Environmental forensics: principles & applications

Library of Congress Cataloging-in-Publication Data Morrison, Robert D. Environmental forensics : principles and applications / by Robert D. Morrison p. cm. Includes bibliographical references and index. ISBN 0-8493-2058-5 (alk. paper) 1. Environmental forensics. 2. Solvents — Environmental aspects. 3. Organochlorine compounds — Environmental aspects. 4. Petroleum chemicals — Environmental aspects. 5. Hydrocarbons — Environmental aspects. 6. Groundwater flow. I. Title. TD193.4.M67 1999 628.5—dc21

99-40624 CIP

This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage or retrieval system, without prior permission in writing from the publisher. The consent of CRC Press LLC does not extend to copying for general distribution, for promotion, for creating new works, or for resale. Specific permission must be obtained in writing from CRC Press LLC for such copying. Direct all inquiries to CRC Press LLC, 2000 Corporate Blvd., N.W., Boca Raton, Florida 33431. Trademark Notice: Product or corporate names may be trademarks or registered trademarks and are used for identification and explanation, without intent to infringe. © 2000 by CRC Press LLC No claim to original U.S. Government works International Standard Book Number 0-8493-2058-5 Library of Congress Card Number 99-40624 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0 Printed on acid-free paper

Preface Environmental forensics is the systematic examination of environmental information used in litigation. The purpose of this book is to provide a working reference for the practicing environmental attorney or environmental consultant. As a working reference, the topics and examples selected are common denominator issues encountered in environmental litigation; as such, this book is not intended to be a treatise on a particular subject but rather to present information that you will likely encounter. Whenever possible, expanded mathematical or chemical discussions were relegated to the Appendices. Chapters 1 and 2 provide a working overview of information about chlorinated solvents and petroleum hydrocarbons. The foundational information in Chapters 1 and 2 was selected to assist you in deciding which forensic tools described in Chapter 4 are applicable to your case. Recognize that the forensic tools described in Chapter 4 are rapidly evolving. Whenever possible, contact the proponents of these technologies directly to ascertain their current capabilities relative to your case. Chapters 3 and 5 provide information on how to identify biased environmental data and suggestions in regard to the applications and review of biased environmental data, as well as suggestions concerning the evaluation of contaminant transport models. Chapter 6 describes techniques for forensically evaluating settlement and trial exhibits and animations. The information in this book is intended to allow you to distinguish between evidence and opinions based on scientific methods vs. junk science. Regardless of your position on an allegation, everyone is well served if valid technical information and interpretations form the basis for an expert witness opinion. Best wishes for a successful and informed environmental career. Robert D. Morrison San Diego, CA

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The Author Robert Daniel Morrison has a B.S. in Geology, an M.S. in Environmental Studies, an M.S. in Environmental Engineering, and a Ph.D. in Soil Physics from the University of Wisconsin at Madison. Dr. Morrison has been working for 27 years in the environmental field on issues related to soil and groundwater contamination. He specializes in the forensic review and interpretation of scientific data used in support of litigation involving soil and groundwater contamination. Dr. Morrison has published articles and books on soil and groundwater contamination topics and has shared this information via lectures throughout the world. He is active in reviewing technical papers on forensics techniques and has served on the editorial boards of Ground Water and Groundwater Monitoring Review and Remediation and currently serves on the editorial board of The International Journal of Environmental Forensics. Dr. Morrison has worked as an expert witness and consultant for the U.S. Department of Justice, the Environmental Protection Agency (EPA), and numerous law firms on cases where environmental forensics were used to allocate responsibility. In the capacity as an expert witness and confidential consultant, Dr. Morrison has provided testimony in numerous cases, some with claims ranging from tens of thousands of dollars to as much as five billion dollars.

