper Nickel-based alloys AA;ETA;L AAETA;L 9611079 9513382 Se Nickel and steel AAF;L 9514699 Se Nickel and steel 95/4700 Journal of Analytical Atomic Spectrometry December 1996 Vol.11 465RTable 1 (continued) Technique; atomization; analyte form* Sample treatment/comments Reference Element Matrix Se Steels and nickel based A A;ETA;L alloys Variety of dissolution schemes presented for one 96/59 gram sample depending on other metals in sample. Se was precipitated by adding 2-3 g ascorbic acid and 5 ml 0.6 g 1-' Pd. Precipitated Se was dissolved in HNO,-HCl then diluted to 10 ml for analysis. Ascorbic acid (3%) was used as a matrix modifier. RSD was 0.8% Samples (0.05 g) dissolved in 4 ml aqua regia then diluted to 25 ml with water. Aliquot treated with 2.5 mg La and 1 mg Ca then made up to 5 ml with water. Detection limit was 2.3 pg g-' Samples dissolved in HCl cooled and filtered. Filtrate mixed with acsorbic acid and KI diluted and then Sn extracted using 10 ml trioctylphosphine oxide (50 g 1-') in IBMK.Analysis by AAS at 235.5 nm using an N,0-C2H2 flame. Inter-laboratory comparison data reported ;Samples (0.05 g) dissolved with 4 ml aqua regia and 0.5 ml HF. Residue boiled with 5 ml 6 mol 1-' HC! for 40 min and diluted to 5 ml with water. Solution diluted 5 fold and reacted with stream of 10% KBH,. Generated hydride preconcentrated in situ onto Pd-coated graphite tube at 200 "C. (Linear calibration to 1.5 ng ml-') .4s for Se; (RSD 1.4%) Si Sn High temperature alloys Iron and steels AA;ETA;L 9513632 9514470 . _ AA;F;L Nickel-based alloys AA;ETA;L 9513637 Te Te Steels and nickel based alloys Zinc metal Nickel alloys and copper metal Tungsten alloys A A;ETA;L 96/59 MS;ICP;L AA or AE;F;L ,4s for Bi.(Detection limit 0.16 ng ml-' ) '4s for As 9611309 9612883 Te Te XR F;-;L '4s for Cu. Calibration linear from 1-3%. (RSD 2.6 1 YO and recovery 99.76%) Zn in dissolved sample reacted with 4-( 2-pyridylazo)resoricinal (PAR). The Zn-PAR complex anion was adsorbed onto trioctylmethylammonium-bromate ion-pair material supported on biphenyl and then dissolved in DMF Sample solutions made with Be T1 and Rh internal standards. Discreet volumes were introduced into ICP using flow injection manifold. (RSD < 3 YO for analyte concentrations > 1 pg ml- ') Samples (5 g) dissolved in 9 mol 1-' HCl evaporated to near dryness then re-dissolved in 50 ml 2 mol I-' HCI. Aliquot (170 pl) passed through anion-exchange column (BIORAD AGl-X8) where Zn was retained and analytes passed directly to ICP-MS.(RSD <5% RSD for 10 ng ml-' concentrations) 7 ml 4.8% thiourea added and then solution heated cooled and filtered. Nitric acid (10 ml) was added to the filtrate and then heated until SO3 appeared. Samples diluted to 100 ml with water prior to analysis. (LODs <0.1 pg g-') Etched selenium dissolved in 80 ml 2 mol 1 - ' HCI Direct analysis of tungsten filaments None Direct sample analysis. (Detection limits about 10 pg g-' for most analytes) Sample surface polished with diamond lapping disc and solid material transferred onto the disc was analysed directly using LA-ICP-MS. (RSD < 10% for elements in reference materials and detection limits 1-10 pg g-') Solid samples analysed with minimal sample preparation. (Detection limits 20 10 and 1 pg g- ' and RSD 4 7 and 3% for Fe Ni and Ag respectively) 2-3 orders of magnitude.Analyte signal ratioed to spectral background (RSDs 1% and 5% for short- and long-term respectively) Direct solid analysis. Calibration curves linear over 9612926 Te AA;F;L 95/38 13 Zn Aluminum alloys Various ( 15) Unalloyed steels MS;ICP;L 9513056 Various ( 5 ) High purity zinc MS;ICP;L 9513531 Various (10) High purity selenium MS;ICP;L 9513532 Various (7) Tungsten Various (10) Steel Various (4) Aluminium MS;GD;S AE;!aser;S XRF-;S 9513572 9 513 8 7 7 95/3880 MS;ICP;S 95/4173 Various ( 8 ) Steels Various (3) Copper alloys AE;laser;S 9514182 Various Precious metals AE;GD;S 9514347 466R Journal of Analytical Atomic Spectrometry December 19.96 Vol. I ITable 1 (continued) Element Matrix Various Zircalo ys Various (4) NdFeB permanent magnet alloy Technique; atomization; analyte form* Sample treatment/comments Reference AE;ICP;L 9514530 Various Molybdenum and A A;ETA;S molybdenum silicide Various (4) Gold/silver fire assay beads MS;ICP;S Various Low-alloyed steels MS;ICP;S Various ( 5 ) Furnace slag and roaster XRF;-;S feed Various (4) Ferro-alloys Various ( 5 ) Crudely refined gold Various (4) Steels Various Copper Various (5) High-purity iron Various Scandium Various Gold Various Aluminium Various Ferromolybdenum and ferroniobium Various (23) Tungsten XRF;-;S AE;ICP;L AE;laser;S XRF;-;L MS;ICP;L MS;ICP;L MS;ICP;S Various XRF;-;S AE;ICP;L MS;ICP;L Dissolved samples (by HN0,-HF) pH adjusted to 951449 1 1.5-2 then extracted with 50% bis- (2-ethylhexyl)orthophosphoric acid in toluene.The organic phase with Zr was further extracted with 6 mol I-' HNO and dioctyl alcohol and all aqueous phases were analysed for trace elements. Isotope dilution was used for calibration Sample (3 g) dissolved in 15 ml 3 mol 1-' HCl and a few drops of HNO then heated till HNO fuming stopped. Nd determined by direct nebulization. Rare-earth elements (Sm Pr Ce and La) determined after preconcentrating on a column of sulfopropyl SI-100 and gradient elution with 0.06-0.19 mol 1-' a-hydroxyisobutyric acid Powdered samples weighed directly into either graphite cup or a boat/platform then placed into the atomizer Trace elements preconcentrated in fire assay beads from geological samples and spark sampled in a specially designed solid-sampling cell.Signal precision from continous sampling of 5 replicates was <6% (RSD). Applicable to metal analysis Solid sampling by spark ablation. (Detection limits 0.08-0.32 pg g-' with 58Fe internal standard) Samples dissolved in lithium tetraborate flux containing oxidizing agent and set in platinum-gold crucibles. Fused glass discslbeads presented to spectrometer for analysis Samples fused with lithium tetraborate and lithium carbonate to form glass discs/beads Samples (0.25 g) heated in 5 ml of HNO cooled 20 ml HC1 was added and then re-heated (process repeated until samples fully dissolved). Aliquots (500 p1) injected into water carrier stream using flow injection system. LODs were <0.7 pg ml-' (or <0.08% m/m). Depth profiling studied using laser-induced plasma emission spectrometry.Precision of 3.5% RSD reported for Zn-Ni coatings (2.7-7.2 pm) and for Sn coatings (0.38-1.48 pm). Thin coating of Cr (20 nm) also detected. (Analysis time was reported to be <60s) Portions ( 5 pl) of dissolved copper samples placed on quartz plate and evaporated. Spectra taken before and after irradiation with spallation neutrons (< 700 MeV) or monoenergetic protons (590 MeV). Difference spectra (irradiated versus non- irradiated) analysed for peak areas Aliquot (200 pl) of dissolved sample (50 mg ml-' in 2 mol 1-' HF) loaded onto anion-exchange column (Dowex 1x8-100). Analytes eluted from column with 200 pl of solution consisting of 0.7 mol 1-' HNO,-0.5 mol 1-' HC1-0.05% HzO bis( 2-ethylhexy1)orthophosphate in toluene leaving analytes in the aqueous phase Solid sampling by laser ablation (Nd YAG) with calibration using gold reference materials.Detection limits were ~ 0 . 1 8 pg g-'. Crudely refined gold from different geological sites could be differentiated using unique elemental fingerprint HGAAS for determination of various elements. Results from a round-robin survey presented Samples prepared by re-melting with iron (15 g FeMo alloy+25 g iron and 12 g FeNb+28 g iron). Calibration standards prepared either by re-melting pure metals with iron or by re-melting a known ferro-alloy with iron. (RSD <O.6%) and HNO,. Line selection and spectral interferences studied. (Average precision 1 % RSD) Scandium extracted into Comparison of ICP-AES FAAS ETAAS and Samples dissolved by microwave dissolution in HF 9514594 9514595 9514708 961355 96/407 961417 96/1039 9611 223 9611 503 9611 573 9611723 96/1811 9612653 9612889 Journal of Analytical Atomic Spectrometry December 1996 Vol.11 467 RTable 1 (continued) Element Various (4) Zinc Various ( 7 ) Steels Matrix Technique; atomization; analyte form* Sample trea tmen t/commen ts Reference AE;ICP;L 9612906 AE;ICP;L Zinc dissolved in HNO taken to dryness and 96/2891 dissolved in dilute KI-HNO,. Solution passed through column packed with BIORAD AGl-X8 anion-exchange resin. Analytes eluted with 3 mol 1-' HNO evaporated to dryness and then re-dissolved in 5 ml HNO heated to dryness with HClO,. Residue taken up in 50% HCl and then 1% benzophenylhydroxylamine in IBMK used to extract interfering species into organic phase Rare- earth analytes remained in aqueous phase for analysis Steel (3 g) dissolved with HC1-HN03-HF and * HG indicates hydride generation and S L G and SL signify solid liquid gaseous or slurry sample introduction respectively.Other abbreviations are listed elsewhere. was used for ICP-MS determination of 15 elements in unal- loyed steel samples (95/3056). Chloride interferences were eliminated by sample dissolution in nitric acid using high pressure (closed vessel) microwave dissolution. Elements were accurately determined in reference material samples with Cali- bration solutions that contained only 2% (m/v) HNO and Be TI and Rh used as internal standards. The forward power of the plasma was adjusted to 1.5 kW and the nebulizer flow rate was optimized at 1.1 ml min-' for this analysis.Different sample introduction systems were used with ICP- MS. Spark ablation (SA) ICP-MS was used for determining Al B Co Mn Nb P Sb Si V and Zr in low-alloyed steels (95/4708). The spark generated aerosol particles passed through a newly designed cyclone chamber which was reported to deliver more uniform sized particles (< 1.0 pm) to the plasma. Calibration was effected with solid steel reference materials and 58Fe was used as an internal standard. Low detection limits were reported (<0.3 pg g-' for most elements except Si B and P) and the precision at 10 times the LOD was <2.5% RSD. A comparison was made between SA-ICP-MS and GD-MS with the same mass detector (95/4596). It was reported that shorter analysis times were obtained by the spark ablation system whereas the glow discharge system had lower detection limits. Sulfur in steel was determined by ETV-ICP-MS.Matrix components greatly affected the analyte signal (96/2805). This was overcome by the use of isotope dilution calibration and the removal of Fe (the major matrix component) by solvent extraction with 4-methylpentan-2-one. A precision of 10% (RSD) at S levels of 2 pg g-' was reported and the LOD was estimated to be 0.05 pg g-'. Hydride generation-electrothermal atomization atomic spec- trometry (HG-ETAAS) was applied to the determination of germanium in low alloy-steel (96/291). Volatile elements were also determined in steels and nickel alloys by directly inserting solid samples into a conventional atomizer for determination by ETAAS (96/C712). Aqueous calibration was successful for the determination of Pb and Bi.Incomplete analyte release required that solid reference material pieces be used for the determination of Sn and Se. A less common approach was taken in determining trace elements in steels by synchrotron XRF (95/3877) focused on a 1 mm2 spot on the sample surface. The results were reported to be in agreement with values obtained by PIXE. Calcium in steel was determined by secondary-ion mass spectrometry (SIMS) in an area of 500 x 700 pm2 (95/3887). This appears to be a good semi-quantitative tool with the limit of detection estimated to be 0.5 pg g-'. Papers using FAAS and XRF 468 R Journal of Analytical Atomic Spectrometry December mainly focused on sample preparation and are summarized in Table 1.1.2. Non-Ferrous Metals and Alloys A considerable number of abstracts appeared in the literature during this review period dealing with different spectrometric methods for the analysis of a wide variety of non-ferrous metals. The majority of papers deal with innovations in sample preparation prior to spectrometric analysis and are summar- ized in Table 1. In general there has been a sustained interest in the development of direct solid sample analysis for metal samples especially for pure metals and precious metal alloys. An overview (95/3800) of laser-induced breakdown spec- trometry (LIBS) was given with respect to the quantitative determination of metal alloy components in solid samples. Elements in aluminium were determined by LIBS using two different experimental procedures (96/1078).The emission from the aluminium matrix was used as an internal reference for elements whose emission lines are in close proximity to the matrix emission wavelength (such as Mg and Mn). However for elements such as Ti the background emission intensity was taken as a reference emission because there are no aluminium emission wavelengths in the spectral region of the required Ti wavelength. A report of time-resolved LIBS was published (95/4180) in which a plasma was formed by using a low energy (10 mJ 10 ns) Q-switched Nd YAG laser in atmospheric air. Au Ag and Cu were determined in jewel etalons by measuring the intensity ratios Cu:Ag Ag:Au and Cu:Au at different wavelengths for alloys of known composition.Ratioing is required because the amount of material ablated by each laser pulse varies considerably. The application of low energy laser pulses minimized the amount of material taken from the sample. In another report quantitative analyses and plasma characteristics were studied for the determination of trace elements in aluminium and copper matrices with LODs observed in the order of 1Opgg-' for most elements (95/3880 95/4182). Solid sampling from a glow discharge for either atomic emission spectrometry (GD-AES) or mass spectrometry (GD-MS) was the focus of a number of abstracts. A novel sampling system has been developed which permits elemental mapping by GD-AES of a solid surface (many tens of square centimeters) at one time (96/647). This was accomplished by sustaining multiple discharges simultaneously over a Macor restrictor plate with sampling holes set in at regular intervals (in a grid pattern).Emissions were selectively multiplexed by Hadamard spatial transform imaging and sorted out by a 1996 Vol. 11matrix multiplication process. Trace elements in a variety of precious metal samples (Au Pt Ag and sterling Ag) have been determined by radiofrequency GD-AES (95/4347). A signifi- cant feature of this work was that the analyte signal intensity was ratioed with the spectral background adjacent to the analytical wavelength. Detection limits were in the range of tens of ppb and were considerably lower than other direct solid sample spectrometric methods. An alternative detection scheme for GD-MS was presented (96/C2044) whereby sec- ondary mass species such as M2+ MAr+ and M2+ were used for element determination which may be useful in overcoming isobaric interferences and gaining more useful informa- tion from the sample.Relative errors in the range of' 15% were shown for element concentrations greater than 1% in aluminum reference materials. The determination of elements in gold by LA-ICP-MS was shown to be quite successful (LOD <0.18 ppm) provided one has adequate reference materials for calibration (96/1733). It was also determined that semi-quantitative elemental linger- prints of crudely refined gold hold sufficient information to distinguish between samples originating from different mines. A special device has been constructed for solid sampling of fire assay beads (gold/silver alloys) by SA-ICP-MS (95/4595).For samples containing 100ppm of Pt Pd Rh and Ir good precision was reported (3-6% RSD). The accuracy of the method was verified with fire assay beads prepared from a geological reference material and LODs varied from 0.6-1.2 ppm. This device appears to have potential in determin- ing trace elements in small samples of precious metals in general. A comparison was made between SA-ICP-AES and LA-ICP-MS for determining trace elements in fine gold and silver for assaying purposes (95/4574). Better LODs were obtained by LA-ICP-MS for most elements (except Fe Mn and Zn). However SA-ICP-AES was preferred due to ease of operation long term stability high sample throughput and relative flexibility in sample shape and size.Flow injection ICP-MS was applied to the determination of a variety of elements in high purity zinc (95/3531 96/1309) whereby a discrete volume of the dissolved sample was passed through an anion-exchange column then eluted directly into the ICP-MS instrument. It has been shown that polyatomic ion interferences in ICP-MS arising from the presence of chloride ions from the dissolution of gold in aqua regia can be overcome by dissolving the gold using hydrobromic iicid in place of hydrochloric acid (96/C2215) and by flow injection hydride generation ICP-MS whereby the analytes are separ- ated from the chloride containing solution (96/C762). A direct flow injection manifold was used in conjunction with ZCP-AES for the determination of base metals in crudely rejined gold (96/417).Concentrated hydrochloric acid was required to maintain high levels of silver in solution. The flow injection manifold was used to minimize the total amount of acid introduced into the nebulizer system and a vented sample introduction hood was designed to isolate the spectrometer and peristaltic pump from corrosive fumes from the samples. Chromium was determined in aluminium by complexation with 8-hydroxyquinolinate and vaporized via a heated tungsten cuvette for determination by ICP-AES (96/1433). In this case the dissolved aluminium matrix appears to be acting as a carrier for the vaporized chromium thereby improving sensi- tivity and slightly lowering the absolute LOD (0.05 ng) in comparison with the absence of the matrix.A solution/suspen- sion of metal samples was made by laser probe sampling of a metal immersed in a reagent solution and then analysed by ICP-AES (96/C918). This was reported to be applicable to a flow injection system. A report of elemental jingerprinring by spark excitation AES (96/1299) claims that information on microhomogeniety and production technology can be gained from interpretation of the data. A method for determining components in a metal melt for process control was developed using wavelength dispersive X - ray spectrometry (96/598). The spectrometer was designed for this industrial environment and was reported to significantly reduce the time of analysis. An iteration equation (95/3400) was designed for calculation of elements in a sample by standardless wavelength dispersive XRF and was applied to the analysis of an aluminium alloy.A review (182 references) of different XRF analysis techniques and applications in a variety of sample types was published (95/4529). The majority of abstracts involving atomic absorption spec- trometry tend to discuss sample preparation and are summar- ized in Table 1. However some novel approaches warrant mention. Arsenic in cadmium was determined by ETAAS with the bulk of the cadmium distilled off under vacuum prior to dissolution (95/343 1). Apparently the As loss was negligible during dissolution. Trace impurities in molybdenum and mol- ybdenum silicide were determined by direct weighing solid sample ETAAS with different atomizer types (95/4594).The LODs were reported to be at the sub-ngg-' level and the determined values were in agreement with values from solution sample preparation. Solid samples (96/C238) were also intro- duced into a graphite furnace by deposition of the particle aerosol generated by laser ablation of metal samples with subsequent determination by ETAAS. Phosphorus was deter- mined indirectly in caesium by FAAS after an elaborate sample preparation ending with determination of Mo from a molybdo- phosphate complex (95/4401). The recoveries for P were reported to be 95-103%. Work with the slotted tube atom trap (STAT) continued from the last review period (95/4261). The determination of Bi in copper-based alloys was compared with/without STAT for nebulized solutions and for hydride generation.The application of STAT generally increased sensi- tivity and lowered the detection limit by a factor of two. There were some interesting abstracts in this review period involving less common methods. Oxygen in titanium was reported to be quantitatively determined in a localized area by SIMS using Cs+ as the primary ion and l60- 64TiO- and 96Ti2- as the secondary ions (96/2316). Atomic fluores- cence spectrometry was used to determine Sb in copper with continuous flow hydride generation (96/274). Precision was 1.2% (RSD) for Sb at 5 ng ml-I and the reported LOD was 22 pg ml-'. Precious metals in silver were determined with ETA laser induced fluorescence (96/C25 1 ). Of special note were two articles which compared various spectrometric methods (and other types).One was a review for determination of precious metals (96/2992) in various samples (785 references). The other compared the determination oftrace elements in aluminium by ICP-AES FAAS and ETAAS (96/1811) for the certification of reference materials. The results of a round-robin survey were also discussed. 2. CHEMICALS 2.1. Petroleum and Petroleum Products This section of the review covers analysis of crude oil and fractions refinery feedstocks and products fuels and lubricants. Also included are analyses of some inorganic materials (e.g. fluid inclusions and environmental samples) where these are clearly related to oil exploration refinery operations or the use of petroleum products. A summary of the literature for the review period is given in Table 2.2.1.1. Crude oil and fractions In the field of oil exploration and production an understanding of reservoir diagenesis is as important as a knowledge of the over-all physical structure of the reservoir itself. In order to gain an understanding of reservoir history source maturity and generation potential and oil/source rock correlations Journal of Analytical Atomic Spectrometry December 1996 Vol. 11 469RTable 2 SUMMARY OF ANALYSIS OF CHEMICALS Technique; atomization; Element Matrix analyte form* PETROLEUM AND PETROLEUM PRODUCTS- A1 Lubricating oil MS;ICP;L Sample treatment/comments Reference 9612342 961C2294 961C2834 9513568 9611 025 9611540 9611726 96/29 7 8 ETV sample introduction used to obviate oxygen addition to plasma and reduce molecular ion interferences originating from organic matrix Direct Injection Nebulizer (DIN) used to eliminate problems due to selective volatilization.(Detection limits ~ 2 0 0 0 and 0.011 ppb for AES and MS respectively) Direct Injection Nebulizer (DIN) used to eliminate problems due to selective volatilization ,Stable C isotopic analysis of bulk and alkane fractions of Eldfisk crude oils-showed evidence for at least two phases of reservoir filling Performance and optimization of combustion interface for isotopic ratio monitoring GC-MS ICarbon and nitrogen isotopic ratios measured by coupling microanalyser with mass spectrometer. (Standard error of 0.2% reported based on > 1000 analyses) GC-isotopic ratio MS used to study compositional fractionation between extractable and covalently bound aliphatic hydrocarbons in source rocks Sample (10 g) ignited ashed at 900 "C (3 h) and residue dissolved in 20 ml 6 mol 1- ' HC1.Resulting solution concentrated to about 5 ml (water-bath) 6 ml La"' or Sr" solution (10 mg g-') added and mixture diluted to 20 ml with H,O Sample combusted in propane-air flame in presence of Cu. Measurement of CuCl molecular emission allowed specific determination of organochlorine compounds (ionic C1 compounds did not give emission signal) fluoride optics used to measure VUV C1 lines at 134.724 138.969 and 138.957 nm Recent developments in ICP optics allowed measurement using VUV lines (< 190 nm) !Spectrometer with patented nitrogen purge system permitted use of VUV wavelengths down to 120 nm. (Limit of detection for C1 in oil < 1 ppm) Samples analysed directly by XRF after 5-fold dilution in mineral spirits and presentation to spectrometer as thin film (to eliminate problems with particulate settling.) Comparison with XRF and ion chromatography results after combustion of sample in oxygen bomb Samples analysed directly using He purged spectrometer 110 fold dilution with tetralin containing 5 mg kg-' Sc internal standard [Detection limit 5 ng kg-l; RSD < 1 % (short term) and <2% (long term) at 1 mg kg-'1 Ntrogen purged spectrometer with magnesium As for A1 Mercury species trapped on Au-Pt wire and then Hg thermally desorbed and measured using CVAAS. Quantitative recoveries for Hgo and (CH3),Hg if collector heated to 8 0 T sampling rates < 2 1 min-' and sample volumes at least 10 1.(Detection limit 30 ng m-3) AES and MS respectively) As for arsenic (detection limits 20 and 0.011 ppb for As for Arsenic Sample (0.5-1 g) dissolved in 50 ml xylene (50 "C) transferred to extraction unit and boiled with 25 ml conc. HC1 for 15 min. Acid fraction was drained off combined with washings and made up to 100 ml with HzO prior to analysis by AAS at 670.8 nm A s for A1 A s for Ca A s for C A s for Fe [detection limit 12 ng kg-'; RSD < 1% (short term) and <2% long term) at 1 mg kg-'1 As Naphtha AE or MS;ICP;L As Refinery products AE or MS;ICP;L C Crude oil MS;-;L C Various C Various C Petroleum source rocks Ca Lubricating oil MS;-;S AA;F;L AE;F;L c1 Lubricating oil 9514468 c1 Waste oil AEP;ICP;L 96/C730 c1 Feedstocks and products CI Lubricating oil AE;ICP;L AE;ICP;L 961C2195 961C2196 c1 Waste oil XRF;-;L 9612644 F Fe Oils and greases XRF;-;L AE;ICP;L 9615 19 961380 Fuel; lubricating oil; crude oil Fe Hg Lubricating oil Natural gas MS;ICP;L AA;CV;G 9612342 9514694 Naphtha AE or MS;ICP;L 96 jC2294 Hg Li Refinery products Lubricating greases AES or MS;ICP;L AA;F;L 961C2834 961324 Mg Mg N Ni Lubricating oil Lubricating oil Various Fuel; lubricating oil; crude oil MS;ICP;L AA;F;L AE;ICP;L MS;-;L 9612342 9 6/29 7 8 9611540 961380 470 R Journal of Anahtical Atomic Svectrometrv.December 1996. Vol. 11Table 2 (continued) Technique; atomization; Element Matrix analyte for,m* PETROLEUM AND PETROLEUM PRODUCTS- Ni Oil; asphaltene; bitumen X RF;-; L Hg Naphtha P Refinery products Pb Gasoline AE or MS;ICP;L AES or MS;ICP;L AE;ICPL Pb Roadside soils AA;F;L Pb Gasoline AE;F;L S Petroleum products XRF;-;L S Petroleum products XRF;-;L S Waste oil XRF;-;L or AE1CP;L Se Refinery waste waters MS;ICP;L V Fuel; lubricating oil; crude AE;ICP;L oil V Oil; asphaltene; bitumen XRF;-;L Zn Lubricating oil AA;F;L Various Fuel oil MS;ICP;L Various Lubricating oil (wear metals) Various Used oil Various (10) Heavy oil Various Lubricating oil Various Oil and wax Various (11) Crude oil AE;ICP;L XRF;-;L AA;ETA or CV;L AA;F;L and/c,r AE;ICP;L AE;ICP;L MS;ICP;L or NAA;-;L Sample treatment/comments Internal standard solution (1 ml 40 pg ml-' Pb in chloroform) added to sample (0.01-0.02 g) and resulting solution pipetted onto mylar film and dried prior to determination of Ni and V using EDXRF.(Detection limit 2 ppm; RSD 7%) As for arsenic (detection limits 300 and 0.34 ppb for AES and MS respectively) As for arsenic Emulsion prepared by vortex mixing sample with tetralin Triton X-100 and H,O (2 min) 3% iodine solution in toluene and 10% Aliquat 336 in decalin added with mixing ( 5 min) to decompose volatile Pb species. (Concentration range 0-10 mg kg-' Study of impact of emissions of Pb from gasoline Pb) engines on roadside soils. Samples homogenized dried and sieved prior to digestion using HCl-HNOJ (3 1) Determination of tetraethyllead in gasoline by gas chromatography with a surface emission flame photometric detector. (Detection limit 0.3 ng; RSD 0.7%) Mesurement based on ratio of sulfur X-ray fluorescence to X-ray scattering intensity.Simulated material consisting of Mo substrate and X-ray absorber used as standard Review (no refs) of XRF for on-line sulfur measurment in refinery processes and products As for C1 but comparison also with results obtained by oxygen bomb combustion followed by ICP- AES Total dissolved and particulate Se determined by digesting samples with H202 and HNO,. Selenite selenate and selenocyanate determined using ion chromatography coupled with ICP-MS (short term) and ~ 2 % long term) at 1 mg kg-'1 As for Fe [detection limit 2 ng kg-'; RSD < 1% As for Ni. (Detection limit = 5 ppm) As for Ca Sample (250 mg) heated with 7 ml 65% HNO and 3 ml 30% H202 in high pressure PTFE vessel using a 10-step microwave oven process cooled in a water-bath and then diluted to 25 ml.(Detection limits for most elements in range 0.02-0.2 mg kg - ') Samples diluted 1 100 or 1 10 with deodourized kerosene. (Limits of detection 0.002-0.07 mg 1- and RSD < 1% for integration time > 500 ms) Determination of Cd C1 Hg Pb S and T1 in used oil feedstocks for cement kilns. Calibrated using multielement standards prepared from organometallic compounds base oil and xylene As Cd Co Cr Cu Hg Mn Ni Pb and V determined using GFAAS or CVAAS after digesting sample with HN0,-H,SO,. Good recoveries for all elements except Hg (70%). (Detection limits 0.004-0.046 mg kg-') Sample ultrasonically treated with 5.5 mol I-' HCI and several drops H,02 for 15-20 min diluted with xylene or toluene and stirred at 60 to 70°C for 30 min. Aqueous phase analysed by AAS for Ca Cr Cu Fe Mn and Zn and ICP-AES for preceding elements plus P and S High temperature nebulizer used to introduce samples directly without solvent dilution.Applicable to most organic materials provided viscosity can be reduced to about 10 CP by heating Study of contribution of formation water produced water drilling fluid and rocks to trace element concentration of a range of exploration samples. Highlighted importance of washing and filtering oils prior to analysis if appropriate oils are to be correlated with each other Journal of Analytical Atomic Spectrometry December 1996 Vol. 11 Reference 961405 96/C2294 961C2834 9611430 9611979 9612902 96/52 1 9611208 9612644 96/C2276 961380 961405 9612978 951373 1 9513839 95lC420 1 9514262 9514495 961C203 961336 471 RTable 2 (continued) Technique; atomization; Element Matrix analyte form* PETROLEUM AND PETROLEUM PRODUCTS- Various Various Synthetic lubricating oils AE;ICP;L (additive elements) Various Vehicle exhaust particulates MS;ICP;L Various Crude oil/water emulsions AA;F;L Various Lubricating oil (additive elements) AE;ICP;L Various Crude oil AE;ICP;L Petroleum products XRF;-;L Viscosity of sample increased by chilling with liquid N or mixing with eicosane prior to forming into disc for analysis by pouring into central well (15 mm diameter x 1 mm deep) of A1 foil covered plastic disc prepared from poly-alpha olefins and trimethylol propane esters cf.standards prepared in mineral oil Airborne particulates collected with low-volume air sampler. Elements of interest (Cd Cu Ni Pb T1 and Zn) separated from interfering matrix elements by solvent extraction with dithizone 0.3 g alkylbenzenesulfonic acid and 15 ml ethanol ignited and heated with 1 ml HNO until brown vapour eliminated.Residue ashed at 550 "C and then cooled ash dissolved in 2 ml HCl-HNO (1 1) and diluted to 50 ml Study of effectiveness of methods for elimination of matrix effects caused by viscosity modifiers. Use of internal standard (Y) provided best alternative with errors reduced to f 2% relative (cf - 8% if no internal standard used) introduction of organic emulsified samples. Whereas emulsions of solvents such as xylene perturbed the plasma crude oil in water emulsions had similar effect to aqueous solutions I3DXRF used to assess effects of weathering (2 7 and 14 d outdoors) on trace element concentrations and ratios.Attempt made to assess applicability of V Ni ratio for passive tagging. (Concentration ranges 0.02-182 ppm) Study of matrix effects caused by synthetic oils Homogenized sample (3 g) heated for 30 min with Plasma diagnostics used to study effect of XRF-;L Ilolidification agent used for sample preparation Various (11) Crude oil Various Lubricating oil and grease ORGANIC CHEMICALS- A1 Commercial formulations As Dimeth ylarsenate XRF;-;L AA;FL AA;ETA; L As Sample treatment/comments As Organometallic compounds MS;ICP;L As Monomethylarsonic acid and MS;ICP;L dimethylarsenic acid As As As 472 R Methylarsonic acid and dimethylarsinic acid AA;F or ETA;L Wood preservatives AAF;L Monomethylarsonic acid and AF;F;L dimethylarsinic acid Organoarsenic compounds AA;ETA;L or AE;ICPL Determination of fosetyl A1 in commercial formulation 'Aliette'.Comparison with ion chromatographic method utilizing measurement of phosphonate anion HPLC with ETAAS for arsenic speciation studies. Total thermal cycle of 40 s feasible (15 s furnace cycle plus 25 s cooling time). Detection limits 5 8 and 15 ng ml-I for As"' As" and dimethylarsenate respectively Speciation of organoarsenic organoiron and organotin compounds using SFC-ICP-MS Speciation of above compounds plus As"' and As" using micellar liquid chromatography with ICP-MS. Samples containing protein could be injected without pre-treatment and no interference due to chloride was found. (Detection limits Automated thermospray interface used to couple 90-300 pg) Study of effects of mobile phase buffer composition and the presence of Na or Ni sulfate in the mobile phase on AS'" As" methylarsonic acid and dimethylarsinic acid retention times using Hamilton PRP-X100 anion exchange column.(Detection limit 10 ng) Sltudy of leaching of chromated copper arsenate preservatives from treated softwoods submerged in sea-water S'peciation of above compounds plus As"' and As" by HPLC using ultrasonic nebulization atomic fluorescence detection. (Concentration range 250-2500 ng As) Comparison of LC-HG-quartz cuvette AAS with LC-HG-ICP-AES for speciation of arsenite arsenate monomethylarsonate and dimethylarsinate in aqueous samples Journal of Analvtical Atomic Svectrometrv. December 1996. Vol. 1 1 Reference 96/41 1 961C728 961956 96/1300 96lC2231 9612468 9612559 9612640 9611945 9513459 9513561 9513610 9513653 95/3930 9514176 95/4386Table 2 (continued) Technique; atomization; analyte form* Element Matrix ORGANIC CHEMICALS- As Organometallics Sample treatmentfcomments Reference 951448 1 961104 961283 9611 103 9611637 961121 9514169 9611434 9513474 9611077 9611 7 13 9513938 9611495 9513479 9 514 1 69 95 j459 1 961640 9611077 9611 434 XRF;-;S Organometallic compounds preconcentrated from ground and waste water samples using Zr-loaded activated charcoal.Optimum pH 3-7. (Recoveries >98% for 1 mg 1-' analyte) Study of release of As Cr and Cu into rain water from wood treated with preservatives using ion exchange chromatography and ICP-AES Inorganic and organometallic As and Hg compounds separated using vesicle mediated HPLC and metals introduced to MIP by volatile species generation. (Detection limits 1-6 ng ml-' As) On-line UV photolysis used to decompose organoarsenic compounds prior to hydride generation in LC-HG-ICP-AES and LC-HG-quartz cuvette AAS SFC-ICP-MS used to determine five organometallic compounds containing As Hg and Sb.Limits of detection 2-3 orders of magnitude lower than with flame ionization detector (FID) Indirect method for determination of organophosphate pesticide malathion. Sample hydrolysed to form dimethyldithiophosphate complexed with Bi"' and extracted into IBMK. Bi determined using FAAS Wavelength double modulation diode laser AAS in modulated low pressure DCP or MIP used for element selective GC determination of haloforms (detection limit 45 pg Br) GC carried out on fused silica column coated with HP-5 with 2 ml min-' He carrier gas.Stationary phase burned off final 2 cm of column which was used as (350 kHz) plasma tube. Addition of 10-15 ml He make-up gas enhanced detection (4 pg s-') and reduced tailing Solid-phase microextractor consisting of silica fibre coated with polydimethylsiloxane used to adsorb pesticides from water. Trapped analytes thermally desorbed into GC-MIP-AES and determined using C and S emission lines. (Concentration range 2-200 pg 1-1) Study of responses for C C1 and 0 in a set of Combustion elemental analyser interfaced to IRMS phenolic compounds via ConFlo interface for measurement of C and N isotopic abundances on a single sample Determination of Ca in calcium carbonate coated tablets Capillary electrophoresis-ICP-MS used to separate metallothionein isoforms and ferritin.Detection limit 4 fg Cd (for 74 nl injections) determined in plasma and seal blubber using GC-MIP-AES after appropriate GPC-HPLC clean-up procedures (detection limits 0.22- 0.25 ng g-' for PCBs in plasma and 5 to 10 ng g-' for methylsulfonyl PCBs in seal bladder) CHC13 and CC14 and 0.01-100 ng ml-' for dichlorotetrafluoroethane using MIP. Corresponding ranges for the DCP were 1-loo00 and 0.1-loo00 ngml-') Determination of chlorinated organic compounds using graphite furnace to introduce samples to stabilized capacitively coupled He Plasma (SCP) Element selective detection of C1 in capillary GC by wavelength modulation diode laser AAS of excited metastable C1 atoms in an MIP. (Detection limits 1 mg I-' or 80 pg s-') PCBs and their methylsulfonyl metabolites As for Br (concentration ranges 1-5000 ng ml-' for As for C As for Br As Wood preservatives AE;ICPL As Organometallic compounds AE;MIP;L As Arsenobetaine and arsenocholine AE;ICP;L or A A;ETA;L As Organometallics MS;ICPL (Bi) Pesticides AA;F;L Br Haloforms AA;DCP or M1P;L Br Organic compounds AE;MIP;L C Pesticides AE;MIP;L C Phenols AE;MIPL C Organic compounds MS;-;L Ca Analgesic tablets Cd Ferri tin AA;F;L MS;ICP;L c1 PCBs and methylsulfonate AE;MIP;L metabolites c1 Haloforms AA;DCP or MIP;L Cl Methanol AE;SCPL c1 Halocarbons AA;MIPL c1 Phenols c1 Organic compounds AE;MIPL AE;MIP;L Joiirnal of Analytical Atomic Spectrometry December 1996 Vol.11 473RTable 2 (continued) Technique; atomization; analyte form* Sample treatment/comments Reference Element Matrix ORGANIC CHEMICALS- Anionic surfactants AA;F or ETA;L Indirect method for determination of sodium 9514057 dodecylsulfate in toothpaste liquid detergents and waste water by formation of ion pair with bis- (2-benzoy1pyridinethiosemicarbazone)coba1t"'. (Detection limit 18 mg 1-') As for arsenic 9513930 A s for arsenic 961104 Alkali extraction and acid digestion used for 961126 speciation and quantification of chromium species (CrV1 and total Cr) in chromated copper arsenate treated building timbers <:u nitrate and Cu citrate determined at different pH levels using ETAAS following a range of solid phase extraction procedures. Results compared with those predicted by NSPEC computer speciation program Indirect method for determination of nitroso and nitrophenols using solvent extraction of ionic associates involving bipyridylocopper(11) or phenanthrolinocopper(11) complexes.(Concentration range 0.01-0.1 mg 1-' nitrophenol) 9513454 A s for arsenic Indirect FI method for determination of dithiocarbamate fungicides (e.g. Ziram) based on IBMK extraction of complex with Cu". (Detection limit 0.07 pmol) 10% v/v HN03 filtered and then diluted to 50 ml with H,O. (Detection limit 0.2 mg kg-') A s for arsenic Indirect FI-AAS method for determination of Sample (3 g) heated (100 "C) for 3 h with 20 ml of salicylic acid in pharmaceuticals (dissolved in water or ethanol solutions) by reaction with copper carbonate incorporated in polyester resin beads.(Concentration range 4-75 mg I-') Samples dissolved in nitric acid (35%) and solutions diluted to 10 ml with H,O. Pd-Mg nitrate used as chemical modifier. (Detection limit 3.9 mg kg-') A.s for arsenic Comparison of methods for determination of Fe in A.s for Cd. Detection limit 184 fg Fe (for 74 nl A nalysis of gadolinium polyaminopolycarbox ylic pharmaceuticals injections) complexes and thermal degradation products using HPLC-ultrasonic nebulizer-ICP-AES Liquid chromatography-hydride generation-ICP- AES used for determination of inorganic and organometallic species of Ge in saline matrix (pg 1- ' concentrations) CIC interfaced to ICP-MS using heated interface. (Detection limit 120 fg Hg) Combination of Wickbold combustion and cold vapour AAS used for determination of Hg in organic compounds and organomercury in environmental samples using GC-MIP-AES after pentylation of ionic compounds using pentylmagnesium bromide.(Concentration range 2.5-10000 pg 1-I) Indirect method for determination of lower aldehydes by reduction of mercuric ion to elemental Hg and measurement using cold vapour AAS. (Concentration range 10-100 nmol methanal; 20-250 nmol ethanal and propanal) Alkylmercury compounds in water preconcentrated on sulfhydryl cotton column eluted with 3 mol 1-' HC1 phenylated using sodium tetraphenylborate and extracted into hexane prior to determination of methyl and ethyl mercury using GC-AES. (Detection limits 10 ng 1-') Simultaneous determination of organotin organolead Cr Wood preservatives Cr Wood preservatives Cr Wood preservatives AA;F;L AE1CP;L AA;F;L c u Copper citrate A A;ETA;L (CU) Nitrophenols AA;F;L 9513842 Wood preservatives Dithiocarbamate fungicides AA;F;L AA;F;L 9513930 9 514084 Traditional Chinese medicines AA;F;L 9514168 c u Wood preservatives Salicylic acid AE;ICP;L AA;F;L 961104 9611384 Cocaine and heroin AA;ETA;L 96/20 17 cu Organometallic compounds Pharmaceuticals MS;ICP;L AA;F;L or XRF; -;S or L MS;ICP;L 9513 56 1 9611 136 Fe Fe 961 1495 Fe Ferritin Gd Pol yaminopol ycarboxylic complexes AE;ICP;L 9 61 1 03 5 AE;ICP;L 9513851 Ge Organogermanium compounds MS;ICP;L AA;CV;L 9511478 9513662 Organometallics Organic compounds 9513670 Organometallic compounds AE;MIP;L AA;CV;L 9513674 Aldehydes AE;MIP;L 9513852 Alkylmercury compounds 474R Journal of Analytical Atomic Spectrometry December 195)6 Vol.1 1Table 2 (continued) Element Matrix ORGANIC CHEMICALS- Technique.; atomization; analyte forin* Sample treatment/comments Reference Hg Organometallic compounds AE;MIP;L Evaluation of three different derivatization methods 9513855 for determination of Hg Pb and Sn compounds in environmental samples by GC-AES determination of methylmercury in environmental samples using commercial GC-AES instrument. (Detection limit 1.2 pg; linear range 1-40 pg 1-' methylmercury) Hg Organomercurials AE;MIP;L Chromatographic conditions optimized for 9513947 As for Cu. (Detection limit 0.03 mg kg-') Hg Traditional Chinese Hg Methylmercury medicines Hg Methylmercury AA;CV;L MS;ICP;G AF;CV;L Hg Alkylmercury compounds AAS;HG;L Hg Organometallics XRF;-;S Hg Organometallic compounds AE;MIP;L Hg Organometallics MS;ICP;L Hi3 Methylated metal species AE;MIP;L Hg Organomercury compounds AF;CV;G Hg Organomercury compounds AF;-;S La Texaph yrins Lu Texaphyrins (Mn) Drugs MS;ICP;L MS;ICP;L AEDCP;L N Organic compounds AE;plasma;L N Organic compounds N Organic compounds Ni Heroin and cocaine 0 Organic compounds 0 Phenols P Organic compounds AE;MIP;L MS;-;L AA;ETAL AE;plasma;L AE; M I P; L AE;plasma;L Measurement of mercury methylation in sediments by using enriched stable mercury isotopes with methylmercury determination by GC-ICP-MS.(Detection limit 1 pg Hg or 0.02 ng g-' dry sediment) procedures (extraction into methylene chloride distillation under N2 flow and alkali digestion) for determination of methylmercury in environmental samples by ethylation-GC-CV-AFS monomethylmercury cation dimethylmercury and diethylmercury using heated quartz furnace with AAS Evaluation of different sample pretreatment HG procedure for speciation of Hg" As for arsenic.Optimum pH for adsorption < 10 As for arsenic (detection limits 0.15 ng ml-' for inorganic Hg and 0.35 ng ml-' Hg for methylmercury) As for arsenic Methylated metal species in water samples volatilized from solution after ethylation using sodium tetraethylborate preconcentrated on a cryogenic trap and then thermally desorbed into GC-AES. (Detection limit 0.6 ng 1-' for 10 ml sample) Organomercurials extracted from soil and water samples using dithizone and determined using HPLC-AF.Differentiation between gaseous organomercury and metallic mercury achieved by adsorption on Carbotrap and gold filters thermal desorption and AF detection Continuous microwave assisted pervaporation- atomic fluorescence used for speciation of inorganic and organic mercury compounds in solid samples. (Concentration range 10-500 pg kg- ') Determination of La and Lu in metal-containing texaphyrins and in tissue samples following treatment with texaphyrin photosensitizers As for La Indirect method for determination of hydrochlorides of antazoline hydralazine and amiloride and quinine sulfate based on precipitation of ion pairs with [Mn(SCN),I2- AES detection in capillary GC. CH,-O or CH,-N used as plasma gases for N and 0 detection. (Detection limits 50 pg s-') Optimum conditions established for simultaneous GC detection of 15N and 14N at 420.17 and 421.46 nm respectively. (Linear range 1.5-19 ng and detection limit 1.9 pg s-' for lSN) 350 kHz He plasma used for N 0 and P selective As for C Cocaine (500 mg) dissolved in 2 ml 35% HNO and solution diluted to 10 ml with H20.Heroin (250 mg) dissolved in 5 ml H20 400 1.11 35% HNO added and solution diluted to 10 ml with more H20. Mg(NO,) used as matrix modifier. (Concentration range 0.8-40 ng 1-') As for N As for C As for N but H,-CH used as plasma dopant (detection limit 39 pg s-') 9514 1 68 95/41 78 9514360 9514363 951448 1 961283 9611637 9611 806 9611990 961301 5 9611456 961 1456 9514166 9513799 961126% 9611713 961282 9513799 9513799 9611077 Journal of Analytical Atomic Spectrometry December 1996 Vol.11 475RTable 2 (continued) Technique; atomization; analyte form* Sample treatmentlcomments Element Matrix ORGANIC CHEMICALS- P Organic compounds Reference 9611338 9 51 1478 9513670 9513790 9513808 9513847 9 5/38 54 9513855 9514168 95/c4312 9 5/46 8 5 961213 AE;ICP;L Sample combustion in oxygen followed by collection of combustion products in dilute hydrogen peroxide used for determination of P using ICP- AES As for Hg. (Detection limit 100 fg Pb) As for Hg. (Concentration range 2.5-2500 pg 1-') Determination of ionic organolead compounds using FI-HG-ETAAS. (Calibration range 0.1 to 5 pg 1-'; detection limit 7 ng 1-') organolead and organotin compounds by GC with atomic spectrometric detection Use of quartz tube atomizer with packed column or capillary GC-AAS for determination of organolead and organotin compounds.