Earlier Volumes in the Series Volume 1 HUTZINGER et al: Aquatic Pollutants — Transformation and Biological Effects Volume 2 ZOETEMAN: Sensory Assessment of Water Quality Volume 3 ALBAIGES: Analytical Techniques in Environmental Chemistry (Proceedings of the First International Congress) Volume 4 VOWLES & CONNELL: Experiments in Environmental Chemistry Volume 5 HUTZINGER et al: Chlorinated Dioxins and Related Compounds (Impact on the Environment) Volume 6 FERGUSSON: Inorganic Chemistry and the Earth (Chemical Resources, Their Extraction, Use and Environmental Impact) A Forthcoming Volume in the Series KARASEK et al: Mass Spectrometry in the Environmental Sciences (Theory and Applications) Other Pergamon Titles of Interest DOUGLAS & MAXWELL: Advances in Organic Geochemistry 1979 HENDERSON: Inorganic Geochemistry JOURNALS ATMOSPHERIC ENVIRONMENT CHEMOSPHERE (Chemistry, Biology and Toxicology as Related to Environmental Problems) ENVIRONMENT INTERNATIONAL GEOCHIMICA ET COSMOCHIMICA ACTA TALANTA Full details of all Pergamon publications/free specimen copy of any Pergamon journal available on request from your nearest Pergamon office. ANALYTICAL TECHNIQUES IN ENVIRONMENTAL CHEMISTRY 2 Proceedings of the Second International Congress, Barcelona, Spain, November 1981 Edited by J. ALBAIGES Environmental Chemistry Unit, Institute of Bio-Organic Chemistry (CSIC), Barcelona, Spain PERGAMON PRESS OXFORD NEW YORK TORONTO · SYDNEY · PARIS · FRANKFURT U.K. Pergamon Press Ltd., Headington Hill Hall, Oxford OX3 OBW, England U.S.A. Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, New York 10523, U.S.A. CANADA Pergamon Press Canada Ltd., Suite 104, 150 Consumers Rd., Willowdale, Ontario M2J 1P9, Canada AUSTRALIA Pergamon Press (Aust.) Pty. Ltd., P.O. Box 544, Potts Point, N.S.W. 2011, Australia FRANCE Pergamon Press SARL, 24 rue des Ecoles, 75240 Paris, Cedex 05, France FEDERAL REPUBLIC Pergamon Press GmbH, 6242 Kronberg-Taunus, OF GERMANY Hammerweg 6, Federal Republic of Germany Copyright © 1982 Pergamon Press Ltd. 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, electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise, without permission in writing from the publishers. First edition 1982 Library of Congress Cataloging in Publication Data Main entry under title: Analytical techniques in environmental chemistry 2. (Pergamon series on environmental science ; v. 7) Organized by Expoquimia and the Societat Catalana de Cîéncies, Fisiques i Matematiques. Includes index. 1. Chemistry, Analytic —Congresses. 2. Environmental chemistry—Congresses. I. Albaiges, J. II. International Congress on Analytical Techniques in Environmental Chemistry (2nd : 1981 : Barcelona, Spain) III. Expoquimia (1981 : Barcelona, Spain) IV. Societat Catalana de Ciències Fisiques, Quimiques i Matematiques British Library Cataloguing in Publication Data Analytical techniques in environmental chemistry 2. (Pergamon series on environmental science; v.7) 1. Chemistry, Analytic Congresses 2. Environmental chemistry Congresses I. Albaiges, J 628.5 QD71 ISBN 0-08-028740-9 In order to make this volume available as economically and as rapidly as possible the author's typescript has been reproduced in its original form. This method un- fortunately has its typographical limitations but it is hoped that they in no way distract the reader. Printed in Great Britain by A. Wheaton & Co. Ltd. Exeter FOREWORD Today, the main goal of environmental chemistry is the understanding of the nature, distribution and fate in the environment of those compounds that es- pecially affect our life's quality. It is apparent that analytical techniques play a fundamental role in the achievement of these objectives and that their continous development is necessary to cope with the new problems constantly arising. Furthermore, a pressure to develop sensitive and reliable methods comes when those responsible for the management of our environment need an objective evaluation of existing or potential hazards. Consequently, the formulation of analytical methods for pollutants has gone hand by hand with the adoption of regulations controlling their release to the environment. The present book contains most of the papers presented at the 2nd Internatio- nal Congress on Analytical Techniques in Environmental Chemistry held in Bar- celona in November 1981. The Congress was organized on the occasion of the 1981-International Chemical Exhibition, by Expoquimia and the Societat Cata- lana de Ciències, Fisiques i Matemàtiques, which celebrated its Golden Jubi- lee. Obviously, the number and variety of analytical methodologies currently in use in environmental chemistry is so vast that a complete coverage in a Congress is presently almost impossible. Therefore, the book can be more illustrative of the general trends in the establishment of analytical techniques for rou- tine use. In this respect, the most outstanding difference with the Procee- dings of the previous Congress (Pergamon Press, 1980) is the extensive appli- cation made of HPLC and