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Acknowledgments Scientists who directly assisted in the preparation of this book include Sherri Komelyan, Kathleen Calsbeck, Jamie Campos, Kevin Vaughn, and Christian Benitez of R. Morrison & Associates, Inc. Numerous colleagues and researchers provided assistance in the form of communication and information. Special thanks to Dr. Jim Bruya, of Friedman & Bruya in Seattle, WA; Dr. James Szecsody, of Battelle Northwest Laboratories in Hanford, WA; Dr. Blayne Hartman, of TEG in Solano Beach, CA; David Kaminski, of QED in Ann Arbor, MI; Kevin Beneteau, of Golder Associates, Calgary, Alberta, Canada; Dr. Barbara Sherwood Lollar, Department of Geology, University of Toronto, Canada; Dawn Zemo, of Geomatrix in San Francisco, CA; and Dr. Ramona Aravena, University of Waterloo, Waterloo, Ontario, Canada. Special thanks to the wonderful group at CRC Press, especially Becky McEldowney, who provided creative insight and inspiration, and Debrah Goldfarb. who provided marketing direction. Special thanks, too, to Sarah Nicely Fortener of Nicely Creative Services in Geneva, IL, for her wonderful editing of this book. Special acknowledgement to my wife, Donna, who tolerated my night stalking and the use of her computer during this effort.

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Contents Chapters 1 through 6 1

An Overview of the History, Chemistry, and Transport of Chlorinated Solvents 1.1 Introduction 1.2 Chronology and Use of Chlorinated Solvents 1.2.1 Trichloroethylene (TCE) 1.2.2 Tetrachloroethylene (PCE, or Perchloroethylene) 1.2.3 1,1,1-Trichloroethane (1,1,1-TCA, or Methylchloroform) 1.2.4 Methylene Chloride (Dichloromethane) 1.3 Chemistry and Properties of Chlorinated Solvents 1.3.1 Terminology and Classification 1.3.2 Chemical Structure and Properties 1.3.3 Henry’s Law Constant (KH) 1.3.4 Liquid Density 1.3.5 Solubility 1.3.6 Viscosity 1.3.7 Vapor Pressure and Density 1.3.8 Boiling Point and Latent Heat of Vaporization 1.3.9 Octanol/Water Partition Coefficient (Kow) 1.3.10 Hydrolysis 1.3.11 Sorption 1.3.12 Biodegradation 1.3.12.1 Anaerobic Degradation 1.3.12.2 Aerobic Degradation 1.4 Transport of Chlorinated Solvents through Soil 1.5 Impact of Cosolvency on Transport through Soil 1.6 Transport of Vapors in Soil 1.7 Transport through the Capillary Fringe 1.8 Transport in Groundwater 1.8.1 Darcy’s Law 1.8.2 Porosity (ne) 1.8.3 Permeability (k) and Hydraulic Conductivity (K) 1.8.4 Retardation 1.8.5 Dispersivity

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1.8.6 1.8.7 1.8.8 References

Free Phase Solvent Transport in Groundwater Transport in Fractures Transport in Fractured Porous Media

2

Chemistry and Transport of Petroleum Hydrocarbons 2.1 Introduction 2.2 Chemistry of Crude Oil 2.3 Chemistry of Refined Products 2.3.1 Gasoline 2.3.2 Diesel 2.4 Chemical Reactions in the Vadose Zone 2.4.1 Henry’s Law Constant (KH) 2.4.2 Liquid Density 2.4.3 Solubility 2.4.4 Viscosity 2.4.5 Vapor Pressure and Vapor Density 2.4.6 Sorption 2.4.7 Retardation 2.4.8 Biodegradation 2.5 Overview of Transport through the Unsaturated (Vadose) Zone 2.5.1 Transport through Soil 2.5.2 Cosolvation and Colloidal Transport 2.5.3 Residual Saturation 2.5.4 Vapor Phase Transport 2.6 Hydrocarbon Interactions at the Capillary Fringe 2.6.1 Hydrocarbon Solubilization from the Capillary Fringe into Groundwater 2.7 Transport in Groundwater 2.7.1 Rate of Transport 2.7.2 MTBE Transport in Groundwater 2.7.3 Length of a Petroleum Hydrocarbon Plume 2.7.4 Transport in Fractures References