(Detection limit 1.1-1.2 pg Pb for tetraethyllead) 'Trimethyllead species in rain water or roadside dust derivatized using sodium tetraethylborate and determined using purge and trap GC-AAS Study of interferences in ultratrace speciation of As for Hg As for Cu. (Detection limit 4 mg kg-') MS;ICP;L AE;MIP;L AA;ETA;L Pb Organometallics Pb Organometallic compounds Pb Ionic organolead compounds Pb Organolead compounds AA;F;L or AE;MIP;L AA;ETA;L Pb Tetraethyllead Pb Trimethyllead species A A;ETA;L Pb Organometallic compounds Pb Traditional Chinese medicines Pb Sludge; paint; fuel AE;MIP;L AA;F;L MS;ICP;S Use of slurry sampling (10% m/v) continuous flow microwave digestion isotope dilution ICP-MS for determination of Pb in environmental samples.(Concentration range pg g-' tong g-') (Optimization of quartz tube atomizer for GC-AAS determination of alkyllead compounds Inorganic lead trimethyllead and triethyllead extracted from urban particulate using 1 YO HN03 separated using HPLC and determined using hydride generation-ICP-MS. (Concentration range 0.01-5 ng ml-') Inorganic lead trimethyllead and triethyllead determined using HPLC-hydride generation- ICP-MS. (Detection limits 0.6-6 ng 1-' Pb) Cocaine (0.5 g) dissolved in 2 ml HN03 (35% v/v) and then diluted to 10 ml with H,O. Heroin (0.5 g) dissolved in 10 ml H,O containing a few drops of 35% HN03. Palladium used as matrix modifier. (Detection limit 31.4 yg kg-') ,4s for Hg.(Detection limit 0.2 ng 1-' for 10 ml sample) Indirect method for determination of glycyrrhizic acid in glycyrrhiza based on reaction with lead nitrate at pH 6.5-7 and measurement of Pb in the precipitate water. Minimum quantifiable limit 1 ng ml-' Pd (in analyte solution) Samples dissolved in 25% v/v 2-butoxyethanol- ,4s for C ,4s for C1 AA,F;L MS;ICP;L Pb Tetramethyllead and Pb Trialkyllead compounds tetraethyllead Pb Pb Alkyllead compounds Illicit drugs MS;ICP;L AA;ETA;L 961273 961309 Methylated metal species AE;MIP;L 9611806 9612555 Glycyrrhizic acid AA;F;L Fosinopril sodium MS;ICP;L 9611653 Pd Pesticides AE;MIP;L PCBs and methylsulfonate AE;MIP;L Organometallics MS;ICP;L Selenide drugs MS;ICP;L metabolites Organometallics XRF;-;S 9513474 9513479 S S As for arsenic As for arsenic.Optimum pH for adsorption=8 Characterization of selenide drugs and their metabolites by HG-ICP-MS and HPLC-ICP-MS Specific method for determination of cross-linked silicones on wool (insensitive to silica or silicates) based on depolymerization of cured silicone by aminolysis with anhydrous n-propylamine and extraction into IBMK As for Hg. (Detection limit 50 fg Sn) !$oil or sediment samples amended with diethylammonium diethyldithiocarbamate extracted with supercritical CO modified with 5% methanol pentylated using pentylmagnesium bromide and organotin compounds determined using GC-AES 9611637 9514481 9612362 Sb Se Se Wool AA;F;L 9514096 Si MS;ICP;L AE;MIP;L 9511478 9511866 Sn Sn Organometallics Organotin compounds 476 R Journal of Analytical Atomic Spectrometry December 15'96 Vol.1 1Table 2 (continued) Techniqu;; atomization; analyte form* Element Matrix ORGANIC CHEMICALS- Sample treatment/comments Reference Sn Sn Sn Sn Sn Sn Sn Sn Sn Sn Sn Sn Sn Organotin compounds MS;ICP;L Chlorides of dimethyltin trimethyltin dibutyltin tributyltin diphenyltin and triphenyltin completely separated within 20 min using micellar liquid chromatography. (Concentration range to 10 mg I-') As for arsenic As for Hg. (Concentration range 2.5-2500 pg 1-') Determination of butyltin compounds in water 9512394 suspended particulate matter soil sediment fish and air using GC-AAS after butylation-hexane extraction using sodium tetraethylborate (detection limit 25 pg Sn per p1 injected volume) As for Pb 9513561 9 513 670 9513691 Organometallic compounds Organometallic compounds Butyltin compounds MS;ICP;L AE;MI P; L AA;F;L Organotin compounds Organotin species AA;F;L or A E; M I P; L AE;MIP;L 01 MS;ICP;L 9513808 9513822 Comparison of analytical strategies using supercritical fluid extraction (SFE) with GC-AES SFC-ICP-MS and other techniques for determination of organotin compounds in aqueous and solid matrices tetraethyltin) As for Pb.(Detection limit 2-3.7 pg Sn for As for Hg Triphenyltin and butyltin compounds determined in marine biomaterials using tetramethylammonium hydroxide solubilization enzymatic hydrolysis and derivatization using sodium tetraethylborate. (Detection limits 2 ng g-' Sn) Organotin compounds in environmental samples determined using GC-MIP-AES after derivatization (pentylation). (Detection limit 0.8 pg Sn using 326.23 nm line) quantification of pentylated organotin standards for calibration of GC-quartz furnace-AAS and ICPMS with ultrasonic nebulizer used as reversed- phase LC detector for determination of inorganic tin trimethyltin triethyltin tripropyltin tributyltin and triphenyltin. (Detection limits 2.8-16 pg Sn) 0.1 mol 1-' HCl in methanolic solution. Sn determined using hydride generation-cold trapping and on-line quartz furnace AAS sample) Good chromatographic performance achieved but electronic pressure control required to achieve acceptable chromatography for tetracyclohexyltin and tetraphenyltin.(Inter-laboratory precision Speciation of organotin compounds using HPLC- ICP-MS (application to EC Measurement and Testing certification programme) GC-ICP-MS interface described and used for determination of organotin compounds Alkyltin compounds leached from sediments using polar solvent containing complexing agent.Compounds derivatized prior to determination using GC-AES or GC-AAS Guidelines for synthesis purity control and GC-AES Tributyltin extracted from sea food samples using As for Hg. (Detection limit 0.15 ng I-' for 10 ml Interlaboratory study involving 10 laboratories. 10-40% RSD) Overview of GC-AES applications Tetraethyltin A A;ETA;L AE; M I P; L A E; M I P; L 9513847 Organometallic compounds Alkyltin compounds 9513855 9513905 Organotin compounds AE; M 1P;L 9513948 Organotin standards AA;ETA;L 9514362 Alkyltin compounds MS;ICPL 96/58 Tribut yltin AA;HG;L 96/74 96/ 1806 961191 1 Sn Methylated metal species AE;MIP;L AE;M 1P;L Sn Pentylated organotin compounds Sn Alkyltin compounds MS;ICP;L 961202 1 Sn Organotin compounds Sn Alkyltin compounds MS;ICP;L 9612433 9613029 AA;F;L or AE;MIP;I.Various Petrochemicals; Various Surfactants pharmaceuticals AE;MIP;L 9513368 9513475 Vesicular mobile phases of the surfactants didodecyldimethylammonium bromide ( DDAB) or dihexadacyl phosphate (DHP) used for determination of several species of As Hg Se and Sn using HPLC coupled with atomic spectrometry Penning ion source allowed selection of degree of molecular fragmentation from electron impact (EI) type spectra through to highly fragmented small molecules and even single atoms (e.g. Br C C1 F and 0) Variation of discharge current in low pressure AE;ICP;L or AA;CV 01 ETA;L Various Organic compounds 9513563 MS;Penning cel1;G Journal of Analytical Atomic Spectrometry December 1996 VoI.11 477 RTable 2 (continued) Technique; atomization; Element Matrix analyte form* ORGANIC CHEMICALS- Various Balm oil MS;-;L Various Volatile organic compounds AE;GD;G Various Bromoperoxidase AE or MS;ICP;L Various Cured epoxy resins AE;MIP;L Various ( 15) Ginseng Various (10) Cotton Various Organic compounds Various Forensic samples Various ( 11) Pharmaceuticals Various Methamphetamine Various Organic materials (heavy elements) Various Oxalic acid Various Organic compounds Various Various Various Paper Various Drugs Various (22) Organic waste Various Organic compounds/ organometallics Various (35) Heroin Various Polyimides AE;ICP;L AA;F;L AE;plasma;L XR F;-;S AA;ETA;L MS;ICP;L or AA;F;L XRF;-;S or L AA;ETA;L or AE;ICP;L AE;MIP;L Various XRF;-;S XRF;-;S AE;ICP;L AE;MIP;L MS;ICP;L AA;ETA;L Sample treatment/comments Coupled GC-isotope ratio-MS used to evaluate origin and authenticity of balm oils Gas sampling glow discharge used for continuous determination of C C1 F and S in molecular gases and vapours by optical emission spectrometry using He discharge gas.(Detection limits low ng s-') Purification of novel metal containing non-heme bromoperoxidase from Pseudomonas putida and determination of Co Fe Ni and Zn prosthetic metal compounds in the enzyme Pyrolysis GC combined with MS FTIR and AES detectors used for characterization of major resin constituents and minor compounds (e.g.coupling agents) in cured epoxy resins various types of ginseng using ICP-AES. (Concentration range 1-1000 mg kg-' approx.) Determination of Ca Cd Cu Fe K Mg Mn Na Pb and Zn reported. (Concentration range 1 to 6500 mg kg-') Low resolution near-IR monochromator used with plasma atomic emission for element specific (Br C1 F I P and S) detection in capillary GC. (Element to carbon selectivities 1000-10 000) Grazing incidence XRF applied to forensic samples- counterfeit 100 dollar bill polyvinyl tape fragments semen trace illegal drugs fingerprints and fake brandy Analgin Nivalin and amidophen dissolved in water ( 5 % m/v); aspirin (5% m/v) dissolved in water with a few drops of ammonia solution (20%); paracetamol ( 5 % m/v) dissolved in acetonitrile after heating on a water-bath.No matrix modifier added Siezed methamphetamine samples (20 mg) dissolved in 20ml water. Ba Br Cu Pd Sb Sr and Pd determined using ICP-MS and Na determined using AAS. Na and Br concentrations found useful in classifying samples into groups LJse of Barkla polarized X-ray radiation for EDXRF analysis of organic materials. (Detection limits < 1 mg kg-') preconcentration for trace-element (Cd Co Cu Fe Hg Ni and Pb) determinations using ETAAS or ICP-AES. (Detection limits 0.1 ng g-' to 1 pg g-') Review (69 refs) of element selective GC detection using plasma AES Review ( 126 refs) of element-specific chromatographic detection by AAS ICP-AES MIP-AES ICP-MS and MIP-MS. The chromatographic techniques HPLC GC SFC and field flow fractionation are considered Determination of fillers (e.g.kaolinite Ca carbonate TiO talc muskovite and sodium aluminosilicate) in commercial papers percutaneous absorption measurements analytes in waste samples subjected to toxicity characteristic leaching procedure (detection limits 0.03-5 ng g-' cf 0.3-700 ng g-' for radially viewed plasma) Review (124 refs) on determination of trace elements by chromatgraphic methods employing atomic plasma emission spectroscopic detection drug seizures for tracing origin and method of manufacture Determination of Ca Cu Fe K Na and Si after dissolution in organic solvent. (Detection limits 0.5 2 5 2 and 25 ng g-' respectively) Determination of essential and toxic elements in Column solid-phase extraction used as Review (19 refs) of applications of XRF in drug Use of axially viewed ICP for determination of Statistical evaluation of trace element composition of Reference 9513574 9513881 95/39 12 9513924 9513952 9514095 9.514415 9514503 9514698 961101 961621 9611030 9611046 9611075 9611165 961 961 961 194 259 40 1 9611535 96,4814 478R Journal of Analytical Atomic Spectrometry December 1996 Vol.1 1Table 2 (continued) Technique; atomization; analyte form* Element Matrix ORGANIC CHEMICALS- Various Organic compounds Various Drugs Sample treatment/comments Reference AE;MIP;L MS;-;L Review of GC-MIP-AES (45 refs) Review (8 refs) of use of isotope ratio MS in drug research and development Coating coverage coatweight distribution and 3-dimensional distribution of paper coating pigments determined using AES from laser generated plasma Review ( 6 refs) of applications of EDXRF for determination of additives and contaminants present in pre- and post-consumer paper products Samples extracted with CH2C12 and concentrated in a Kurderna-Danish flask prior to measurement by GC-MIP-AES using element specific detection (Br C1 I N and S) 9611857 9612453 9612500 Various Paper AE;laser;S Various Various Paper Herbicides XRF;-;S AE;MIP;L 9612770 96/29 18 INORGANIC CHEMICALS AND ACIDS- Ag Lead sulfide concentrate AA;F;L The AA method was compared with the fire assay procedure.The precision was comparable but the accuracy was greater 1 g of fly ash was extracted with 20 ml of He purged H20 under nitrogen.The pH was varied from 1-12. Samples taken at periods of 3 hr-3 d at temperatures ranging from 18-55 "C were examined.As"'/As" were separated using HPLC Influence of the bath composition on precision was studied An investigation of the best analytical wavelengths for the determination of B in various fertilizer compositions was reported. Multiple linear regression in conjuction with experimental design was employed to determine the best B wavelength to use for a given sample matrix Manitol was used as a chemical modifier for ETV sample introduction . An eighty-four fold increase in sensitivity was reported using the modifier Ammonium nitrate Si and V20 modifiers employed to control interferences. Pyrolysed and Zr coated tubes used to improve graphite tube lifetimes Sodium di-n-propyldithiophosphinate tested as means of improving the sorption proprities of activated carbon.Optimization of this procedure for the recovery of Bi prior to ICP-AES determination particle size placed in the sample cell; 2.5 ml of ethanal were added and the sample suspended and then measured compounds and the resulting solution heated. 5 ml of pyrogallol were then added and the solution diluted to 50ml Interference study on the effects of cations and organics. KCN used to control interferences Cd extracted with IBMK + KI. Effects of acidity and concentration of reducing agents were studied Application of closed pressure digestion systems reported 0.2 g sample decomposed using HN03-HC10 (4 + l) solution evaporated H 2 0 added and solution centrifuged. 1 ml of 20 mg ml-' SrC03 and 2 ml of sodium acetate-acetic acid buffer+ 1 ml of 10% Na2C03 added and the solution centrifuged after 30 min.Precipitate dissolved in few drops HCI and diluted to 5 ml Cd used as internal standard LOD = 15 mg 1-' Sample ground and a portion (0.5 g) of known Speciation of Ca in ternary mixtures of Ca 5-10 ml of H,O were added to the sample solution 9512298 961 1 28 6 9514175 As"'/" Coal fly ash MS;ICP;L Au Plating bath solutions AA;F;L B Fertilizers AE;ICP;L 9514077 961120 B Ba Bi Trichlorosilane Common salt - MS;ICP:L AA;ETA;L AE;ICPL 961272 9614043 9613001 Br Activated carbon X RF;-;S 9612984 Ca Ca Ca compounds Tungstic Acid AA;F;L AA;F;L 9513462 9612927 Ca Cd Cd Cd AA;F;L AA;F;L AE 1CP;L AA;F;L 96/38 14 9513781 9514078 9613621 Passivation solution (Cd Fertilizers/soils plating) Tobacco c1 c1 c u Photographic developer solutions Di-isocy anates WDXRF:-.L XRF;-;L XRF;-;L Samples spiked with monochlorobenzene and A portable EDXRF spectrometer was interfaced to 9513493 961487 sonicated for 10 min the electrolytic cell to allow on-line control of cell Cu concentration Electrolytic cell solution Journal of Analytical Atomic Spectrometry December 1996 Vol.11 479RTable 2 (continued) Technique; atomization; Element Matrix analyte form* INORGANIC CHEMICALS AND ACIDS- c u Coal Ash AA;-;L Sample treatmentJcomments Reference Sample decomposed using a mixture of HCl-HF-HC10 and extraction of Cu-diethyldithiocarbamate complex with Bu acetate at pH 9 Cu separated by TLC and the spot from the plate removed treated with 2 mol 1-' HNO filtered and the filtrate dissolved in 1 mol 1-' HC1 Reversed phase ion-pair HPLC used for speciation of Cr"''v'.Optimization of separation conditions described. LOD=24 pg 1-' Cr"' 40 pg 1-' CrV' Ion Chromatography used for Cr speciation Two-stage procedure for separation of Cr'"/Crv' involving adsorption of CrV' onto Zr-loaded activated charcoal followed by co-precipitation of Cr"' with Fe"' hydroxide and adsorption of the precipitate onto activated charcoal. (LOD = 0.0042 mg 1-' Cr"' 0.0013 mg 1-' CrV') Direct injection of the analyte solution to the graphite tube FIA sample preparation,' introduction system. Fe precipitated as hydroxide 9611065 cu Industrial wastewater AA;F;L 9612921 Cr Various MS;ICP;L 9611024 961 13 19 9612024 Cr Galvanic baths Cr Plating liquors AE;ICP;L EDXRF;-;L Fe High purity phosphoryl Fe Caustic soda chloride A A;ETA;L AA;F;L 9 5/43 5 5 951442 1 AE;ICP;L Zr carrier added to the analyte solution pH adjusted with NH4Cl-NH,OH solution heated and then cooled to coprecipitate FeOH.The precipitate was filtered washed and dissolved in HC1 mixed in a hydride generation system. Iodine gas formed as a result was introduced directly into the ICP. A hundred-fold increase in sensitivity was reported HNO and the sample solution as the iodide were 9613640 Fe Electrolytic solutions (Zn-bromide batteries) AE;ICP;L 9513783 - I Phosphate/carbonate food additives AA;-;L AA;ETA;L 96/14 961290 Use of chemical modifiers investigated. PdCl Ce( NH,),(NO,) thioacetamide and H,O2-HC1 were compared. The performance of the modifiers were dependent on acid concentration.(LOD = 0.1 mg kg-' Hg) Oxidation with KMnO M:ethod applied to artifical flue gases. No interferences were observed from trace amounts of CO HCl SO2 and NO -. Bread crumbs extracted with H,O and the filtered extract applied to three 3 ml Sax bond elutes in series. After addition of H20 and 0.2 mol 1-' ammonium acetate KBrO was eluted with 0.5 mol 1-' ammonium acetate. A 50 pl portion was separated using ion chromastography and the eluent introduced to the ICP-MS Effect of matrix compostion on 4 Mg wavelengths was examined. Multiple linear regression was employed to evaluate the influence of matrix composition. Mg' 83.826 was considered the best line HN03-HC104-HzS04. After cooling the digest was neutralized with 4 mol l-'NaOH.The solution was then treated with 5 ml of 0.56 rnol 1-' NH,OH 1.2 moll-' HNO 0.32 mol 1-' H3P04 and 300 mg 1-' aluminium nitrate Synchrotron source employed XRF imaging used to look at single diamond crystals. A novel quantification technique for Ni was described 101 ml of sample was digested with 4.5 ml Dust was collected on Teflon filters H:PLC procedure used to separate Sb"'/Sbv LOD = 0.003 g 1-' Sb"' 0.005 g 1-' SbV 100 ml of sample was made 1 moll-' in HCl and the solution treated with 5 g of hydrazine sulfate and boiled for 30 min. The inorganic Se" and SeV' were coprecipitated with 25-500 pg of Te and the precipitate collected on a nitrocellulose filter Sulfuric acid Flue gases AA;-;L AE;MIPG 961930 9 513 37 3 Zn-MnO dry battery KBrO (Flour improver) AA;-;L MS;ICP;L 9514015 9513843 Fertilizer AE;ICP;L 9611 9 10 95 13374 Mg Mo Tetrathiomolybdate AA:F;L XRF;-;S EDXRF;-;S AE;ICP;L AA;ETA;L 9611 2 15 Ni Synthetic diamond Post-abatement dust Cu electrolyte solutions 9611 196 9611042 Pb Sb 9 6/28 9 5 Se High salt waste waters 480 R Journal of Analytical Atomic Spectrometry December 1996 Vol.11Table 2 (continued) Technique; atomization; analyte fox-m* Element Matrix INORGANIC CHEMICALS AND ACIDS Sb Pb/Zn concentrates Sample treatmentlcomments Reference AA;F;L Sample (0.5-1 g) heated with 1 g KHSO,+ 10 ml 9612983 H2S04 cooled and 10 ml of H,O + 1 g hydrazine added. Mixture was heated then 20 ml of 7.5 mol 1-' HCL and 1 ml of NaNO added and mixture extracted with di-isopropyl ether. Organic extracts partitioned with 0.5% NaHSO and aqueous portions analysed Zn Ammoniacal ore leaching Various (4 ) solutions Gaseous hydrogen chloride XRF;-;L A A;ETA;G 9512845 961292 Automated sampling system for sample introduction.Calibration against aqueous standards. (LOD 1-40 Pg) Microwave digestion procedure employed Laser spectrometer combining both flame and electrothermal atomization employed. LOD in the 1-10 fg level pollutants around Sn mining and smelting operations determined Methods desribed for the monitoring of Sn Composition of crystals grown by the gel method A review of the use of XRF in production control Several foils and crystal analysers were examined for the analysis of light elements. (LOD = 100 ppm for Cl S) 0.25 g sample and 0.5 g of lithium tetraborate placed in Pt crucible fused at 1000 "C for 45 min and then 25 ml of HNO added.Solution was heated 10-15 min at 50-60 "C and transferred to a 250 ml polypropylene flask. Procedure was repeated with second aliquot of HNO and then made up to volume Analytes preconcentrated from matrix by addition of copper(1) chloride and analysed using ETV-ICP- MS H,S04 + 6 ml of 40% HF. The mixture was heated until the sample dissolved and the excess HF had been removed. After cooling H,O was added and the solution heated until the appearance of SO fumes. Solution diluted with 2-3 ml H,O and 0.4 ml H,O added chlor-alkali membrane electrolysers 200 mg of sample mixed with 2 ml of conc. Analysis of impurity elements in brine used in Various (40) Coal Various (10) Shale MS;ICP;L AE:laser;S 961376 961413 Various (6) Soil pollutants EDXRF;-;- - 961468 Various (6) Rare earth molybdate Various Cement Various (3) Silicone grease crystals EDXRF;-;S 961498 961539 9611 177 Various (55) Coal fly ash M S;ICP;L 9611281 Various (2) Trichlorosilane MS;ICP;L Various (9) Potassium titanylphosphate AA;F;L 9611308 9611382 Various (4) Brine AE;ICP;L 9612019 Various Ni oxide S SM S;-$ Dry NiO mixed with graphite (l:l) presparked for 30 min to remove impurities.Experimental sensitivity factors determined using NIST 673 NiO FIA sample introduction employing preconcentration of analytes by coprecipitation with Fe(OH) - 96/23 59 Various (2) Caustic soda AA;F;L 96/25 52 Various (3) Alkali salts Various (7) Air filter AA;F;L XRF;-;S 9612554 9612654 A comparison of impurities in five materials commonly used to make air filters 0.5 g sample digested with 10 ml aqueous NH for 4 h in covered PTFE vessel.The digest was treated with 5 ml of H202 and boiled for 30 min. This procedure was repeated and 5 ml of HCl or HNO added to resulting digest and the solution heated to near dryness. The residue was dissolved in HCI and Ga,O,) (2+2+ 1) and the resulting mixture formed into an electrode 10 ml H,SO,-HNO + 3 ml HF added dropwise to powdered sample and heated. H20 was added and solution filtered. Residue ashed in Pt crucible placed in a PTFE vessel with 3 ml H,S04 (1 1) + 3 ml HN0,-HF (1 9) and heated at 180 "C for 16 h. Resulting solution combined with filtrate and diluted Method for separation of analytes from matrix using cellulose collector 90 mg of sample added to 10 mg carrier (C AgCl 96lC28 28 Various (17) Ammonium tungstate 9612929 AE;ICP;L Various ( 5 ) Scandium oxide Various (1 1) Titanium disilicate AE;d.c. arc$ AE;ICP;L 96/29 12 9612879 Various (8) W products AE;ICPL Jotirnal of Analytical Atomic Spectrometry December 1996 Vol.1 1 481 RTable 2 (continued) Technique; atomization; Element Matrix analyte form* INORGANIC CHEMICALS AND ACIDS- Various (29) Various Various Various Various (6) Various (18) Various Various (6) Various (4) Electrofilter ashes Mongolian coal - Inorganic gases Silica gel High purity chemical Fertilizer Zirconium tetrafluoride Nickel carbonyl reagents NUCLEAR MATERIALS- Ag Uranium l4C Air Fe Zirconium oxide Fe Zirconium I Environmental samples Pu Uranium matrix 79Se Radioactive waste 99Tc Rainwater 99Tc Environmental 99Tc Rainwater Th Sea-water U Rainwater Various Waste streams Various Waters (actinides) (actinides) MS;ICP;L XRF;-;S - ICM S;-;- AA;ETA;slurry AE;-;- - A A; ETA; L AA;F;L AE;ICP;L AMS;S XRF;-;S T1MS;L MS;ICP;L and NAA MS;ICP;L MS;ICP;L MS;ICP;L MS;ICP;L M S;ICP;L T1MS;L MS;ICP;L XRF;-;L MS;ICP;L Sample treatmentlcomments Results obtained from three standard reference materials compared Coal sample pressed into pellets 2.5 cm diameter (2-3 tons dynamic pressure) A review of the use of MS methods in inorganic chemistry (7 refs) A review/discussion on isotopic chromatographic spectral analysis of inorganic gases Stability of slurries investigated.Standard addition used for quantification MOS grade HC1 HF and HNO analysed by emission spectroscopy. (LOD = 0.2-4 ng ml - ') Review of the analysis of fertilizers by atomic spectrometry Sample decomposed in autoclave and residue dissolved in HC1 0.1 g sample dissolved in HCl by heating to near dryness.The residue was mixed with 5 ml HNO and treated with 0.5 ml HF and evaporated to near dryness. The resulting residue was mixed with 5 ml of HClO and heated to fuming before dissolving in 10 ml of HCL ( 1 1) big separated from U using triisobutylfosphine sulfide in xylene and back extracted into 5% NaHSO,. Solutions measured using ICP-AES reactors one BWR and one PWR and measured using accelerator mass spectrometry. Results obtained compared well with liquid scintillation counting Powdered zirconium oxide was pressed on boric acid and irradiated under He medium to determine Fe.Calibration graphs were linear over the range 10-2500 mg kg-' Fe Sample dissolved and spiked with 54Fe zirconium removed by ion exchange and Fe further purified by back extraction. A silica gel-boric acid ionization enhancer was used to obtain stable Fe' currents. Fe determined to ppm levels detection limit of 0.2 ng ml-' obtained. Soil and plant were heated in an oxygen stream and the evolved I trapped in Na,SO,; 1251 added as a tracer. Detection limit in soils 0.02 mg kg- '. Problems with the measurement of lZ9I discussed I'on chromatography used to separate interfering actinides prior to measurement of Pu by ICP-MS Hydride generation used separate 79Se from 79Br and polyatomics prior to measurement using high resolution ICP-MS without addition of nitric acid hydrochloric acid sodium hydroxide or ammonia trace 99Tc after dissolution and separation from 99Ru trioctylamine-xylene and Tc back extracted into 1 mol 1-' K2C03; Ru removed by extraction with cyclohexanone.Detection limit 0.04 ppt '"'Th and 232Th determined in Norwegian sea-water High resolution ICP-MS and ultrasonic nebulizer used to determine U to 0.06 pg 1-' for 235U. 238U-235U ratios calculated On-line process control of actinide waste streams from ion exchange processes using EDXRF Off-line preconcentration of actinides using selective polymer beads. Pneumatic or ultrasonic nebulization and ICP-MS used to determine actinides in a variety of waters Airborne 14C was collected from two Swedish Water samples filtered and measured directly L,osses of Tc during preconcentration with and High resolution ICP-MS used to determine ultra F'reconcentrated rainwater extracted with Reference 9613239 9613408 9513544 9513652 9513660 9513666 9514009 951441 1 9514521 9612979 9612412 961299 9611 6 1 8 96lC2034 961C2265 961C2076 9 5/45 56 9612409 96/24 10 9612394 9513601 961382 9 6/C 67 6 482 R Journal of Analytical Atomic Spectrometry December 1996 Vol.1 1Table 2 (continued) Technique; atomizatic 1 n; analyte form* Sample treatment/comments Reference Element Matrix NUCLEAR MATERIALS- Various Actinide matrix W E ) Various Soils (actinides) Various Biological samples and (halides) radioactive waste Various Plant tissue W E ) AES;ICP;L MS;ICP;L MS;ICP;L M S;ICP;L 9611658 Use of a 200 p1 volume microcolumn to separate and preconcentrate Ce Eu La Nd Pr Sn Sr and Y in lithium chloride-potassium chloride matrices containing uranium.Using the microcolumn a 100 fold preconcentration was achieved Long-lived actinide isotopes determined in soil leachates. Use of an ultrasonic nebulizer improved detection limits to 50 mBq 1-' for 239Pu and 2 pBq I-' for 235U. Extraction chromatography used to separate and preconcentrate the actinides prior to measurement Br C1 and I determined in biological reference material using HR-ICP-MS. 12'1 measured in radioactive wastes. Iodine introduced to the plasma in elemental form to improve detection limits Microwave digestion compared with conventional dissolution. Detection limits found to be in the ppt range for REE determined 9611343 96/C2077 961301 3 * HG indicates hydride generation and S L G and S1 signif:; solid liquid gaseous or slurry sample introduction respectively.Other abbreviations are listed elsewhere. petroleum geochemists are increasingly making use of isrb3topic ratio measurements in addition to identification of biomarkers (typically measured using GC-MS). In one such study carried out during the review period (95/3568) the authors measured both biomarker and carbon isotopic data from the bulk and n-alkane fractions of 27 oils from the Eldfisk and satellite North Sea fields and provided evidence for at least two phases of reservoir filling. In interpreting isotopic data however. great care must be taken to ensure that fractionation effects do not influence results.For example Love et al. (96/1726) have shown that significant compositional fractionation effects can occur between the free molecular (bitumen) phase and those covalently bound to the insoluble kerogen network in imma- ture source rocks such that the former is not necessarily a low relative molecular mass indicator of the constituents of the bulk kerogen. For measurements of this type gas chromatogra- phy-isotope ratio mass spectrometry (GC-IRMS) is generally the preferred approach. An interface has been described for on-line combustion of GC effluents and removal of water vapour prior to introduction (of produced COz) to an [RMS instrument (96/1025). Combustion was carried out using tubu- lar reactors packed with CuO or NiO and water vapour was removed (from the combustion products) using Nafion tubing.The simultaneous measurement of carbon isotopic ratios and GC-MS spectra (e.g. for biomarker measurement) using an IRMS and ion trap MS connected in parallel to one GC has also been reported (95/3562). In the past several attempts have been made to use trace element fingerprints in addition to biomarkers and is titopic data to gain additional information on oil classiJcatioiis and source rock correlations (see for example 96/416). However most of these studies have been hampered due to contami- nation from formation/produced waters drilling fluids and reservoir rocks. Olsen and co-workers (96/336) have used NAA and ICP-MS to carry out a detailed study of contaminants introduced to a series of crude oils from these sources.[t was shown that oil samples must be water washed and filtered to remove barite contributions to Cu Fe Ga Mn and Pb and formation/produced water contributions to As and Br concen- trations in the oils. Also elements such as Cd Pb and Zn were picked up by oils migrating through ore bodies of these metals. Prior to examining the contributions of water barite and migration oils could only be classified according to their Co Ni and V concentrations but the new understanding acquired from this work has extended the range of useful elements to include As Bi Co Fe Mn Mo Ni Sb V and Zn. Understanding of formation water chemistry also plays a key role in building up a picture of reservoir diagenesis. Unfortunately elemental analysis of bulk formation water rarely gives direct information regarding the composition of the fluids at the time of reservoir formation due to migration ingress of meteoric/sea-water complex water-rock interactions and contamination from drilling fluids and produced water. One largely untapped source of information regarding original formation water composition are the fluid inclusions often found trapped inside the reservoir rocks.Although several methods have been applied for bulk analysis of a number of fluid inclusions (e.g. thermal decrepitation crushing and leach- ing) analysis of the elemental composition of individual fluid inclusions has proved elusive. An attempt has been made to measure Sr concentrations in individual fluids inclusions using synchrotron XRF (8 x 12 pm beam size) but difficulties in correcting for inclusion geometry gave rise to large errors ( 10-39% standard deviation) and necessitated analysis of numerous inclusions within the same population in order to minimize errors (96/1251).True analysis of individual fluid inclusions has however been achieved by Shepherd and Chenery (96/1250) using UV laser ablation-ICP-MS. Use of a quadrupled Nd YAG operating at 266 nm allowed spatial resolutions below 2 pm to be achieved and permitted analysis of single aqueous inclusions of diameter 10-100 pm and up to 60 pm below the sample surface. Calibration using synthetic microwells or NIST SRM 611 glass was shown to be suitable for determination of element concentrations relative to stron- tium (95/1803). RSDs of around 25% were achieved for element ratios.In addition to elemental ratios as discussed above Rb-Sr isotopic ratios can provide further information on age provenance and chemical interaction history of the ancient fluids trapped in the inclusions. An evaluation of bulk extraction procedures for these analyses has been carried out using synthetic fluid inclusions (96/1249). Accurate determi- nation of 87Sr 86Sr was achieved with both methods (crushing and leaching and thermal decrepitation and leaching) but only the former method was found to give accurate results for 87Rb 86Sr due to the reaction of Rb with glass at temperatures above 500 "C. Analyses of the bulk composition ofthe reservoir Journal of Analytical Atomic Spectrometry December 1996 Vol. 11 483Rrocks themselves are also obviously critical factors in under- standing the structure and diagenesis of the reservoir.Sams et al. have carried out validation of a geochemical logging tool for major element analysis in boreholes by comparison with analyses of core samples carried out using ICP-AES (96/33 1). Statistically significant biases were observed (- 55% to + 5%). Mercury in natural gas is not only a potential environmental problem but perhaps even more seriously it can also catalyse corrosion/fracturing of downstream aluminium components (a particularly serious problem for heat exchangers). Mercury in natural gas can be determined by trapping the mercury com- pounds in strongly oxidizing solutions and measuring by cold vapour AAS or AFS. However the reagents used in these methods can give rise to relatively high blank levels and the method is not ideally suited to field applications (e.g. offshore) due to the hazardous reagents used.An alternative approach is to trap the mercury on a solid collector (usually involving amalgamation of the Hg with noble metals) prior to thermal desorption into an AAS or AFS instrument. Studies have been carried out to evaluate the efficiency of various noble metal collectors for trapping of mercury compounds (95/4694). Collectors filled with Au-Pt wire were found to be more efficient than those filled with Au or Pt wire and quantitative sampling for metallic mercury and dimethylmercury was achieved using the former collector heated to 80 "C at sampling rates less than 2 1 min-' provided sampling volumes of at least 10 1 were used.Precision for field measurements was 8-15% RSD and the limit of detection was 30mg rn- for a 101 sample. Mercury can also cause problems if present in other light feedstocks (e.g. naphtha) due to poisoning of downstream catalysts as well as environmental and corrosion problems as discussed above. Other elements which can form relatively volatile species (e.g. As and P) can also cause similar problems. Determination of volatile trace elements in light feedstocks is problematical because of potential losses during digestion procedures and problems with selective volatilization if conventional nebulization is used for direct sample introduc- tion for atomic spectrometry (e.g. ICP-AES or ICP-MS). An elegant solution to this problem has been reported by Botto (96/C2294) which uses a direct injection nebulizer (DIN) for direct sample introduction to ICP-AES and ICP-MS. Oxygen was added to the auxiliary plasma gas to prevent build-up of carbon on the injector tip.Detection limits for ICP-AES were disappointing (> 2000 20 and 300 ng g-' for As Hg and P respectively) due to background interference from the organic matrix but those obtained using ICP-MS (0.01 1 0.01 1 and 0.34 ng g- ' respectively) were very good. The method can potentially be extremely fast since it has been claimed that using a DIN for direct sample introduction to a plasma it was possible to analyse samples at rates up to 240 per hour (96/C2834). X-ray Jluorescence is commonly used throughout the pet- roleum industry for determination of Ni Vand S in crude oil and fractions.However for some heavy fractions solubility in common solvents can be limited and this can give rise to problems due to settling of material on the cell windows (particularly if the samples are not freshly prepared prior to analysis). One possible solution to this problem which was reported involved increasing the sample viscosity by chilling with liquid nitrogen or mixing with eicosane prior to forming into a disc for analysis using a plastic dish with a central well covered with aluminium foil (96/411). An alternative approach involved homogenizing the sample (0.01 to 0.2 g) with 1 ml of internal standard solution (40 mg 1-l Pb in chloroform) pipetting a portion onto a Mylar foil evaporating the solvent and analysing using EDXRF (96/405).Detection limits of 5 and 2 mg kg-' were obtained for V and Ni respectively but the precision of the method was relatively poor (7% RSD). Measurement of sulfur concentrations in rejnery products and processes is becoming increasingly important particularly in the light of increasingly stringent environmental legislation. XRF is ideally suited to on-line measurement of sulfur in these products and can potentially give significant advantages due to the ability to monitor critical streams continuously. A review (no references) has been published dealing with advances in on-line measurement of sulfur in petroleum products and includes a discussion on installation and commissioning of equipment (96/1208). XRF has also been used to carry out trace metal analysis in fresh and weathered (2 7 and 14d) crude oils (96/2559).An attempt was made to assess the applicability of V:Ni ratios for passive tagging of oils. Speciation of selenium in petroleum rejinery and municipal waste waters has been carried out using ion chromatography- ultrasonic nebulization-ICP-MS (96/C2276). Selenite selenate and selenocyanate were determined with limits of detection in the 0.6-0.8 mg I-' range using a gradient programme involving ammonium borate and ammonium perchlorate. The method was used to study oxidative conversion of selenocyanate in refinery waste water to selenite and subsequent coprecipitation with iron hydroxide. A method for determination of gaseous nitrogen in natural gas using low pressure MIP-AES has also been reported.2.1.2. Fuels The measurement of concentrations of trace metals in atmos- pheric samples is gaining in importance reflecting the growing world-wide concern over levels of atmospheric pollution. A method has been reported for the determination of six elements (Cd Cu Ni Pb Ti and Zn) in atmospheric particulate samples using isotope dilution ICP-MS (96/956). Although isotope dilution effectively eliminates multiplicative interferences such as matrix suppression the method can still be prone to additive type interferences caused by isobaric or molecular ion overlaps in the mass spectrum. The authors successfully eliminated this problem by solvent extraction with dithizone which had a low affinity for interfering elements (e.g. Mo Sn Ti V and alkali and alkaline earth elements) but a high affinity for the heavy metals of interest.The method was tested using a Vehicle Exhaust Particulates CRM. One of the main contributors to over-all concentrations of lead in the atmosphere is undoubt- edly Pb expelled by engines running on leaded gasoline. A study has been carried out on the impact of traffic volume and distance from roads on agricultural soils (96/1979). By using conventional acid digestion (3 1 HC1-HNO,) in a closed pyrex container and AAS the authors showed that Pb concen- tration in soils close to roads was dependent on traffic volume distance from road and depth from which the sample was taken. Owing to the impact of leaded gasoline emissions on the environment the amount of lead in gasoline is being regulated and gradually replaced with unleaded fuels.Thus it is necessary to determine the concentration of Pb in gasolines at lower concentrations than previously required. This can readily be achieved using solution techniques such as AAS or ICP-AES provided that labile lead species are first converted to non-volatile lead compounds. A common approach is to use iodine to decompose the alkyllead compounds followed by complexation with Aliquat 336 (tricaprylmethylammonium chloride). However even when this approach is used problems can still occur with direct introduction of the resulting gasolines into ICP-AES owing to the high concentrations of volatile organic compounds reaching the plasma (carbon deposition plasma overload background emission etc.).Brenner et al. (96/1430) have reported a novel solution to this problem involving introducing the gasoline to the plasma in the form of an emulsion. Gasoline samples were vortex mixed with Triton-X and water for 2min 5% iodine solution in toluene was added with mixing for 5min and 10% Aliquat 336 in 484 R Journal of Analytical Atomic Spectrometry December 1 !)96 Vol. 11decalin was added. The method was suitable for the determi- nation of Pb at themg kg-' level and gave good agreGment for NIST standard reference fuels. The method is also suitable for use with gasoline spillage cases where the samples may consist of mixtures of fuel and water or water emulsified fuels. Where determination of the chemical form of lead in gasoline is required (e.g. tetramethyl or tetraethyllead) it is common practice to utilize a combination of GC with an atomic spectrometric detector (e.g.GC-AAS GC-AES GC-ICP-MS). Determination of tetraethyllead in gasoline by GC with a home-made surface emission flame detectclr has been reported during the review period (96/2902). The reported RSD was 0.7% and the detection limit was 0.3 ng. Although it is clear that vehicle exhaust emissions can make a significant contribution to atmospheric pollution an even larger contribution for many elements is emissions from ther- mal power plants. In Germany and Italy maximum emission levels of various metals from fuel oil fired power plants have recently been set according to the relative toxicity of the elements. Although concentrations of nickel sulfur and vanadium are routinely measured in fuel oils determination of other trace elements has generally been less extensively studied. In view of the increasing interest in these other trace elements (because of their potential contribution to enl iron- mental pollution and also their potential ability to poison upgrading catalysts) some effort has been devoted towards development of suitable analytical methodology.Bettinelli et al. (95/3731) have reported a method for determination of 20 elements in fuel oil by ICP-MS after acid mineralization in a microwave oven. Samples (250 mg) were digested with 7 ml 65% HN03 and 3 ml H202 in a high pressure PTFE jessel using a 10 step microwave oven programme. After cooling the samples were made up to 25ml with water prior to analysis.Detection limits were generally in the range 20-100 ngg-'. Results were in good agreement with certified values (where available) and with results obtained using NAA. Even better limits of detection have been reported for determination of 10 elements in fuel oil using GFAAS and CVAAS after more conventional sulfuric acid-nitric acid digestion in a round- bottomed flask fitted fitted with a condenser. The principle reason for the improvement in detection limits in this case was the use of a larger sample size ( 5 g in a final volume of 100 ml c$ 250 mg in a final volume of 25 ml for 95/3731). The main disadvantage