Table Of ContentChlorinated Solvents
A Forensic Evaluation
Robert D. Morrison
Post Office Box 195, Hawi, Hawaii 96719
Email: [email protected]
Brian L. Murphy
1255 N Gulfstream Avenue, Sarasota, Florida 34236
Email: [email protected]
ISBN: 978-1-84973-196-6
A catalogue record for this book is available from the British Library
# Robert Morrison and Brian Murphy 2013
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Preface
Environmentalforensicsisdefinedasthesystematicandscientificevaluationof
physical, chemical and historical information for the purpose of developing
defensible scientific and legal conclusions regarding the source or age of a
contaminant release into the environment. Within this general definition,
environmentalforensicshasevolvedintoarecognizedscientificdisciplinewith
numerous applications, especially regarding chlorinated solvents.
The purpose of this book is to consolidate and introduce the reader to the
production history and forensic techniques available to age date and identify
the source of a chlorinated solvent release. Given the large number of
chlorinatedsolventsthatarepotentiallycontaminantsofconcern,information
in this book is restricted to the following commonly encountered chlorinated
solvents: trichloroethene (TCE), perchloroethylene (PCE), carbon tetrachlor-
ide, methyl chloroform (also known as 1,1,1-trichloroethane or TCA) and
CFC-113. Given the association of PCE and TCE with dry cleaning and
degreasing, respectively, chapters dedicated to these industries and forensic
opportunities are included. An effort was made to include dates and/or date
ranges wherever possible to assist you in age bracketing the availability of
these chlorinated hydrocarbons and/or their associated stabilizers.
Itisourhopethattheinformationinthisbookisusefultoyouinyourwork
and provides a basis for further ideas in the evolution of environmental
forensic techniques for chlorinated hydrocarbons. We wish you great success
in your environmental investigations and thank you for your participation in
this emerging science.
Robert D. Morrison
Brian L. Murphy
v
Contents
Chapter 1 Physical and Chemical Properties of Selected Chlorinated
Solvents
1.1 Introduction 1
1.2 Physical and Chemical Properties 2
1.2.1 Viscosity 2
1.2.2 Vapor Pressure 3
1.2.3 Solubility 3
1.2.4 Henry’s Law Constant (K ) 4
H
1.2.5 Relative Vapor Density 6
1.2.6 Boiling Point 6
1.2.7 Molecular Weight 6
1.2.8 Hydrolysis 7
1.2.9 Hildebrand Solubility for Soil 8
1.2.10 Hansen Solubility 9
1.2.11 Hydrophilic/Lipophilic Balance (HLB) 9
1.3 Degradation Concepts and Nomenclature 10
1.4 Degradation of Chlorinated Compounds 11
1.4.1 Tetrachloroethylene (PCE) 12
1.4.2 Trichloroethylene (TCE) 13
1.4.3 Methyl Chloroform (1,1,1-TCA) 13
1.4.4 Carbon Tetrachloride 14
1.4.5 CFC-113 (1,1,2 trichloro-1,1,2 trifluoroethane) 15
1.5 Conclusion 16
References 16
vii
viii Contents
Chapter 2 Stabilizers and Impurities
2.1 Introduction 22
2.2 Stabilizer Categories 22
2.2.1 Antioxidants 23
2.2.2 Light Inhibitors 23
2.2.3 Thermal Stabilizers 24
2.2.4 Acid Acceptors 24
2.2.5 Metal Inhibitors 25
2.3 Stabilizer Tests 25
2.3.1 Acid Acceptance Value (AAV) 26
2.3.2 Kauri Gum Index (Kauri Butanol K ) 27
b
2.3.3 Partitioning Experiments 28
2.3.4 Vapor Degreaser Experiments 29
2.3.5 Aluminium Scratch Test 29
2.3.6 Stabilizer Synergy Testing 30
2.3.7 Accelerated Oxidation Test 31