ICP for the analysis of organic and inorganic pollu- tants, as well as the higher concern in the detection of mutagenic species both in air and drinking waters. The papers have been classified in two main sections devoted, respectively, to the analysis of organic and inorganic pollutants and preceded by some others dealing more generally with monitoring strategies or case histories. v vi Foreword I hope that all this information will stimulate further research in such an exciting field. At this point, I would like to express my personal gratitude to the many scientists of 32 countries who attended the Congress and contributed with their presentations or discussions. Thanks are also due to Pergamon Press for ensuring the diffusion of this information within the scientific community. Finally, the organizers acknowledge the financial support of the Direccion General del Medio Ambiente (Ministerio de Obras Publicas y Urbanismo), Comis- sio Interdepartamental de Recerca i Innovacio Tecnologica (Generalität de Ca- talunya) and Expoquimia (Feria de Barcelona). The personal assistance of all members of the Committees, notably of D. Barcelo, X. Guardino and J.M. Otero, is deeply appreciated. J. Albaigés MONITORING STRATEGIES THE ROLE OF ANALYTICAL CHEMISTRY IN A TOXIC SUBSTANCE SPILL INTO THE AQUATIC ENVIRONMENT I. R. DeLeon, E. B. Overton and John L. Laseter Center for Bio-Organic Studies, University of New Orleans, Lakefront, New Orleans, Louisiana 70148, USA ABSTRACT On July 22, 1980, a major chemical spill occurred 40 miles southeast of New Orleans in the Mississippi River Gulf Outlet (MRGO), a man-made deep draft channel connecting the Port of New Orleans with the Gulf of Mexico. The spill resulted from the collision of a containerized cargo vessel (M/V TESTBANK) with a bulk ore carrier (M/V SEA DANIEL). Large quanti- ties of technical grade pentachlorophenol (PCP), hydrobromic acid, vinyl polymer, as well as other items of the containerized cargo were lost into the 35-ft deep channel. Ruptured drums released ethyl mercaptan into the atmosphere. An estimated 12 tons of toxic PCP were lost into the estu- arine environment immediately adjacent to major shrimp fisheries and oyster beds. The Center for Bio-Organic Studies of the University of New Orleans assisted in the design and implementation of a multiphase analytical chemistry support program to complement the response efforts by federal and state agencies. The program was designed to assist in locating the bulk of spilled PCP and to monitor the distribution and movement through- out the environment of PCP and its major metabolites and production- related impurities. Latter stages of the program involved monitoring the effectiveness of cleanup activities and the short-term impact of the PCP on the environment. Over 300 water, sediment and biota samples were col- lected and analyzed. The exposure to PCP of response and cleanup workers was monitored by the analysis of approximately 200 blood and urine sam- ples. Existing analytical methods were refined to meet the special requirements of the spill situation. In order to assist participating state and federal agencies, an interlaboratory calibration program was also established. The activities of our laboratory during this incident, and the importance of a broad but flexible analytical chemistry support program to comple- ment the response organization's efforts during a toxic chemical spill are discussed. 1 2 I. R. DeLeon, E. B. Overton and J. L. Laseter KEYWORDS Pentachlorophenol; toxic chemical spill; chlorinated organics; spill response efforts; analytical chemistry; aquatic environment. INTRODUCTION The July 22, 1980, pentachlorophenol (PCP) spill in the Mississippi River Gulf Outlet (MRGO), a man-made deep draft ship channel connecting the Port of New Orleans with the Gulf of Mexico, is one of the largest toxic chemi- cal spills in U.S. maritime history. The collision of two ocean-going vessels 40 miles southeast of New Orleans, Louisiana, damaged and dumped overboard several containers of cargo into the ship channel. Lost over- board was one entire bulk container from the M/V TESTBANK containing tech- nical grade PCP (approximately 12 tons) wrapped in individual 50 lb. heavy paper bags. Also, individual drums of hydrobromic acid, and sacks of vinyl polymer entered the waters. Several containers of ethyl mercaptan were ruptured and released their noxious fumes into the surrounding atmo- sphere. The approximate location of the spill site is shown in Fig. 1. Fig. 1. Map of the PCP spill impacted area showing the MRGO; the Mississippi River (A), Bayou Yscloskey (B), the spill site (C), Lena Lagoon (D), and Castle Martello (E). A portion of the northern Gulf of Mexico coital region showing Louisiana and the spill impacted area Q/])te in the inset. The role of analytical chemistry 3 Soon after the collision, all ship traffic in the MRGO was halted, and the inhabitants of a nearby fishing community were evacuated. The U.S. Coast Guard immediately assembled a