with this method however was that the reaction had to be carried out slowly (3 h) otherwise a 'violent and harmful reaction was induced'! Good recoveries were reported for As Cd Co Cr Cu Mn Ni Pb and V although proldems were experienced with Cd and Pb in distillate samples due to high background signals in GFAAS.Recovery for Hg was only 71%. In recent years some power plants have been utilizing a novel fuel oil replacement based on water-oil emulsions (e.g. Orimulsion). However since these are normally manufactured from very heavy oils or bitumens levels of trace elements can be particularly high potentially resulting in high levels of metallic emissions if clean up procedures (e.g. precipitiitors) are not used. A method for determination of metallic elements in crude oil-water emulsions has been reported (96/1300). The method involved heating a homogenized sample (3 g) for 30 min with 0.3 g of alkylbenzenesulfonic acid and 15 ml of ethanol in a quartz dish igniting and heating with 1 in1 of nitric acid until brown fumes were eliminated.The residutz was transferred to a muffle furnace and heated at 550°C to burn off carbon. The cooled ash was dissolved with a few drops of H 2 0 and 2 ml of HC1-HNO (1 l) and the resulting solution diluted to 50 ml with water prior to analysis using flame ,4AS. 2.1.3. Lubricating oils Every year sees more papers published describing the determi- nation of additive and/or wear metals in lubricating oils using ICP-AES. The most common approach is to use straightfor- ward dilution with an organic solvent (e.g. 95/3839) and standard methods [eg. American Society for Testing and Materials (ASTM) and Insititute of Petroleum (IP) methods] exist for these determinations.However it is increasingly being realized that significant errors can occur with these methods due to the presence of viscosity modifiers in modern multi- grade oils. Carey and Mattern (96/C2237) have studied various methods for reducing these interferences-use of an internal standard matrix matching microwave digestion and ultrasonic nebulization. Use of an internal standard (in this case yttrium) proved to be the most effective and practical method and successfully reduced errors to within 2% relative (i.e. similar to the precision of the method). A similar conclusion has been reached by ASTM who are currently changing their standard methods to make minimum 20-fold dilution and use of an internal standard mandatory. Analysis of synthetic motor oils (eg.made from poly-alpha-olefins and trimethylol propane esters) can pose an additional challenge since these compounds can affect plasma conditions in addition to the changes in nebulization efficiency commonly caused for example by viscosity index improvers and surfactants in the oil (96/C728). Careful choice of internal standard(s) is therefore likely to be required if these materials are to be analysed. Although direct solvent dilution is by far the most convenient method for determination of additive elements in lubricating oils problems such as those described above can sometimes affect results. It is therefore often useful to check results using a total digestion method in order to eliminate completely the interference effects caused by the organic compounds.A fairly conventional approach has been described which involved ashing l o g of sample dissolving the ash in 20 ml of 6 mol 1-' HC1 concen- trating to 5 ml adding 6 ml of 10 mg g- La"' or Sr" solution (to eliminate interference from phosphate) and diluting to 20 ml prior to the determination of Ca Mg and Zn using air- acetylene FAAS (96/2978). Although this may be a useful method it is always preferable if possible to use one of the standard reference methods (published for example by ASTM or IP). Another problem with direct solvent dilution methods is that if wear particles in the samples are larger than a few microns 100% recovery will not be achieved (incomplete sample transport and atomization). In order to achieve 100% recovery for samples containing larger wear particles it is necessary to include a digestion step.One such method has been published during the review period which involved ultra- sonically treating the oil with 5.5 mol 1-' HCl and several drops of H202 for 15-20 min diluting with toluene and stirring for a further 30min at 60-70°C and then analysing the aqueous phase using AAS or ICP-AES (95/4495). Using ICP- AES the method was successfully applied to the determination of Ca Cr Cu Fe Mn P S and Zn. However for most condition monitoring applications it is the trends in wear metals which are more important than the absolute concen- trations themselves and so provided the. measured concen- trations correlate well with degree of wear obtaining 100% recovery is not critical.This is the case for most normal wear processes and the extra time and effort associated with the use of digesion techniques can rarely be justified on a routine basis where very large numbers of samples must often be analysed within a short period of time. Whereas additive and wear metals in lubricating oils are most commonly determined using ICP-AES determination of chlorine concentrations normally requires the use of alternative techniques such as XRF or microanalytical combustion tech- niques (because of the inability of conventional ICP-AES instruments to measure C1 concentrations down to mg kg-' levels). The requirement to measure chlorine concentrations in oils (particularly waste oils) is becoming increasingly important with the current emphasis on reduction of chlorinated Jour!ial of Analytical Atomic Spectrometry December 1996 Vol.11 485Rhydrocarbons in the environment and the ability to measure C1 simultaneously with a wide range of other elements using ICP-AES is therefore an attractive prospect. Several newer commercial instruments allow extended wavelength coverage in the UV/VIS down to 120 nm permitting the use of sensitive C1 lines in the 13G140nm region (96/C2195 and 96/C2196). Detection limits of less than 1 mg kg-' have been reported and so the method is potentially suitable for the analysis of waste oils although consideration must be given to the variety of chlorine compounds which can be encountered in these samples and their respective volatilities (96/C730). The pres- ence of particulates and/or emulsified water in waste oil samples can also cause problems with direct ICP-AES analysis although combustion in an oxygen flask prior to analysis using ICP-AES and ion chromatography has been shown to be an effective method for determination of S and C1 in these waste oils (96/2644).This approach is relatively time consuming however and so direct analysis using XRF may be a more attractive option. The authors have shown that problems with settling of particles could be largely overcome by using a thin film method for sample presentation to the XRF spectrometer. The use of XRF for rapid determination and control of Cd C1 Hg Pg S and Ti concentrations in used oil feedstock to a cement kiln has been reported (95/C4201). In some cases it may be necessary to distinguish between organic and inorganic chlorine compounds.Galkin and Karyakin (95/4468) have described a novel method for determination of organo- chlorine compounds in lubricating oils using molecular emission of Cu" chloride formed by combustion of the compounds in a propane-air flame in the presence of copper (95/4468). Inorganic chlorine compounds did not give an emission signal. 2.2. Organic Chemicals and Solvents This section of the review covers the analysis of organic chemicals and solvents. Also included is work dealing with the determination of organic and organometallic compounds in environmental samples where these are related to industrial processes or products. A summary of work published during the review period is given in Table 2. 2.2.1.Chemicals Environmental considerations form an integral part of over- all business strategy within a modern industrial company and in recent years significant progress has been made in minimiz- ing the environmental impact of industrial processes and products. Unfortunately in the past environmental consider- ations were not always given as high a priority as they are today and over the years there is no doubt that industrial products and by-products have been a significant source of environmental pollution. Examples include pesticides fungi- cides chlorinated hydrocarbons (e.g. PCBs) Cr and As from wood preservatives Hg from several industrial sources such as mercury cells used in the chloralkali industry Sn from antifoulants and Pb from a number of sources including gasoline additives and paint.Methods for determination of total concentrations of most elements in environmental samples are fairly well established and so few of the papers published during the review paper dealt solely with these applications. One recent development however is the availability of axially viewed ICP-AES instrumentation. Limits of detection for these instruments are typically an order of magnitude lower than those attainable using convential radial viewing of the ICP and this opens up the possibility of carrying out determinations using ICP-AES which would previously have required use of alternative techniques such as GFAAS or ICP-MS. Alavosus et al. (96/1259) have evaluated an axially viewed ICP-AES spectrometer for determination of 22 elements in toxicity characteristic leaching procedure samples from a landfill site.Limits of detection ranged from 5 (K) to 0.03 (Mg) ng ml-' compared with 700(K) to 0.3 (Be)ngml-' for a radially viewed plasma. For environmental samples determination of the total concen- tration of elements is rarely sufficient since it is well known that toxicity can vary enormously depending on the chemical form of the element. Methods for chemical speciation are generally much less well developed than for total concen- trations and this is therefore currently one of the most active areas of research in atomic spectrometry. The most common approach for chemical speciation is to combine chromato- graphic separation with atomic spectrometry. A review (126 references) has been published which covers the principles of element-specific choromatographic detection using atomic absorption emission and mass spectrometry with applications drawn from the environmental petrochemical geochemical agricultural and chemical fields (96/1075).Due to the relatively widespread availability of robust commercial instrumentation one of the most common of these hybrid techniques is GC-AES. Several reviews have been published during the review period (95/3368 96/1046 96/1401 96/1857) covering applications of GC-AES for chemical speciation of analytes which are relatively volatile (or which can be made volatile by derivatization). Pedersen-Bjergaard and Griebrokk have described a system in which a 350kHz plasma was sustained inside the end of a 0.32 mm i.d. capillary column and used for element specific detection of Br Cl N 0 and P by AES (95/3799 96/1434).Owing to the small volume of the detector cell the energy density of the plasma was high and the plasma could be sustained using only 2-3 ml min-' of helium GC carrier gas. However it was found to be advantageous to add 10 to 15 ml min-' of helium make up gas to stabilize the plasma and reduce peak tailing. For N and 0 specific detection it was also necessary to use methane mixed with oxygen or nitrogen as plasma dopant. Even with this high level of doping however nonspecific responses from eluting hydrocarbons were observed and element to carbon selectivities were only 100 1 (N) and 40 1 (0). For phosphorus-selective detection use of hydrogen- methane as plasma dopant provided a selectivity of 2300 1 and a detection limit of 39 pg s-'.GC-AES has been used for the determination of nitrogen-containing herbicides in water (96/29 18) polychlorinated biphenyls (PCBs) and methyl- sulfonyl metabolites in seal blubber and plasma (95/3479) and organophosphorus pesticides in environmental waters (95/3474). In the latter application a novel approach was adopted which involved adsorbing the analyte onto a silica fibre coated with 100 pm polydimethylsiloxane (placed in the water sample for 20 min) and then thermally desorbing (205 "C) into the GC. Carbon and sulfur selective chromatograms were recorded at 193 and 181 nm respectively and provided linear calibrations over the range 2-200 ng ml-I. As discussed in last year's review (96/416) AAS detectors based on wavelength modulated diode lasers have been shown to have extremely low limits of detection for determination of halogens and appeared to offer high potential for use as relatively low cost sensitive halogen specific detectors for GC.Niemax and co-workers (96/640) have described application of this technique for C1 specific GC detection using a helium microwave induced plasma. Limits of detection were however very disappointing (1 mg I-' or 80 pg s-'). The problem was found to be due to slow fluctuations of background absorption and in more recent work the authors were able to eliminate the problem through additional modulation of the absorption obtained by switching the plasma on and off with a frequency of a few kHz (95/4169). Using the latter approach limits of detection below 3 ng ml-' were obtained for species such as chloroform and carbon tetrachloride using splitless injection of 0.5 pl samples.Other relatively low-cost halogen specific detectors that have been reported during the review period include a gas sampling 486 R Joairnal of Analytical Atomic Spectrometry December 1 996 Vol. 11GD-AES (95/3881) and a low power He SCP based instrLiment utilizing a fibre optic link and an interference filter AES spectrometer (95/4591). In the former application molecular gases and organic vapours were introduced into an exponential dilutor and carried by support gas through a silica capillary and into the GD (limits of detection were in the ng s-' range for C Cl F and S). In the latter application chlorinated hydrocarbons (including pesticides) were introduced into the plasma by electrothermal vaporization of methanol solu.lions.Chromated copper arsenate (CCA) is commonly employed as a wood preservative. All three metals can however be leached into the environment under varying conditions The release of As Cr and Cu species into simulated rain water (96/104) and in a marine environment (95/3930) have been studied using ICP-AES and AAS respectively. Specific dei ermi- nation of CrVr using alkaline leaching followed by AAS has also been reported (96/126). Fortunately although the samples studied contained 0.3-0.4% m/m total chromium less than 100 mg kg-' was found to be in the more toxic CrV' form. The various chemical forms of arsenic can exhibit wide ranging levels of toxicity e.g.As"' and AsV species are toxic whcreas arsenobetaine and arsenocholine are virtually non-toxic. Determination of the chemical form of arsenic in environlziental samples is therefore an essential consideration. The ion chroma- tographic behaviour of arsenite arsenate methylarsonic acid (MMA) and dimethylarsinic acid (DMA) on a Hamilton PRP- XlOO anion exchange column has been studied using I;AAS and GFAAS detectors (95/3653). All the species were effectively separated in a few minutes and could be detected at arsenic levels above about 10 ng (100 pl injection). Unfortunately ion- exchange columns can have limited lifetimes and so reversed phase HPLC can be a more attractive option. Woller et al. (95/4176) have described use of a modified C Rutin HPLC column with a 20 mmol 1-' Na,HPO buffer solution of pH 6 containing 0.5% of methanol and 0.1 % of 10 mmoll-' ditiode- cyldimethylammonium bromide as the mobile phase for deter- mination of the above arsenic species using a cool flame AFS detector with sample introduction using an ultrasonic nebul- izer (95/4176).Limits of detection were 35 50 20 and 2Ong for AS"' As" DMA and MMA respectively for a 2'50 pl injection. Even lower detection limits have been obtained by coupling reversed phase HPLC with ETAAS using an mto- mated thermospray interface (95/3459). The interface consisted of a fused silica capillary inserted into a heated stainless steel tube through which effluent from the HPLC was injected for 2 s onto the pre-heated (150 "C) graphite furnace platform.A total thermal programme of 40s was possible and limits of detection were 5 8 and 15 ng ml-' for As"' AsV and DMA respectively. Low limits of detection (90-300 pg) for determi- nation of arsenic species have also been reported using 1CI'-MS in combination with micellar liquid chromatography (95/16 10). This method had the further advantage that samples containing protein (e.g. urine) could be injected without pre-treatment and showed no interference due to chloride. The use of ICP-MS with SFC for multi-element (As Hg and Sb) determination of organometallic compounds has also been reported (96/1637). Although ICP-MS probably represents the ultimate in sensitive detectors for arsenic speciation it is rather expensive for inany laboratories to use on a routine basis.Simpler lob-cost detectors are therefore often more appropriate. Hydride gener- ation coupled with quartz tube AAS has been demonstrated to be a suitable method for determination of AS'" AsV RlMA and DMA in aqueous samples and can be considered cheap enough to be applied in most laboratories (95/4386). Some arsenic species however e.g. arsenobetaine and arsenocholine cannot be determined using this approach without first being transformed into simpler species which are able to form hydrides. On-line photolytic decomposition has been shown to be suitable for this purpose (96/1103). Hydride generation has also been used with MIP-AES for HPLC determination of arsenic compounds (96/283). In this case vesicle forming surfactants were used as mobile phase and provided signal enhancements of 75-100%.The method was applied to As speciation in natural water and human urine and detection limits for the toxic arsenic compounds As"' AsV DMA and MMA were in the range 1-6 ng ml-'. The method was also applied to the speciation of mercury compounds (using cold vapour generation with SnC1,) and gave limits of detection of 0.15 and 0.35 ng ml-' for inorganic Hg and methylmercury respectively. Whereas speciation of metallic species in liquid samples can be fairly readily achieved using a combination of chromato- graphic separation and atomic spectrometric detection speci- ation in solid samples can be more problematical since there is no guarantee that species will necessarily be preserved during sample digestion. Direct speciation in solid samples is therefore preferred where possible but unfortunately few methods exist for carrying out these determinations. A novel method has been reported for mercury speciation in solid samples which involved continuous microwave assisted pervaporation with atomic fluorescence detection (96/3015).The solid sample was placed in a pervaporation cell and either SnC1 (for inorganic mercury) or oxidizing solution followed by SnCl (for total mercury) was added using a syringe. The cell was placed in a microwave device and the Hg produced swept to the fluores- cence detector via a gas-liquid separator. The linear range was 10-500 ng g-' and a sampling frequency of 10-12 samples per hour was claimed. Contaminated soils can contain not only metallic and ionic mercury but also various forms of alkylmer- cury.Thus it is necessary to distinguish not only between organic and inorganic mercury but also to determine the various forms of alkylmercury. The behaviour of eight organ- omercury compounds in contaminated soils has been investigated using lysimeter experiments (96/1990). Organomercury com- pounds in the soil and percolating water samples were deter- mined using dithizone extraction followed by HPLC-AFS while differentiation between organic and metallic mercury in gaseous samples (air above the soil) was accomplished by adsorption on Carbotrap and gold filters thermal desorption and atomic fluorescence detection. Evidence was observed for transformation of organic to inorganic mercury. An increas- ingly common method for the speciation of organomercurials in environmental samples is GC-AES.Using this approach low limits of detection (1.2 pg) and linear range of 1-40 ng ml-' has been reported for methylmercury in marine tissue samples (95/3947). Generally these methods require a derivatization step to convert non-volatile compounds into more volatile compounds which can be successfully separated on a GC column. A comparison has been carried out of three different derivatization techniques (direct aqueous phase ethylation or phenylation and chelation extraction followed by Grignard reaction) for determination of Hg Pb and Sn compounds in tissue samples using GC-MIP-AES (95/3855). Procedures for sample pre- treatmen t prior to e t h ylat ion (solvent ex traction distillation under nitrogen and alkali digestion) have also been evaluated for the determination of methylmercury in various aqueous and solid environmental samples using GC-CV-AFS (95/4360).An extremely sensitive method for the determination of alkylmercury compounds in water samples using GC-MIP- AES has been reported by Mena et al. (95/3852). Alkylmercury compounds were pre-concentrated on micro-columns of sulfyd- ryl cotton eluted using 3 mol 1-' HCl treated with buffer solution phenylated using sodium tetraphenylborate and then extracted into 1 ml of hexane. Detection limits of 10 ng 1-' were reported for methyl- and ethylmercury. The rate of mercury methylation in sediments has been studied using enriched stable mercury isotopes with measurement of isotopic ratios using GC-ICP-MS (95/4178).Methylmercury ion was Jouriial of Analytical Atomic Spectrometry December 1996 Vol. 11 487 Rseparated from the sediments by distillation converted to methylethylmercury using sodium tetraethylborate and ana- lysed after purge and trap collection on a Tenax absorber and thermodesorption into the GC column. A limit of detection of 0.02 ng g-' for Hg in dry sediment sample was obtained. More than 3% of the mercury added to the lake sediment was methylated within 21 days and evidence suggested that the system was still not in equilibrium after this period. Major sources of organotin compounds in the environment include fungicides anti-fouling paint biocides thermal stabiliz- ers for PVC and catalysts used for production of silicones and polyurethane foams.Of these tributyltin leached from antifoul- ing paints is one of the most significant contributors to the pollution of marine environments. The tributyltin degrades to other alkyltin compounds principally mono- and dibutyltin and can be concentrated up in fish tissues with bioconcentr- ation factors of several thousand fold. Although the toxic effects of butyltin compounds on different organisms are well established the genotoxic potential has received less attention. Kuballa et al. (95/3691) have studied the genotoxicity of various butyltin compounds and have carried out determi- nation of the distribution of these compounds between water suspended particulate matter soil sediment fish tissues and air in the highly polluted River Elbe in Germany using GC-quartz tube-AAS.A simple analytical procedure was presented based on ethylation with sodium tetraethylborate and extraction into hexane. No pre-extraction steps were apparently required and limits of detection of 25 pg Sn per microlitre injected volume were reported. Other workers have reported that limits of detection for GC-AAS can be reduced to around 2-5 pg Sn by optimization of the quartz tube atomizer (95/3847). For determination of the butyltin com- pounds in marine biotissues Kuballa et al. used solubilization with tetraethylammonium hydroxide prior to ethylation. A similar approach has also been used for the determination of triphenyltin and butyltin in these materials using GC-MIP- AES (95/3905) and gave limits of detection of 2 ng g-' (as Sn).With sediment samples however it has been shown that monobutyltin can have a strong affinity for the sediment and that polar solvents and strong acidic conditions in combi- nation with a suitable complexing agent may be necessary in order to achieve good extraction efficiencies (96/3029). Complexation (diethylammonium diethyldithiocarbamate) has also been used with SFE (COz modified with 5% ethanol) for determination of 13 alkyltin compounds in sediment and soil samples using GC-MIP-AES (95/1866). Limits of detection were approximately 1 ng ml-' of Sn (corresponding to approxi- mately 0.2 ng of compound per gram of sample) but even with the use of the complexing agent monoalkyltin compounds could not be recovered from the samples. The use of SFE with GC or SFC using various atomic spectrometric detectors for the determination of organotin compounds in aqueous and solid matrices has been reviewed by Bayona and Cai (95/3822).Simultaneous determination of organotin organolead and organomercury compounds in environmental samples using GC-MIP-AES (95/3670) has been reported and a new arrangement in which an MIP was directly coupled to the GC (without interface) and quartz fibres used to transmit emitted light to the spectrometer has been applied to the speciation of organotin compounds (95/3948). Simultaneous determi- nation of methylated species of tin lead and mercury in water by purge-and-trap injection GC-MIP-AES has also been reported (96/1806). In the last case limits of detection of 0.15 0.20 and 0.60 ng 1-' were achieved for methylated tin lead and mercury species respectively.A GC-MIP-AES method for determination of selected organotin compounds has been developed by the US Environmental Protection Agency and as part of an evaluation excercise an interlaboratory study has been carried out using pentylated organotin compounds (96/1911). Ten laboratories participated in the study and each received 5 pentylated organotin standards 3 pentylated soil or sediment extracts and 1 pentylation blank. Of 720 individual results 60 (8.3%) were identified as outliers (with two labora- tories accounting for most of the outliers!). It was found that electronic pressure control on the injection inlet was required in order to achieve acceptable chromatography for tetracyclo- hexyltin and tetraphenyltin.The intralab precision of the method ranged from 1.3 to 22% RSD depending on the compound and the interlab precision ranged from 11 to 40% RSD over the concentration range tested. Guidelines for the synthesis purity control and quantification of pentylated organotin standards have also been published (95/4362). For the ultimate in detection limits for the determination of organometallic species derivatization GC techniques can be applied with ICP-MS detection (95/1478 96/2433). In the former study limits of detection of 50 100 and 120fg were reported for Sn Pb and Hg compounds respectively. ICP-MS has also been used with reversed phase HPLC for the determi- nation of inorganic tin trimethyltin triethyltin tripropyltin tributyltin and triphenyltin in harbour sediment and water samples (96/58).Using an ultrasonic nebulizer to introduce the carrier solution into the plasma limits of detection of 2.8-16 pg tin were obtained for the various species. The application of HPLC-ICP-MS within the EC Measurement and Testing programme for production of organtin certified reference materials has been discussed by Rivas et al. (96/2021). Reversed phase HPLC-ICP-MS has also been applied to the determination of trimethyllead (TML) and triethyllead- (TEL) (degradation products of tetraalkyllead gasoline additives) in urban particulate material (96/273). Coupling of the HPLC to the ICP was achieved by mixing the mobile phase with 6% H,02 and 0.08 moll-' HC1 and reacting with 10% NaBH in 0.01 moll-' NaOH to form volatile lead hydride which was swept into the plasma by a stream of argon (via a gas-liquid separator).Limits of detection (6 0.6 and 1 ng ml-' respectively for Pb" TML and TEL) and repeat- ability were comparable to or better than those for an LC-ICP-MS system with a conventional pneumatic nebulizer. As with other organometallic species involatile alkyllead com- pounds can be converted into more volatile materials suitable for gas-phase separations by derivatization. Craig et al. (95/3854) have described a method for the determination of trialkyllead species in rain water and roadside dust which involved derivatization with sodium tetraethylborate purging the derivatized species from solution and trapping in a silanized quartz U-trap packed with 10% OVlOl on Chromasorb W-HP and cooled by liquid nitrogen.The derivatized alkyllead com- pounds were driven from the trap by heating at 63"C separ- ated according to their volatility and detected using AAS. Alternatively as with alkyltin compounds derivatized species can be determined using GC-MIP-AES although interferences due to matrix coextractives and reagent impurities introduced during sample preparation can sometimes cause problems (95/3808). Although identifying the source and form of lead in contaminated soils is an important consideration the ultimate fate of the lead contamination is perhaps even more important. Bacon et al. (95/4285) have addressed this issue by using isotope ratio mass spectrometry to analyse grass samples grown on soils spiked with isotopically enriched lead.Up to 50% of the lead in unwashed grass grown on the spiked soils had its origin within the soil and at least 10% of this remained after washing. Furthermore approximately 10% of the lead measured in grass grown on adjacent unspiked soil was found to have originated from the spiked soil. A major problem in the field of chemical speciation determinations has been lack of availability of suitable certified reference materials. Over recent years however some steps have been taken to try to address this problem. A review (23 references) of certijed 488 R Journal of Analytical Atomic Spectrometry December 1996 Vol. 11reference materials for speciJic chemical forms of elements has been published by Quevauviller (95/4473) with particular emphasis on the work carried out under the EC Measurement and Testing Programme (formerly BCR).Several innovative indirect methods for determinutit )n of organic compounds using atomic spectrometry have been pub- lished during the review period. The most common approaches have involved solvent (typically IBMK) extraction of analyte- metal complexes and determination of the concentration of metal in the solvent using FAAS. These have included methods for determination of malathion pesticide involving reaction of the hydrolysis product dimethyldithiophosphate with Bi"' (96/121) determination of dithiocarbamate fungacide (Ztram) by complexation with Cu" (95/4084) and determination of some nitrophenols (not monosubstituted) involving com- plexation with bipyridylcopper(I1) or phenanthrolinecopper (11) (95/3842).Improvements in sensitivity for this type of method can be obtained using GFAAS or cold vapour AAS in place of the more conventional FAAS approach. Both FAAS and GFAAS have been used with an indirect method for the determination of anionic surfactants (sodium dodecylsulfate) in toothpaste,commercial liquid detergents and waste water samples by formation of an ion pair with bis- (2-benzoylpyridinesemithiocarbazone)cobalt (111) and extrac- tion of the complex into isopentyl acetate-isopentanol (8.5 1.5) mixture (95/4057). A method based on cold vapour AAS has been described for the determination of nanomole quantities of lower aldehydes (95/3674). The method was hased on the oxidation of aldehydes to the corresponding acids by the mercury(11) ion which was in turn reduced to elemental mercury and determined using CV-AAS.The method was reported to be highly selective and could be used for the determination of methanal ethanal and propanal in the pres- ence of ketones alcohols acid esters ethers organic chlorides and epoxides. Indirect methods are commonly applied for the determination of active and other organic components in pharmaceuticals since the matrices are usually known and generally highly controlled reducing the likelihood of unexpected interferences. A flow- injection FAAS method has been reported for determindtion of salicylic acid in pharmaceuticals (96/1384).The method was based on reaction of the analyte with copper carbonate entrapped in polyester resin beads (preparation described ) and determination of the released Cu" using FAAS.The calibration graph was linear over the concentration range 4-75 mg I-' and a sample throughput of 257 per hour was claimed by the authors. Interferences from foreign compounds were investi- gated and tabulated. A method has also been described for determination of the hydrochlorides of antazoline hydralazine and amiloride and quinine sulfate in pharmaceutical prep- arations based on precipitation of the complexes with manga- nese thiocyanate and determination of Mn in the filtrates using DCPAES (95/4166). Determination oftrace elements in drugs is an important area in its own right which has received considerable attention during the review period. In cases involving siezed illicit drugs trace element fingerprints can provide useful information regarding the geographical origin of the drugs.The most commonly applied approach is GFAAS. Barmejo-Barrera and co-workers have studied various matrix modifiers for the determination of Cu (96/2017) Ni (96/282) and Pb (96/?090) in cocaine and heroin using this technique. By using appro- priate chemical modifiers it was possible to carry out the above determinations using a simple dissolution technique (water for heroin and 35% nitric acid for cocaine) with no sample pre-treatment. Limits of detection obtained were 3.9 32 and 31 pg kg-l respectively for Cu Ni and Pb. Arpadjan and Alexandrova (95/4698) however have claimed that rnany drugs (e.g. aspirin Analgin paracetamol Nivalin and ami- dophen) can effectively fulfil the role of chemical modifier obviating the use of additional modifiers.UniversaE temperature programmes for modifier free ETAAS of 11 elements in pharma- ceuticals were presented. It was noted however that As and Sb could not be determined in all medicines without use of chemical modifiers. In general origin tracing of illicit drugs requires statistical evaluation of the concentrations of a large number of trace elements. ETAAS being generally a single element technique is therefore not ideally suited to this appli- cation and rapid multi-element techniques such as ICP-MS are preferred. Use of ICP-MS for origin tracing of seized methamphetamine and heroin has been reported (96/101 96/1535). The application of ICP-MS for the measurement of La and Lu texaphyrin photosensitizers in liver homogenates (96/1456) determination of Pd in fosinopril sodium (96/1653) and for the characterization of selenide drugs and their metab- olites using hydride generation ICP-MS and HPLC-ICP-MS (96/2362) have also been described.Other publications which may be of interest to workers in the pharmaceutical field include a discussion on the use of IRMS in drug research and development (96/2453) a comparison of analytical methods for the determination of iron in pharmaceuticals and a review covering applications of XRF in drug percutaneous absorption measurements (96/1194). 2.2.2. Solvents Introduction of organic solvents to plasma sources can be problematical due to both plasma stability and carbon build- up on the plasma torch and in the case of ICP-MS on the interface cones in particular.In addition to prohibiting direct analysis in some cases the organic solvent can also give rise to spectral and molecular ion interferences. These problems have limited the use of conventional solvent extraction sample preconcentration procedures. Increasingly however new sample introduction approaches which allow solvent remoual prior to sample introduction to the plasma are being applied to allow direct analysis of a wide range of organic solvents. An ultrasonic nebulizer-membrane separation interface has been evaluated for the analysis of chelated trace metals by ICP-AES and ICP-MS (96/C2285). The possibility of using oil-based standards in chloroform for universal calibration was investigated and the role of membrane desolvation on analyte recovery and on the level of molecular ion intensity was reported.It was found that in order to minimize analyte losses due to chelate volatizisation the boiling-point of the extraction solvent should be as low as possible. The use of this system resulted in reduced spectral interferences and improved detec- tion limits. The possibility of using a universal calibration for the ICP-AES analysis of multiple organic solvent systems for use in the petrochemical industry has been investigated (96/C2247). An ultrasonic nebulizer coupled to a microporous membrane desolvator (MMD) was employed for the direct introduction of organic solvents. In order to achieve universal calibration the following conditions were required the volu- metric flow to the nebulizer had to be constant matrix effects due to residual solvent loading had to be negligible and the nebulization efficiencies of the sample and solvents relative to the calibration sample had to be known.Using this system with a 140mm MMD direct analysis of pentane was possible at uptake rates of 1.3 ml min-' providing detection limits comparable to those obtained for aqueous solution using the ultrasonic nebulizer. The performance of a commercial mem- brane tubular desolvation system (Cetac Technologies Inc.) and a flat sheet membrane desolvation system have been compared (96/C733). The parameters examined included both analyte transport and desolvation efficiencies. The application of flow injection to the determination of Cu Mn Fe and Pb in organic solvents by ICP-OES has been Jouriial of Analytical Atomic Spectrometry December 1996 Vol.11 489Rreported (95/4520). Solvents studied were methanol ethanol isoamyl alcohol formaldehyde acetone cyclohexanone ethyl acetate 1,2-dichloroethane and cyclohexane; a double capillary nebulizer was employed for sample introduction. The effect of the organic solvent on plasma stability analyte signal intensity and carbon build-up on the plasma torch were investigated. The effects of organic solvents on the determination of Se by ICP-MS with both pneumatic nebulization and flow injection sample introduction coupled with hydride generation have been studied (95/4709). The addition of alcohols reduced the polyatomic interference and gave rise to a ten-fold enhance- ment of the Se signal.The effect of ethanol loading of a 40 MHz ICP has been investigated (96/3022). A comparison was made between aqueous and organic solution with ethanol added. The electron density increased as the ethanol content of the aqueous solutions increased and the addition of ethanol led to an increase in sensitivity. In contrast the addition of ethanol to the organic solvent (xylene) gave a reduction in electron density and a corresponding reduction in sensitivity. Signal enhancements in ethanol for the determination of Se and As by ICP-MS have also been reported (96/2395). The effects of both plasma power and nebulizer flow rate on the magnitude of the signal enhancement were studied. A study has been carried out on the effects of organic solvent load on the radial emission profiles for MgI MgII CI and CN (96/592).Zones in the plasma were identified in which the emissions of these species were proportional to solvent load and plasma excitation conditions. 2.3. Inorganic Chemicals and Acids As with previous reviews a recurring theme concerns efforts to improve methodology associated with the analysis of samples with high dissolved solids. Three main approaches dominate direct introduction of solutions through improvements in nebulization techniques (and optimization of resulting analyte response); direct introduction of solids; and matrix elimination either prior to analysis or coupled on-line via FIA or chromato- graphic techniques. Cluster analysis has been applied to the analysis of high saline and serum solutions by ICP-MS (95/3444).The degree of signal suppression depends on the ionization potential and mass of the elements in question and compromises the choice of a single internal standard. A matrix of signal suppressions for 25 elemental responses in serum (9 g 1-l NaCl) and saline solutions ( 5 g 1-l NaCl) under various conditions were compared using the cluster analysis technique. Four groups of elements exhibiting the same behav- iour were identified and for each group a suitable internal standard was chosen. This approach significantly improved the accuracy and precision of the analyses compared to when a single internal standard was used. The combined use of emission and MS detection (plasma optical emission mass spectrometry POEMS) has been investigated for the analysis of solutions containing high dissolved solids.The combination of a relatively large sampler and skimmer cones in the mass spectrometer coupled with a novel sample introduction system allowed determination of analyte levels from ppt to YO levels using the same instrument (96C876). In order to achieve this remarkable dynamic range however memory effects in both the sample introduction system and in the ICP-MS interface must be controlled. The interference effects of Ca Sr Mg on the determination of Li in brine solutions by flame atomic emission spectrometry have also been reported (95/3833). Three types of interference effects were described; band emis- sion due to Sr and Ca compounds scatter of Li emission and Li ionization.Interferences were investigated using both factorial and univariate approaches with the factorial de- sign method providing the most satisfactory optimization conditions. A large number of abstracts describing developments in improved sample introduction techniques were received during the review period. Activity in this subject area has increased substantially and perhaps reflects the availability of commercial systems applied to real-world applications. A comparison has been made between analytical figures of merit obtained using pneumatic ultrasonic and thermospray sample introduction systems in conjunction with three different ICP-AES systems (95/4581). A Leeman Labs air-path echelle spectrometer coupled to a 27 MHz ICP was used with an ultrasonic nebulizer and a fused SiO aperture thermospray.For low dissolved solids ultrasonic and thermospray nebulizers gave similar LOD improvements (a factor of twenty) over conven- tional pneumatic nebulization. For solutions containing high dissolved solids the thermospray showed similar optimized conditions to those obtained for solutions containing low dissolved solids. In contrast the ultrasonic nebulizer required changes in both power and gas flow to maintain a stable discharge. Consequently these changes degraded the LODs achieved with this nebulizer for high dissolved solids compared with those obtained at lower solids concentrations. As a result the improvement over conventional pneumatic nebulization under these conditions was only a factor of four. In another study the analytical characteristics of a thermospray sample introduction system coupled to ICP-MS were investigated and compared with a conventional pneumatic system and with the same pneumatic system coupled to the desolvating unit nor- mally employed with the thermospray (95/4171).In the pres- ence of salts [NaNO Ca(NO,),] analyte ion signal suppressions were more severe in the former than for the other two arrangements. Conversely in the presence of mineral acids ( H,SO H,PO,) the systems gave similar suppressions. Ultrasonic and Meinhard high efficiency nebulizers have been adapted for the analysis of corrosive samples by ICP-MS (96/2407) with nebulization efficiencies ranging from 10-60%. The authors described a desolvation and condensation assembly which allowed on-line thermal separation of analyte/ matrix and reduced all major acid components (HF HC1 HNO H,SO and methanol) by 90-98%.The analyte ma- trix ratio that could be tolerated increased by a factor of 5-25 fold and detection limits improved by a factor of 2-20. Non- metals (B Si Se Br I) were washed out and could not be determined in the ng 8-l range. For 68 other analytes recover- ies were in the order of 95%. The application of ultrasonic nebulization to the analysis of mineral acids surfactants and petrochemical solvents using ICP-MS has been described (96/C791). Polyatomic ion formation was studied as a function of instrument operating parameters for the various sample matrices. In another paper (95/4393) the performance of six different types of nebulizer were compared in terms of their long-term stability for aerosol generation from multielement solutions containing differing salt concentrations.The need to couple efficiently small volume sample introduc- tion devices with atomic spectrometry techniques has become increasingly important as the use of coupled techniques (required for determining speciation information) has become more prevalent. The performance characteristics of two spray chambers with small internal volumes ( 10ml) have been assessed (96/C2280). Peak broadening is a significant factor when coupling FI or HPLC to ICP-MS at a variety of flow rates. The solution uptake rate of high efficiency nebulizers such as the Meinhard design may have a significant influence on the performance of available spray chamber designs.In this study a range of sample uptake rates were examined. To match the optimal flow rate of a capillary column (0.32 mm id) a sample uptake rate of 3-5 yl was required. The performance of the spray chambers was assessed considering factors such as peak width and shape dispersion and sensitivity. Arsenic Sn and Hg species were determined in environmental samples. 