~~~ Ame ri can Petroleum Ins titute BIOACCUMULATION: HOW CHEMICALS MOVEFROM THE WATER INTO FISHAND OTHERAQUATIC ORGANISMS Health and Environmental Sciences Department Publication Number 4656 May 1997 STDmAPIIPETRO PUBL 'ib5b-ENGL 1997 0732270 0565044 840 One of the most significant long-term trends affecting the future vitality of the petroleum industry is the public's concerns about the environment, health and safety. Recognizing this trend, API member companies have developed a positive, forward-looking strategy called STEP: Strategies for Today's Environmental Partnership. This initiative aims to build understanding and credibility with stakeholders by continually improving our industry's environmental, health and safety performance; documenting petformance; and communicating with the public. API ENVIRONMENTAL MISSION AND GUIDING ENVIRONMENTAL PRINCIPLES The members of the American Petroleum Institute are dedicated to continuous efforts to improve the compatibility of our operations with the environment while economically developing energy resources and supplying high quality products and services to consumers. We recognize our responsibility to work with the public, the government, and others to develop and to use natural resources in an environmentally sound manner while protecting the health and safety of our employees and the public. To meet these responsibilities, API members pledge to manage our businesses according to the following principles using sound science to prioritize risks and to implement cost-effective management practices: To recognize and to respond to community concerns about our raw materials, products and operations. To operate our plants and facilities, and to handle our raw materials and products in a manner that protects the environment, and the safety and health of our employees and the public. To make safety, health and environmental considerations a priority in our planning, and our development of new products and processes. To advise promptly, appropriate officials, employees, customers and the public of information on significant industry-related safety, health and environmental hazards, and to recommend protective measures. To counsel customers, transporters and others in the safe use, transportation and disposal of our raw materials, products and waste materials. To economically develop and produce natural resources and to conserve those resources by using energy efficiently. To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and waste materials. To commit to reduce overall emission and waste generation. To work with others to resolve problems created by handling and disposal of hazardous substances from our operations. To participate with government and others in creating responsible laws, regulations and standards to safeguard the community, workplace and environment. To promote these principles and practices by sharing experiences and offering assistance to others who produce, handle, use, transport or dispose of similar raw materials, petroleum products and wastes. Bioaccumulation: How Chemicals Move from the Water into Fish and Other Aquatic Organisms Health and Environmental Sciences Department API PUBLICATION NUMBER 4656 PREPARED UNDER CONTRACT BY: JAMESN. HUCKINS JIMMIE D. Pm JAMINTHOMAS MIDWESTSCIENCE CENTER U.S. DEPARTMENTOF INTERIOR 4200 NEWHAVEN ROAD COLUMBIA,MO 65201 MAY 1997 American Petroleum Institute STD-API/PETRO PUBL 4bSb-ENGL 1777 = 0732290 05b504b bL3 FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED. API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, MANUFAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, AND OTHERS EXPOSED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDER LOCAL, STATE, OR FEDERAL LAWS. NOTHING CONTAINED IN ANY API PUBLICATION IS TO BE CONSTRUED AS GRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANU- FACTURE, SALE, OR USE OF ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LEïTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- ITY FOR INFRINGEMENT OF LETERS PAmNT. All rights reserved. No part of this work muy be repmdwed, stored in a retrieval system, or transmitted by any means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission from the publishe,: Contact the publisher, API Publishing Services, 1220 L Street, N. U!, Wmhington, D.C. 20005. Copyright 6 1997 American Petroleum Institute iii ~~ ~ ~~ STD-API/PETRO PUBL 4bSb-ENGL 1777 m 0732270 0565047 557' m ACKNOWLEDGMENTS THE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT API STAFF CONTACT Alexis E. Steen, Health