Environmental Analysis HANDBOOK OF ANALYTICAL SEPARATIONS Series Editor: ROGER M. SMITH In this series: Vol. 1: Separation Methods in Drug Synthesis and Purification Edited by K. Valk6 Vol. 2: Forensic Science Edited by M.J. Bogusz Vol. 3: Environmental Analysis Edited by W. Kleib6hmer HANDBOOK OF ANALYTICAL SEPARATIONS - VOLUME 3 Environmental Analysis Edited by WOLFGANG KLEIBOHMER Institut fiir Chemo- und Biosensorik D-48149 Miinster, Germany 2001 ELSEVIER Amsterdam - London - New York - Oxford - Paris - Shannon - Tokyo ELSEVIER SCIENCE B.V. Sara Burgerhartstraat 25 EO. Box 211, 1000 AE Amsterdam, The Netherlands © 2001 Elsevier Science B.V. All rights reserved. This work is protected under copyright by Elsevier Science, and the following terms and conditions apply to its use: Photocopying Single photocopies of single chapters may be made for personal use as allowed by national copyright laws. 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Except as outlined above, no part of this work may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without prior written permission of the Publisher. Address permissions requests to: Elsevier Science Global Rights Department, at the mail, fax and e-mail addresses noted above. Notice No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drugs dosages should be made. First edition 2001 Library of Congress Cataloging-in-Publication Data Environmental analysis / edited by Wolfgang Kleibrhmer. p. cm -- (Handbook of analytical separations; v. 3) ISBN 0-444-50021-9 1. Environmental chemistry--Methodology. 2. Chemistry, Analytic--Methodology. 3. Pollutants--Analysis. I. Kleibrhmer, Wolfgang. II. Series QD63.$4 H36 2000 vol. 3 [TD193] 660'.2842 s--dc21 [628.5'028'7] 2001046022 British Library Cataloguing in Publication Data Environmental analysis. - (Handbook of analytical separations; v. 3) 1. Environmental chemistry 2. Separation (Technology) I. Kleibrhmer, Wolfgang 577.1'4 ISBN 0444500219 ISBN: 0-444-50021-9 @ The paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper). Printed in The Netherlands. Editor's preface This book is not supposed to be an addition to the long list of excellent textbooks dealing with analytical separation techniques in environmental analysis. The objective of this work is to give an up-to-date review on both new solutions for well-known, but still lasting, problems and on solutions for new problems/questions in environmental analysis. Therefore the book covers a critical compilation of analytical methods for the de- termination of a wide range of environmental priority pollutants, including amines, polycyclic aromatic hydrocarbons, pesticides, phenols, PCBs, and also including organometallic species, polycyclic aromatic sulphur heterocycles and metabolites of polycyclic aromatic hydrocarbons. For all environmental pollutants, an overview and an assessment of value of a broad range of relevant methods including conventional techniques but also of advanced separation and sample preparation techniques are given, with all possible matrices being considered. The book does not only give up-to-date material on sampling and sample pre-treat- ment, extraction techniques, clean-up, pre-fractionation, different types of chromato- graphic methods and quality assurance, but also information on actual and upcoming analytical problems, such as the determination of polycyclic aromatic sulphur heterocy- cles and of metabolites of PAH. The final chapter is devoted to the important role of analytical separation methods in water quality control. Experienced and well-known authors have contributed their knowledge and expertise to their individual chapters. I hope this volume will prove helpful, and I would like to thank all colleagues who accepted to be involved in this project for their enthusiasm and dedication as well as for their cooperation. Last, but not least, I thank Reina Bolt at Elsevier Science for her active collaboration and patience during the production of this book. Wolfgang Kleib6hmer This Page Intentionally Left Blank VII Series editor's preface This volume on Environmental Analysis is the part of what is growing to be the Handbook of Analytical Separations. This volume reflects the importance of analytical separation methods in monitoring and identifying the many compounds of environmental importance. It includes chapters on the main groups of analytes of interest from PAHs and PCBs to phenols, sulphur compounds and pesticides. These methods illustrate the wide range of analytical techniques that have been employed in the measurement of environmental constituents and different matrices that have been examined. The Handbook of Analytical Separations will be a comprehensive work, which is intended to recognise the importance of the wide range of separation methods in analytical chemistry. Since the first report of chromatography almost a 100 years ago, separation methods have expanded considerably, both in the number of techniques and in the breadth of their applications. The objective of the Handbook is to provide a critical and up-to-date survey, rather than a detailed review, of the analytical separation methods and techniques used for the determination of analytes across the whole range of applications. The Handbook will cover the application of analytical separation methods from partitioning in sample preparation through gas, supercritical and liquid chromatography to electrically driven separations. The intention is to provide a work of reference that will provide critical guidance to the different methods that have been applied for particular analytes, their relative value to the user and their advantages and pitfalls. The aim is not to be comprehensive but to ensure a full coverage of the field weighted to reflect the acceptance of each alternative method to the analyst. The individual self-contained volumes will each encompass a closely related field of applications and will demonstrate those methods which have found the widest applica- tions in the area. The emphasis is expected to be on the comparison of published and established methods which have been employed in the application area rather than the details of experimental and novel methods. The volumes will also identify future trends and the potential impact of new technologies and new separation methods. The volumes will therefore provide up-to-date critical surveys of the roles that analytical separations play now and in the future in research, development and production, across the wide range of the fine and heavy chemical industry, pharmaceuticals, health care, food pro- duction and the environment. It will not be a laboratory guide but a source book of estab- lished and potential methods based on the literature that can be consulted by the reader. I am pleased to acknowledge that the value of the Handbook will be dependent on the volume editors and the contributors that they will bring to each topic. It is their experience and expertise that will provide the insights into the present and future development of separation methods. Roger M. Smith Series Editor This Page Intentionally Left Blank IX Contents Editor’s Prejace ............................................................ V Series Editor’s Preface ..................................................... VII List of Contributors ........................................................ XVII . Chapter 1 Gas chromatographic analysis of environmental amines with selective detectors H . Kataoka. S . Yamamoto and S . Narimatsu ........... 1 1.1 .................................................... 1 toxicity of environmental amines .................... 1 1.1.2 Selective detection of amines by gas chromatography ............ 5 1.1.3 Objective and scope of this review .............................. 6 1.2 Selective detectors for gas chromatography of amines .................. 7 1.2.1 Thermionic detector ....... 8 1.2.2 Flame photometric detector .............................. 11 1.2.3 Electron-capture detector . . 12 I .2 .4 Chemiluminescence detector ................................... 14 1.2.5 Mass selective detector ........................................ 15 1.3 Applications in environmental amine analysis .......................... 17 1.3.1 Aliphatic amines ..................... .. 19 1.3.2 Aromatic amines .... ............................. 22 1.3.3 N-Nitrosamines ..... ....................................... 24 1.3.4 Heterocyclic amines ........................................... 2.5 1.4 Conclusions .......................................................... 29 1 ..5 References ...................................... 31 . Chapter 2 Modern techniques for the analysis of polycyclic aromatic hydrocarbons H.K. Lee ..................................................... 39 2.1 Introduction .......................................................... 39 2.2 Development of instrumental techniques for PAH analysis ......... 40 2.2.1 Gas chromatography ........ .................. 43 2.2.2 High-performance liqui 45 2.2.2.1 Stationary phases ..... .............. 46 2.2.2.2 Mobile phase 47 2.2.2.3 Detection ............................................ 48 2.2.3 Supercritical fluid chromatography ............................. 50 2.2.4 Capillary electrophoresis ....................................... 51 2.2.4. I Micellar electrokinetic chromatography ............... 52