3

Identification of Biased Environmental Data 3.1 Introduction 3.2 Geologic Characterization 3.2.1 Boring Log Terminology 3.3 Interpretation of Geologic Information 3.4 Soil Collection for Chemical Analyses 3.4.1 Soil Sampling Equipment 3.4.2 Subsampling and Sample Transfer 3.4.3 Soil Compositing

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3.5

Groundwater Characterization 3.5.1 Monitoring Well Location 3.5.2 Installation of Groundwater Monitoring Wells 3.5.3 Sampling Plan 3.5.4 Groundwater Purging 3.5.5 Groundwater Sampling 3.5.6 Sampling Equipment and Sequence 3.5.7 Equipment Decontamination 3.5.8 Sample Containers 3.5.9 Sample Filtration, Preservation, and Holding Times 3.5.10 Field Measurements 3.5.11 Field Quality Control Samples 3.6 Soil Vapor Surveys 3.6.1 Interpretation of Soil Vapor Data 3.7 Analytical Methods 3.7.1 Misidentification of Analytes 3.7.2 Laboratory Documentation 3.7.2.1 Chain of Custody 3.7.2.2 Document Control/Control Log 3.7.2.3 Signature List 3.7.2.4 Logbook Cover Sheet 3.7.2.5 Sample Kit Preparation Log 3.7.2.6 Field Logs 3.7.2.7 Sample Receipt Checklist and/or Log 3.7.2.8 Sample Preparation Logbook 3.7.2.9 Sample Analysis Log 3.7.2.10 Instrument Run Log 3.7.2.11 Instrument Maintenance Log 3.7.2.12 Certificates of Analysis 3.7.2.13 Laboratory Certification 3.7.3 Laboratory Quality Control Samples References 4

Forensic Techniques Used in Environmental Litigation 4.1 Introduction 4.2 Aerial Photography 4.3 Underground Storage Tank Corrosion Models 4.4 Inventory Reconciliation 4.5 Commercial Availability of a Chemical 4.6 Chemicals and Formulations Unique to a Manufacturing Process or Activity 4.6.1 Polychlorinated Biphenyls 4.7 Petroleum Refinery Throughput Analysis 4.8 Chemical Identification of Petroleum Hydrocarbons

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4.8.1 Analytical Strategy 4.8.2 Proprietary Additives: Petroleum Hydrocarbons 4.8.3 Anti-Knock Additives (Alkyl Leads) 4.8.4 Lead Scavengers 4.8.5 Oxygenates 4.8.6 Trace Inorganics 4.8.7 Petroleum Dyes 4.8.8 Octane Rating 4.9 Radioactive Isotope Dating 4.9.1 Dating Groundwater with Isotopes 4.9.2 Isotopic Analysis for Petroleum Hydrocarbons 4.9.3 Lead Isotope Analysis 4.9.4 Lead Isotope Analysis for Gasoline Fingerprinting 4.9.5 Isotope Analysis of Crude Oil and BTEX 4.9.6 Isotope Analysis of Gas Samples 4.9.7 Isotopic Analysis of Chlorinated Solvents 4.10 Chemical and Biological Degradation Models: Petroleum Hydrocarbons 4.10.1 Weathering and Biomarkers 4.10.2 Biodegradation Models 4.10.3 Pristane/Phytane Ratios 4.10.4 BTEX Ratios 4.10.5 Challenges to BTEX Ratio Methods 4.11 Chemical Degradation Models: Chlorinated Solvents 4.12 Rapid Optical Screening Tool™ Testing References 5