and Environmental Sciences Department MEMBERS OF THE BIOMONITORING TASK FORCE Philip Dom, Shell Development Company, Chairperson Raymon Arnold, Exxon Biomedical Sciences, Inc. Marie BenKinney, Moble Oil Corporation Janis Farmer, BP American R&D William Gala, Chevron Research and Technology Company Jerry Hall, Texaco Research Michael Hmass, AMOCO Corporation Denise Jett, Phillips Petroleum Company Eugene Mancini, ARCO James OReilly, Exxon Production Research Company Lawrence Reitsema, Marathon Oil Company C. Michael Swindoli, Dupont Environmental Remediation Service Michael Tucker, Occidental Chemical Company Car1 Venzke, Citgo Petroleum Corporation CONTRACTOR'S ACKNOWLEDGMENTS We thank Mr. Randal Clark, Mrs. Ginger Gibson, Mrs. Linda Goetting, Mr. Jon Lebo, and Dr. Carl Orazio for their technical assistance in the completion of this work. We also appreciate the interest and support of Scott Folwarkow of the Westem States Petroleum Association, and Dr. Gary Rausina of the Chevron Research and Technology Company. Finally, we give special thanks for the guidance of Dr. William Gala and Alexis Steen. iv ~ STD-API/PETRO PUBL qbSb-ENGL 1797 0732270 05b50LiB 97b W TABLE OF CONTENTS Section Paae EXECUTIVE SUMMARY ............................................ ES-I 1. INTRODUCTION ............................................... 1-1 2 . FACTORS AFFECTING BIOACCUMULATION ........................ 2.1 PHY S ICAL-C HEM I CAL PRO PERTI ES ......................... 2. 1 Polarity ............................................ 2.1 Molecular Size ...................................... 2.2 Summary .......................................... 2-4 ENVIRONMENTAL VARIABLES ............................. 2.5 Overview of Variables ................................. 2.5 Organic Carbon Sorption .............................. 2.6 Acidity ............................................. 2-9 Salinity ........................................... 2.10 Environmental Degradation Processes ..................2.1 1 ORGANISM-RELATED FACTORS ........................... 2.1 3 Uptake from Water .................................. 2-14 Dietary Uptake ..................................... 2.14 Depuration of Accumulated Residues ................... 2-16 Toxicity and Bioaccumulation .......................... 2-18 Kinetic Models of Bioaccumulation ...................... 2-20 Model Terms and Concepts ........................... 2.21 Application of Models to Biological Data .................2-22 Half-Lives of Bioaccumulated PAHS .................... 2-23 Estimation of Potential BCF Using QSAR Models .......... 2-24 FOOD CHAIN-RELATED FACTORS ......................... 2-25 Theory ........................................... 2-25 Biomagnification .................................... 2.26 An Example ....................................... 2.28 3 . APPROACHES FOR ASSESSMENT ............................... 3-1 TISSUE RESIDUE OPTION ................................. 3-1 Method Evaluation ................................... 3-2 EFFLUENT OPTION ....................................... 3.2 Method Evaluation ................................... 3-2 SEDIMENT ASSESSMENT OPTION .......................... 3-3 Method Evaluation ................................... 3-3 OVERVIEW OF EPA ASSESSMENT METHODS ................3-4 OTHER POTENTIAL APPROACHES .......................... 3-4 Transplanted Sentinel Organisms ....................... 3-4 SPMDTechnology ........................................ 3-5 REFERENCES ..................................................... R-1 GLOSSARY ....................................................... G-I ~ ~ ~ STD-API/PETRO PUBL qb5b-ENGL 1777 = 0732290 05b5047 322 = LIST OF FIGURES Fiaure Paae 2-1. Effects of increasingly polar substituents on the water solubility and lipophilicity of organic compounds ................................. .2-2 2-2. Effects of increasing molecular size on the water solubility and lipophilicity of organic compounds (PAHs) .................................... .2-3 2.3. Molecular size of contaminants and a lipid relative to the postulated pore sizeofafishgill ................................................2-3 2-4. The effects of pH on the or the lipophilicity of a weak organic acid .....2-10 2-5. Chemical structures of selected organic compounds having increasing environmental persistence and lipophilicity .......................... 2-12 2-6. Multiple routes of chemical uptake, elimination and growth dilution exhibited by various aquatic species ............................... 2-13 2-7. Selected PAHs, having bay