490 R Journal of Analytical Atomic Spectrometry December 1996 Vol. 11A has been applied as a means of both high efficiency sample introduction and analyte preconcentration for ETV-ZCP-MS analysis (95/4703). For the eight elements studied a two niinute deposition at a flow rate of 0.25 ml min-' gave an improve- ment of two orders of magnitude over conventional nebulization/spray chamber sample introduction.The eflect of varying several parameters on both the ICP and deposition process were reported. The deposition and insertion procedures were automated and RSD values at the 1 mg 1-1 Concentration level were reported to be around 5%. Good agreement was obtained for the analysis of a number of standard reference materials using this system. The direct introduction of samples for ICP-MS analysis of semiconductor grade chemicals has been described (96/1745). Given the high purity specification required for these chemicals directly analysing the sample is advantageous as it eliminates the possibility of contamindtion which may be caused if sample pretreatment steps are required. Both direct nebulization using an anti-corrosive injection system and introduction by ETV were evaluated for the analysis of HF HNO and Hz02.For the analysis oi' HF limits of detection for elements which were affected by molecu- lar ion interferences (e.g. Cr Ni Zn) were in the 0.5 ng ml-' range. For elements not affected by such interferences ( L i Be Mg Mn and Ga) detection limits were in the 0.1 ng ml-' range. Iron could not be determined by conventional ne huliz- ation due to interference of argon oxide. However using ETV sample introduction detection limits for Fe were 0.2 ng ml- '. ICP-OES has been applied to the on-line analysis ofelemental pollutants in gaseous efluents (95/4185). A thermodynamic study established the need to control the water content of the gas and a torch design able to withstand changes in thermal conductivity was developed. Calibration was achieved using an aerosol produced from a standard solution injected thIough a batch-type ultrasonic nebulizer and a desolvation unit. Detection limits were reported for a number of environmentally significant elements from 25 pgrn- for As to around 1 pg m-3 for Cu Cr Mn Ti and Zn.These detection limits are below the threshold limits allowed in gaseous effluents for many industrial processes. The requirement to separate analytesfvom complex matzrials prior to analysis is an all too familiar requirement for most atomic spectrometry techniques. Traditionally separa tions have been based on off-line procedures. However in recent years developments in on-line sample preparation systems have resulted in sample preparation methodologies being modified or developed for use in such systems.An on-line matrix removal method for the determination of trace metals in highly salted waters using anion and c.ition exchange cartridge columns has been reported (96/C2 142). The pH of the samples were adjusted by the addition of appropriate amounts of HNO or NH solutions. A chelating reagent APDC or 8-hydroxyquinoline was added to the sample and heavy metals were neutralised by complexing with the chelates; 50 p1 of this solution were injected into a stream of pure water using a six-way valve. Potential interfering cations and anions such as Na' Ca2+ C1- and SO4'- which did not form chelates were retained in the ion exchange cartridges whilst the neutral chelates of the heavy metals passed through the columns and were introduced to the ICP.This system allowed rapid matrix removal but did not pre-concentrate analyte elements of interest. Some chelates of heavy metals were also adsorbed onto the columns as a result of non- selective hydrophobic interactions between the column support materials and the chelates. A novel iminodiacetate chelating agent immobilized onto a controlled pore glass support has been used as a method of analyte matrix separation for ICP-MS (96/2809). This reagent was used with a commercial automated system and has been shown to be effective for the analysis of effluent samples. A sampling frequency of 10 per hour was reported and calibrations from pure and saline solutions demonstrated good linearity indicating that retention of analytes was unaffected by matrix loading on the column.A wash cycle between samples was required to remove residual matrix elements from the column. An on-line system for separation and preconcentration of noble metals (Au Pd Pt Ir) with both flame and electrothermal atomic absorption spectrometry has been reported (96/C1411). An aminopyridine resin was used for the extraction stage. The choice of eluent was found to be a critical parameter. Flow injection micro- sampling dilution has been combined with the zone pene- tration technique to produce an on-line system capable of achieving 27 000-fold dilutions with a sampling frequency of 45 per hour (95/3809). The method was applied to the direct determination of Mg in the g I-' range in brines without sample dilution.A multi-purpose dialyser unit designed for use in flow injection analysis has been applied to the determi- nation of copper in industrial effluents by atomic absorption spectrometry (95/4687). The advantage of using this system was the ability to deal with the wide variation in copper levels present in the samples and the removal of particulate matter from the sample which eliminated the possibility of nebulizer blockages. The system was claimed to be capable of analysing 120 samples per hour. As with previous reviews abstracts describing the analysis ofacids continue to be received. The abstracts tend to fall into two classes; the actual determination of elements in samples of interest e.g. contaminants in semiconductor grade acid or where acid solutions are used to test the performance of sample introduction devices or to study interference effects.In the present review period the abstracts tended to fall into the latter of these two classes. The mechanism of mineral acid interferences in ICP-AES has been investigated (95/4270). Fundamental studies describing pneumatic generation and aerosol transport for five mineral acids (HC1 HNO HC10 and H3P04) have been described. The parameters investigated included analyte signal response; sample uptake rate; primary and secondary droplet size distributions; total analyte transport rates; and excitation temperature. A reduction in the analyte transport rate and the reduction of the plasma temperature were implicated as principal causes of interference. However the magnitude of the contribution of each of these factors is dependent on the type of acid and the uptake mode.The origin of the differences in interference effect is related to the physical properties of the acids which modify both the sample uptake rate and/or the droplet size distribution of the aerosols. The influence of aerosol formation and transport in acid solutions in ICP-OES has been investigated by other workers (95/4718). In this study the role of ionization and excitation from that of sample introduction was separated by maintaining the plasma operating conditions such that the atom :ion ratio of Mg was kept constant. Perchloric acid up to a concentration of 50% v/v was used as the test acid. Several types of pneumatic nebulizers were compared a concentric nebulizer (Meinhard); a Perkin-Elmer cross flow nebulizer; and a Perkin-Elmer cone spray nebulizer.Signal depression resulting from the acid depended on the nebulizer type the carrier gas flow rate and the spray chamber design. At perchloric acid concentrations higher than 1 % v/v results obtained suggested that the depress- ive effect on the Mg atom line intensity (MgI 285 nm) could not be explained by changes in aerosol density alone but also by a variation in the analyte concentration in the fraction of analyte that reached the plasma. The results obtained with the pneumatic nebulizers were compared with those achieved using an ultrasonic nebulizer with a desolvation system. Acid effects were more significant when the ultrasonic nebulizer was used which was explained on the basis of a reduction in the production of aerosol using the former systems.The effect of Jourrral of Analytical Atomic Spectrometry December 1996 Vol. 11 491 Rnitric and hydrochloric acids on rare earth elements (REE) intensities in ICP-AES has been reported (95/4721). In the presence of nitric acid the response observed from the group of REE studied did not show any particular trend with increasing acid concentration. In contrast in the presence of hydrochloric acid the REE responses were comparable. Both pneumatic concentric and ultrasonic nebulizers (with desolv- ation) were employed in the study. These effects were similar irrespective of the type of nebulizer used. However the magni- tude of the interference observed for HNO was reduced when the ultrasonic nebulizer was employed due to the removal of the HNO by the desolvation stage.The excitation temperature measured for increasing HNO concentrations varied from about 7500K for aqueous solution to 7000K in 7mol1-1 HNO whilst no appreciable difference in excitation tempera- ture was observed with HCl concentrations upto 10 mol 1-'. It was concluded that the effects observed for HC1 were related to physical effects in the aerosol transport system although when the ultrasonic nebulizer was used the measured excitation temperature decreased by 500 K. In the case of the nitric acid no direct correlation was observed between thermal and spec- tral characteristics and the depressive effect of the acid nor could it be attributed to any transport effects.The increasing importance of identifying and quantifying chemical species rather than total amount of element present is reflected in the significant increase in the numbers of abstracts received detailing developments in this area. Medical biological and environmental applications have all been reported on during the current review period. The toxicity of arsenic species is greatly dependent on its chemical form. The methylation of arsenic acid to monomethylarsenic acid signifi- cantly lowers its toxicity. To provide an accurate evaluation of the risk of environmental As exposure it is necessary to quantify all As species present. Assessments based on total As levels do not give a true picture and may overestimate the risk since it is the level of the more toxic forms of As not the total amount that is significant.As discussed in Section 2.2 the low limits of detection provided by ICP-MS make it an ideal technique to couple with chromatographic techniques for the determination of low levels of As species. However the use of ion chromatography which provides a good separation method has difficulties when coupled with ICP-MS since the salt content of the eluents normally employed can lead to blockage of the sampling cones of the ICP-MS interface. This can be avoided if the hydride generation technique is adopted because this allows introduction of the gaseous hydride to the plasma without the dissolved solids. This introduces an additional problem in that the hydrochloric acid employed in the generation step can be transported to the plasma via conventional gas-liquid separators to manifest itself as ArC1 which interferes in the determination of monoisotopic As.This can also be avoided if a microporous membrane such as PTFE is employed in the gas-liquid separator. The evaluation of microporous tubing for use in speciation of As compounds by ion chromatography with ICP-MS detection utilizing hydride generation sample introduction has been reported (96/C2300). The studies centred on the design of the phase separator and its incorporation into the hydride generation system long-term stability of the membrane and selection of an appropriate membrane. An on-line ion exchange preconcen- tration system has been developed for the separation and determination of the As species monomethylarsonate (MMA) and AsV by ICP-AES (96/60).A strongly basic anion exchange resin AGl-X8 was employed for the separation of the two As species. The pH and flow rate of the eluent were optimized to achieve quantitative retention elution conditions. By using an ultrasonic nebulizer the detection limits obtained were in thengl-' range. The speciation of As"' and AsV in coal fly ash using coupled HPLC-ICP-MS has also been reported (95/4175). The concentration of these species released into water from coal fly ash was found to be dependent on the pH of the extracting solution and the type of coal fly ash (location collected type of coal and combustion conditions). A small amount of conversion of As"' to AsV was found particularly at lower pH extraction conditions. This was thought to be partially caused by the grinding conditions.The use of an ultrasonic nebulizer in the determination of As speciation has been reported to cause a shift in the As oxidation state from As"' to As" (95/3055). This was determined by collecting aerosol fractions and analysing them by ion chromatography. This analysis indicated that the As"' might be oxidized to AsV as the aerosol traverses the ultrasonic nebulizer. Treatment of samples with 1 mg 1-' sodium hypochlorite was found to remove this effect. A liquid chromatography method coupled with ICP-MS detection has been reported for the speciation of methylmercury mercury(I1) chloride and ethylmercury in sea-water (96/1439). A mobile phase of 1% v/v aceonitrile and 0.005% mercaptoethanol in 0.006 mol I-' ammonium acetate was used.An off-line sample preconcentration step using dithiocarbamate was required for the analysis of sea-water samples. An on-line procedure for the determination of inor- ganic Sb species by HPLC-hydride generation ICP-MS has been described (95/4701). Sb"' and SbV were separated on a strong anion exchange column using phthalic acid as the mobile phase. Optimization studies to establish the best con- ditions for both separation and hydride generation were reported. Sb"' and SbV have also been determined in electrolyte solutions used for Cu refining by HPLC-ICP-OES (96/1042). In this procedure the sample solution was introduced into a cation exchange column using a 0.1 mol 1-' thiourea mobile phase. Sb"' was retained on the column whilst SbV was eluted.The mobile phase was then changed to 1 mol I-' lithium chloride to elute SbV. The eluents were sequentially introduced to the ICP. Using this system four samples per hour could be analysed with LODs of 0.003 g 1-l Sb"' and 0.005 g 1-l SbV. A procedure for the determination of trace amounts of SeV which combines hydride generation AAS with on-line flow injection pre-concentration has also been reported (96/2488). 2.4. Nuclear Materials Traditionally neutron activation analysis and a p and y spectrometry have been used in the analysis of nuclear mate- rials; however inductively coupled plasma mass spectrometry (ICP-MS) is becoming the method of choice for the determi- nation of the long-lived radioisotopes. A comparison of alpha spectrometry and ICP-MS has been made (96/C2859) and a new preparative strategy developed to allow either measure- ment technique to be used.Comparison of both techniques indicated that for many applications the two techniques are interchangeable. A review has been written (96/1742) detailing the determination of isotopes of I Np Pu Ra Tc Th and U. The determination of 239Pu in ocean sediment has been investi- gated (96/1762). When using alpha spectrometry counting times of around 1000 min or more were required but ICP-MS reduced the total analysis time significantly resulting in a cost and turnaround saving. A review of bioassay techniques for the actinides has been undertaken (96/2922) and the various analytical measurement techniques were described and assessed in the light of the ICRP recommendations for monitoring workers in the nuclear industry. The authors concluded that ICP-MS does not yet have the sensitivity required for this type of analysis but does show promise.Electrothermal vaporization (ETV) has been used as a sample introduction technique for ICP-MS to improve the detection limits for uranium and radium (95/3366). Further sensitivity enhancement using sample preparation techniques such as multiple deposition pre-concentration and chemical modifi- 492 R Journal of Analytical Atomic Spectrometry December ,! 996 Vol. 11cation were described. The vaporization and atomization of uranium from a graphite tube atomizer have been investigated using electrothermal atomization atomic absorption spectrometry and ETV-ICP-MS (95/4739).The ETA-AAS studies indicated that uranium atoms formed above 2400°C but the ETV- ICP-MS studies indicated an appearance temperature of 1100°C for uranium which means that uranium oxide was vaporized at this lower temperature. Addition of Freon to reduce the formation of uranium carbide is also recommended. Use of actinide selective polymer beads to pre-concentrate and separate uranium thorium and uranium progeny in water samples (spring lake river and tapwater) has reduced the detection limits to below lppq with ultrasonic nebulization ICP-MS (96/C676). Iodine is an important environmental indicator and ICP-MS has been used for the measurement of natural iodine and I2’I in environmental samples (96/1661 and 96/C2034). Water samples were treated with sodium sulfite and iodine (and other halides) were measured directly using ICP-MS. Soils and plants were more complicated since the iodine had to be extracted prior to measurement by heating the sample in an oxygen stream and collecting the iodine in a suitable medium.Detection limits obtained for 1291 were limited by the presence of I2’Xe impurity in the plasma gas (argon). ICP-MS has also been used for the determiaation of 99Tc in rainwater(95/4556). 95T~ was used as a tracer to investigate possible losses of Tc during pre-concentration by evaporation. The losses were negligible providing the sample was not heated to dryness. A further pre-concentration step which involved extraction with trioctylamine in xylene gave an instrumental detection limit of 0.04 ng I-’ (96/2410). The Tc was back extracted in two stages and the final measurement solution was deionized water.”Ru was removed by extraction with cylclo hexanone. Various tandem techniques have been reported for the measurement of the actinides using ICP-MS. Flow injecticln (FI) ICP-MS has been used for the measurement of uranium in environmental samples (96/2340). A 30-fold pre-concent ration and separation of the matrix was achieved using TRU a commercially available resin however only data for ground- water was presented. Ion chromatography linked with IC P-MS has been used to determine Pu in waste streams (96/C2265). It is extremely difficult to measure 239Pu in the presence of uranium because of interference from uranium hydridl:. This method describes the separation of uranium from plutonium using cation exchange (CS10 Dionex USA) prior to measure- ment using ICP-MS.The superior sensitivity advantage of high resolutiorr ICP- MS (HR-ICP-MS) should improve the detection limits .ittain- able for the determination of the actinides in many sample types but relatively few abstracts have been received. This is probably due more to the limited number of instruments in use than to shortcomings in the technique. Uranium has been determined in rainwater using HR-ICP-MS fitted with an ultrasonic nebulizer sample introduction system (95/36Ol). An ultimate detection limit of 0.06 pg 1-’ was obtained for 235U and 235U 238U ratios were calculated. Low levels of 9’Tc in marine algae and sediment have been measured using HR-ICP-MS (96/2409).The samples were leached with nitric acid and three extraction procedures were employed to separate and pre-concentrate the Tc. HR-ICP-MS has also been used to determine the halides (Cl Br and I) in biological standard reference materials and I2’I in radioactive waste simples (96/C2077). A better detection limit for iodine was achieved by introducing the analyte to the ICP-MS in elementai form. A novel hydride generation HR-ICP-MS technique has been used to determine selenium-79 in radioactive waste siimples (96/C2076). Hydride generation improves the sensitivity and also helps overcome some of the isobaric and molecular ion interferences. Thermal ionization mass spectrometry (TIMS) has been used for the determination of 230Th and 232Th in seawater (96/2394).Depth profiles of both isotopes were determined and were characterized by a surface minimum a subsurface maximum and intermediate concentrations that progressively decreased towards the bottom of the sea Isobaric interference from 238Pu on the determination of 238U has been investigated and three different methodologies for overcoming this interference were presented (96/2399). Use of a multicollector detection system was also investigated (95/4645) and the application of this to synthetic samples was described. Isotope dilution and TIMS have also been used to determine trace amounts of Fe in zirconium (96/16 18). Signal suppression and interference caused by the zirconium matrix was avoided by use of a two- stage purification process. Using this procedure it was possible to determine mg g-’ levels of Fe in zirconium metal and other applications are possible.An increasing number of papers are appearing using reson- ance ion mass spectrometry (RIMS) for the analysis of the long-lived radioisotopes. The technique is based on stepwise excitation and ionization of atoms with resonant laser light followed by mass analysis. This technique has been limited to a small number of research institutes owing to the complexity of the experimental set-up; however a review (with 20 refer- ences) of the determination of radionuclides has been published (96/1716). Three different experimental approaches have been developed to address the different requirements of each radio- isotope’s different physical chemical and environmental properties (96/1719).For example the actinides were measured using triple resonance ionization and time-of-flight mass spec- trometry while a high efficiency laser ionization source was used to determine Tc isotopes and collinear fast beam spec- troscopy for the quantitative determjnation of strontium-90 and strontium-89 in environmental samples. An ion exchange technique for the separation of Pu from a polycarbonate filter and subsequent measurement using RIMS has been developed (96/1479). Several types of filaments have been investigated for the determination of Pu using RIMS (96/1480). The best results were obtained from use of tantalum as a backing and titanium as a covering. Ultra-trace analysis of long-lived radioisotopes in the environment using alpha beta and gamma spectrometry ICP-MS and accelerator mass spectrometry (AMS) has been discussed and the use of RIMS proposed for the analysis of Tc to approximately 2 x lo6 atoms detection limit (96/1468).A review with 64 references detailing the principles per- formances and applications of laser spectroscopy to the analysis of actinides and radioisotopes has been published (95/4143). The advantages and drawbacks of each of eight laser techniques were discussed and compared with ICP-MS. The determination of uranium series isotope ratios using mass spectrometry (TIMS and ICP-MS) has been reviewed (95/3599). Good agreement was found for the determination of plutonium isotope ratios (240Pu/239Pu) in sediment cores from the Irish Sea using ICP-MS and TIMS (96/2411). Accelerator mass spectrometry has been used to determine Pu to detection limits around Bq of 239Pu; this is better than alpha spectrometry and technical improvements to the accelerator should reduce these detection limits by a further ten-fold (95/C4301).Inductively coupled plasma atomic emission spectrometry (ICP-AES) still continues to be used for the analysis of nuclear materials; however separation of uranium was important to remove potential spectral interference. This technique has been used for the determination of Ti V and Mo in nuclear quality uranium oxide. The uranium was removed by ion exchange and the three analytes measured using ICP-AES (95/4459). Detection limits were around 0.08-0.6 x g with a recovery of 94-99%. Ion exchange using a micro-column has been used g which is equivalent to Journal of Analytical Atomic Spectrometry December 1996 Vol.11 493Rto separate and pre-concentrate by around 100 times some of the rare earth elements and Sr and Y from salt matrices containing uranium (96/1343). Silver was separated from uran- ium using tri-isobutylphosphine sulfide in xylene and deter- mined using ICP-AES a detection limit of 2Opgg-' was obtained (96/2979). An interesting alternative to conventional ICP-AES is coupling a laser to the system and analysing samples using laser ablation (96/954 and 96/1096). The main advantage of this approach is that the sample does not need to be dissolved prior to measurement which means that handling of active samples is minimized (95/3403). This tech- nique has been used to determine major and minor elements in various matrices (uranium-zirconium fuel berylium plu- tonium etc.).It has also been used to determine uranium isotope ratios using a two monochromator ICP-AES instru- ment. Laser ablation was compared with conventional nebulization and the isotope ratios obtained confirmed using TIMS. X-Ray fluorescence spectrometry (XRF) was used to measure iron in zirconium oxide by pressing the powdered zirconium oxide onto a boric acid substrate and irradiating in a helium medium at 50 mA and 50 kV (96/299). On-line analysis of process anion exchange eluates for actinides and other analytes has been carried out using a commercial energy dispersive XRF (96/382). The analysis was only semiquantitative but pre- concentration to lower detection limits and a more rigorous calibration protocol to provide more quantitative data was envisaged.3. ADVANCED MATERIALS 3.1. Polymeric Materials and Composites Like a bad penny the analysis of Pb in paints continues to turn up in this review and this year is no exception. The driving force for much of the published work this time around has been the development of portable or jeld screening test instruments. XRF has traditionally been popular in this area and Driscoll et al. (96/314) have reported a field method using a SEFA-Pb portable XRF instrument with a high resolution (N cooled) Si(Li) detector and a 10mmCi 57C0 source. No detection limits were given for Pb in paints but results corre- lated well with low resolution instrument data. An alternative portable battery-powered tungsten coil AAS has been reported (96/2505 96/C886).The finished spectrometer could be powered by a normal 12 V car battery and had dimensions of 19 x 8 x 3 in. Instrument characteristics included a limit of detection of 20pg of Pb linear range covering 2 orders of magnitude RSD of around 5% and accuracy of 95-97% (NIST SRM 1579a). The workers concluded that the most limiting parameter was detector noise and that performance could be improved by increasing the optical throughput of the system. A portable laser-induced breakdown spectroscopy instrument has also been developed (96/2507) The instrument weighs just 14.6 kg and operates from 115 V. Fibre optics are used to collect the light produced from a hand-held laser probe. Disappointing limits of detection (0.8% m/m) for Pb in paint were quoted because the instrument uses the less sensitive 220.35 nm PbII line due to interferences on the stronger 405.78 nm PbI line.The use of ICP-MS for the determination of Pb isotopic ratios has also attracted attention. Hall (96/C2304) has reported some interesting work on the identifi- cation of old white Pb-based paints. Problems encountered included the fact that the source lead carbonate was usually mixed with other Pb-based pigments. Using a two source Pb mixing equation ICP-MS Pb isotope data could be used to identify the manufacturer of old paint samples. One step further on from this is the use of Pb isotopes to detect the exposure source of Pb (96/C702). Experimental details included the observation that Th if used as an internal standard degraded within-run precision for isotope ratio measurements. The workers suggested that Pb exposure in a number of subjects was a result of aerosol dust which in turn was a composite of disturbed paint surfaces. Other workers have concentrated on the quality control of this type of analysis. Protocols for preparing method evaluation materials from real-world Pb-containing paints and dusts has been reported (96/1192).The materials have been used in a round-robin exercise involving techniques such as AAS ICP-AES and XRF. Such performance exercises have been reviewed by Harper et al. (96/1189). The report includes a summary of method performance evaluations both for laboratory based methods and field measurement techniques.A comparison of Pb paint field screening test methods has also been published (95/4054). If the number of abstracts is anything to go by XRF is one of the most utilized analytical techniques for the analysis of polymeric materials. A method for the direct determination of Ga on polyurethane foam has been developed (95/3402). Gallium chloride is easily extracted from 6 mol 1-l HCl on to comminuted polyether-type polyurethane foam. Ga was detected to (i-)60ngml-' with a linear range of 0.1-2.33 pg m1-l. The procedure was successfully applied to the determination of Ga in a variety of aluminium bauxite and industrial residue samples. A variation on this theme has been developed for the analysis of Au by XRF after absorption onto a polyurethane foam disc (96/365).Water traces were however found to affect the Compton scattering background intensity. A linear range of 0-300 pg limit of detection of 0.4 pg and RSD of 1.52% were reported. Good agreement to certified reference values was obtained. A quantitative method for the determination of cotton j b r e maturity by XRF has been published (96/537). Samples were prepared by grinding (100 mg) and pressing at 20 kpsi into a 31 mm diameter pellet. The prepared pellet was analysed using Rh continuum excitation and a Ti secondary target (20 kV 1 mA) in a He atmosphere. An Li drifted Si detector was used. Calibration was achieved using NIST SRM apple leaves diluted with cellulose powder. Significant relationships between cotton maturity parameters and Ca concentration were found.The analysis of plastics by AA and AE methods continues to appear. A short review of the latest dissolution techniques for AAS and ICP-AES detection has been compiled (95/3935). Trace amounts of Sb Mn and Co have been determined in poly(ethy1ene terephthalate) (PET) films by solid sampling ETAAS (95/3380). The temperature program was critical to avoid fusion of the PET film which would interfere with the complete charring of the sample. Standard additions had to be used for quantification purposes. Results were in good agreement with those from traditional acid digestion with FAAS detection although the solid sampling techniques dem- onstrated poorer precision. Tin has been determined in unplas- ticized poly(viny1 chloride) pipes by Zeeman ETAAS (95/3684). Samples were suspended in 4% acetic acid using Ca(NO& as a matrix modifier.Recoveries of 95-106% with RSDs of 3.4% are reported. Finally an interesting report by Forsyth et al. (95/C4330) on the determination of organotin leachates from chlorinated poly(viny1 chloride) pipes caught this reviewer's eye. Drinking water samples collected from CPVC pipes were analysed for organotins by solid phase extraction followed by GC-AAS detection. Dialkyltin levels of approximately 30-100 ng g- have been found depending on the water temperature. Monoalkyltin was also identified. 3.2. Semiconductor Materials Several reviews on the use of total rejlectance X-ray fluorescence for the analysis of semiconductor materials have been published (96/2607,96/1119,96/2609) in the last year.Hockett (96/2792) 494 R Journal of Analytical Atomic Spectrometry December 1996 Vol. 1 1estimates that there are approximately 100 TXRF instruments in use in the semiconductor industry. TXRF is ideally suited to the determination of trace element contamination on semi- conductor surfaces has detection limits of between lo9 and 10" atoms per cm2 and the depth of analysis is typically in the tens of nanometers (96/511). An interesting comparison of TXRF with radiochemical methods has been made by Fester et al. (96/2564). The authors used both techniques to monitor contamination levels of Co Cr Fe Ni and U under various preparation conditions. They found that the results were comparable at levels of 1011-1013 atoms per cm2 pro\ iding the surface distribution was homogeneous but that the differ- ences became more significant close to the detection limits.It was reported that radiochemical analysis of Co Cr and Ye has detection limits of at least an order of magnitude lower than vapour phase deposition (VPD) TXRF. A review of stand.irdiz- ation issues for TXRF and VPD-TXRF has been published (96/1150). Reference samples are required for quantitative TXRF and VPD-TXRF analysis and the approaches to making and using these reference samples varies among riianu- facturers and users worldwide. Some of the basic issucs are reviewed and summarized in this paper. Yoshihiro c't al. (96/1153 96/2766) have published two papers on the prep- aration of calibration samples for TXRF. The technique involves immersion of the silicon wafers in intentionallj con- taminated alkali hydrogen peroxide solution; they found that the metal ions were adsorbed on the surface oxide layei with a thickness of approximately 1 nm.The authors examined adsorption isotherms depth profiles and stability of wafers prepared for Ca Co Fe Mn Ni and Zn. The possibility of TXRF as a candidate for the I S 0 standard for determination of contaminant element content of silicon wafers was discussed at a recent conference (96/C2851). Several round-robin tests have been carried out and the results of the most recent were discussed. Cleaning of the silicon wafer is one of the most frequent processes in the manufacturing sequence for integrated circuits. The purpose of the cleaning procedure is to remove contaminants and the industry uses the highest purity chemi- cals available to limit the possibility of adding Contaminants from the chemicals themselves.The chemicals are usuallv well characterized and analysed to exacting standards prior I o use in the process stream. However over 50% of the yield losses in integrated circuit manufacture are thought to be due to contamination left on the wafer surface after cleaning Sees and Hall (96/581) have used TXRF to investigate mztallic impurities on silicon wafers after cleaning with ultra-pur e and standard grade chemicals. They concentrated on the cleaning procedure with SC-1 an ammonia solution-hydrogen pel oxide mix and found that ultra-pure chemicals gave less contami- nation as expected. TXRF with a special energy dispersive spectrometer has been used to measure the light element such as A1 C F Mg N Na and 0 on silicon (96/1154).The angular dependence of the fluorescence signal from low atomic number atoms implanted in silicon excited by monoenergetic radiation of various energies was calculated. The excitation energy in the experiments was monochromatized Cr-K radi- ation. Yakushiji et al. (96/1158) have reported spurious peaks such as Fe-K and Ni-K radiation observed during the determination of trace determination of metal impurities on silicon wafers. The intensity of the spurious peaks varied with changes in the incident azimuth angle and intensity of the primary X-ray beam and was found to be due to impurities along the path of the X-rays. The use of synchrotron X-ray sources for TXRF (SR-TXRF) offers an improvement in sensi- tivity by one or two orders of magnitude.A sensitivity of 3 x lo8 atoms cm-2 for the third row transition metals was recently demonstrated using this technique (96/1155). SR-TXRF has been reviewed and a new quantification method for the determination of such low levels of analytes based on relative sensitivity factors proposed (96/1151). Ni was deter- mined on a silicon wafer surface using SR-TXRF (96/1216). A detection limit of 13 fg was obtained for Ni at a beam current of 73 mA. Secondary ion mass spectrometry is another important tech- nique in the analysis of semiconductor materials. A review of both TXRF and SIMS for the determination of ultra-trace contaminants on silicon surfaces has been written (96/2458). The basic principles of SIMS and its application to semi- conductor analysis have been reviewed (96/1690 96/4653 96/2320).Contamination during ion implantation has also been investigated using SIMS (96/1751). Routine detection limits of < atoms cmP2 have been obtained for the deter- mination of boron in antimony-doped silicon using SIMS (96/3718). The technique was not affected by the high levels of antimony present and based on the statistics obtained from a control sample the analytical precision was approximately 8% at a boron concentration of 1.7 x 1014 atoms cmP2. Oxygen flooding of the surface during SIMS measurement provides a technique capable of detecting 10" atoms cm-2 or less of many surface elemental contaminants (96/1681). SIMS depth profiling experiments have been used to determine the layered structure impurity distribution and current induced changes in polymeric light emitting diodes (LEDs) (96/2389).Two systems were studied and results indicated evidence of current induced degradation effects. A new procedure to obtain accu- rate SIMS depth profiles of Na in silicon dioxide was investi- gated (96/2396). The silicon samples were treated with HF to etch off some of the oxide and the surface analysed by SIMS after coating with Ag. The Na depth profile was obtained by plotting the Na+ intensity at the Ag/Si02 interface against the etched depth. Electrothermal atomization atomic absorption spectrometry is still an important tool in the determination of ultra-trace analytes in semiconductor samples. Impurities on silicon wafers have been determined by ETAAS (96/1093 96/2894) after dissolution of the surface layer in a droplet of hydrofluoric acid.Detection limits of 108-109 atoms cm-2 for a 6 in wafer were obtained which are similar to those currently quoted for TXRF. Silicon has been determined in photoresist using ETAAS (95/4370). Pre-conditioning of the furnace with calcium improved the Si response by 50% and gave a detection limit of 0.02ng. High purity gallium was analysed for Sb and Fe content by dissolving the sample in nitric and tartaric ,acids and measuring the resulting solutions using ETAAS (95/3430). Zeeman background correction ETAAS and a L'vov platform was used to determine In in gallium arsenide (95/4255). The use of the L'vov platform Zeeman background correction and standard additions helped overcome interference from the gallium arsenide matrix.Chemical modification and ETAAS were used to determine T1 in telluride thermoelectric material (95/4693). The modifier used was a mixture of tartaric acid- ascorbic acid-magnesium nitrate (1 2 1) and the detection limit for T1 was calculated to be 0.6 ng ml-'. A few papers on the application of inductively coupled plasma mass spectrometry to semiconductor analysis have been pub- lished. A combination of VPD and ICP-MS was used to measure around 60 elements on wafer surface by Tan et al. (96/1746). Detection limits of < 108-1010 atoms cm-2 for bare wafers and 10 ppb to 10 ppm on dielectric oxide layers were found. Accuracy was demonstrated by spike recovery studies and by intercomparison of methods with Japanese laboratories.Correlations were made between the trace metals content of cleaning chemicals (SC-1) and metal contaminants on wafers. Tan (96/2951) used VPD and a combination of ICP-MS with a capillary nebulizer and ETAAS to determine nine elements on wafer surfaces. Electrothermal vaporization (ETV)-ICP-MS offers better sensitivity of measurement and also requires very small sample volumes and therefore should offer advantages Journal of Analytical Atomic Spectrometry December 1996 Vol. 11 495Rover nebulization ICP-MS for the analysis of silicon wafer surfaces. Hub and Amphlett (95/3550) have used ETV-ICP-MS for the determination of eight elements in hydrofluoric acid and buffered oxide etch two chemicals used routinely in semiconductor manufacture and on silicon wafers.For wafer analysis the surface oxide coating is dissolved by VPD or DSE (droplet surface etching) and the dissolved analytes measured using ETV-ICP-MS. Using this protocol they obtained detection limits of 0.2-2 x lo9 atoms per cm2 for eight elements on 6in wafers. The authors pointed out that ETV- ICP-MS combines the sensitivity benefits of ETAAS and the simultaneous multi-element analytical advantage of TXRF with the possibility of being able to measure the light elements such as Al Mg and Na which are difficult to determine using TXRF. Isotope dilution (ID) ETV-ICP-MS has been used to determine Cu Zn and Pb on wafer surfaces (96/2354). The wafer surface was etched with 200 pl of a mixture of nitric and hydrofluoric acids and the impurities determined at 3 x 108-8.7 x lo9 atoms per cm2 in the resulting solution using ID-ETV-ICP-MS. Other workers (96/1457) have used a micro- concentric nebulizer (MCN) to introduce the small sample volumes obtained from VPD or DSE to the ICP-MS instru- ment.Detection limits of 1 ppt for Cr and 25 ppt for A1 were obtained with detection limits for Mo Zn Ni Na W and Cu falling between. The authors were also able to determine K to 10 ppt Ca to 28 ppt and Fe to 13 ppt using cold plasma conditions in the same multi-element run. Two recent confer- ence papers (96/C2222 96/C757) also describe a combination of cool or reduced power plasma conditions with and without a microconcentric nebulizer and ICP-MS for the analysis of semiconductor materials.The cool plasma is reported to overcome polyatomic interference on low mass analytes and hence allow the measurement of 39K 56Fe and 40Ca in semicon- ductor process solutions. Inductively coupled plasma emission spectroscopy (ICP-AES) is used for the analysis of semiconductor materials when speed of analysis is required and the instrument can meet the industry’s detection limit requirements. Impurities in quartz sand and silicon powder have been determined using ICP- AES (96/1058). The sample was dissolved in hydrofluoric and nitric acids and buffered with boric acid before measurement. Interference from silicon was also investigated. ICP-AES has been used to determine Ag Al As Cd Cu Fe Ni Pb Sn Te and Zn in high purity indium (96/1370). The same group of workers presented the data for the determination of Al Ca Cd Cr Cu Fe In Mg Mn and Zn in gallium arsenide using ICP-AES at a recent conference (96/C943).Gallium was separated from the impurities by extracting with diethyl ether saturated with hydrochloric acid. Glow discharge mass spectrometry (GDMS) has been used to perform high sensitivity (ppt) measurements of semi- conductors and metals (96/1800). The advantages of this technique are the ability to analyse solid samples directly and depth profiling capabilities However the main disadvantage in semiconductor analysis is that the sample is used as the cathode in a d.c. glow discharge and therefore must be con- ducting to some extent which presents major difficulties in the analysis of silicon wafers.Use of a radiofrequency source for GDMS has been presented as means of overcoming this limitation of the technique (96/C859). A radiofrequency glow discharge ion source has been optimized and characterized for a high resolution mass spectrometer (95/4715) and has been used to analyse gallium arsenide wafers (96/2386). The potential use of accelerator mass spectrometry (AMS) to the analysis of semiconductor samples has been explored in two papers published during the review period (95/4617 96/1701). This technique is reported to be more sensitive than SIMS for some elements because it is capable of electron stripping molecular ions which can cause interference effects when using SIMS. It will be interesting to see how AMS develops for semiconductor and other analysis. Analysis of cleanroom air has been undertaken using ETAAS ICP-MS and ion chromatography (96/1048).Impurities were trapped in an impinger and measured using the most appropriate technique. 