Contaminant Transport Modeling 5.1 Introduction 5.2 Liquid Transport through Pavement 5.3 Vapor Transport through Pavement 5.4 Contaminant Transport in Soil 5.4.1 Challenges to Contaminant Transport Models for Soil 5.4.2 Colloidal Transport 5.4.3 Preferential Pathways 5.4.4 Cosolvent Transport 5.5 Contaminant Transport in Groundwater 5.5.1 Types of Groundwater Models 5.5.2 Selection of Boundary Conditions, Grids, and Mass Loading Rates 5.5.3 Software Applicability 5.6 Application of Groundwater Modeling in Environmental Litigation 5.6.1 Confirmation Models

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5.6.2 5.6.3 5.6.4 5.6.5 5.6.6 References 6

Reverse Models Hydrogeologic Variables Contaminant Properties Challenges to Reverse Models Challenges to Phase-Separate Reverse Models

Forensic Review of Environmental Trial Exhibits 6.1 Introduction 6.2 Exaggerated Vertical and Horizontal Scales 6.3 Selective Data Presentation 6.4 Data Contouring 6.4.1 Manual Contouring 6.4.2 Computer Contouring 6.4.2.1 Inverse Distance Method 6.4.2.2 Kriging 6.4.2.3 Minimum Curvature Method 6.4.2.4 Sheppard’s Method 6.4.2.5 Polynomial Regression 6.4.3 Color-Coded Data References Appendices

A

Sample Calculation for the Transport of PCE Vapor through Concrete Pavement A.1 Introduction A.2 Sample Calculation References

B

Sample Calculation for the Transport of PCE Liquid through Concrete via Diffusion B.1 Introduction B.2 Sample Calculation References

C

Properties of Alcohol Oxygenates and Ether Oxygenates

D

Advective and Partitioning Transport Equations of Radon for Detecting Diesel in Groundwater D.1 Introduction D.2 Derivation D.3 Conclusions References

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E

Chemical and Commercial Synonyms for Selected Chlorinated Solvents and Aromatic Hydrocarbons References

F

Laboratory Terms and Definitions

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Chapters 1 through 6

1

An Overview of the History, Chemistry, and Transport of Chlorinated Solvents

PCE formulated by Faraday in 1821.

1.1 INTRODUCTION Chlorinated solvents are one of the most frequently encountered contaminants in environmental investigations (Siegrist, 1993). Trichloroethylene (TCE) and tetrachloroethylene (PCE), for example, were detected in 945 groundwater-supplied drinking systems in an Environmental Protection Agency survey of drinking wells in the United States. In September 1997, TCE and PCE were detected at 852 and 771, respectively, of the 1420 National Priority List (NPL) or Superfund sites in the United States (Butler and Hayes, 1999). As a result of the frequency of detection and toxicity of chlorinated solvents, millions and often billions of dollars are alleged in litigation associated with their investigation and remediation.

1.2 CHRONOLOGY AND USE OF CHLORINATED SOLVENTS The global production and use of chlorinated solvents began after World War II, with volumes gradually increasing through the 1950s and 1960s. In the early years of solvent use, the military was the primary consumer. From 1978 through 1988, the total production of chlorinated solvents in the United States declined modestly, by about 11%. After 1988, the decline was more substantial, amounting to about 45% between 1978 and 1985. The decrease in the demand of chlorinated solvents during 1978 to 1985 reflects the production ban on 1,1,1-trichloroethane (1,1,1-TCA, or TCA) and Freon-113 (1,1,2-trichloro-1,2,2-trifluoroethane). Another factor in this decrease was the increased regulations on TCA, tetrachloroethylene (PCE), and

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TABLE 1.1 Chlorinated Solvent Uses in the U.S. in 1988 Application

TCEa

PCEb

MCc

TCAd

Freon-113e

Total

Vapor degreasing Drycleaning Intermediate Cold cleaning Electronics Aerosols Paint stripping Adhesives Coatings Flexible foam Pharmaceuticals Textiles Food processing Pesticides Other Total demand Production

