Page iii Extraction Methods for Environmental Analysis JOHN R. DEAN University of Northumbria at Newcastle, UK Page iv Copyright © 1998 John Wiley & Sons Ltd, Baffins Lane, Chichester, West Sussex PO19 IUD, England National 01243 779777 International ( +44) 1243 779777 e-mail (for orders and customer service enquiries): [email protected] Visit our Home Page on http://www.wiley.co.uk or http://www.wiley.com 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, photocopying, recording, scanning or otherwise, except under the terms of the Copyright Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency, 90 Tottenham Court Road. London WIP 9HE, UK, without the permission in writing of the Publisher Other Wiley Editorial Offices John Wiley & Sons, Inc., 605 Third Avenue, New York. NY 10158-0012, USA WILEY-VCH Verlag GmbH, Pappelallee 3, D-69469 Weinheim, Germany Jacaranda Wiley Ltd. 33 Park Road, Milton, Queensland 4064. Australia John Wiley & Sons (Asia) Pte Ltd, Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809 John Wiley & Sons (Canada) Ltd, 22 Worcester Road, Rexdale, Ontario M9W ILI, Canada Library of Congress Cataloging-in-Publication Data Dean. John R. Extraction methods for environmental analysis / John R. Dean p. cm. Includes bibliographical references and index. ISBN (0-471-98287-3 (cloth : alk. paper) 1. Extraction (Chemistry) 2. Environmental chemistry—Technique. 1. Title QD63.E88D43 1998 97—48744 628.5'01'543—dc21 CIP British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 0 471 98287 3 Typeset in 10/12 Times by Techset Composition Ltd, Salisbury, England Printed and bound in Great Britain by Bookcraft (Bath) Ltd This book is printed on acid-free paper responsibly manufactured from sustainable forestry, in which at least two trees are planted for each one used for paper production Page v To Lynne, Samuel and Naomi Page vii CONTENTS Preface xi 1 1 Environmental Analysis 1. 1 Introduction 1 1.2 Sampling Strategies 3 1.2.1 Sampling Water Matrices 4 1.2.2 Sampling Soils and Sludges 4 1.3 Storage of Samples 5 1.4 Brief Introduction to Practical Chromatographic Analysis 6 1.5 Quality Assurance in Environmental Analysis 10 References 11 Bibliography 11 Part I: Aqueous Samples 2 15 Aqueous Sample Preparation 2.1 Environmental Case Study: Pesticides 15 2.1.1 Environmental Fate and Behaviour of Pesticides 18 References 21 3 23 Classical Approaches for the Extraction of Analytes from Aqueous Samples 3.1 Liquid-Liquid Extraction 23 3.1.1 Theory of Liquid-Liquid Extraction 23 3.1.2 Solvent Extraction 25 3.1.3 Solvent Evaporation Methods 27 3.2 Purge and Trap for Volatile Organics 33 References 34 4 35 Solid Phase Extraction 4.1 Types of SPE Media 35 4.2 Cartridge or Disk Format 36 4.3 Method of SPE Operation 40 4.4 Solvent Selection 42 Page viii 4.5 Factors Affecting SPE 43 4.6 Selected Methods of Analysis for SPE 43 4.7 Automated and On-line SPE 46 4.8 Selected Applications of Automated On-line SPE 48 References 61 5 63 Solid Phase Microextraction 5.1 Theoretical Considerations 65 5.2 Experimental 66 5.3 Methods of Analysis: SPME-GC 67 5.3.1 Volatile Organics in Water: Direct Extraction 67 5.3.2 Volatile Organics in Water: Headspace Concentration 70 5.3.3 Pesticides from Aqueous Samples 72 5.3.4 Phenols 75 5.3.5 Analysis of Analytes from Solid Matrices 78 5.4 Methods of Analysis: SPME-HPLC 83 5.5 Miscellaneous Applications 84 5.5.1 Characterisation of Alcoholic Beverages 84 5.5.2 Analysis of Human Breath 86 5.5.3 Analysis of Cigarette Smoke Condensate 88 5.5.4 Headspace SPME of Cinnamon 88 5.5.5 Tetraethylead and Inorganic Lead in Water 90 5.5.6 Solid Phase Microextraction-Electrodeposition Device 90 5.5.7 Analysis of Polar Analytes using Derivatisation/SPME 90 References 94 Bibliography 94 Part II: Solid Samples 6 99 Solid Sample Preparation 6.1 Introduction 101 References 106 7 107 Liquid-Solid Extraction 7.1 Introduction 107 7.2 Experimental 107 7.3 Selected Methods of Analysis 109 7.3.1 Soxhlet 110 7.3.2 Soxtec (Automated Soxhlet) 110 7.3.3 Shake-Flask 112 7.3.4 Shake-Flask versus Sonication 114 7.3.5 Shake-Flask versus Reflux (Soxhlet) 117 7.3.6 Sonication versus Soxhlet 118 7.3.7 Other Approaches 119 References 121 123 8 Supercritical Fluid Extraction 8.1 Definition of a Supercritical Fluid 125