3.3. Glasses Since its introduction laser ablation has been a very popular sample introduction technique for the spectrometric analysis of glass. However for the period under review nothing of real significance has caught this reviewer’s eye. One paper (96/374) using LA-ICP-MS studied the homogeneity of 4 NIST glass standard reference materials. Within the reported analytical uncertainty NIST 611 612 and 614 are apparently homo- geneous whereas NIST 1834 is inhomogeneous on a scale of 100 mg with respect to several trace elements. Thankfully workers in the field of X-ray Juorescence (XRF) seem to have been more productive.Most effort has been concentrated on sample preparation or direct analysis of individual glass particles. A fast (45 min) preparative procedure which consisted of casting the glass melt directly into a pre- heated graphite mould followed by annealing for 30 min at 500 “C has been described (96/484). Element X-ray intensities were found to be highly reproducible (< 1 Yo). The workers claim that the method is suitable for vitrification process control purposes permitting on-site monitoring of glass com- position. An alternative method has been reported (96/522) using a Pt sample vessel and a multiple melt-cool cycle. It was claimed that the method is particularly useful for samples from which gas bubbles are formed during melting.Other crucibles consisting of Pt-Au-Rh mixtures have been utilized for XRF glass sample preparation (96/1125). Most of the preparative methods described were used to overcome problems in sample homogeneity. Rindby et al. (96/275 1) reported using the intensity correlations between pairs of elements for detecting topological variations between solid samples by micro-beam XRF. The method was used to analyse irregularly shaped millimetre sized glass fragments. A mathematical model for fluorescent correlation has been for- mulated from the data. Another approach to the problem has been reported by Lankosz and Pella (96/1010 96/1011). The method described used polychromatic X-ray micro-beam exci- tation for the quantitative analysis of individual particles (50-160 pm) by XRF.The coherent and incoherent tube target lines scattered from the sample were used to calculate the average atomic number and mass thickness of the sample. Irregularly shaped particles were analysed using a known equation usually applied to flat samples of intermediate thick- ness. The procedure has been tested on glasses of known composition with good accuracy and RSDs of between 4 and 25% for spherical particles. Finally the field of archaeometry has become a fruitful area for the analysis of glass materials. For example one application reported during the review period involved use of secondary neutral mass spectrometry (SNMS) to study glass corrosion phenomena (96/2382). Using the recently developed high fre- quency mode (HFM) of the electron gas SNMS the workers were also able to obtain ‘fingerprint’ mass spectra for ceramic samples. The study of ancient glasses has also become popular Roman (96/1830) Mediaeval (96/2998) early Thuringian (95/4038) and ancient (95/4039) glasses have been analysed by ICP-AES X-ray microprobe and XRF respectively.3.4. Ceramics and Refractories Since its introduction over a decade ago inductively coupled plasma mass spectrometry has penetrated practically all areas 496R Journal of Analytical Atomic Spectrometry December 1996 Vol. 11of elemental analysis. Ceramic materials have proved to be no exception although this year most of the reported work has been confined to conference presentations. High resolution- inductively coupled plasma mass spectrometry instruments are now making an appearance with the analysis of Al,03 ceramic powders being reported (96/C2221). After dissolution by press- ure digestion with HCl the solutions were diluted to an equivalent A1,03 content of 400 pg ml-I.A suite of elements were determined at low resolution (m/Am = 300) whereas "V 52Cr 5sMn s6Fe and 69Ga were performed at high resolution (m/Am = 3000) to overcome polyatomic interferences. Good agreement was obtained when compared with a low resolution quadrupole ICP-MS method which involved a matrix removal stage based on hexamethylene dithiocarbamate (HRIDC). Other reports included the use of ICP-MS for the analysis of silicon carbide powders for 35 elements (95/3554). The method was extended to Mg Ca Sc and Ti by employing matrix removal by evaporation after high pressure acid decomposition in a mixture of HN03-H,S04-HF.Ceramics and refractory materials can be notoriouslj diffi- cult to digest and with these materials efficient sample prep- aration/dissolution is critical for a successful analysis One way around this problem is to use direct sampling techniques such as electrothermal vaporization coupled with ICP-AES or ICP-MS although as yet these techniques may not havt been fully exploited mainly owing to problems with reproducl bility. In this vein a novel ETV-ICP-AES configuration ha5 been reported (95/4724 96/C221). The system was based on in-line resistive heating of a graphite crucible with powdered Sic mixed with a CoF and BaO modifier in a 1 1 1 proportion. The transport path to the base of the torch considered critical in this type of device has been kept down to 9 mm.Detzction limits were reported to be in the pg range for Al Fe Ti and V. A disposable graphite cup system has been developed (95/4593) for ICP-AES using PdC1 as a matrix modifier. The aspect of calibration has been addressed by several wakers (95/3433 96/C663) as well as the use of Freon-12 (CF,('12) to aid volatilization. Advances in the analysis of silicon carbide thin JiEm have continued. The analysis is important as the structure of the films radically alters their physical properties. The use of SIMS and XPS has been studied for the characterization of hydrogenated amorphous Sic thin films (95/4624). All the a-Si,-,C, H films studied consisted of a homogeneous layer on a c-Si substrate.The analysis also provided values of the dielectric function of the layered material. A multi-technique approach has been utilized for the study of porous silica membranes (95/4652). Techniques used included SIMS Raman scattering FTIR XPS and AES. Matrix effects on the SIMS analysis of ceramic-copper powder pellets has also been pub- lished (95/4106). The field of archaeometry is fast growing and the analysis of ancient ceramics by spectroscopic methods has become very popular. Neutron activation analysis has traditional11 been the method of choice in the past but with the advent of fast reliable digestion procedures e.g. microwave methods and sensitive instrumentation (e.g. ICP-AES and ICP-MS). spec- troscopic techniques are catching up (96/2323).Lithium :,orate (both meta and tetra) fusions are the sample dissolution methods of choice with either Pt crucibles (96/2485) or graphite crucibles (96/2876) at 100&1100 "C followed by dissolution using HN03. Elemental content has been used to track move- ments of materials (96/C911) and trace trade routes (96/1998) as well as for the identification of different types of pottery (96/1831 96/1834). Other workers have used XRF to study kiln sites (96/1163 96/2578). The analysis of non-conducting materials by both rf-GDMS and d.c.-GDMS has been reviewed and compared (95/ 1489). Work has concentrated on sample preparation with s'everal schemes being reported. The use of secondary cathodes has been evaluated for d.c.-GDMS (96/1520). Optimum discharge conditions and analytical characteristics were reported.The electrical resistivity of the sample was found to be an important factor determining the capabilities of the technique especially with respect to detection power. De Gendt et a!. (95/4188) reported the quantitative analysis of Fe-rich samples by GDMS. Various iron ore reference materials were mixed 1 7 with either Cu or Ag powder as a conducting host matrix. Internal repeatability was less than 6% with external repeat- ability less than 10% for flat electrodes. Variation in sensitivity factors for various non-conducting materials (iron ores sinters firebrick and bauxite) was better than 25%. Another approach has been direct analysis of non-conducting samples by rf-GDMS (95/3524). Parameters such as discharge pressure orifice distances and cryogenic cooling were optimized to deliver semi-quantitative results within a factor of 2 of the certified concentrations for reference materials.Several matrix separation and removal methodologies have been published for a variety of sample matrices. HPLC-ZCP- MS has been used for the interference-free analysis of all rare earth elements in rock samples (95/4368) using a cation exchange column (not specified) and a 2-hydroxy- 2-methylpropanoic acid mobile phase. Detection limits of 0.4-30 ng ml-' for all REEs were obtained. Traces of Ca and Mg in rare earth oxides byjow injection analysis coupled with fluorescent detection using calcein (95/3643) have been deter- mined. To discriminate between Ca and Mg 8-hydroxy- quinoline (for Mg) and EGTA (for Ca) were used as masking agents.Matrix concentrations of up to 500 mg 1-' could be tolerated with detection limits of 0.1 mg g-' for Ca and 0.04 mg g-' for Mg. Ten trace elements have been quantified in EuO by using di-( 2-ethylhexy1)phosphonic acid-resin and a dilute HNO mobile phase with ICP-AES detection (95/4447). The removal of SbO matrix has been achieved by hydride vaporization using HBr allowing the interference free analysis of Th and U by ICP-MS (96/1534). As in previous years numerous papers described methods for the analysis of rare earth elements in oxide matrices. A summary of these methods is provided in Table 3. Slurry samples when coupled with ETAAS continue to play a part in the analysis of refractory materials.Trace metals in Zr02 slurries were analysed by suspending 5- 150 mg of sample in 10 ml of H,O (96/2955). For Ca Fe and Na the slurry was diluted up to 100-fold while for Al Cd and Si H3B0,-HF diammonium hydrogen phosphate-magnesium nitrate and cal- cium nitrate modifiers were added respectively. Detection limits for a range of elements were 1-20 ng g-' for a 20 pl injection. Modifiers seem to be just as important for slurry- ETAAS as for conventional ETAAS analyses with a mixture of (NH,),HPO,-Mg( NO3) being used for the determination of silicon nitride powders (95/3767). However the use of modifiers can be avoided by using a cup and boat solid sampling technique (95/4594). In this case Ca K Mg Na and Zn in high purity Mo metal and Mo silicide powders for microelectronic applications were determined.Since contami- nant levels were significantly reduced using this approach detection limits of 0.06 ng g-' for Zn and 0.5 ng-' for Na could be achieved. The analysis of cement and concrete type materials continues to attract attention. A new fusion agent consisting of oxalic acid Li2B40 and Li,C03 (1 1 1) has been utilized (96/1383). Fusion was carried out in a Pt crucible for 10 min at 925"C followed by dissolution of the fusion cake in 10% HCl prior to determination of Al Fe K Na Si and Ti by AAS. Ca and Mg could only be analysed after addition of lanthanum(m) nitrate. A substantial number of reports on the use of XRF for the analysis of cement and related materials have been published this year (96/1185 96/1238 96/2623 96/2656).Joutxal of Analytical Atomic Spectrometry December 1996 Vol. 1 1 497RTable 3 SUMMARY OF ANALYSES OF ADVANCED MATERIALS Element Matrix Technique; atomization; analyte form* POLYMERIC MATERIALS AND COMPOSITES- Au Polyurethane XR F;-; S Ga Polyurethane XRF;-;S Mg Acrylonitrile-butadiene- MS;ICP;L Mn Polymer aluminium chloride AA;F;L styrene P POlY ( P - XRF;-;S phen ylenebenzoxazole) P Polymers AF;ET-LEAFS;S Pb Paint XRF;-;S Pb Paint MS;ICP;L Pb Nitrocellulose paint AA;-;L Pb Paint S Rubber AA;W-coil; L AA;F;L Sb Polyethylene terephthalate MS;ICP;L Sn PVC AA;ETA,L Sn (organo-) Chlorinated poly(viny1 AA;F;L chloride) Te Plasticizers AE;ICP;L Various Polymers MS;ICP;L Various (3) Poly(ethy1ene terephthalate) AA;ETA;S Various Rubber XRF;-;S Various (6) Polyimides AA;ETA;L SEMICONDUCTORS- B Silica and silicon c u Silicon wafers S1MS;S MS;ICP;L Sample treatment/comments Reference 9612472 Au absorbed on polyurethane discs.(Linear range Gallium chloride extracted from 6 mol 1- HC1 on to 961365 9513402 0-300 pg LOD 0.4 pg and RSD 1.52%) polyurethane foam and quantitatively determined by XRF Semi-quantitative analysis carried out on acid digests of the polymeric materials. (LOD 50 pg kg- ') 1 g of sample boiled with 1 ml of HNO before addition of 5 ml of 0.5 mol I-' sulfosalicylic acid. Mn was directly determined by acetylene-air flame AAS Sample cut into 1.25 in discs and analysed by XRF. The instrument was operated at 8 kV 0.05 mA with a Ru tube for excitation. LOD was 40 mg kg-' RSD 5.8% recoveries 90.6-113.6% and linear range 150-4100 mg kg-' A novel dissolution method that utilized trifluoroacetic acid and toluene was used for validation purposes.RSDs of 11-12% were obtained for the solid sampling method A high resolution portable XRF instrument was developed. For Pb in paint the lines detected were Kcq and Ka2 lines at 75 and 72.8 keV Pb based paints were characterized by the Pb isotope ratio data obtained from ICP-MS. Pb isotope ratio 'fingerprints' of paint manufacturers have been identified 'The pigments in paint were selectivley separated by propylene glycol ether-butanone solvent mixture followed by determination using AAS and dithizone spectrometry Development of a portable AAS instrument is described. LOD was 20 pg (20 p1 sample volume) ;Samples were microwave digested in HN0,-H202 and treated with BaC1,.S was determined indirectly by determining the excess Ba 9611571 9513388 9 513 399 9613 14 961C2304 9611987 9 612 5 05 9 6/29 8 2 4s for Mg (LOD < 1 mg kg-') :Sample suspended in 4% acetic acid. Ca(N0,)2 used as matrix modifer. Recoveries were in the range 9611571 9513684 9 5- 106 YO Drinking water samples were collected from CPVC 9 5/c43 30 pipe and analysed by solid-phase extraction followed by GC-AAS. Dialkyltin and monoalkyltin compounds were identified in leachate waters The 214.282 nm line was used giving LOD of 4 ng ml-' Microwave digestion in concentrated HNO and H,SO,. Indium used as internal standard (20 Mn and Sb were analysed by solid sampling ETAAS. Concentrations in PET films ranged from Volatile hydride was generated by NaBH reduction.9513897 9511670 9513380 10-8 to 10-4 g 8 - 1 Rubber samples either vulcanized or pulverized by 951c4203 using liquid N were analysed by application of two different radioactive sources. Method was verified by NAA methylpyrrolidone or dioxane for solid samples. LODs of 0.5-25 ng g-l were obtained for Ca Cu Fe K Na and Si Samples were dissolved in 10 ml purified N - 961 18 14 ]Detection to < lo' atoms B cm-2 on Sb doped Si substrates using SIMS. Precision and accuracy acceptable Isotope dilution and ETV-ICP-MS used to determine Cu Zn and Pb on silicon wafers. Detection limits 3 x lo8 to 8.7 x lo9 atoms cmP2 9513718 9612354 498R Journal of Analytical Atomic Spectrometry December 1 S)96 Vol. 11Table 3 (continued) Element Matrix SEMICONDUCTORS- Technique; atomization; analyte form* Eu A,B thin films AF;ICPL Fe Gallium arsenide Fe Gallium In Gallium arsenide X R F;-;S AA;ETA;L AA;ETA;L K Phosphorus diffusion source AA;F;L Na Phosphorus diffusion source AA;F;L Na Silica/Silicon S1MS;S Ni Silicon wafers XRF;-;S 0 GaN Sb Gallium Si Photoresist S1MS;S AA;ETA;L AA;ETA;L T1 Monocrystals of Bi'Te AA;ETA;L Various Silicon wafers H F and BOE MS;ICP;L Various (3) Semiconductor process chemicals Various (7) Silicon wafers Various (1 1) VPD droplets Various (60) Silicon wafer MS;ICP;L X RF;-;S M S;ICPL MS;ICP;L Various Semiconductor process MS;ICP;L chemicals Various (6) Silicon wafers X RF;-;S Various (9) Silicon GLASSES- As Glass MS;ICP;L and A A; ETA; L XRF;-;S and SEM;S Sample treatment/comments Reference 9612794 9513430 9514255 961395 961395 96 12396 9611216 9513716 9513430 9514370 An etching solution and electrochemical oxidation 9513789 were used to remove layers of 0.5 to several microns.PbEuTe-PbTe and PbEuSe-PbSe heterostructures investigated. Eu removed measured using ICP-AFS Depth profiling of Fe on GaAs was performed using TXRF. Detection limit of 10" atoms Fe cm-' on GaAs surfaces obtained ETAAS detection limits obtained were 5 ng ml-' Sb and 1.5 ngml-' Fe Zeeman background correction standard additions and L'vov platform used to overcome matrix interference. Recovery of 96-97.4% and detection limit of 2.5-3 ng ml-' obtained measurement of Na and K. Standard additions used to overcome interferences from A1 and P,O As per K Depth profiling of Na in SiO on a silicon substrate.Gallium dissolved in nitric-tartaric acid mixture Microwave digestion of sample and flame AAS Surface coated with silver and depth profile obtained using SIMS determine Ni to a detection limit of approximately 13 fg Surface of GaN exposed to oxygen and monolayer of oxide on surface studied using SIMS As per Fe Furnace pre-conditioned by addition of calcium which was dried and ashed at 590°C before addition of the sample. The Ca improved the sensitivity by about 50% to give a detection limit of 0.02 ng added as modifiers. Detection limit of 0.06 ng ml-' obtained Analysis of Al Mg Na Fe and other analytes on silicon wafers HF and buffered oxide etch (BOE) using ETV-ICP-MS. Detection limits 0.2-2 x lo9 atoms cm-'. Main advantage is analysis of Fe where KI is used as a modifier polyatomic interference and permit measurement of Ca Fe and K by ICP-MS for TXRF analysis of light elements (uiz. Al C F Mg N Na and 0) Microconcentric nebulizer (MCN) and cold plasma conditions used to determine Ca Fe and K and MCN and normal plasma conditions to determine Al Cr Cu Mo Na Ni W and Zn to low ppt detection limits in VPD droplets Vapour phase deposition used to remove surface layer and solution obtained measured using ICP-MS.Detection limits for silicon wafers < 10' to 1O'O atoms cm-' and 10 ppb-10 ppm for dielectric oxide layers Combination of microconcentric nebulizer and cold plasma conditions to determine a suite of analytes in SC-1 SC-2 and TMAH analysis of Ca Co Fe Mn Ni and Zn on silicon wafers VPD used to remove surface layer and resulting solution measured using ETAAS and ICP-MS (magnetic sector).Sensitivity of both techniques similar Synchrotron radiation excited TXRF used to Tartaric acid ascorbic acid and magnesium nitrate Cold plasma conditions used to overcome 96/C757 A special energy dispersive spectrometer described 9611 154 9611457 96/C2222 Standard sample procedure described for TXRF 9612766 961295 1 9514693 9513550 9611 746 Samples were K20-CaO glass containing approximately 8% As'O 9514038 Jouriial of Analytical Atomic Spectrometry December 1996 Vol. 11 499RTable 3 (continued) Element Matrix GLASSES- c u Fe K Li Si Sn Various Various Various Borate glass Borate glass Glass Glass Glass fibres in rat lungs Tin coatings for glass Glass High-B borosilicate glass Glass Various Various Various Glass reference materials Waste glasses Glass Various (4) Borate glass Various (10) Vehicle headlight glass Various Glass fragments CERAMICS AND REFRACTORIES- A1 Silicon carbide Ba Fly ash Ca Bismuth trioxide H Carbon fibres Bismuth trioxide Y-Ba-Cu-0 system Mg Oxide Pb Rare earth compounds phases Technique; atomization; analyte form* Sample treatment/comments AA;F;L AA;F;L AE;laser;S AE;plasma;S AA;-;- XPS;S AE;ICP;L and XRF;-;S AE;ICP;L MS;ICP;S MS;ICP;L XRF;-;S XRF;-;S AA;F;L XRF;-;S XRF;-;S AE;ICP;S XRF;-;S AA;F;L SIMS;-;S AA;F;L M S;laser;S MS;ICP;L Cu" was determined by d.c.polarography. Total Cu was measured by AA using air-acetylene flame. After HCI digestion Cu' was determined by difference N and diluted with H,O.Total Fe was determined using air-acetylene flame after addition of 7 m mol 1-l-alizarine red sulfonate XeCl excimer (20 ns 25 mJ) was focused on glass samples at reduced pressure (1-10 Torr) XeCl excimer (20 ns 25 mJ) was focused on glass samples at reduced pressure (1-10 Torr) Rats were exposed to glass fibre and sacrificed at weekly intervals. Amount of glass fibre in the lungs increased linearly with time to about 0.3 mg Depth profiling was achieved using Ar' and HF etching as well as mechanical abrasion. Sn speciation was dermined from the Sn 3d 4p 4d and Sn," Auger peaks Li,B,O at 1000 "C with subsequent dissolution in HNO mixture. For multicomponent glass a sodium borate-carbonate fusion was used Calibration curves for LA-ICP-MS were achieved using a series of geochemical reference standards.Ce Y and Zr calibrations were non-linear. Internal standards (usually a low abundance isotope of a major element) were used to normalize raw intensities with HN0,-HF ( 1 +9) (7 d at 150 "C). The residue was taken up in 8 moll-' HNO melt directly into a graphite cast and annealing for 30 min at 500°C Average atomic number and mass thickness were calculated from incoherent scatter data. Irregularly shaped particles could be analysed using a well known equation usually used for flat particles Signal depressing interference from matrix was eliminated by using alizarin red sulfonate which forms a stable metal-alizarinate complex Powered sample was suspended in EtOH filtered and fixed with an aqueous collodion solution.As Fe K Na and Zr showed correlation to different glass types between the intensities from different fluorescent lines. The method could be used study inhomogeneous samples LO mg sample was dissolved in 2 mol 1-l HC1 under Following grinding the samples were fused with Samples were dissolved in HF or HF-HC10 Samples were powdered under acetone and digested Glass discs were prepared in 45 min by casting the Quantitative method based on correlation graphs Reference 9612882 9612896 96/28 15 96/28 15 961115 96/C 1 75 9514039 9 5/43 64 9514674 961374 961484 961101 1 9611037 961123 5 9612751 Direct analysis using LA-ICP-MS. Since no reference 961C2821 materials were available a standards additions method based on interpolation was used Sample preparation process did not involve hazardous solvents.Ba and Sr could be used to 'fingerprint' for the presence of fly ash 9611185 RSDs of 2.78-2.98% quoted 9513832 SIMS showed that H content of the core was greater 95/41 10 than in the coating. (Strength of a C-H material increases with H content) As for Ca Quantitative phase analysis of inhomogeneous oxide materials in the Y-Ba-Cu-0 system using LIMS Isotope ratios '07Pb 'O'Pb and "*Pb 'O'Pb were measured by ICP-MS. The initial composition and origin of the samples by 'fingerprint' method was demonstrated 9 513 8 32 9611648 9513553 500R Journal of Analytical Atomic Spectrometry December 1996 Vol. 11Table 3 (continued) Technique; atomization; Element Matrix analyte form* CERAMICS AND REFRACTORIES- Pb Ceramic glazes X R F ;-; S sc Red mud Sr Fly ash Ti Silicon carbide Th Antimony(II1) oxide U Antimony(I1r) oxide Various (4) Silicon carbide Various ( 10) Tantalum carbidelnitride Various (12) Titanium oxide Various (36) Silicon carbide Various (14) Yttrium oxide Various (14) Lutetium oxide Various (9) Silicon nitride Various Scandium oxide Various (14) Europium oxide Various Boron nitride Various Aluminium nitride Various (14) Yttrium oxide Various (4) Silicon carbide Various (6) Molybdenum metal Various Strontium titanate Various Rare earth oxides ( R W AE;ICP;L XRF;-;S AE;ICP;S MS;ICP;L MS;ICP;L AE;ICPS AE1CP;L AE;ICP;L MS;ICP;L M S ; I C P; L MS;ICP;L AA;ETA;S AE;-;L AE;ICP;L AE;ICP;L AE;ICP;L AE;ICP;L AE;ICPS A A;ETA;S MS;ICP;L MS;ICP;L Sample treatment/comments Qualitative analysis of Pb by '"Cd-induced XRF.For housewares Pb identification did not always correspond to Pb leachability Sample was fused with NaKCO,-Na,B,O at 1100 "C. 25 ml was passed through a Dowex 50W-X8 column. The eluate was extracted with 0.05 mol 1-' di(2-ethylhexy1)phosphoric acid (pH = 0). Sc was stripped from the organic phase with NaOH As for Ba As for A1 Antimony matrix was removed by halide vaporization using HBr. Detection limit was 0.03 ng g-' As for Th. (Detection limit 0.02 ng g-') A modifier of CoF,-BaO ( 1 1) was used to decompose the Sic for the analysis of Al Fe Ti and V using ETV-ICP-MS The carbide was decomposed in HN0,-H,O,-HF mixture in a PTFE bomb and treated with H$O,. The nitride needed HF-H,O and was treated with H,BO,-HNO Ca Co Cr Fe Mg Mn Nb Ti W and Zr were determined 0.25 g sample was treated with 10 ml of H,SO and boiled.The cooled mixture was filtered and the residue ashed in a Pt crucible and dissolved in Dissolution was achieved by HN0,-H,SO,-HF HF-HNO mixture. For all 36 elements the detection limits were improved with matrix removal by evaporation of the dissolved solution Detection limits were 0.003-0.02 ng ml- ' presence of the Lu matrix. This was overcome by the use of In as an internal standard. Recoveries were 90-103% and RSDs 1.4-4.2% Ammonium dihydrogenphosphate-magnesium nitrate modifier and slurry were placed sequentially into the graphite tube. Radiotracers showed that Si was retained (80%) at 2200 "C but was removed at 2500 "C Hydroxylamine hydrochloride and carbon powder were used as buffers which improved the vaporization process of REE impurities upon chlorination Instrumental parameters optimized.Recoveries were between 88-112% and RSDs better than 11% 0.3 g sample decomposed with HF-HCl mixture at 200°C for 16 h. Remaining solid phase was treated with H2S04 at 2300°C for 16 h. (Detection limits ranged from 0.1 ppm Ca to 18 ppm Si) 0.3 g sample decomposed with 15 ml HCl in a PTFE pressure vessel at 200 "C for 24 h. (Detection limits ranged from 0.1 ppm for Ca to 4 ppm for Si) 0.2 g sample was dissolved in HCl evaporated to dryness then dissolved in 5% HCl. Detection limits were 0.0002-0.01 Yo for REEs. Recoveries were 83-120% with RSDs 3.2-9.8% Disposable graphite cups with PdCl modifier used for determination of Al Fe Ti and V using ETV- Fourteen rare earth impurities were determined.Suppresion of analyte signal was observed in the Silicon nitride powders were slurried in H,O. ICP-AES Using a cup and boat method contamination was considerably reduced. Cu K Mg Mn Na and Zn were determined with detection limits 0.06-4.5 ng 8-l The sample was decomposed with HC1-HF mixture in PTFE pressure vessel. Au was used as an internal standard. Impurities in the SrTiO at the sub pg ml-' level were detected 10 mg sample was heated with 50% HNO,. Internal standards (In Rh Cs and Rh) were added Joirrnal of Analytical Atomic Spectrometry December 1996 VoE. 11 Reference 9.513869 9612875 9611 185 96fC2821 9611534 9611534 9513433 9513438 9513439 9513554 9 513 5 66 9513617 9513767 9513787 9514245 9514505 9514505 9514549 9 51459 3 9514594 9514634 961366 501 RTable 3 (continued) Technique; atomization; analyte form* Element Matrix SEMICONDUCTORS- Various Superconductors Sample treatment/comments Reference 96/37 1 9611 169 9611326 9611283 9611502 9611566 961C2046 96lC2125 961C2221 96/23 23 9612503 96/C28 3 7 9612876 9612955 AE;ICP;L XRF;-;S Carrier gas flow was shown to be critical in lowering detection limits for alkaline earth analyses A double briquetting technique with correction constants was used to improve accuracy for both enhancement and absorption effects.Al Ca Mg and Si were determined 0.1 g was dissolved in 5 ml HCI and 5 ml Li solution (40 g 1- ') was added. (Ce Nd Pr and Sm determined with detection limits of 0.012 0.021 0.012 and 0.009 pg ml-' respectively) Samples fused with oxalic acid-Li,B,O and Li,CO at 925 "C in Pt crucible and then dissolved in HCI.(A] Fe K Na Si and Ti were determined) Sample solutions were prepared containing 1 g 1-' Eu and 10 pg 1-' internal standard (I5'In for lighter REEs and ,''TI for heavier REEs) Samples were analysed for Ce Ho La Lu Pr Tb Tm and Y by isotope dilution-SSMS. (Recoveries were 85-114% and RSDs 4-21%) 4 mixture of Na,O and LiBO in conjuction with microwave digestion was used. Problems with Ni contamination were encountered. (Al Cu Cr Fe Mg Mn Ni Ti V and Zn determined) standards a stoichiometric mixture of high purity La2(C03) SrCO MnO and ultrapure graphite was prepared Samples were decomposed by pressure digestion with HCl. B Ba Co Cu Ga La Ni Ti Zn and Zr were determined in low resolution.52Cr 56Fe 69Ga and "Mn determinations were performed using high resolution (m/Am = 3000) ]High-pressure microwave digestion with HF-HNO mixture was used. Data for 23 elements was plotted against INAA concentrations. Correlation coefficients were > 90% reagent to stop carbide formation in ETV-ICP-MS determination of Ca Cd Cu Mn Pb Ti V and Zn concentrations above 1 mg rn1-l. Tm was not quantified due to 153Eu160 + spectral interference Powdered samples were fused with LiB04 in graphite crucibles at 1100 "C for 30 min and then dissolved in 10% HNO,. K and Na were determined by FAES For Ca Fe or Na the slurry was diluted 100-fold while for Al Cd and Si modifiers (H,BO,-HF diammonium hydrogenphosphate-magnesium nitrate and calcium nitrate respectively) were added Direct analysis using LA-ICP-MS.Due to lack of Freon- 12 was used as a gas-phase halogenation Severe interferences observed at matrix Various (4) Slag cements Various (4) Lanthanum oxide AE;DCP;L Various (6) Cement Various Europium oxide Various (8) Gadolinium oxide Various (10) Silicon carbide AA;-;L M S;ICP;L MS;spark;L AE;ICP;L Various Solid oxide fuel cells Various (14) Aluminium oxide M S;ICP;S MS;ICP;L Various (50) Ceramics M S;ICP; L Various ( 8 ) Zeolites AE;ICP;S Various (13) Europium oxide Various (9) Ceramics MS;ICP;L AE;ICP or flame;L Various Zirconium dioxide AA;ETA;S CATALYSTS- Mo Noble Pb Pd metals Pd Activated carbon 96/2314 XPS;S and S1MS;S Surface and bulk structure determined by XPS TOF-SIMS and XRD. TOF-SIMS and XPS valence bands showed presence of polymeric Mo species Samples of predetermined size irradiated and analysed by XRF Samples digested using HNO HC1 HF and HClO in PTFE beakers on a hotplate Samples digested using HCl-HNO in Carius tubes and undissolved residues treated with HF.Final analysis by ID-ICP-MS For surface and sludge determinations 2-2.5 mol I-' HC1 extraction was used. For solid samples a mixture of HCl-HNO plus HClO under pressure at 120 "C was required (PTFE vessel) A.s for Pd A.s for Pd Measurement of distribution of V on composite catalyst particles. Results consistent with cracking activity data Catalyst film on C electrodes Auto catalysts Auto catalysts XRF MS;ICP;L MS;ICP;L 9612666 961 1497 961 1497 AE;MIP;L 9612027 Spent catalysts Auto catalysts Auto cataylsts Cracking catalysts MS;ICP;L MS;ICP;L S1MS:S 9611497 9611497 9513712 Pt Rh V 502 R Journal of Analytical Atomic Spectrometry December 1996 Vol.11Table 3 (continued) Element Matrix CATALYSTS- w W-)I-AI,O~ Various Platinum catalyst Various Catalysts Various Ni-Mo catalysts Various Catalysts Various Catalysts Techniqut:; atomization; analyte form" EPMA;S AE;ICP;L AA;F;L AE;ICP;L S1MS;S SIMS;S Sample treatment/comments Reference 961982 9513624 95/3650 Determination of W concentration depth profile 250 mg sample dissolved in 10% HC1. Y added as internal standard Microwave assisted digestion using HN03-HF. Fluoroboric acid (60% v/v) added to final solutions Comparison of H3PO4 H,S04 HNO and HClO micro-wave digestion methods. All mixtures gave similar results Review (182 refs.).Applications of SIMS in catalyst analysis. Comments on phenomena such as sputtering and ionization Review. Use of various post-ionization techniques to reduce matrix effects and to increase sensitivity for surface analyses 95/3884 951461% 9612346 ~~~~ ~~~ * HG indicates hydride generation and S L G and SL signify solid liquid gaseous or slurry sample introduction respectively. Other abbreviations are listed elsewhere. On-line process control by XRF methods are also popular with reports of automated system control (96/1224) and on-stream XRF analysers (96/2605). The characterization of high temperature superconductor (HTSC) materials both for elemental content and surface/ interface properties has become a major application for spec- troscopists (96/4108).Depth profiling by SNMS (96/1768) and studies of the binding energies of various components in Bi-based cuprate superconductors e.g. Bi2Sr2CaCu208 6 by SIMS (96/4123) have been reported. In the latter report results were compared with those of similar measurements of BiO CuO and CaCO samples to ascertain detailed information on the surface binding energies for these compounds. ICP-AES has been used for the analysis of high temperature supercon- ductors (96/371). If the sample carrier gas flow was optimized for the analysis of alkali metals detection limits of 1 x 1OP3-9.7 x with respect to the dissolved solid could be achieved. Laser ablation as a means of solid sampling for .ttomic spectrometry has the potential to be universally appliec to all materials of the ceramic or refractory type.Laser-induced uaporization-mass spectrometry (LIMS) has been used to meas- ure the vapour pressure of refractory materials especially for various U-0 vapour species (96/2428). The total l'apour pressure at 4300 K was deduced to be 3.9 atm. LIMS h a also been used to study the oxide phases in the Y-Ba-Cu-0 system (96/1648). The formation of polynuclear ions (cluster:,) as a result of the laser sputtering of oxides was examined and from this it was possible to carry out quantitative analysis of inhomogeneous oxide materials. Lasers (under various guises and couplings) have also been used for fundamentai stud- ies such as to identify ablation products from (BC2N) mate- rials (96/4124) to characterize charged species from Pb(Ti0,48Zr0.52)3 targets (96/1628) to prove the existcnce of Rydberg state atoms (96/2415) and finally to study the syn- thesis of lanthanide oxide clusters (96/1629).3.5. Catalysts As has been shown by previous ASU reviews secondtiry ion mass spectrometry has been and continues to be the most popular analytical tool for the analysis and characterization of industrial catalytic materials. This year the strength of the technique in this area has been underlined by the publication of a comprehensive review (182 references) by Borg and Niemantsverdriet (95/4618). Technical details such as sputter- ing ion emission ionization and neutralization was discussed. The application of SIMS to gain information about catalytic interactions with gas promoters and poisons was also described as well as surface reactivity studies adsorption and surface reactions.This last and extremely important aspect of catalytic functionality has also been addressed by Cherepin (96/2346). The author provides an overview of progress in instrumentation and ion formation with particular emphasis on the sensitivity and lateral and depth resolution capabilities of various post-ionization techniques such as electron beam plasma and multiphoton ionization (resonant and non- resonant). In a more specific paper Chao et al. (95/3712) used SIMS to study vanadium passivation on composite cracking catalyst particles comprising REE exchanged zeolite mixed with calcium-exchanged clay. The results obtained were con- sistent with cracking activity data and show that vanadium preferentially accumulated on the clay material.A wide range of techniques has been utilized by Rondon et al. (96/2314) such as X-ray diflraction X-ray photon spec- troscopy and time-of-flight SIMS for the characterization of Mo-C catalysts. A series of Mo-C catalysts were prepared by adsorption of (NH4)6Mo,0,4~4H20 on to activated carbon. It was found that pH was the driving mechanism for Mo adsorption. Surface and bulk analysis of the Mo-C catalysts by XPS and XRD indicated the presence of a highly dispersed mono-layer-like Mo phase. ToFSIMS however showed that the catalysts contained polymer Mo species which was consist- ent with the predicted speciation based on Mo solution chemistry. Obtaining concentration profiles in heterogeneous catalysts has always been a problem for workers in this field.A technique using electron-probe microanalysis has been developed by Viturro et al. (96/982) for measuring the W concentration on rough spherical material of a W-y-Al,O support catalyst. Using a large number of experimental points accurate infor- mation about the depth profiles of W could be obtained in a short time. The workers discuss the possibility of the technique being extended to metallurgical and mineralogical materials. As in other sectors of analytical chemistry the utilization of microwave digestion techniques for the dissolution of catalytic materials continues to receive attention. Comparisons of different dissolution procedures continue to be popular. Ali (95/3884) has compared different acid media for the microwave digestion of Ni-Mo hydrotreating catalysts.It was found that H2S0 and H3P0 destroyed the matrix better than aqua regia and that Mo required higher power and longer exposure in order to be efficiently dissolved. A mixture of nitric and Joiirnal of Analytical Atomic Spectrometry December 1996 Vol. 11 503Rhydrofluoric acids has also been used for the analysis of oil and petrochemical catalysts (95/3650). Elemental analysis of the resulting solutions was carried out using AAS with greater than 96% recoveries for a variety of elements being reported. The accurate analysis of precious metals and contaminants in auto-catalysts continues to attract attention (96/1497). A mixture of HNO HC1 HF and HC10 was used to analyse for Pb by isotope dilution ICP-MS.Pt and Pd were also determined using ID-ICP-MS but after a HC1-HNO dissolu- tion in Caruis tubes. Rh was quantified using In internal standardization. Correction had to be made for mass bias drift of mass bias and relative sensitivity factors. A round-up of other noble group determinations include analysis of Pd in spent catalysts by MIP-AES (96/2027) Pd and Rh (plus 11 other elements) in platinum catalysts by ICP-AES after HC1 dissolution (95/3624) and Pt and Ru in catalyst film on carbon electrodes by XRF (96/2666). LOCATION OF REFERENCES The full list of references cited in this Update have been published as follows 95/1160-95/1597 J. Anal. At. Spectrom. 1995 10(6) 155R-171R 95/1598-95/C2275 J. Anal. At. Spectrom. 1995 10(7) 173R-198R.95/2276-95/2891 J. Anal. At. Spectrom. 1995 10( 8) 229R-251R. 95/C2892-95/3361 J. Anal. At. Spectrom. 1995 10( lo) 31 1R-328R. 95/3362-95/4189 J. Anal. At. Spectrom. 1995 10( 1 l ) 329R-358R. 95/C4190-95/4746 J. Anal. At. Spectrom. 1995 10( 12) 402R-422R. 96/C1-96/416 J. Anal. At. Spectrom. 1996 11( l) 1R-17R. 96/417-96/C947 J. Anal. At. Sprxtrom. 1996 11 (2) 67R-85R. 96/948-96/1357 J. Anal. At. Spectrorn. 1996 11(3) 87R-101R. 96/1358-96/1802 J. Anal. At. Spectrorn. 1996 11(4) 187R-203R. 96/1803-96/2015 J. Anal. At. Spectrom. 1996 11( 5) 205R-212R. 9612016-96/2799 J . Anal. At. Spectrom. 1996 11 (6) 239R-269R. 96/2800-96/3038 J. Anal. At. Spectrorn. 1996 11( 7) 271R-280R. 96/3039-96/3400 J. Anal. At. Spectrom. 1996 11 (8) 327R-339R. 96/3401-96/3788 J. Anal. At.Spectrom. 1996 11 (9) 341R-354R. 96/3789-96/4160 J. Anal. At. Spectrom. 1996 11( lo) 395R-408R. Abbreviated forms of the literature references quoted (excluding those 1:o 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 9511478 J. Anal. At. Spectrom. 1995 10 105. 9511489 J. Anal. At. Spectrom. 1995 10 167. 9511670 J. Anal. At. Spectrom. 1995 10 303. 9511866 Anal. Chem. 1994 66 3788. 9512394 J. Anal. At. Spectrom. 1995 10 363. 9513055 J. Anal. At. Spectrom. 1995 10 443. 9513056 J. Anal. At. Spectrom. 1995 10 449. 9513273 Nucl.Instrum. Methods Phys. Res. Sect. B 1994 85 356. 9513374 Fresenius’ J. Anal. Chem. 1995 351 139.9513376 Bunseki Kagaku 1994,43,1009.95/3380 Bunseki Kagaku 1994,43 1193.9513382 Fenxi Huaxue 1994,22 1135. 9513386 Lihua Jianyan Huaxue Fence 1994 30 341. 9513388 Lihua Jianyan Huaxue Fence 1994 30 368. 9513399 Talanta 1994 41 2087. 9513400 Talanta 1994 41 2121. 9513402 Talanta 1995 42 45. 9513403 Analusis 1994 22 445. 9513408 J . Radioanal. Nucl. Chem. 1994 185 27. 9513420 Australian Standards AS 1329.2- 1994 1994 12. 9513421 Australian Standards AS 1329.3- 1994 1994 12. 9513422 Australian Standards AS 1329.5- 1994 1994 12. 9513423 Australian Standards AS 1329.6- 1994 1994 12. 9513424 Standards Australia AS 1329.7- 1994 1994 12. 9513425 Australian Standards AS 1329.8-1994 1994 12.9513426 Australian Standards AS 1515.1-1994 1994 12. 9513427 Australian Standards AS 1515.2-1994 1994 12. 9513428 Zavod. Lab. 1994 60( 12) 19. 9513430 Vysokochist. Veshchestua 1994 121. 9513431 Vysokochist. Veshchestva 1994,125.9513433 Fresenius’ J . Anal. Chem. 1995 351 158. 9513438 Bunseki Kagaku 1995 44 123. 9513439 Bunseki Kagaku 1995 44 157. 9513444 Microchem. J. 1995 51 73. 9513454 Anal. Proc. (London) 1995 32 133. 9513459 Anal. Chem. 1994 66 4375. 9513462 Ciencia 1994 2 87. 9513474 J. Chromatogr. A 1994 683 175. 9513475 J. Chromatogr. A 1994 683 233. 9513479 J. Microcolumn Sep. 1994 6 605. 9513493 Am. Lab. (Fairfield Conn.) 1994 26 24K. 9513503 Yankuang Ceshi 1994 13(2) 125. 9513504 Yankuang Ceshi 1994 13(2) 145. 9513531 Anal. Sci.1995 11 13. 9513532 Anal. Sci. 1995 11 115. 9513544 Chim. Ind. (Milan) 1993 75 8. 9513550 Fresenius’ J. Anal. Chem. 1994,350 587.9513553 Fresenius’ J. Anal. Chem. 1995 351 129. 9513554 Fresenius’ J . Anal. Chem. 1995 351 110. 9513557 ISIJ Int. 1994 34 997. 9513561 J. High Resolut. Chromatogr. 1995 18 33. 9513562 J. High Resolut. Chromatogr. 1995 18 28. 9513563 J. Mass Spectrom. 1995 30 134.9513566 Zhongguo Xitu Xuebao 1994,12,68.95/3568 Org. Geochem. 1994 22 383. 9513572 Nucl. Instrum. Methods Phys. Res. Sect. B 1995,96 87.9513574 Pharmazie 1995,50 60. 9513599 V T T Tied. 1993 1503 17. 9513601 Radioisotopes 1995,44,85.95/3610 J. Chromatogr. A 1995,694,425.9513617 Fenxi Shiyanshi 1994,13,17.95/3624 Guangpuxue Yu Guangpu Fenxi 1995 15 41. 9513632 Fenxi Huaxue 1995 23 284.9513637 Lihua Jianyan Huaxue Fence 1995 31 75. 9513643 Anal. Chim. Acta 1994 295 151. 9513650 Analyst (London) 1994,119 1705.9513653 Appl. Organomet. Chem. 1994,8 129. 9513662 Fresenius’ J. Anal. Chem. 1994 349 502. 9513670 J. High Resolut. Chromatogr. 1994 17 527. 9513674 Mikrochim. Acta 1994 116 57. 9513684 Weisheng Yanjiu 1994 23 83. 9513691 Analyst (Cambridge UK) 1995 120 667. 9513712 Appl. Catal. A 1995 121 217. 9513716 Izu. Akad. Nauk Ser. Fiz. 1994,58 63.9513718 J. Electrochem. SOC. 1994,141 3453. 504 R Journal of Analytical Atomic Spectrometry Decembe r 1996 Vol. 1195/3731 J. Anal. At. Spectrom. 1995 10 555. 95/3767 Anal. Chem. 1995 67 354. 95/3783 Fenxi Ceshi Xuebao 1994 13 71. 95/3785 Fenxi Huaxue 1994 22 752. 95/3787 Fenxi Huaxue 1994,22,859.95/3789 Fresenius’ J.Anal. Chem. 1994 349 424. 95/3790 Fresenius’ J. Anal. Chem. 1994 349 738. 95/3799 J. Chromatogr. A 1994 686 109. 95/3800 J. Fiz. Malays. 1993,14,43. 9513808 Mikrochim. Acta 1994 113,287. 95/3809 Microchem. J. 1994,50,145.95/3813 Orient. J. C hem. 1994,10,1.95/3822 Trends. Anal. Chem. 1994,13,327.95/3832 Yejin Fenxi 1994 14 55. 95/3833 ACH Models Chem. 1994 131 597. 95/3837 Anal. Chim. Acta 1995 299 393. 9513839 At. Spectrosc. 1995 16 79. 95/3842 Collect. Czech. (‘hem. Commun. 1994 59 2227. 95/3843 Food Addit. Contam. 1994 11 633. 95/3847 Fresenius’ J. Anal. Chem. 1995 351. 403. 95/3851 Fresenius’ J. Anal. Chem. 1995 351 449. 9513852 Fresenius’ J. Anal. Chem. 1995 351 456. 95/3854 Fresenius’ J. Anal. Chem. 1995 351 467. 95/3869 J. AOAC Znt.1995 78 407. 95/3877 Nucl. Instrum. Methods Phys. Res. Sect. B 1993 79 545. 95/3880 Appl. Spectrosc. 1995 49 499. 95/3881 Appl. Spectrosc. 1995 49 616. 9513884 Appl. Spectrosc. 1995 49 682. 95/3897 An. Quim. 1993 89 597. 9513899 Anal. Cell. Pathol. 1994 6 345. 95/3905 Appl. Organomet. Chem. 1994 8 451. 95/3924 Fresenius’ J. Anal. Chem. 1994 349 283. 95/3930 Holzforschung 1994 48 463. 95/3935 Idemitsu Giho 1993 36 750. 95/3938 J. Chem. Educ. 1994 71 800. 9513947 J. Chromatogr. A 1994 683 245. 9513948 J. Chrornatogr. A 1994 683 269. 95/3952 Microchem. J. 1994 50 131. 9514009 CLB Chem. Labor Biotech. 1993,44,218.95/4015 Inst. Chem. Eng. 1994. 148.95/4038 Glass Sci. Technol. (Frankfurt/ Afain) 1994 67 N98. 95/4039 GIT Fachz. Lab. 1994 38 1119. 9514054 J. Hazard. Muter.1994,40,1.95/4057 Indian J . Chem. Technol 1994 1 98. 9514077 Ober-aechen Werkst. 1994 35 29. 95/4078 Pr. Nauk. Inst. Technol. Nieorg. Nawozow .Miner. Politech. Wroclaw 1994 40 100. 95/4084 Quim. Anal. (Barcelona) 1992 11 173. 95/4095 Text. Chem. Color.. 1994 26 32. 95/4096 Text. Res. 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ISSN:0267-9477    