47.1 — 7.0 14.1 3.2 — — — — — — 1.0 — — — 72 82

18.1 120.0 80.0 6.7 1.3 3.0 — — 7.0 — — 2.0 — — 20.0 258 226

5.8 — — 17.2 16.9 20.0 50.0 5.0 — 23.2 14.4 — 4.2 1.0 49.3 207 229

106.0 — 22.5 17.0 40.8 40.8 — 26.0 17.2 — — 7.0 — 3.0 10.5 298 328

17.7 2.0 5.3 40.2 0.6 0.6 — — — — — 0.5 — — 7.5 78 78

194.7 122.0 114.6 90.2 78.6 64.4 50.0 31.0 24.2 23.2 14.4 10.5 4.2 4.0 87.3 913 943

a b c d e

TCE = trichloroethylene. PCE = tetrachloroethylene. MC = methylene chloride. TCA = 1,1,1-trichloroethane. Freon-113 = trichlorotrifluoroethane.

methylene chloride (MC). The total global capacity for chlorinated solvents in 1994 was about 1.7 million metric tons, with the U.S. accounting for about 36% of the total, followed by Western Europe and Japan at 40% and 23%, respectively. Table 1.1 summarizes the consumption of chlorinated solvent use in the U.S. in 1988 for various industries and applications (IRTA, 1994). The primary use of chlorinated solvents is vapor degreasing. In vapor degreasing, solvents are boiled (150 to 250∞F), thereby producing a heated vapor zone within the degreaser. A single-chamber vapor degreaser contains heating coils at the bottom to boil the liquid solvent, and cooling coils surround the top to contain the vapor (see Figure 1.1). Metal parts are lowered into the solvent vapor zone for cleaning, usually in a metal basket. The warm solvent condenses on the colder parts, dissolving the contaminants or oil into the solvent. In some instances, a spray wand is manually used to spray the solvent vapor on the parts in the basket. The vapor zone height is limited by the cooling coils that condense the solvents and return them to the liquid at the bottom of the degreaser. The mixture drains to a water/solvent separator, where the heavier solvent sinks to the bottom and the condensed water and dissolved solvent are disposed. While many vapor degreasers are more sophisticated, with vacuum

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FIGURE 1.1 Single-stage vapor degreaser.

systems, multiple chambers, attached distillation units for removing the soils from the solvent, ultrasonics, and mechanized basket trays, the general operating principle is the same. Cold cleaning is another degreasing technique. Cold cleaning is similar to vapor degreasing, except that the solvent is maintained at room temperature or is heated to a temperature below the solvent’s boiling point. Like vapor degreasing, metal parts are dipped into the liquid solvent, and the contaminants are dissolved and removed from the metal. Cold cleaning is less effective than vapor degreasing because the solvent is not boiled clean. The heated solvent used in vapor degreasing is also more effective in degreasing than the same solvent used at room temperature for the same purpose. The dominant cold cleaning solvent is 1,1,1-TCA. Equipment related to vapor degreasers includes distillation or evaporation stills used to recover solvents. The two types of stills are batch and continuous. In a batch still (also differential, Raleigh, or pot distillation), a fixed amount of spent solvent is placed inside a heated evaporation chamber from which the condensed vapor is withdrawn. Continuous, multistage distillation (also fractional distillation) is used when there is a need for a high degree of distillation purity, if the amount of spent solvent to be recovered is large, or when differences in solvent volatility are small. Continuous distillation is accomplished in a column equipped with trays or packing materials to facilitate contact between the liquid and vapor phases. Liquid is introduced continuously into the column at the top while the vapor moves upward, becoming more enriched with the more volatile compounds. The high boiling compounds thereby become concentrated in the liquid.

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TABLE 1.2 Solvent Compatibility with Distillation Stills Distillation Model/Manufacturer SD-15 Acra Electric; Schiller Park, IL LS-JR Finish Engineering; Erie, PA ER8; Westport, MA RS-20 Recyclene Products; San Francisco, CA

Boiling Range (∞F) N/A 100–320