spill response organization to assist and coordinate the assessment of the problem, the location of the spilled cargo, and the recovery and cleanup of the spilled materials. Closure of the MRGO deprived the Port of New Orleans of an estimated $500,000 per day in lost operating revenue for the duration of the spill incident. Further, the spill occurred immediately adjacent to major shrimp fish- eries and one of the most commercially significant oyster harvesting regions in Louisiana. Therefore, it was of paramount interest to locate and remove as much of the spilled toxic materials as soon as possible inorder to resume normal activities. Protection of the health and safety of the residents and onsite technical and cleanup personnel was a high priority. A preliminary survey of the collision site and spill incident revealed that the majority of containers of hydrobromic acid, ethyl mercaptan, and vinyl polymer were intact and presented no immediate hazard. However, an entire container holding 24,000 pounds of PCP was lost in the ship channel and this was recognized as a serious threat to the environment and marine life in adjacent waters. Prudent action by state regulatory agencies established a 400 square-mile health and environmental safety zone sur- rounding the spill site and closed the zone to all fishing and oyster harvesting. Plans were made to bring cleanup and recovery equipment to the scene but several important facts concerning the spill and its implication were not known. For example, was the PCP cargo container intact? Was PCP escaping into the aquatic environment at a significant rate to damage marine life? How could the location of the lost PCP container be rapidly determined? Was PCP harmful to humans associated with the cleanup efforts? What were its physical, chemical and toxicological properties? Once information to answer these questions was ascertained, other more specific questions became apparent and needed clarification. This report contains a discus- sion of our activities and the role of the analytical chemistry laboratory in response to a hazardous chemical spill into the marine environment. EXPERIMENTAL Sampling Methodology Water samples were taken at various depths using a 4-liter National Bureau of Standards-type subsurface water sampler. Biota (oysters) were taken from existing oyster beds using a clam dredge. Sediment samples were taken by a petit ponar grab sampler. Blood samples (10 mL) were drawn in vacutainers and urine samples (50-100 mL) were collected in glass bottles. Human body fluid samples were delivered to the laboratory within 2 hours after collection. Analytical Methodology The analytical methodologies employed in this investigation were develop- ed in part to serve the immediate needs of the response effort created by the spill of pentachlorophenol into the MRGO. Existing methodologies had to be adapted, modified, or replaced in order to accommodate the unique requirements of a dynamic spill response effort. Such efforts require 4 I. R. DeLeon, E. B. Overton and J. L. Laseter the use of available equipment and supplies; quick turn-around times for analyses; conclusive, unambiguous analytical results; and the ability to adapt the analytical methodology to meet the lower detection limits, specificity, and other analytical parameters essential to the sample matrices and analyses required during a spill response. Below is a description of the methodologies which were employed in this incident. Materials. Hexane, dichloromethane, acetone, ethyl acetate, and iso- propanol were distilled-in-glass quality (Burdick and Jackson, Muskegon, Michigan) and were used as received. All other reagents were ACS reagent grade or equivalent. Glassware was cleaned by washing with detergent and water, then by dipping in a 5% NaOH solution, rinsing with water, dipping in chromic acid cleaning solution, and finally rinsing with deionized water. All sample containers, sample tubes and vials were equipped with teflon-lined caps or aluminum foil liner to prevent contamination of the sample from the cap liner. Extraction and Cleanup of PCP Cargo Material. A sample of the cargo PCP material was obtained and prepared for analysis of other phenolic and non-phenolic compounds by a procedure adapted from Buser (1975) and Harless and co-workers (1980) as follows: A 1-gram sample of the dry PCP material was dissolved in 100 mL of CH2CI2. The PCP solution was washed 4 times each with 45 mL of pH 10 water made from HPLC grade water and 1 M KOH. The aqueous washings were discarded; the CH2CI2 layer was dried over anhydrous grangular Na2SC>4, then concentrated to about 1 mL. The concentrate was re- dissolved in 100 mL hexane and rewashed with 25 mL of 1 M KOH. The hexane solution was then washed 3 times each with 50 mL of concentrated H2SO4. The acid washings were discarded; the hexane solution was washed with water and neutralized with powdered Na2CC>3. The hexane layer was decanted, concentrated, and chromatographed on a 10 cm x 1 cm column of alumnia (MCB chromatography grade) with CCL4 and CH4CI2. Both fractions were saved, their solvents displaced with benzene and analyzed. Extraction Procedures for Water Samples. Two extraction procedures were employed for water samples. One procedure, Procedure A, was used for large sample volumes, and for samples which were preserved by CH2CI2 addition. The other procedure, Procedure B, was developed for small sam- ple volumes and for samples which were preserved by refrigeration, rather than by CH2CI2 addition. (a) Procedure A. The volumes of water and of the preservative CH2CI2 in the sample container were measured to determine the ratio of CH2C12/H2° for each sample. An aliquot of water was taken (usually 1-3 L of water) and acidified with concentrated HCL to pH1. The acidi- fied water was then extracted with 60 mL of CH2CI2 three times. To the combined extracts was added an aliquot of the CH2CI2 preserva- tive, proportional to the original CH2CI2/H2O ratio. The resulting CH2CI2 mixture was dried with granular anhydrous Na2S04 and con- centrated on a rotary evaporator to approximately 5 ml. The volume was further adjusted under a stream of dry nitrogen as required. The final extract was analyzed by glass capillary GC-MS, or was derivatized and then analyzed by glass capillary GC with electron capture detection. The role of analytical chemistry 5 (b) Procedure B. A 500 mL aliquot of the sample was taken and acidified with 6N HCl to pHI. The acidified water was extracted with 30 mL hexane three times. The combined extracts were concentrated as required using a rotary evaporator and a stream of dry nitrogen. The final extract was analyzed by glass capillary GC-MS, or was derivatized and then analyzed by glass capillary QC with electron capture detection. Extraction Procedure for Biota Samples. A representative sample of the tissue was thawed and homogenized. A 5 gm aliquot of this homogenate was diluted with 5 mL of water and 1 mL of 6N HCl. The diluted and acidified sample was mixed thoroughly on a vortex mixer, and allowed to stand for 5 minutes. To this mixture was added 10 mL of an 8:1:1 hexane-ethyl acetate-isopropanol mixture, followed by mixing on a vortex mixer, and centrifugation at 2000 rpm for 5 minutes. The layers were separated and the top layer was transferred to another vial. To the aqueous layer was added two more 10 mL portions of the extraction solvent mixture. Each addition was followed by mixing, centrifugation,·and separation of the layers as described above. The top layers were combined, dried with granular anhydrous Νε^^* an(^ concentrated on a rotary evaporator and under a stream of dry nitrogen. The final extract was analyzed by glass capillary GC-MS, or was derivatized and then analyzed by glass capillary GC with electron capture detection. Extraction Procedure for Sediment Samples. The sediment samples were thawed, homogenized, and an aliquot, usually 50-100 g, was transferred to a 500 mL jar. The sample was diluted with 100 mL of water and 5 mL of 6N HCl. To the diluted sample was added 100 mL of hexane. The sample was shaken on a table shaker for 30 minutes, followed by centrifugation at 1000 rpm for 5 minutes. The solvent layer was separated and collected. The jar was rinsed twice with 50 mL portions of hexane. The hexane extract and washings were combined and concentrated as required using a rotary evaporator and a stream of dry nitrogen. The final extract was analyzed by glass capillary GC-MS, or was derivatized and then analyzed by glass capillary GC with electron capture detection. Extraction Procedure for Blood and Serum Samples. A 2 mL aliquot of whole blood or serum was transferred to a large vial. The sample was diluted with 10 mL of water. The diluted sample was mixed by shaking and acidified by the addition of 3 mL of 1 N HCl. The acidified sample was mixed until it turned brown. The sample was allowed to stand for 5 minutes, and was then extracted three times with 5 mL of 2:1 hexane- CH2CI2· Each time the sample was shaken until an emulsion formed, then centrifuged at 1500 rpm for 10 min. The extracts were combined, dried with granular anhydrous Ν&2304, and concentrated as required using a rotary evaporator and a stream of dry nitrogen. The final extract was analyzed by glass capillary GC-MS, or was derivatized and then analyzed by glass capillary GC with electron capture detection. Extraction Procedure for Urine Samples. The urine sample was mixed thoroughly and a 5-10 mL aliquot was transferred to a centrifuge tube. The sample was diluted with 5 mL water and 3 mL of 1N HCl. The acidified sample was extracted with 5 mL of 2:1 hexane-CH2Cl2 three times. Each time the mixture was mixed vigorously on a vortex mixer and then centrifuged at 2000 rpn for 10 minutes. The organic extracts were combined, dried with granular anhydrous Na2S0 , and concentrated as 4 required on a rotary evaporator and under a stream of dry nitrogen. The final extract was derivatized and then analyzed by glass capillary GC with electron capture detection.