DOI:10.1039/JA996110461R

出版商:RSC    

年代:1996

数据来源: RSC

摘要:

GLOSSARY OF ABBREVIATIONS Whenever suitable elements may be referred to by their chemical syrnbols and compounds by their formulae. The following abbreviations may be used without definition. ac AA AAS AE AES AF AFS AOAC APDC ASV BCR CCP CMP CRM cv cw dc DCP DDC DMF DNA ECD EDL EDTA EDXRF EIE EPMA ETA ETAAS ETV EXAFS FAAS FAB FAES FAFS FANES FAPES FI FPD FT FTMS GC GD GDL GDMS Ge ( Li ) HCL hf HG HPGe HPLC IAEA IBMK ICP ICP-MS ID IR IUPAC LA LC 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 dc plasma diethyldithiocarbamate N N-dimethylformamide deoxyribonucleic acid electron capture detection electrodeless discharge lamp e t h ylenediaminete traace tic acid energy dispersive X-ray fluorescence easily ionizable element electron probe microanalysis electrothermal atomization electrothermal atomic absorption spectrometry electrothermal vaporization extended X-ray absorption fine structure flame AAS fast a tom bombardment flame AES flame AFS furnace atomic non-thermal excitation spectrometry furnace atomization plasma excitation spectrometry 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-methylpentan-2-one) inductively coupled plasma inductively coupled plasma mass spectrometry isotope dilution infrared International Union of Pure and Applied Chemistry laser ablation liquid chromatography (ammonium pyrrolidin- 1-yl dithioformate) spectroscopy LEAFS LEI LMMS LOD LTE MECA MIP MS NAA NaDDC NIES NIST NTA OES PIGE PIXE PMT PPm PTFE PVC rf REE(s) RIMS RM RSD SEC SEM SFC Si (Li) SIMAAC SIMS SR SRM SSMS STPF TCA TIMS TLC TMAH TOP0 TRIS TXRF uhf uv VDU vuv WDXRF XRF LOQ PPb QC S/B SIN UV/VIS laser-excited atomic fluorescence spectrometry laser-enhanced ionization laser-microprobe mass spectrometry limit of detection limit of quantification local thermal equilibrium molecular emission cavity analysis microwave-induced plasma mass spectrometry neutron activation analysis sodium diethyldithiocarbamate National Institute for Environmental Studies National Institute of Standards and Technology nitrilo triacetic acid optical emission spectrometry particle-induced gamma-ray emission particle-induced X-ray emission photomultiplier tube parts per billion parts per million poly (tetrafluoroethylene) poly(viny1 chloride) quality control radio frequency 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 tetramethylammonium hydroxide trioctylphosphine oxide 2-amino-2-( hydroxymethy1)propane- 1,3-diol total reflection X-ray fluorescence ultra-high frequency ultraviolet ultraviolet-visible visual display unit vacuum ultraviolet wavelength dispersive X-ray fluorescence X-ray fluorescence Commonly Used Symbols 4 relative atomic mass Mr relative molecular mass r correlation coefficient S standard deviation Sr relative standard deviation Journal of Analytical Atomic Spectrometry December 1996 Vol.11

ISSN:0267-9477    

DOI:10.1039/JA996110508R

出版商:RSC    

年代:1996

数据来源: RSC

摘要:

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K. Chaudhuri J. Mandal A. Volatilization of mercury by resting mercury-resistant bacterial cells. Bull. Environ. Contam. Toxicol. 1996 56 259. (Dept. Biochem. Univ. Coll. Sci. Calcutta 700 019 India). Gupta M. Chandra P.Bioaccumulation and physio- logical changes in Hydrilla uerticillata (1.f.) Royle in response to mercury. Bull. Enuiron. Contam. Toxicol. 1996 56 319. (Aquatic Botany Lab. Natl. Botanical Res. Inst. Lucknow 226 001 India). Hamoutene D. Romeo M. Gnassia M. Lafaurie M. Cadmium effects on oxidative metabolism in a marine seagrass Posidonia oceanica. Bull. Enuiron. Contam. Toxicol. 1996 56 327. (Lab. Toxicol. Marine Fac. Med. Univ. Nice-Sophia Antipolis 06107 Nice France).9614698 9 6/46 99 9614700 9614701 9614702 9614703 9614704 9614705 9614706 9614707 9614708 9614709 9614710 96/47 1 1 Scharenberg W. Ebeling E. Distribution of heavy metals in a woodland food web. Bull. Environ. Contam. Toxicol. 1996 56 389. (Inst. Toxikol. 24105 Kiel Germany). Vijayram K.Geraldine P. Regulation of esscntial heavy metals (Cu Cr and Zn) by the freshwater prawn Macrobrachium malcolmsonii (Milne Edwards). Bull. Enuiron. Contam. Toxicol. 1996 56 335. (Res. Dept. Zoology Periyar EVR Coll. Tiruchirappalli 620 023 India). Rastogi S. C. Pritzl G. Migration of some toxic metals from crayons and water colors. Bull. Enuiron. Coritam. Toxicol. 1996 56 527. (Ministry Environ. and Energy Natl. Environ. Res. Inst. 4000 Roskilde Denmark ). Kaji T. Mishima A. Yamamoto C. Fujiwara Y. Sakamoto M. Kozuka H. Koizumi F. Bismuth induces metallothionein but does not protect against cadmium cytotoxicity in cultured vascular endothelial cells. Bull. Environ. Contam. Toxicol. 1996 56 630. (Fac. Pharm. Sci. Hokuriku Univ. Kanazawa 920-1 1 Japan). Perez-Coll C.S. Herkovits J. Stage-dependent uptake of cadmium by Bufo arenarum embryos. Bull. Ent iron. Contam. Toxicol. 1996 56 663. (Programa Segur idad Quim. Inst. Ciencias Ambientales Salud 1405 Buenos Aires Argentina). Yang H.-N. Chen H.-C. Uptake and eliminaticn of cadmium by Japanese eel Anguilla japonica at various temperatures. Bull. Environ. Contam. Toxicol. 1996 56 670. (Inst. Zoology Natl. Taiwan Univ. Taipei 107 Taiwan China). Rodamilans M. Torra M. To-Figueras J. Corbella J. Lopez B. Sanchez C. Mazzara R. Effect of the reduction of petrol lead on blood lead levels of the population of Barcelona (Spain). Bull. Environ. Contam. Toxicol. 1996 56 717. (Toxicol. Unit Hospital Clinic and Provincial Univ. Barcelona 08036 Barcelona Spain). Rabitsch W. B. Metal accumulation in terrestrial pulmonates at a lead/zinc smelter site in Arnoldstein Austria.Bull. Environ. Contam. Toxicol. 1996 56 734. (Dept. Ecophysiol. Inst. Zoology Univ. Vienna 1090 Vienna Austria). Hamza-Chaffai A. Romeo M. El Abed A. Hcavy metals in different fishes from the Middle Eastern Coast of Tunisia. Bull. Environ. Contam. Toxicol. 1996 56 766. (Ecole Natl. Ingenieurs Sfax 3038 Sfax Tunisia). Dhawale S. S. Lane A. C. Dhawale S. W. Effecis of mercury on the white rot fungus Phanerochaete chr vso- sporium. Bull. Environ. Contam. Toxicol. 1996 56 825. (Dept. Biol. Indiana Univ. Purdue Univ. Fort Wayne Fort Wayne IN 46805 USA). Gaggi C. Zino F. Duccini M. Renzoni A. Levels of mercury in scalp hair of fishermen and their families from Camara de Lobos-Madeira (Portugal) a prelimi- nary study.Bull. Environ. Contam. Toxicol. 1996 56 860. (Dipt. Biol. Ambientale Univ. Siena 53100 Siena Italy). Miranda M. G. Ilangovan K. Uptake of lead by Lemna gibba L influence on specific growth rate and basic biochemical changes. Bull. Environ. Coniam. Toxicol. 1996 56 1000. (Dept. Hydrobiol. Univ. Autonoma Metropolitana-Iztapalapa Mexico DF 09340 Mexico). Absil M. C. P. van Scheppingen Y. Concentrations of selected heavy metals in benthic diatoms and sediment in the Westerschelde Estuary. Bull. Enuiron. Coni am. Toxicol. 1996 56 1008. (Centre Estuarine and Coastal Ecol. Netherlands Inst. Ecol. 4401 EA Yersf$ke Netherlands). Rodrigues A. L. S. Rocha J. B. T. Pereira M. E. Souza D. 0.6-Aminolevulinic acid dehydratase activity 96/47 12 9614713 96/4714 96/47 15 9614716 96/47 17 96/47 1 8 96/47 19 9614720 9614721 9614722 9614723 in weanling and adult rats exposed to lead acetate.Bull. Environ. Contam. Toxicol. 1996 57 47. (Depto. Bioquim. Centre Ciencias Biol. Univ. Fed. Santa Catarina 88040-900 Florianopolis SC Brazil). Bianchini A. Gilles R. Toxicity and accumulation of mercury in three species of crabs with different osmoregulatory capacities. Bull. Enuiron. Contam. Toxicol. 1996 57 91. (Lab. Animal Physiol. Univ. Liege 4020 Liege Belgium). De Gregori H. I. Pinochet C. H. Arancibia J. M. Vidal B. A. Grain size effect on trace metals distribution in sediments from two coastal areas of Chile. Bull. Environ. Contam. Toxicol. 1996 57 163. (Inst. Quim. Univ. Catolica Valparaiso Casilla 4059 Valparaiso Chile).Skinner C. H. Schwob J. L. Charge-coupled-device detection of soft X-rays for grazing-incidence spec- trometers. Appl. Opt. 1996 35( 22) 4321. (Physics Lab. Princeton Univ. Princeton NJ 08543 USA). Nelms S. M. Greenway G. M. Koller D. Evaluation of controlled-pore glass immobilized iminodiacetate as a reagent for automated on-line matrix separation for inductively coupled plasma mass spectrometry. J. Anal. At. Spectrom. 1996 11 907. (Univ. Hull Hull N Humberside UK HU6 7RX). Begerow J. Turfeld M. Dunemann L. Determination of physiological platinum levels in human urine using magnetic sector field inductively coupled plasma mass spectrometry in combination with ultraviolet photolysis. J. Anal. At. Spectrom. 1996 11 913. (Dept. Anal. Chem. Med. Inst.Umwelthygiene 40225 Duesseldorf Germany). Jarvis K. E. Williams J. G. Alcantara E. Wills J. D. Determination of trace and ultra-trace elements in saline waters by inductively coupled plasma mass spectrometry after off-line chromatographic separation and preconcentration. J. Anal. At. Spectrom. 1996 11 917. (NERC ICP-MS Facility Centre Anal. Res. Environ. Imperial Coll. Ascot Berkshire UK SL5 7TE). Alvarado J. S. Erickson M. D. Determination of long- lived radioisotopes using electrothermal vaporization- inductively coupled plasma mass spectrometry. J. Anal. At. Spectrom. 1996 11 923. (Environ. Res. Div. Argonne Natl. Lab. Argonne IL 60439 USA). Barrero Moreno J. M. Ignacio Garcia Alonso J. Arbore P. Nicolaou G. Koch L. Characterization of spent nuclear fuels by ion chromatography-inductively coupled plasma mass spectrometry. X Anal.At. Spectrom. 1996 11 929. (European Commission JRC Inst. Transuranium Elements 76125 Karlsruhe Germany). Schelles W. De Gendt S. Van Grieken R. E. Optimization of secondary cathode thickness for direct current glow discharge mass spectrometric analysis of glass. J. Anal. At. Spectrom. 1996 11 937. (Dept. Chem. Univ. Antwerp (UIA) 2610 Antwerpen Belgium). Risnes A. Lund W. Comparison of systems for eliminating interferences in the determination of arsenic and antimony by hydride generation inductively coupled plasma atomic emission spectrometry. J. Anal. At. Spectrom. 1996 11 943. (Dept. Chem. Univ. Oslo 03 15 Oslo Norway). Todoli J. L. Canals A. Hernandis V. Behaviour of a single-bore high-pressure pneumatic nebulizer operating with alcohols in inductively coupled plasma atomic emission spectrometry.J. Anal. At. Spectrom. 1996 11 949. (Depto. Quim. Anal. Univ. Alicante 03071 Alicante Spain). Wagatsuma K. Classification of emission lines of the Group IIIB elements aluminium gallium and indium excited by Grimm glow discharge plasmas using several Journol of Analytical Atomic Spectrometry December 1996 Vol. 11 51 3R9614724 9614725 96/4726 9614727 9 6/47 2 8 9614729 96/4730 961473 1 96/C473 2 96/C473 3 96/C4734 514R different plasma gases. J . Anal. At. Spectrum. 1996 11 957. (Inst. Materials Res. Tohoku Univ. Sendai 980 Japan). Ince A. T. Dawson J. B. Snook R. D. Comparison of the analytical performance of flame atomic magneto- optic rotation spectrometry in the Faraday configur- ation with that of flame atomic absorption spectrometry.J. Anal. At. Spectrum. 1996 11 967. (Dept. Instrumentation and Anal. Sci. (DIAS) Univ. Manchester Inst. Sci. and Technol. (UMIST) Manchester UK M60 1QD). Luterotti S. Short multifactorial plan for the determi- nation of trace metals in complex matrices by flame atomic absorption spectrometry. J. Anal. At. Spectrom. 1996 11 973. (Dept. Anal. Chem. Fac. Pharm. Biochem. Univ. Zagreb 10000 Zagreb Croatia). Tsalev D. L. D’Ulivo A. Lampugnani L. Di Marco M. Zamboni R. Thermally stabilized iridium on an integrated carbide-coated platform as a permanent modifier for hydride-forming elements in electrothermal atomic absorption spectrometry. Part 2. Hydride gener- ation and collection and behaviour of some organoele- ment species.J. Anal. At. Spectrom. 1996 11 979. (1st. Chim. Anal. Strumentale CNR 56100 Pisa Italy). Tsalev D. L. D’Ulivo A. Lampugnani L. Di Marco M. Zamboni R. Thermally stabilized iridium on an integrated carbide-coated platform as a permanent modifier for hydride-forming elements in electrothermal atomic absorption spectrometry. Part 3. Effect of L-cysteine. J . Anal. At. Spectrum. 1996 11 989. (1st. Chim. Anal. Strumentale CNR 56100 Pisa Italy). Slaveykova V. I. Rastegar F. Leroy M. J. F. Behaviour of various arsenic species in electrothermal atomic absorption spectrometry. J. Anal. At. Spectrom. 1996 11 997. (Ecole Europeenne Chim. Polymeres et Materiaux Strasbourg Lab. Chim. Anal. et Minerale 67 008 Strasbourg Cedex France). Lopez-Garcia I.Sanchez-Merlos M. Hernandez- Cordoba M. Rapid determination of selenium in soils and sediments using slurry sampling-electrothermal atomic absorption spectrometry. J. Anal. At. Spectrum. 1996 11 1003. (Dept. Anal. Chem. Fac. Chem. Univ. Murcia 30071 Murcia Spain). Garcia Campana A. M. Ales Barrero F. Roman Ceba M. Sensitive spectrofluorimetric method for the determi- nation of ethylenediaminetetraacetic acid and its salts in foods with zirconium ions and Alizarin Red S in a micellar medium. Anal. Chim. Acta 1996 329 319. (Dept. Anal. Chem. Fac. Sci. Univ. Granada 18071 Granada Spain). Wu H. Wang H. Studies of the influence of the surfactant sodium dodecyl sulfate on the fluorescence properties of kinetin. Anal. Chim. Acta 1996 329 161. (Dept.Chem. Lanzhou Univ. Lanzhou 730000 China). Prokisch J. Kovacs B. Gyori Z. Theoretical and practical problems in hyphenation of a liquid chromato- graph and an atomic emission (ICP) or atomic absorption (AAS) instrument. Fourth International Symposium on Hyphenated Techniques in Chromatography Bruges Belgium February 7-9 1996 (Central Lab. Debrecen Agric. Univ. 401 5 Debrecen Hungary). Terasahde P. Pantsar-Kallio M. Manninen P. K. G. Speciation of arsenic by HPLC-ICP-MS. Fourth International Symposium on Hyphenated Techniques in Chromatography Bruges Belgium February 7-9 1996 (Lahti Control and Res. Lab. 15210 Lahti Finland). Raynor M. W. Moodley V. E. Pretorius W. G. Balcerzak M. Electrospray interface for micro LC-ICP with AES and MS detection. Fourth International Symposium on Hyphenated Techniques in Chromatography Bruges Belgium February 7-9 1996 961C4735 96/C473 6 96lC47 3 7 (Dept.Chem. and Applied Chem. Univ. Natal Dalbridge 4014 South Africa). David F. Billiet H. Sandra P. Analysis of selenoamino acids by CGC-AED. Fourth International Symposium on Hyphenated Techniques in Chromatography Bruges Belgium February 7-9 1996 (Res. Inst. Chromatography 8500 Kortrijk Belgium). Jickells S. Analysis of plastics monomers oligomers and additives in food contact materials and measure- ment of migration to foods and food simulants using LC-MS ICP-MS and SEC-FTIR. Fourth International Symposium on Hyphenated Techniques in Chromatography Bruges Belgium February 7-9 1996 (Ministry Agric. Fisheries and Food CSL Food Sci. Lab. Colney Norwich UK NR4 7UQ). Stan H.-J.Capillary gas chromatography and atomic emission detection-a useful instrumental method in pesticide residue analysis of plant foodstuffs and water. Fourth International Symposium on Hyphenated Techniques in Chromatography Bruges Belgium February 7-9 1996 (Inst. Food Chem. Technical Univ. 1000 Berlin 65 Germany). 96/C4738 Michalke B. Schramel P. Hyphenation of CE to ICP-MS as element specific detector for metal speci- ation. Fourth International Symposium on Hyphenated Techniques in Chromatography Bruges Belgium February 7-9 1996 (Inst. Okologische Chem. GSF Forschungszentrum Umwelt und Gesundheit GmbH 85758 Oberschleissheim Neuherberg Germany). 961C4739 Mullins C. B. An improved method of sample introduc- tion for flame atomic absorption spectroscopy.Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (Varian Optical Spectrosc. Instruments Walton-on- Thames Surrey UK KT12 2QF). 96/C4740 Shaw P. Georgitis S. Besson T. Is sensitivity the be all and end all in ICP-MS? Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (Varian Associates Ltd UK). 96/C4741 Morton S. F. N. Rock P. E. Singh S. The application of Zeeman GFAAS and multimedia techniques to human toxicity studies. Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (Unicam Atomic Absorption Cambridge UK CB1 2SU). 96/C4742 Offley S. G. Morton S. F. N. An approach to system validation applied to atomic absorption spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (Unicam Atomic Absorption Cambridge UK CB1 2SU). 961C4743 Volynsky A.B. Catalytic processes in graphite furnaces used for electrothermal atomic absorption spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (Section Anal. and Hoechstreinigung Univ. Ulm 89069 Ulm Germany). 96/C4744 Hutton R. C. Watson P. Grotte-Bartscher B. Laser sampling with plasma spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (Cetac Technol. Inc. Crewe UK CW1 1YX). 96/C4745 Watson P. Hutton R. C. Smith F. G Matrix elimination protocols for ICP-MS.Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (CETAC Technol. Inc. Crewe UK CW1 1YX). 96/C4746 Izquierdo A Strutt P. Baxter M. Lewis J. Crews H. An investigation into the factors affecting the determination of selenium in food matrices using hydride generation/ICP-MS. Eighth Biennial National Atomic Spectroscopy Symposium University of East Journal of Analytical Atomic Spectrometry December 1996 Vol. 1196/C4747 96/C4748 96/C4749 96/C4750 96/C4751 96/C4752 96/C4753 96/C4754 96/C4755 96/C4756 96JC4757 96/C475 8 Anglia UK July 17-19 1996 (CSL Food Sci. Lab. Conference Center Belgium February 7-9 1996 (Lahti Norwich UK NR4 7UQ). Control and Res. Lab. 15210 Lahti Finland). Strutt p. Baxter M.Lewis J. Crews H. FOX T. 96/C4759 Webster C. Clarkson P. Cooke M. Atomic emission Fairweather-Tait S. The use of stable isotopes and detection-sometimes a very useful technique. Fourth hydride generation ICP-MS to determine selenium in International Symposium on Hyphenated Techniques urine from human studies. Eighth Biennial National in Chromatography St John’s Conference Center Atomic Spectroscopy Symposium University of East Belgium February 7-9 1996 (Environ. Res. Center Anglia UK July 17-19 1996 (CSL Food Sci. Lab. School Sci. Sheffield Hallam Univ. City Campus Norwich UK NR4 7UQ). Sheffield UK S1 1WB). VoellkoPf u.9 Paul Cold Plasma ICP-MS. Some 96/C4760 Sandra P. Hyphenation in capillary GC. Toward the practical considerations. Eighth Biennial National 21st Century.Fourth International Symposium on Atomic Spectroscopy Symposium University of East Hyphenated Techniques in Chromatography St John’s Anglia UK July 17-19 1996 (Bodenseewerk F‘erkin- Conference Center Belgium February 7-9 1996 (Dept. Elmer GmbH D-88647 Ueberlingen Germany). Org. Chem. Univ. Ghent 9000 Gent Belgium). Bowman J. Fairman B. Catterick T. Development of a multi-element HG-ICP-MS method for the simul- taneous determination of arsenic antimony and sel- enium in waters. Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (Lab. Government Chemist Middlesex UK TW 11 OLY). Hodges R. J. Plozza T. E. Characterisation of Adam’s catalysts by ICP analysis. Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19,1996 (Monash Univ.Gipiisland Campus Churchill Australia 3842). Nichol C. W. Littlejohn D. Fell G. S Distribulion of selenium in human plasma. Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (Dept. Pure and Applied Chem. Univ. Strathclyde Glasgow UK G1 1XL ). Rivas C. Ebdon L. Hill S. J. Tin speciation in biological samples utilising isotope dilution-HPLC- ICP-MS. Eighth Biennial National Atomic Spectroscopy Symposium University of East Anglia UK July 17-19 1996 (Anal. Chem. Res. Unit Dept. Environ. Sci. Plymouth UK PL4 8AA). Agrawal Y. K. Preconcentration and simultaneous determination of iron( 11) and iron( 111) by inductive coupled plasma atomic emission spectrophotometry.Eighth Biennial National Atomic Spectrcwopy Symposium University of East Anglia UK July t7-19 1996 (Chem. Dept. Sch. Sci. Gujarat Univ. Ahmedabad 380 009 India). Basily A. B. Abdel-khalek M. A. Spectroscopic technique for the study of trace elements in water hyacinth as indication of pollution. Eighth Biennial National Atomic Spectroscopy Symposium Uni\ ersity of East Anglia UK July 17-19 1996 (Natl Res. Center Cairo Egypt). Donard 0. F. X. Hyphenated techniques in chroniatog- raphy. Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s Confcrence Center Belgium February 7-9 1996 (Lab. Photophysique et Photochim. Mol. Univ. Bordeaux 33405 Talence France). Caruso J. A. Chromatography-plasma mass spec- trometry new departures for elemental speciation.Fourth International Symposium on Hyphmated Techniques in Chromatography St John’s Confkrence Center Belgium February 7-9 1996 (Dept. (’hem. Univ. Cincinnati Cincinnati OH 45221-01 72 USA). Mester Z. Woller A. Fodor P. Development of some hyphenated systems for As speciations. Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s Conference Center Belgium February 7-9 1996 (Dept. Chem. Univ. Horticulture and Food Ind. 11 14 Budapest V tllanyi 35 Hungary). Pantsar-Kallio M. Manninen P. K. G. Speciation of chromium in waste water samples by coupled column IC-ICP-MS. Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s 96/C476 1 Gilon N. Potin-Gautier M. Astruc M. Optimization of chromatographic parameters for the determination of selenium species using HPLC-ETAAS hyphenated technique.Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s Conference Center Belgium February 7-9 1996 (Lab. Chim. Anal. Univ. Pau et Pays L’Adour 64000 Pau France). 96/C4762 Mol H. G. J. Hankemeier T. Brinkman U. A. Th. Gas chromatographic determination of pesticides using combined mass spectrometric and atomic emission detection. Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s Conference Center Belgium February 7-9 1996 (Dept. Anal. Chem. Free Univ. 1081 HV Amsterdam Netherlands). 96/C4763 Mitchell S. C. Lewis A. C. Bartle K. D. On-line LC-GC-AED/LC-GC-MS for the analysis of PAC in fuel and environmental samples.Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s Conference Center Belgium February 7-9 1996 (School Chem. Univ. Leeds Leeds UK LS2 9JT). 96/C4764 Rosenberg E. Silgoner I. Grasserbauer M. Determination of volatile organic compounds in water by GC-AED-a comparison between purge & trap and solid-phase micro extraction. Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s Conference Center Belgium February 7-9 1996 (Inst. Anal. Chem. Vienna Univ. Technol. 1060 Vienna Austria). 96/4765 Owens A. Fraser G. W. Keay A. Wells A. McCarthy K. J. Hill S. F. Hughes E. A. Smith A. D. Suller V. Surman M. Mapping X-ray absorption fine structure in the quantum efficiency of an X-ray charge-coupled device.X-Ray Spectrorn. 1996 25 33. (Dept. Phys. and Astronomy Leicester Univ. Leicester UK LE1 7RH). 96/C4766 Porschmann J. Remmler M. Kopinke F.-D. Hyphenated techniques in characterizing coal wastewat- ers and associated sediments. Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s Conference Center Belgium February 7-9 1996 (Centre Environ. Res. Leipzig-Halle 043 18 Leipzig Germany). 96,424767 Grasserbauer M. Rosenberg E. Potential of GC-MIP for environmental trace analysis. Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s Conference Center Belgium February 7-9 1996 (Inst. Anal. Chem. Vienna Univ. Technol. 1060 Wien Austria). 96/C4768 De Smacle T. Vanhaecke F. Moens L. Dams R. ICP mass spectrometry a highly sensitive and selective detection method for the determination of organometals after separation with CGC.Fourth International Symposium on Hyphenated Techniques in Chromatography St John’s Conference Center Belgium February 7-9 1996 (Lab. Anal. Chem. Inst. Nuclear Sci. Ghent Univ. 9000 Ghent Belgium). Journal o f Analvtical Atomic Soectrometrv. December 1996 Vol. 11 515R96/C4769 Cave M. Trick J. Measurement of uncertainty in inductively coupled plasma atomic emission spec- trometry (ICP-AES). Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (British Geological Survey Keyworth Nottingham UK NG12 5GG). 96/C4770 Moharram M. A. Ibrahim J. M. Hegazy A. Hussin A. A. Moharram A. A. Spectroscopic study of organic and inorganic constituents of malignant bladder’s tissues.Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Spectroscopy Dept. Phys. Div. Natl. Res. Centre Dokki Egypt). 96/C4771 Mermet J.-M. Kanicky V. Analysis of silicate rocks and limestones by laser ablation inductively coupled plasma atomic emission spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Lab. Sci. Anal. (URA CNRS 435) Univ. Claude Bernard Lyon 1 69622 Villeurbanne Cedex France). 96/C4772 Mitrovic B. Milacic R. Pihlar B. Speciation of aluminium by cation-exchange FPLC directly coupled to ICP-AES. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (J Stefan Inst.61000 Ljubljana Slovenia). atomic absorption spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Anal. Chem. Nutrition and Bromatol. Fac. Chem. Univ. Santiago de Compostela Santiago de Compostela Spain). 96/C4780 Bermejo-Barrera P. Annllo-Sendin R. M. Aboal- Somoza M. Bermejo-Barrera A. Indirect method for the determination of iodide in tap water by solvent extraction-electrothermal atomic absorption spec- trometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Anal. Chem. Nutrition and Bromatol. Fac. Chem. Univ. Santiago de Compostela Santiago de Compostela Spain). 96/C4781 Tanaka T. Matsuno M. Woo J.-C. Kawaguchi H. Effect of the addition of various gases to radio- frequency argon glow-discharge mass spectrometry.Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Materials Sci. and Eng. Nagoya Univ. Nagoya 464-01 Japan). 96/C4782 Bishay Basily A. Abd-El-Aal M. S. Spectroscopic investigation of phosphorus in soil samples. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Natl. Res. Center Cairo Egypt). ~- 96/C4773 Poluzzi V. Lutman A. Trentini P. Cavalchi B. Coan p Ascanelli M. ~ ~ ~ ~ ~ l i A. ~ ] b ~ ~ i ~ i G. Davoli V. Ciani I. Gava G. Determination of iodine in urine by two different ICP-MS procedures and instrumentations and by HPLC with electrochemical detection. Comparison of the results. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Presidio Multizonale Prevenzione A.U.S.L.42100 Reggio Emilia Italy). 96/C4783 Bermejo-Barrera P. Moreda-Pineiro A. Moreda- Pineiro J. Bermejo-Barrera A. Fast slurry sampling- electrothermal atomic absorption spectrometry methods for the Pb Cd and Mn determination in human scalp hair samples. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Anal. Chem. Nutrition and Bromatol. Fac. Chem. Univ. Santiago de Compostela Santiago de Compostela Spain). 96/C4774 Bellido-Milla D. Hidalgo-Hidalgo de Cisneros J. L. Hernandez-Artiga M. P. Jimenez-Jimenez A. Viability of multivariate analysis of variance in the determination by atomic absorption spectrometry of the metal content in welding fumes.Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dpto. Quim. Anal. Univ. Cadiz 11510 Puerto Real Spain). 96/C4775 Bordera L. Mora J. Todoli J. L. Canals A. Hernandis V. Microwave thermal nebulizer on line sample digestion and inductively coupled plasma- optical emission spectrometry detection. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dpto. Quim. Anal. Univ. Alicante 03071 Alicante Spain). 96/C4776 Gras L. Todoll J. L. Mora J. Canals A. Hernandis V. Microwave desolvation of acid solutions in induc- tively coupled plasma-optical emission spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dpto.Quim. Anal. Univ. Alicante 03071 Alicante Spain). 96/C4777 Hashemi P. Olin A. Equilibrium and kinetic properties of a new iminodiacetate based chelating ion exchanger. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Anal. Chem. Uppsala Univ. 751 21 Uppsala Sweden). 96/C4778 Bermejo-Barrera P. Martinez-Alfonso N. Bermejo- Barrera A. Preconcentration of gallium and indium with amberlite XAD-2 resin coated with 1-( 2-pyridylazo)-2-naphthol. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Anal. Chem. Nutrition and Bromatol. Fac. Chem. Univ. Santiago de Compostela Santiago de Compostela Spain). 96/C4779 Bermejo-Barrera P. Moreda-Pineiro J.Moreda- Pineiro A Bermejo-Barrera A. In situ preconcentration of mercury vapour in iridium-coated graphite tubes for the determination of mercury in sea water samples by 96/C4784 Bermejo-Barrera P. Dominguez-Gonzalez R. Bermejo-Barrera A. Cocho de Juan J. A. Fraga- Bermudez J. M. Zinc speciation in cow milk infant formula and maternal milk by HPLC-FAAS. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Anal. Chem. Nutrition and Bromatol. Fac. Chem. Univ. Santiago de Compostela Santiago de Compostela Spain). 96/C4785 Montes Bayon M. Camuna Aguilar J. F. Pereiro Garcia R. Sanz-Medel A. Simultaneous determination of halides in environmental samples by microwave induced plasma atomic emission spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Phys.and Anal. Chem. Fac. Chem. Univ. Oviedo 33006 Oviedo Spain). 96/C4786 Montes M. Garcia Alonso J. I. Sanz-Medel A. A fast screening method for drinking water quality monitoring using ICP-MS. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Phys. and Anal. Chem. Univ. Oviedo 33006 Oviedo Spain). 96/C4787 Boulo P. R. Soraghan J. J. Sadler D. A. Littlejohn D. Creeke A. Automatic feature extraction from graphite furnace television (GFTV) images for echanced instrumental set-up. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Signal Processing Div. Dept. Electronics and Electrical Eng. Univ.Strathclyde Glasgow UK G1 1XL). 96/C4788 Chadwick G. P. Davidson C. M. Hitchman M. L. Littlejohn D. The analysis of sediment interstitial water by electrothermal atomic absorption spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Pure and Applied Chem. Univ. Strathclyde Glasgow UK G1 1XL). 96/C4789 Anderson P. Davidson C. M. Ferreira P. C. S. Duncan A. L. Effects of sample size and moisture 51 6 R Journal of Analytical Atomic Spectrometry December 1996 Vol. 1 1content on metals released by sequential extraction of soil. Eighth Biennial National Atomic spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Pure and Applied Chem. Univ. Strathclyde Glasgow UK G1 1XL). 96/C4790 Shuttler I.L. Schlemmer G. Portala F. Feurrstein M. Method development considerations for simul- taneous multielement ETAAS. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Bodenseewerk I’erkin- Elmer GmbH 88647 Ueberlingen Germany). 96/C4791 Holmes J. D. Smith P. R Evans-Gowing R. Richardson D. J. Russell D. A. Sodeau J. R. Formation and characterisation of extracellula r cad- mium sulfide crystallites of Klebsiella aerogenes. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (School Chem. Sci. School Biol. Sci. Univ. East Anglia Norwic h UK NR4 7TJ). 96/C4792 Fisher A. S. Waldock M. Hill S. J. Development of a standardised leaching rate method for antifouling paints. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept.Environ. Sci. Univ. Plymouth Plymouth UK PL4 8AA). 96/C4793 Armstrong L. Stockwell P. B. Corns W. T. A new fully automatic gas chromatography system designed specifically for mercury speciation. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19,1996 (PS Anal. Ltd. Orpington Kent UK BR5 3HP). 96/C4794 Guy A. Jones P. Hill S. J. The development of a high performance liquid chromatography-plasma spec- troscopy technique for the speciation of antimony( 111) and (V). Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Environ. Sci. Univ. Plymouth Plymouth Devon UK PL4 8AA). 96/C4795 Murphy J. Jones P. Hill S.J. Determination of total mercury in environmental and biological samples by flow injection cold vapour atomic absorption spec- troscopy. Eighth Biennial National 4tomic Spectroscopy Symposium Univ.East Anglia U K July 17-19 1996 (Dept. Environ. Sci. Univ. Plymouth Plymouth Devon UK PL4 8AA). 96/C4796 Jameel M. Ebdon L. Hill S. J. Automated determi- nation of sulphide as hydrogen sulphide in waste streams by gas phase molecular absorption spec- trometry. Eighth Biennial National 4tomic Spectroscopy Symposium Univ.East Anglia U K July 17-19 1996 (Dept. Environ. Sci. Univ. Plymouth Plymouth UK PL4 8AA). 96/C4797 Lofthouse S. Sargent C. Robb P. Crews H. Baxter M. The determination of platinum group metals in foods. Eighth Biennial National Atomic Specti oscopy Symposium Univ.East Anglia UK July 17-19 1996 (CSL Food Sci.Lab. Colney Norwich UK NR4 7UQ). 96/C4798 Langford N. J. Owen L. M. W. Crews H.. M. A method for sample pretreament of biological samples prior to measurement of cadmium and lead by I(’P-MS. Eighth Biennial National Atomic Specti oscopy Symposium Univ.East Anglia UK July 17-19 1996 (CSL Food and Sci. Lab. Colney Norwich UK NR4 7UQ). 96/C4799 Foulkes M. E. Menendez E. The enzymolysis extrac- tion of toxic and non-toxic arsenic species from vegetable matter and their detection by HPLC-ICP-MS. Eighth Biennial National Atomic Spectj-oscopy Symposium Univ.East Anglia UK July 17-19 1996 (Anal. Chem. Res. Unit Dept. Environ. Sci.. Univ. Plymouth Drake Circus Plymouth UK PL4 6AA). 96/C4800 Muniz C. S. Nickson R. A.Worsfold P. J. Preconcentration and speciation of inorganic sclenium by flow-injection with CCD based ICP-OES detection. Eighth Biennial National Atomic Spectroscopy Symposium Univ-East Anglia UK July 17-19 1996 (Dept. Phys. and Anal. Chem. Fac. Chem. Univ. Oviedo 33006 Oviedo Spain). 96/C4801 Menendez E. Hill S. J. Foulkes M. E. The separation and direct determination of trace chemical species in highly complex mixtures from industrial sources. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Anal. Chem. Res. Unit Dept. Environ. Sci. Univ. Plymouth Plymouth UK PL4 8AA). 96/C4802 Nickson R. A Hill S. J. Worsfold P. J. On-line preconcentration of trace metals in seawater using an iminodiacetate resin with ICP-AES detection.Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19,1996 (Dept. Environ. Sci. Univ. Plymouth Plymouth Devon UK PL4 8AA). 96/C4803 Sulaiman A. B. Sharp B. L. Capillary electrophoresis- inductively coupled plasma-mass spectrometry for metal chelates studies. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Chem. Loughborough Univ. Loughborough UK LE11 3TU). 96/C4804 Costley C. T. Dean J. R. Carroll J. Garden L. M. Marshall J. Determination and identification of methyl- mercury using GC-MIP-AES. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Chem. and Life Sci. Univ. Northumbria Newcastle Newcastle upon Tyne UK NE1 8ST). 96/C4805 Harnly J.M. Advantages of CCD arrays for continuum source atomic absorption spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Beltsville Human Nutrition Res. Center Food Composition Lab. USDA Beltsville MD 20705 USA). 96/C4806 Croft L. J. Littlejohn D. Marshall J. Gardiner P. H. E. The use of various analytical techniques to investigate the mechanisms of chloride interferences and modifers on indium in electrothermal atomic absorption spectrometry (ETAAS). Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Pure and Applied Chem. Univ. Strathclyde Glasgow UK G1 1XL). 96/C4807 Parsons P. J. Zong Y. Y. Investigations of a background overcorrection error in the determination of lead in bone using Zeeman electrothermal atomis- ation atomic absorption spectrometry.Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Environ. Health and Toxicol. New York State Dept. Health State Univ. New York Albany and Wadsworth Center Albany NY 96/C4808 Georgitis S. J. Plantz M. Anderson S. Shaw P. Stroh A Tyler G. Recent advances in cool plasma work. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Varian Instruments North America USA). 96/C4809 Gregson D. Batey J. Overcoming interferences in elemental mass spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium UniviEast Anglia UK July 17-19 1996 (VG Elemental Winsford Cheshire UK CW7 3BX).96/C4810 O’Connor G. Ebdon L. Evans H. E. Fundamental studies of a low pressure inductively coupled plasma source for molecular and atomic mass spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Environ. Sci. Univ. Plymouth Plymouth UK PL4 8AA). 96/C4811 Volynsky A. B. Krivan V. Platinum group metals as chemical modifiers for the determination of selenium in the presence of sodium chloride. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East 12201-0509 USA). Jotrrnal of Analytical Atomic Spectrometry December 1996 Vol. 1 1 51 7 R96/C48 12 96/C48 13 96/C48 14 96/C48 15 96/C48 16 96fC48 17 96/C48 18 96/C4819 96fC4820 96/C4821 9 6/C48 22 96fC4823 518R Anglia UK July 17-19 1996 (Sektion Anal.und Hoechstreinigung Univ. Ulm 89069 Ulm Germany). Butler 0. T. Howe A. M. An international standard for determination of metals and metalloids in airborne particulate matter by ICP-AES. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Health and Safety Lab. Sheffield UK S3 7HQ). O’Hanlon K. Ebdon L. Foulkes M. The effect of easily ionisable elements on simple matrices and slurries using ICP-AES with an SCD detector. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Plymouth Anal. Chem. Res. Unit Dept. Environ. Sci. Univ. Plymouth Plymouth Devon UK PL4 8AA). Coe G. Riby P. The on-line digestion of soils and sludges for trace metals analysis. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Thames Water Utilities Mill Harbour Lab.London UK). Voellkopf U. Paul M. PPT detection limits and extended dynamic range-are they compatible? Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Bodenseewerk Perkin-Elmer GmbH 88647 Ueberlingen Germany). Sadler D. A. Littlejohn D. Perkins C. V. Multi- element optimisation of the operating parameters for ICP-AES with a CCD detection system. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Pure and Applied Chem. Univ. Strathclyde Glasgow UK G1 1XL). Batho A. Analysis of environmental samples using a combined ICPOES-MS system. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Thermo Unicam Ltd.Cambridge UK CB1 2SU). Metcalfe F. L. Perkins C. V. An array detector echelle spectrometer giving intrinsically detailed line profiles. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dev. Dept. Unicam Atomic Absorption Cambridge UK CB1 2SU). Cook J. M. Robinson J. J. Staines R. Billett M. The influence of geology on stream water trace element chemistry elucidated by flow injection ICP-MS. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Anal. Geochem. Group British Geol. Survey Keyworth Nottingham UK NG12 5GG). Anderson P. Davidson C. M. Duncan A. L. Littlejohn D. Ure A. M. Use of sequential extraction and column leaching experiments to assess the liability of heavy metals in contaminated soil.Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Pure and Applied Chem. Univ. Strathclyde Glasgow UK G l 1XL). Watkins P. J. Coles B. J. Improved detection limits and precision in the determination of low levels of REEs by ICP-AES using correlated background correc- tion (CBC). Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Geol. Imperial Coll. Sci. Technol. and Med. London UK SW7 2BP). Fairman B. Catterick T. Investigations into the potential of ETV-ICP-MS for the multi-element deter- mination of the hydride forming elements in water samples. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Lab.Government Chemist Teddington Middlesex UK TWll OLY). Lamble K. J. Hill S. J. Development of an on-line microwave digestion-cold vapour atomic fluorescence spectrometry method for the determination of mercury 1 96/C4824 96fC482 5 96/C48 26 96/C4827 96fC4828 96/C4829 96/C4830 96/C483 1 96/C48 3 2 96/C4833 Journal of Analytical Atomic Spectrometry December 1996 Vol. 1 1 in solid environmental samples. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Environ. Sci. Univ. Plymouth Plymouth UK PL4 8AA). Brahma N. Stockwell P. B. Corns W. T. Evans E. H. Ebdon L. A new approach to the on-line determi- nation of mercury in process streams using atomic fluorescence spectrometry.Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (PS Anal. Ltd. Orpington Kent UK BR5 3HP). Steers E. B. M. Leis F. A pulsed glow discharge source with supplementary microwave excitation. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (SECEAP Univ. North London Holloway London UK N7 8DB). Marcus R. K. Problem solving with radio frequency glow discharge atomic emission spectroscopy. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Chem. Howard L. Hunter Chem. Lab. Clemson Univ. Clemson SC 29634-1905 USA). Fernandez-Garcia M. Pereiro R. Bordel N. Sanz Medel A. In-depth profile analysis of painted car sheets by radiofrequency glow discharge-optical emission spectrometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept.Phys. and Anal. Chem. Fac. Chem. Univ. Oviedo 33006 Oviedo Spain). Potts P. J. Webb P. C. Williams-Thorpe 0. A new procedure for the in situ quantitative analysis of bulk rock samples by portable X-ray fluorescence spec- trometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Earth Sci. Open Univ. Milton Keynes UK MK7 6AA). Aldous K. M. Mills E. Slavin W. Qiao H. Parsons P. J. A portable electrothermal atomic absorption spectrometer for blood lead screening. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Wadsworth Center New York State Dept.Health Albany NY 12201-0509 USA) . Roberts F. Ebdon L. Hill S. J. The diagnostic potential of trace metal profiles in blood and urine measured by inductively coupled plasma mass spec- trometry as markers of bone resorption in patients with skeletal metastases. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Plymouth Anal. Res. Unit Dept. Environ. Sci. Univ. Plymouth Plymouth Devon UK PL4 8AA). White M. A. Panayi A. Iversen B. S. Sabbioni E. The determination of ultratrace elements in human body fluids by simultaneous ETAAS for establishing reference values in the general population. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Environ. Inst. European Commission Joint Res.Centre Ispra Italy). Nelms S. M. Greenway G. M. Evaluation of a new iminodiacetate chelating material for on-line matrix separation with inductively coupled plasma mass spec- trometry. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (School Chem. Univ. Hull Hull North Humberside UK HU6 7RX). Halls D. J. Warren J. M. Assessment of exposure to mercury in dental practice. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Trace Element Unit Dept. Clinical Biochem. Glasgow Royal Infirmary Univ. NHS Trust Glasgow UK G4 OSF).96/C48 34 96/C483 5 96/C48 36 96/C48 3 7 961C4838 96/C48 3 9 96/C4840 96lC484 1 96/C4842 96/C4843 96/C4844 961C4845 961C4846 96lC4847 Hodges R.J. Sample presentation techniques in emission analysis. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia CK July 17-19 1996 (Monash Univ. Gippsland Campus Churchill 3842 Australia). Hutton R. C. Watson R. P. McLeod C. Cox A. Considerations to achieving high sample throughput with ICP-OES and MS. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Cetac Technol. Inc. Crewe UK c w 1 1YX). Lewis J. Bohle S. Crews H. Application of HPLC and ICP-MS instrumentation in the investigation of organo-metal speciation. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (CSL Food Sci. Lab. Colney Norwich UK NR4 7UQ). Caruso J. A. Elemental speciation toward a more informed future.Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia LIK July 17-19 1996 (Dept. Chem. McMicken Coll. Arts and Sci. Univ. Cincinnati Cincinnati OH 452 3-0037 USA). Sulaiman A. B. Sharp B. L. New approaches in elemental speciation. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia IJK July 17-19 1996 (Dept. Chem. Loughborough Univ. Loughborough UK LE11 3TU). Littlejohn D. Anderson P. Davidson C. M. Ure A. M. A strategy for the analysis of industrial soils by atomic spectrometry techniques. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Univ. Strathclyde Glasgow UK G1 1XL). Miller-Ihli N. J. Slurry sampling and atomic spec- troscopy. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia IJK July 17-19 1996 (Food Composition Lab.Beltsville Human Nutrition Res. Center Beltsville MD USA). Tanner S. D. Ion optics in ICPMS modeling intuition and blind luck. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia I JK July 17-19 1996 (PE-SCIEX Concord ON Canada L4K 4V8). Marshall J. Atomic spectrometry-getting more out of what you put in. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia I JK July 17-19 1996 (ICI Res. and Technol. Center Wilton Middlesbrough UK TS90 8JE). Brenner I. B. A membrane interface for trace element determination using solvent extraction and 1 CP-MS. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Ginzton Res. Center Varian USA).Howard A. G. Hydride techniques in trace element speciation. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia lJK July 17-19 1996 (Chem. Dept. Univ. Southampton Southampton UK). Ellis A. T. Exploring unknowns in XRF analysis. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17- 19 1996 (Ind. Anal. Group Oxford Instruments A bingdon Oxfordshire UK OX14 1TX). Fairweather-Tait S. J. Inorganic stable isotopes and nutrition research. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Inst. Food Res. Norwich Lab.. Colney Norwich UK NR4 7UA). Parry S. J. Neutron activation analysis in support of valid analytical measurements. Eighth Biennial National Atomic Spectroscopy Symposium IJniv.East 9 6/C48 48 96/C4849 96/C4850 96/C485 1 961C4852 96/C48 5 3 96/48 54 9614855 9614856 96/48 5 7 9614858 9 6/48 5 9 9614860 Anglia UK July 17-19 1996 (Centre Anal.Res. Environ. Imperial Coll. Sci. Technol. and Med. Ascot Berkshire UK SL5 7TE). Hieftje G. M. Toward the next generation of atomic mass spectrometers. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Chem. Indiana Univ. Bloomington IN 47405 USA). Donard 0. Trace metal speciation and progress in atomic spectroscopy. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Lab. Photophys. et Photochim. Mol. Univ. Bordeaux 1 33405 Talence France). Mermet J. M. Axial viewing in inductively coupled plasma atomic emission spectrometry toy or real improvement? Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Lab.Sci. Anal. Univ. Lyon 69622 Villeurbanne Cedex France). Adams F. Adriaens A. Janssens K. Micro and surface analysis in archaeology. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Chem. Univ. Antwerp (UIA) 2610 Wilrijk Belgium). Furuta N. How isotope ratio measurement by ICP-MS is enabling us to expand fields of application. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept. Chem. Fac. Sci. and Eng. Chuo Univ. Tokyo 112 Japan). Hill S. J. Trace metal speciation-from research to routine analysis. Eighth Biennial National Atomic Spectroscopy Symposium Univ.East Anglia UK July 17-19 1996 (Dept.Environ. Sci. Univ. Plymouth Plymouth UK PL4 8AA). Mohr G. J. Wolfbeis 0. S. Optical nitrite sensor based on a potential-sensitive dye and a nitrite-selective carrier. Analyst (Cambridge U. K . ) 1996 121( lo) 1489. (Inst. Org. Chem. Karl-Franzens Univ. 8010 Graz Austria). Hirata T. Lead isotopic analyses of NIST standard reference materials using multiple collector inductively coupled plasma mass spectrometry coupled with a modified external correction method for mass discrimi- nation effect. Analyst (Cambridge U. K . ) 1996,121( lo) 1407. (Lab. Planetary Sci. Tokyo Inst. Technol. Meguro Toyko 152 Japan). Sooksamiti P. Geckeis H. Grudpan K. Determination of lead in soil samples by in-valve solid-phase extrac- tion-flow injection flame atomic absorption spec- trometry.Analyst (Cambridge U. K . ) 1996 121( lo) 1413. (Mineral Resources Region 3 Chiang Mai 50200 Thailand). Tan Y. Blais J.-S. Marshall W. D. Slurry preparation by high-pressure homogenization for the determination of heavy metals in zoological and botanical certified reference materials and animal feeds by electrothermal atomic absorption spectrometry. Analyst (Cambridge U. K.) 1996 121( lo) 1419. (Dept. Food Sci. and Agric. Chem. Macdonald Campus McGill Ste.-Anne-de- Bellevue Quebec Canada H9X 3V9). Perez-Cid B. Lavilla I. Bendicho C. Analytical assessment of two sequential extraction schemes for metal partitioning in sewage sludges. Analyst (Cambridge U. K.) 1996 121(10) 1479.(Area Quim. Anal. Univ. Vigo 32004 Orense Spain). Esen C. Kaiser T. Schweiger G. Raman investigation of photopolymerization reactions of single optically levitated microparticles. Appl. Spectrosc. 1996 50( 7) 823. (Ruhr Univ. Bochum 44780 Bochum Germany). Pakhomov A. V. Nichols W. Borysow J. Laser- induced breakdown spectroscopy for detection of lead in concrete. Appl. Spectrosc. 1996 50( 7) 880. (Dept. Journal of Analytical Atomic Spectrometry December 1996 Vol. 11 51 9R9614861 9614862 9614863 96/48 64 96/48 6 5 9 614 866 9614867 9 614868 9614869 9614870 961487 1 9614872 520 R Phys. Michigan Technol. Univ. Houghton MI 49931 USA). Vandervoort K. G. Butcher D. J. Brittain C. T. Lewis B. B. Scanning tunneling microscope images of graphite substrates used in graphite furnace atomic absorption spectrometry. Appl.Spectrosc. 1996 50( 7) 928. (Dept. Chem. and Phys. Western Carolina Univ. Cullowhee NC 28723 USA). Rivier C. Mermet J.-M. Use of normalized relative line intensities for qualitative and semi-quantitative analysis in inductively coupled plasma atomic emission spectrometry using a custom segmented-array charge- coupled device detector. Part 11 applications to qualitat- ive analysis with line-rich matrices. Appl. Spectrosc. 1996,50( 8) 959. (Lab. Sci. Anal. Univ. Claude Bernard- Lyon 69622 Villeurbanne Cedex France). Duan Y. Li Y. Du Zhaohui. Jin Qinhan Olivares J. A. Instrumentation and fundamental studies on glow discharge microwave-induced plasma (GD-MIP) tandem source for optical emission spectrometry.Appl. Spectrosc. 1996 50( 8) 977. (Dept. Chem. Jilin Univ. Changchun 130023 China). Hettipathirana T. D. Davey D. E. Analytical perform- ance in flow-injection simultaneous multielement induc- tively coupled plasma optical emission spectrometry employing a cyclonic spray chamber. Appl. Spectrosc. 1996 50(8) 1015. (Sch. Chem. Technol. Univ. South Australia The levels SA 5095 Australia). Daniel R. G. McNesby K. L. Miziolek A. W. Application of tunable diode laser diagnostics for temperature and species concentration profiles of inhibited low-pressure flames. Appl. Opt. 1996 35(21) 4018. (U.S. Army Res. Lab. Aberdeen Proving Ground Neuber A. A. Janicka J. Hassel E. P. Thermally assisted fluorescence of laser-excited OH A 2C+ as flame diagnostic tool. Appl. Opt.1996 35(21) 4033. (Tech. Hochschule Darmstadt 64287 Darmstadt Germany). Partridge W. P. Jr. Klassen M. S. Thomsen D. D. Laurendeau N. M. Experimental assessment of O2 interferences on laser-induced fluorescence measure- ments of NO in high-pressure lean premixed flames by use of narrow-band and broadband detection. Appl. Opt. 1996 34( 24) 4890. (Flame Diagnostics Lab. Sch. Mech. Eng. Purdue Univ. West Lafayette IN Montcalm C. Kearney P. A Slaughter J. M. Sullivan B. T. Chaker M. Pepin H. Falco C. M Survey of Ti,B- and Y-based soft x-ray-extreme ultraviolet multi- layer mirrors for the 2- to 12-nm wavelength region. Appl. Opt. 1996 35(25) 5134. (Inst. Natl. Rech. Sci. Energie Materiaux Univ. Quebec Varennes Quebec Canada J3X 1S2). Moon H. S. Kim J. B. Park J. D. Kwon B.K. Cho H. Lee H. S. Magneto-optic trap of Rb atoms with an injection-seeded laser that operates at two frequen- cies. Appl. Opt. 1996 35(27) 5402. (Dept Phys. Education Korea Natl. Univ. Education Chungbuk 363-791 South Korea). Arnon S. Kopeika N. S. Probing and monitoring aerosol and atmospheric clouds with an electro-optic oscillator. Appl. Opt. 1996 35( 27) 5427. (Dept. Electrical and Computer Eng. Ben Gurion Univ Beer Sheva 84105 Israel). Parameswaran T. Snelling D. R. Estimation of spatial averaging of temperatures from coherent anti-stokes Raman spectroscopy. Appl. Opt. 1996 35(27) 5461. (Atlantis Scientific Systems Ottawa Ontario Canada K2C OR6). Golimowski J. Golimowska K. UV-photooxidation as pretreatment step in inorganic analysis of environmental samples.Anal. Chim. Acta 1996 325 111. (Fac. Chem. Warsaw Univ. 02-093 Warsaw Poland). MD 21005-5066 USA). 47907-1288 USA). 96/4873 ‘36148 74 !>6/48 7 5 9614876 9614877 96/4878 96/4879 9614880 961488 1 9 6/48 82 9 4/48 8 3 9 15/48 84 Journal of Analytical Atomzc Spectrometry December 1996 Vol. 11 Mikac N. Wang Y. Harrison R. M. Intercomparison of alkyllead compound determination in mussels and water by two analytical techniques gas chromatography atomic absorption spectrometry and differential pulse anodic stripping voltammetry. Anal. Chim. Acta 1996 326 57. (Centre Marine Res. Zagreb Inst. Ruder Boskovic 10 000 Zagreb Croatia). Shkinev V. M. Fedorova 0. M. Spivakov B. Ya. Mattusch J. Wennrich R. Lohse M. Speciation of metals associated with natural water components by on-line membrane fractionation combined with induc- tively coupled plasma atomic emission and mass spectrometries.Anal. Chim. Acta 1996 327 167. (Vernadsky Inst. Geochem. and Anal. Chem. Russian Acad. Sci. Moscow 117975 Russia). Weir D. G. Blades M. W. Characteristics of an inductively coupled argon plasma operating with organic aerosols. Part 4. Noise power spectra. J. Anal. At. Spectrom. 1996 11 1011. (Dept. Chem. Univ. British Columbia Vancouver BC Canada V6T lZ1). Liu K. Tan H. Huang Z. Huang M. Mechanism of peak drift of a grating monochromator and a designed sequential inductively coupled plasma spectrometer with an intelligent wavelength calibrating device. J. Anal. At. Spectrom. 1996 11 1019. (Inst. Chem. Metallurgy Acad. Sinica Beijing 100080 China). Jakubowski N.Thomas C. Stuewer D. Dettlaff I. Schram J. Speciation of inorganic selenium by induc- tively coupled plasma mass spectrometry with hydraulic high pressure nebulization. J. Anal. At. Spectrom. 1996 11 1023. (Inst. Spektrochem. und Angewandte Spektroskopie 4401 3 Dortmund Germany). Christodoulou J. Kashani M. Keohane B. M. Sadler P. J. Determination of gold and platinum in the presence of blood plasma proteins using inductively coupled plasma mass spectrometry with direct injection nebulization. J. Anal. At. Spectrom. 1996 11 1031. (Dept. Chem. Birkbeck Coll. Univ. London London UK WClH OPP). Coedo A. G. Dorado M. T. Padilla I. Alguacil F. J. Study of the application of air-water flow injection inductively coupled plasma mass spectrometry for the determination of calcium in steels.J. Anal. At. Spectrom. 1996 11 1037. (Centro Nacional Investigaciones Metalurgicas (CSIC) 28040 Madrid Spain). Zhang L. S. Combs S. M. Using the installed spray chamber as a gas-liquid separator for the determination of germanium arsenic selenium tin antimony tel- lurium and bismuth by hydride generation inductively coupled plasma mass spectrometry. J. Anal. At. Spectrom. 1996 11 1043. (Soil and Plant Anal. Lab. Soil Sci. Dept. Univ. Wisconsin-Madison/Extension Madison WI 53705-4453 USA). Zhang L. S. Combs S. M. Determination of selenium and arsenic in plant and animal tissues by hydride generation inductively coupled plasma mass spec- trometry. J. Anal. At. Spectrom. 1996 11 1049. (Soil and Plant Anal. Lab. Soil Sci. Dept.Univ. Wisconsin- Madison/Extension Madison WI 53705-4453 USA). Smith C. M. M. Harnly J. M. Characterization of a modified two-step furnace for atomic absorption spec- trometry for selective volatilization of iron species in hemin. J . Anal. At. Spectrom. 1996 11 1055. (US Dept. Agric. Beltsville Human Nutrition Center Food Composition Lab. Beltsville MD 20705 USA). Ellis L. A. Roberts D. J. Novel method to determine mercury in sediment using a gold coated dual bent tube atom trap. J. Anal. At. Spectrom. 1996 11 1063. (School Chem. Univ. Bristol Bristol UK BS8 1TS). Gaspar A. Posta J. Roth R. On-line chromatographic separation and determination of chromium(n1) and chromium(v1) with preconcentration of the chro- mium(n1) using potassium hydrogen phthalate in various samples by flame atomic absorption spec-trometry.J. Anal. At. Spectrum. 1996 11 1067. (Dept. Inorg. and Anal. Chem. Kossuth L. Univ. 4010 Debrecen 10 Hungary). 96/4885 Zhang X. Cornelis R. de Kimpe J. hlees L. Speciation of toxicologically important arsenic species in human serum by liquid chromatography-hydride generation atomic absorption spectrometry. J. 4nal. At. Spectrum. 1996 11 1075. (Lab. Anal. Chem. Inst. Nuclear Sci. Univ. Gent 9000 Gent Belgium). 96/4886 Bermejo-Barrera P. Moreda-Pineiro J. Moreda- Pineiro A. Bermejo-Barrera A. Use of flow injection cold vapour generation and preconcentration on coated graphite tubes for the determination of cadmium in sea-water by electrothermal atomic absorption spec- trometry. J. Anal. At. Spectrom. 1996 11 108 1.(Dept. Anal. Chem. Nutrition and Bromatol. Fac Chem. Univ. Santiago de Compostela 15706 Santiago de Compostela Spain). Van Dalen G. Determination of cadmium in edible oils and fats by direct electrothermal atomic ahsorption spectrometry. J. Anal. At. Spectrom. 1996 11 1087. (Unilever Res. Lab. 3 133 AT Vlaxrdingen Netherlands). LeBlanc A. Urine selenium determination bj electro- thermal atomic absorption spectrometry influence of urinary phosphates on the trimethylselenium ion signal. J . Anal. At. Spectrum. 1996 11 1093. (LI Centre Toxicol. Quebec Sainte-Foy PQ Canada G1 V 4G2). Lamble K. J. Hill S. J. Determination of mercury in slurried samples by both batch and on-line microwave digestion-cold vapour atomic fluorescence spec- trometry. J. Anal. At.Spectrum. 1996 11 1099. (Dept. 96/4887 96/4888 96/4889 Environ. Sci. Univ. Plymouth Plymouth UK PL4 8AA). Sadler D. A. Littlejohn D. Use of multiple emission lines and principal component regression for quantitat- ive analysis in inductively coupled plasma atomic emission spectrometry with charge coupled device detection. J. Anal. At. Spectrom. 1996 11 1105. (Dept. Pure and Applied Chem. Univ. Strathclyde Glasgow UK G1 1XL). Benhayoune H. Characteristic and continuous fluores- cence correction for electron probe microanalysis of thin coatings at oblique incidence. J. Anal. At. Spectrorn. 1996 11 1113. (LASSI/DTI CNRS UFR Sciences 51687 Reims Cedex 2 France). Schaffer U. Krivan V. Automated large volume slurry preparation in slurry sampling electrothermal atomic absorption spectrometry.J. Anal. At. Spectrum. 1996 11 11 19. (Sektion Anal. und Hochstreinigung Univ. Ulm 89069 Ulm Germany). Laborda F. Gomez M. T. Jimenez M. S. Mir J. M. Castillo J. R. Gas-liquid separator for automated hydride generation and atomic absorption spec- trometry. J . Anal. At. Spectrom. 1996 11 1121. (Anal. Spectroscopy and Sensor Group (GEAS) Dept. Anal. Chem. Fac. Sci. Univ. Zaragoza 50009 Zaragoza Spain). Doherty W. Outridge P. M. Gregoire D. C. Technique for the introduction of dry atomic vapours for improved optimization and diagnostic studies of laser ablation inductively coupled plasma spectrometry. J. Anal. At. Spectrom. 1996,11 1123. (Anal. Chem. Lab. Geological Survey Canada Ottawa ON Canada K1A OE8). 96/4890 96/489 1 96/4892 96/4893 96/4894 Journal of Analytical Atomic Spectrometry December 1996 Vol.1 1 521 RThe Society for Applied Spectroscopy... KEEP ABREAST OF NEW AND INNOVATIVE TECHNOLOGY .... Our Society can provide you with the latest in research technology and practical knowledge. We also provide the essential link for networking with your peers - with options such as a membership directory internet access and an annual conference. There are awards for achievements student programs and on-line services. 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ISSN:0267-9477    

DOI:10.1039/JA996110509R

出版商:RSC    

年代:1996

数据来源: RSC

摘要:

Trace Metal Speciation via Supercritical FI u id Extract i on-Liq u id C h rom a tog ra p hy- Inductively Coupled Plasma Mass Spectrometry NOHORA P. VELA* AND JOSEPH A. CARUSOT Department of Chemistry University of Cincinnati P.O. Box 21 0. 72 Cincinnati OH 45221 -01 72 USA Supercritical fluid CO was used for the extraction of organotin compounds present in fish. A sample of tuna fish was spiked with trimethyltin chloride tributylin chloride and triphenyltin chloride. Parameters such as cartridge size type of modifier and type and temperature of the restrictor were evaluated for the spiked sample. Extraction conditions were optimized by measuring total metal content using ICP-RfS detection. The extracts were also analysed by LC-ICP-MS. Optimized extraction conditions were applied to a fish tissue CRM that contained tributyltin and triphenyltin. LC-ICP-MS analysis indicated that the extracted species varied with the modifier used.Extraction efficiencies for the CRM were lower when compared with the results obtained for the spiked samples using the same extraction conditions. However extraction efficiencies were up to 80% for trimethyltin arid 40% for triphenyltin with the fish tissue CRM when 1% water was added as a modifier and diethyldithiocarbamic acid ammonium salt or pyrrolidinecarbothioic acid ammonium salt were added as complexing agents. Keywords Metal speciation supercritical JEuid extractiorz; liquid chromatography; inductively coupled plasma mass spectrometry; modiJer ; complexing agent; organotin compounds Metal speciation has become a topic of multi-disciplinary interest.It has expanded to the areas of clinical,'-3 envircnmen- tal,4 a q ~ a t i c ~ ~ and geological chemistry.6 The role thaf metal speciation plays in these fields has been related to the degree of mobility bioavailability and toxicity of certain species in a given sample. Several reviews of metal speciation have been published7-" as well as research papers dealing with the speciation of arsenic,12-16 m e r c u ~ y ~ ~ * ' ~ lead,Ig selenium,20'21 vanadium, chromium,22 and antimony.26 Most of these papers focus on optimizing chromatographic and plasma conditions to separate and detect analytes of interest. \ alidity of the methods is usually demonstrated by running spiked samples or CRMs that are usually certified for total metal content and only a few of the CRMs include information about species concentration.Methods developed for metal speciation are applicable to different sample types (waters biological fluids aquatic organisms soils and sediments I most of which require sample pre-treatment (clean-up extraction or preconcentration) before the speciation analysis. The choice of sample pre-treatment is critical since the selection must consider the efficiency of the procedure and the effect that it might have in preserving or changing the original species present in the sample. Consequences of grinding and effect of extraction conditions on the arsenic species released from coal * Present address ManTech Environmental Research Service Corporation R. S. Kerr Environmental Research Laboratory 919 Kerr Research Drive Ada OK 74821-1198 USA.t To whom correspondence should be addressed. Journal of Analytical Atomic Spectrometry fly-ash are discussed by Wang et ~ 1 . ~ ~ They report some conversion of As"' to AsV at low pH extraction. Storage for a long period of time of sample extracts that contain arsenic is not recommended since decomposition of arsenobetaine to trimethylarsine oxide and two other unidentified arsenic species has also been observed.28 A programme to develop and implement extraction schemes for metal determination in soils and sediments has been promoted by the European Community Bureau of Reference ( BCR).29-32 The method includes a sequence of extractions that potentially provide information on how the metals are bound to sediment (metals bound to carbonates or to iron/ manganese oxides or to organic/sulfidic material).Interlaboratory trials show that the procedure is repeatable and reproducible for extractable metal content.30 Metal speci- ation of marine samples usually includes a preliminary step of organic solvent and/or acid extraction and sometimes sonic- ation and evaporation.13-15*'7.20.24~25 Solid-phase extraction on solid sorbents (discs) as a means of analyte preconcentration is common for aqueous samples.'2J8-21 Among less conven- tional extraction procedures it is important to mention leach- ing,16 microwave-assisted acid leaching,33 supercritical fluid extraction ( SFE)34-46 and a combination of solid-phase extrac- tion followed by SFE.42347 Interest in using supercritical fluids (SFs) for sample prep- aration originates in the common effort to reduce the consump- tion disposal and long-term exposure to organic solvents.The exceptional characteristics of SFs as solvents are based in their gas-like and liquid-like proper tie^.^'-^' Characteristics of supercritical fluids that are attractive from an extraction view- point include viscosity diffusion coefficients and density. Viscosities and diffusion coefficients of SFs are much lower than those of a liquid and approach the values of gases. These two dynamic properties of SFs contribute to improved rates of mass transfer for solutes resulting in faster extractions when compared with liquid extraction. SFs can achieve densities in the typical range of a liquid (0.3-0.8 g ml-I).Densities are easily obtained by adjusting pressure and temperature. Higher solvent densities and better solvating power are obtained with SFs at low temperatures an advantage for the extraction of thermally labile compounds and substances that are easily oxidized during a regular extraction. However increases in the extraction temperature sometimes favour solubility of the analyte in the SF. The most common SF used for extractions is CO (critical temperature 31 "C; critical pressure 72.9 atm). CO is non-toxic non-flammable relatively inexpensive and easy to obtain commercially at high purities. The disadvantage of SF CO is the lack of efficiency in extracting polar com- pounds due to its non-polar characteristics. Therefore addition of 'modifiers' and/or complexing agents are procedures that allow the extraction of polar compounds with CO,.Modifiers are solvents which function to facilitate the interaction between the SF and the analyte as well as to diminish the matrix- Journal of Analytical Atomic Spectrometry December 1996 Vol. 11 (1 129-1 135) 1 129analyte interaction to improve mass transfer of the analyte to the SF. Compounds that are typically used to form chelates for solvent extraction of metals are utilized as complexing agents in SFE. Various papers have been published regarding the use of SFs for the extraction of arsenic cadmium copper lead manganese mercury selenium tin zinc lanthanides and actin- i d e ~ . ~ ~ - ~ ~ Extraction efficiency is measured as total metal extracted. Relatively few papers describe the use of SFE as a sample preparation technique for trace metal ~peciation.~'-~~ Organotins are compounds of particular interest for speci- ation studies as well as good candidates for SFE.The toxicity of tin-containing compounds depends on the number and chemical form of the organic substituents linked to the central atom. In general tri- and tetra-organotins are the most toxic and a decrease in the number of organic substituents is correlated with less toxicity up to the point where inorganic tin is even beneficial for some organism^.^'*^^ Tin has been detected in waters sediments and marine p r o d ~ ~ t s . ~ ~ - ~ ~ ~ ~ ~ ~ Tributyltin (TrBT) and triphenyltin (TrPT) are frequently found in fish since they are used as antifouling paint agents for fish nets and ship hulls.Pollution by TrBT and TrPT is a serious problem since they accumulate in the lipophilic tissues of the fish.53 Previous results in these laboratories using SFC indicate reasonable solubility of organotins in SFs for the separation of tin compounds of different polarity (tri- and tetra-organotins) in a single run.54 Oudsema and Poole4' reported on the extraction of organot- ins in a marine paint and spiked into a potato and almond matrix using C 0 2 modified with 0.3% formic acid. On-line analysis of the extract was performed by SFC with flame ionization detection. A combination of liquid-solid extraction on a disc followed by in situ Grignard ethylation and SFE has been carried out to extract TrBT and its degradation products from synthetic ~ e a - w a t e r .~ ~ Capillary GC with flame photo- metric detection (FPD) was used to determine the organotins extracted. TrBT in sediments has also been extracted using SFE followed by GC-FPD.43 Liu et al.44 have described the SFE of six tetraalkyltin and seven ionic organotins from spiked topsoil using C 0 2 modified with 5% methanol. Owing to the low recovery in the extraction of some of the tri and di-organotins sodium diethyldithiocarbamate was added as a complexing agent. Some of the organotins needed to be derivatized for GC-atomic emission analysis. Recoveries ranged from 70 to 100% for most of the organotins when the modifier and complexing agents were used. Exceptions were for the extraction of butyltin trichloride and diphenyltin dichloride for which recoveries were only about 40%.Using a fractional factorial experimental design Liu et aL4' optimized the complexation/SFE of organotins spiked into topsoil and clay soil. The complexing agent used was diethylammonium diethyldithiocarbamate and the solvent C 0 2 with 5% meth- anol. Optimized extraction conditions were applied to two sediment CRMs (PACS-1 and SRM 462) and the extracts after derivatization were analysed by GC-AES. Total recovery for the extraction of TrBT from the two CRMs was reported. Different results were found for the extraction of dibutyltin in the same samples. For this compound extraction efficiencies varied from 45 to 95%. Our laboratory has also been involved in developing tech- niques for the SFE of organotins present in biological samples and preliminary results have already been published.46 This paper describes recent developments using SFE as a sample preparation technique for speciation studies.Organotins were extracted from spiked tuna fish and from a fish tissue CRM. Effects of cartridge size modifiers complexing agents restrictor type and restrictor temperature were among the parameters evaluated. Sample extracts were analysed for total metal con- tent using ICP-MS detection. Analysis of the species extracted was performed by LC-ICP-MS. The organotins studied were trimethyltin chloride tributyltin chloride and triphenyltin chloride. EXPERIMENTAL Instrumentation The SFE instrument consisted of an Isco Series 2200 system (Lincoln NE USA) which includes two Model 260 D syringe pumps an SFX 2-10 extractor unit and a heated restrictor unit.The instrument provides separate temperature controls for the extractor and restrictor units. Extraction cartridges of 0.5 2.5 and 10ml were utilized for the extraction. Two types of capillary restrictors were used fused silica coated with polyamide and stainless steel (SS) (both 40 cm x 50 pm id). The chromatographic instrumentation was a Model 300 DX metal-free HPLC system (Dionex Sunnyvale CA USA). The LC system has an EDM2 eluent de-gas module an AGP gradient pump and a Model 9125 metal-free injector with a 100 p1 PEEK sample loop (Rheodyne Cotati CA USA). The plasma mass spectrometer used was a VG PlasmaQuad I1 STE (VG Elemental Winsford Cheshire UK). A double-pass Scott-type spray chamber was used jacketed and cooled to 5 "C with a Neslab Endocal refrigerated chiller (Neslab Instrument Portsmouth NH USA).The operating conditions for the ICP-MS system coupled to the LC system were forward power 1.5 kW; argon coolant gas flow rate 16 1 min-'; auxili- ary gas flow rate 1.5 1 min-l; argon nebulizer gas flow rate 0.75 1 min-'; and oxygen flow rate as secondary nebulizer gas 0.08 1 min-'. The ICP-MS instrument was set either in the scanning mode for total metal determination or in the single- ion mode for the LC-ICP-MS experiments to monitor the major isotope of tin at m/z= 120 (32.37% abundance). Reagents and Biological Materials The C 0 2 used was of SFC/SFE-grade obtained from Air Products (Middletown OH USA). Optima-grade methanol (Fisher Scientific Pittsburgh PA USA) was used for the SFE studies.Other solvents evaluated as modifiers for the extraction were acetone hexane dichloromethane ethyl acetate trichlor- oethane and tetrahydrofuran (THF) all obtained from Fisher Scientific. The organotin compounds trimethyltin (TrMT 99% purity) tributyltin (TrBT 95% purity; metal basis) and triphenyltin chlorides (TrPT 95% purity) were obtained from Alfa Products (Danvers MA USA) and used without further purification. Stock solutions (1000 ppm of Sn) corrected for the purity of the compound were prepared in HPLC-grade methanol (Fisher Scientific). A wet sample support matrix obtained from Isco was mixed with the fish samples to facilitate the extraction. Complexing agents diethyldithiocarbamic acid ammonium salt (DDCA) and pyrrolidinecarbothioic acid ammonium salt (PCA) were obtained from Aldrich (Milwaukee WI USA). A 5ppm aqueous solution of the complexing agents was used for the extractions. Two biological samples were used.The first consisted of a spiked tuna fish which was prepared from canned tuna fish obtained in a local grocery store. The tuna fish was initially dried at 100°C and homogenized. After the tuna had been spiked with the organotins the sample was air-dried and stored for at least 2 d before carrying out any extraction. The second sample was a fish tissue CRM (No. l l ) which was obtained from NIES (National Institute for Environmental Studies Japan Environmental Agency) and used to demon- strate the ability of SFE to extract 'native' organotins from marine samples.This fish tissue has a certified concentration of 1.3 pg g-' as tributyltin chloride and a reference value of 6.3 pg g-' as triphenyltin chloride. 1 130 Journal of Analytical Atomic Spectrometry December 1996 Vol. 11Chromatographic Conditions The extract collected in 10 ml of methanol was filtered using a 0.2mm nylon and glass membrane housed in a 25 mm poly( propylene) filter (Alltech Associates Deerfield IL USA). Without any additional treatment the sample was then iniected into the LC-ICP-MS system. The separation of the tin- containing compounds was performed by reversed-phase ion- pair LC following the procedure described e1sewhe1-e.~~ A PRP-1 guard column and a PRP-1 analytical column were obtained from Hamilton (Reno NE USA). The ana!ytical column was a 150 x 4.1 mm id column with 5 pm particie size packing.The mobile phase contained 94% methanoi 5% water 0.046 moll-' acetic acid and 0.012 moll-' ammonium acetate to yield a pH of 6. Sodium pentanesulfonate (PIC-B5 Eastman Kodak Rochester NY USA) at a concentration of 4 mmol 1-' was also added to the mobile phase and used as the ion-pair reagent. The flow rate of the mobile phase was adjusted to 1 ml min-'. RESULTS Preliminary Investigation of Extraction Conditions Using Spiked Tuna Fish Initial information about the conditions required to extract organotins from 'real' fish samples was obtained by extrxting spiked tuna fish samples with CO and analysing the extract by ICP-MS for total tin content. Parameters evaluated in the univariate mode were pressure (2500-7200 psi at 500 psi intervals) temperature (60,80 and 100 "C) and static extr,iction time (5 15 30 and 45min). For all the experiments and according to previous results for successive extractions conduc- ted in our laboratory dynamic extraction for 15niin is sufficient since longer extraction periods do not pi,ovide significant improvements in the extraction effi~iency.~~ Preliminary results for this type of sample indicated better recoveries at pressure temperature and static extraction times of 6000 psi 80 "C and 30 min respectively.Recoveries for the extraction of TrMT TrBT and TrPT in the spiked tuna fish varied from 22 to 40%. This indicates that the extrxtion process for organotins even from spiked fish samples is complex and that it is necessary to consider other parameters in order to increase the extraction efficiency.The other vari- ables evaluated were cartridge size addition of modifiers restrictor type restrictor temperature and addition of com- plexing agents. Effect of Extraction Cartridge Size Using the SFE conditions described in the previous scction the effect of the cartridge size was evaluated by extracting the spiked tuna fish (0.15 g) in cells of different internal diameter. Following the manufacturer's recommendations and ax indi- cated in Table 1 different amounts of support matrix were mixed with the same amount of the sample in order to pack completely the extraction cell. Table 1 shows similar extraction efficiencies for the small and medium size extraction cells. A decrease in the efficiency of the extraction was observed with the larger diameter extraction cartridge.Similar result have been reported by other w o r k e r ~ ~ ~ q ~ * and explained by the inverse relationship between the mass transfer within the cell and the extraction cell diameter.48 Given these results the following experiments were conducted using the medium size extraction cell. Effect of Modifiers in the Extraction of Spiked Samples Several solvents such as methanol acetone ethyl acetate hexane dichloromethane water THF and trichloroethane were investigated as modifiers for the extraction of the spiked tuna fish. In these experiments 200pl of the solvent were added directly to the extraction cartridge. The results are presented in Fig. l(u) giving recovery as total tin.Fig. l(u) indicates that the extraction efficiency of the spiked material can be increased up to 80% by using either acetone or water as modifier. The use of other modifiers such as methanol ethyl acetate hexane and THF gave recoveries ranging from 48 to 58%. The extracts were also analysed by LC-ICP-MS and the results for three of the modifiers (water methanol and trichloro- ethane) are presented in Fig. 1 (b). The chromatographic analy- sis of the samples indicates that TrBT and TrMT are easier to extract than TrPT. Also it is important to note that for both high and low extraction efficiencies the three organotins are extracted and their concentration is proportional to the total tin concentration in the extract. 60 20 - Trichloroethane TrMT TrBT TrFT Organotin Fig.1 (a) Variation in the extraction efficiency of organotins spiked in fish tissue using different modifiers. (b) Chromatographic analysis of the extract from the spiked tuna fish. Variation in the percentage recovery for several organotins using three modifiers for the extraction Table 1 Effect of extraction cell size on the recovery of tri-organotins spiked in tuna fish (n = 3) Extraction cell size Cell id/mm Amount of spiked sample/g Amount of support matrix/g Recovery of TrMT ( O h ) Recovery of TrBT (YO) Small Medium Large 6.9 7.6 15.1 0.15 0.15 0.15 0.07 0.68 3.10 28.9 & 1.4 43.7 & 2.3 30.7 1.6 36.6 & 1.7 6.1 & 0.3 17.3k1.1 Journal of Analytical Atomic Spectrometry December 1996 Vol. 11 1 131Effect of Restrictor Type and Restrictor Temperature The analyte collection conditions given by the restrictor type and restrictor temperature were evaluated.As was previously mentioned two types of restrictors were evaluated fused silica and stainless steel (SS). The effect of the fused-silica restrictor temperature on the recovery of organotins was also evaluated. Fig. 2(u) indicates the combined effect of modifier and restrictor type on the recovery of organotins spiked in tuna fish. Results indicate that when acetone is used as a modifier similar recoveries are observed for TrMT and TrPT with either of the restrictors. For TrBT the use of silica is favourable over the SS restrictor. With methanol as the modifier there is a slight improvement in the recovery of TrMT and TrPT when the extract is passed through an SS restrictor.This is not observed for TrBT since with methanol as a modifier better results were obtained with the silica restrictor. Fig. 2(u) also indicates that for the three organotins studied and for their extraction using water as co-solvent the use of the fused-silica restrictor provides higher recoveries. Accordingly from the results pre- sented here the silica restrictor is a better choice for trans- porting the extract from the extraction cartridge to the collection tube. Fig. 2(b) shows the results obtained when the silica restrictor is maintained at two different temperatures 20 and 60 "C. Comparable recoveries of the organotins are observed for the two silica restrictor temperatures when acetone is the co-solvent. With methanol as a modifier there is a marked improvement in the recovery of organotins if the silica restrictor is heated to 60 "C.Fig. 2(b) shows that when using a heated restrictor (60 "C) and methanol as co-solvent recoveries of TrBT and TrPT are similar to or even better than those obtained with water as a modifier. These results might be due to the fused silica becoming more fragile with small amounts of methanol at lower (20°C) than at higher temperatures (60 "C). Consequently the effect of methanol on the fused silica is not only to shorten the lifetime of the restrictor but also 100 I@) 80 i 60 40 20 n E n - Acetone Methanol Water $ 0 u i 80 60 40 20 n " Acetone Methanol Water Modifier Fig.2 Effect of (a) restrictor type and (b) restrictor temperature on the recovery of organotins spiked in tuna fish.T(1) is 20°C and T(2) is 60°C possibly to affect the transport of the extract to the collection tube. Fig. 2(b) also shows comparable recoveries of TrBT and TrPT when considering the two fused restrictor temperatures and water as a modifier. The extraction of TrMT indicates better results when using water as a co-solvent and a fused- silica restrictor at room temperature. Effect of Modifiers in the Extraction of the CRM The CRM was extracted under some of the extraction con- ditions optimized for the spiked tuna fish. These conditions were pressure 6000 psi; temperature 80 "C; static extraction time 30 min; dynamic extraction time 15 min; extraction cell size medium; SF CO,; restrictor type fused silica; and restrictor temperature 60°C.The amount of CRM used for the extraction was 0.5 g and it was mixed with 0.6 g of the support matrix. The extract was collected in methanol and filtered in the same fashion as for the spiked material. Four of the modifiers evaluated for the spiked material were also used for the extraction of the CRM. Acetone water or dichloro- methane were added directly to the extraction cartridge (200 pl). Methanol was combined with the CO using a T-shaped connection and a second syringe pump. Results for the extraction efficiency of the CRM with and without modifier are presented in Fig. 3(u) which indicates that without a modifier the extraction efficiency as total tin is about 10%. Addition of modifiers increases the amount of tin-containing compounds extracted from the CRM by a factor of 2-3. Comparing the extraction efficiencies presented in Fig.3 (a) similar results are obtained when using 10% methanol (38.3 +2.1%) and water (36.9 f 1.8%). Previous results also indicate no significant difference in the recovery when the methanol is added directly to the cartridge (200 pl) or by using the second syringe pump (5% v/v methanol). Fig. 3(b) shows the chromatographic results for tin concen- tration of the species after LC-ICP-MS. As indicated in Modifier 10% Methanol Methanol Lnorg. Tin TrBT TrPT Tin compounds Fig.3 (a) Results for the extraction of the fish tissue CRM using several modifiers. (b) Variation in the tin concentration of several species using different modifiers for the extraction 1 132 Journal of Analytical Atomic Spectrometry December 1996 Vol.11I TrMT I\ - TrBT TrPT 4 I I I d.1 1 1 1 1 1 I I I i 4 6 8 10 12 0 2 Time/min Fig. 4 Comparison of LC-ICP-MS traces obtained for (a) standard mixture of organotin compounds 100 pl injection of 5 ppb solution (0.5 ng) (b) scan at m/z= 120 for the extract obtained from thc CRM using CO (c) scan at m/z= 120 for the extract obtained fri)m the CRM using C02 modified with 5% methanol Fig. 3(b) an additional peak is detected probably correspond- ing to inorganic tin.46 The addition of methanol to the CO increases the solvent polarity and thereby enhances the extrac- tion of polar components such as some forms of inorganic tin that elute in the dead volume. Fig. 4 compares the different chromatograms for (a) a standard mixture of tri-organotins (b) extract obtained with CO and (c) extract obtained with C 0 2 modified with 5% methanol.Retention times for TrBT and TrPT are the same for the three chromatograms. Thus the possibility of a shift in the retention time for TrMT is unlikely. Complete confirmation of the identity of this additional peak would require the use of other techniques. Another possible explanation for this additional peak would be the breakdown of the organotins under the extraction conditions. However this possibility was eliminated by extracting the spiked tuna fish under the same conditions; no extra peaks were observed. An additional advantage of using chromatography to monitor the extraction is also indicated in Fig. 3. Comparing the results obtained with CO modified with 5 and 10% methanol there is an improvement in extrac- tion efficiency when using a higher methanol concentration.Chromatographic results indicate that there is an increase in the amount of TrBT and TrPT extracted but the major gain is in the inorganic tin concentration. The results discussed here demonstrate that although total tin content is one approach to evaluate extraction efficiency chromatographic anat ysis is necessary for verification and determination of each of the species extracted. Also by analysing the extract by LC-ICP-MS it is possible to determine whether the initial species present in the sample are preserved during SFE Fig. 5 presents the LC-ICP-MS trace for the extract obtained from the CRM using CO with acetone as a modifier.The major components are TrBT and TrPT with only trace amounts of TrMT and inorganic tin. The LC-ICP-MS traces for the extract obtained with C 0 2 modified with either water or dichloromethane are similar to that shown in Fig. 5. Addition of Complexing Agents and Modifiers for the Extraction of the CRM The use of complexing agents such as DDCA and PCA for the extraction of the fish tissue CRM was also investigated. Two different extraction temperatures were evaluated 80 and 100 "C. Table 2 compares the results as total tin content for the extraction of the CRM using different temperatures and complexing agents. According to these data and without addition of modifier better results are obtained at 100°C and by using PCA as complexing agent. The addition of 5% methanol to the SF increases the efficiency of the extraction given as total tin concentration.Fig. 6 shows the chromatog- ram of the extract on adding DDCA to the fish tissue and extracting with (a) C 0 2 and (b) C 0 2 with 5% methanol. By comparing the retention times of TrBT and TrPT in the standard mixture with those in Fig. 6 it is possible to confirm the presence of TrBT and TrPT in the extract. From the intensity scale in Fig. 6 it is evident that the addition of methanol to the CO improves the extraction efficiency of TrBT and TrPT. The other effect of adding methanol as was noted previously is the presence of an extra peak that corre- sponds to a form of tin that is not retained on the column and may correspond to inorganic tin. Fig. 7 compares the tin concentration for the different species as a function of the complexing agent and the SF with and without water as a modifier.Fig. 7(a) indicates that when C 0 2 is used as the solvent higher recoveries are obtained with PCA as the complexing agent. The addition of water to the CO increases the extent of the extraction for all the tin components as compared with the use of CO only [compare Fig. 7(a) and (b)]. Fig. 7(b) also indicates similar tin concentrations for TrPT 700 6 8 10 12 O L 0 I ' 2 ' 4 ' ' ' ' ' ' ' ' ' Time/min Fig.5 Chromatogram of the extract obtained from the fish tissue CRM using CO and acetone as a modifier Table 2 Effect of complexing agents on the recovery of tin compounds extracted from a fish tissue CRM (n = 2) Experiment No. TemperaturerC Modifier added Complexing agent Recovery.(%) 80 80 100 100 100 100 No No No No No 5% methanol DDCA* PCAt DDCA* PCAt DDCAI DDCA~ 33+3 34+ 3 41 + 3 43+3 36+3 49+3 ~ ~ * 200 pl of a 5 ppm solution of DDCA. 200 pl of a 5 ppm solution of PCA. * 20 mg of DDCA. Journal of Analytical Atomic Spectrometry December 1996 Vul. 11 1 133Fig. to tl 0.4 0.2 EL ,u 0.6 I (a) I - - = Inorg. Tin (b) Inorg. Tin 0 2 4 6 8 10 12 Time/min 6 LC-ICP-MS analysis of the extract obtained by adding DDCA he CRM and extracting with (a) CO and (b) CO with 5% methanol ----- (a) TrPT TrBT Inorg. Tin TrMT Tin containing compounds TrPT TrBT Inorg. Tin TrMT Tin containing compounds Fig.7 Effect of different complexing agents on the extraction of organotins from the fish tissue CRM using (a) CO and (b) CO with 1 YO water TrBT and TrMT in the extract when using water as a modifier and adding DDCA or PCA for the extraction.Fig. 8 presents the results as extraction efficiency by comparing the certified value of the CRM with the concentration calculated in the extract obtained with and without addition of complexing agent. Recoveries of TrBT are about 80% while efficiencies in the extraction of TrPT are in the range 35-40%. Addition of Trm CO = TrW CO with 1% water 90- 80 70 E 5 50 240 30 20 10 0 None DDCA PCA Complexing agent Fig. 8 agents and CO with and without modifier (1% water) Comparison of extraction efficiency using different complexing a complexing agent has a greater effect in improving the extraction efficiency for TrPT than for TrBT. 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ISSN:0267-9477    

DOI:10.1039/JA9961101129

出版商:RSC    

年代:1996

数据来源: RSC