2.4 Stabilizers and Patent Literature 35
2.5 Diagnostic Stabilizers 40
2.5.1 Methodology 41
2.5.2 Epichlorohydrin 42
2.5.3 1,2,3-Trichoropropane (TCP) 44
2.5.4 1,4-dioxane 45
2.5.5 Thymol 49
2.6 Use of PCE Stabilizers for Source Identification 50
2.7 PCE Stabilizers and Impurities for Release
Reconstruction 52
2.8 Accumulation of PCE as an Impurity in TCE
Distillation Still Residue 54
2.9 TCE Stabilizers for Source and Date of Manufacture
Estimates 56
2.10 TCE Stabilizers and Impurities for Release
Reconstruction 57
2.11 Methyl Chloroform Stabilizers and Impurities for
Release Reconstruction 59
2.12 Feedstock Impurities in TCE, PCE and Methyl
Chloroform for Age Dating 60
2.13 Conclusion 65
References 65
Chapter 3 Perchloroethylene (PCE)
3.1 Introduction 77
3.2 PCE Production 77
3.2.1 Production Processes 79
Contents ix
3.3 PCE Stabilizers 87
3.4 Manufacturing Impurities 91
3.5 Applications 91
3.5.1 Dry Cleaning 93
3.5.2 Automotive Products 96
3.5.3 Degreasing 100
3.5.4 Pesticides 100
3.5.5 PCE as a Dielectric Fluid 101
3.5.6 Flushing Electrical Transformers Containing
PCBs 106
3.5.7 Cold Cleaning 107
3.5.8 Precursor in the Synthesis of Fluorocarbons 107
3.5.9 Cold Flotation Testing 108
3.5.10 Degreasing Circuit Boards 108
3.5.11 Textile Scouring 109
3.5.12 Film Cleaning 110
3.5.13 Miscellaneous 110
3.6 Conclusion 110
References 111
Chapter 4 Trichloroethylene (TCE)
4.1 Introduction 119
4.2 Regulatory Context 120
4.3 PCE Production 121
4.3.1 Production of TCE from Acetylene 122
4.3.2 Production of TCE from 1,1,2,2-TeCA 123
4.3.3 Production of TCE from Ethylene 123
4.3.4 Production of TCE from Ethylene Dichloride 125
4.3.5 Production of TCE from Dichloroethylene 125
4.4 TCE Stabilizers 125
4.5 Manufacturing Impurities 131
4.6 Manufacturers’ Specifications 133
4.7 Military Specifications 135
4.8 Applications 136
4.8.1 Vapor Degreasing 139
4.8.2 Chemical Intermediate 141
4.8.3 Spotting Agents 142
4.8.4 Adhesives 143
4.8.5 Solvent Extraction 143
4.8.6 Anesthetic 144
4.8.7 Asphalt Testing 145
4.8.8 Aerosol Products 145
4.8.9 Phosphatizing 145
4.8.10 Textiles 147
x Contents
4.8.11 Wool Scouring 147
4.8.12 Cleaning Oil Tanks in Ships 147
4.8.13 Miscellaneous 148
4.9 Conclusion 149
References 149
Chapter 5 Carbon Tetrachloride
5.1 Introduction 160
5.2 Production History 160
5.3 Manufacturing Processes 164
5.3.1 Chlorinolysis of Hydrocarbons 164
5.3.2 Production of Carbon Tetrachloride from
Methane 166
5.3.3 Production of Carbon Tetrachloride from
Carbon Disulfide 168
5.3.4 Methanol Hydrochlorination–Methyl Chloride
Chlorination 169
5.4 Stabilizers 170
5.5 Impurities in Carbon Tetrachloride 171
5.6 Historical Applications 171
5.6.1 Production of Chlorofluorocarbons 172
5.6.2 Fumigants 172
5.6.3 Dry Cleaning 173
5.6.4 Vapor Degreasing 175
5.6.5 Circuit Interrupter 176
5.6.6 Household Products 176
5.6.7 Fire Extinguishers 177
5.6.8 Miscellaneous 177
5.7 Conclusion 178
References 178
Chapter 6 Methyl Chloroform (1,1,1-TCA)
6.1 Introduction 186
6.2 Regulatory Context 186
6.3 Production 187
6.3.1 Production of Methyl Chloroform from Vinyl
Chloride 188
6.3.2 Production of Methyl Chloroform from
Vinylidene Chloride 190
6.3.3 Non-Catalytic Chlorination of Ethane 191
6.4 TCA Stabilizers 194
Contents xi
6.4.1 Cold Cleaning and Vapor Degreasing
Stabilizers 195
6.4.2 1,4-Dioxane 198
6.5 Impurities 201
6.6 Applications 202
6.6.1 Metal Degreasing 203
6.6.2 Aerosol Products 206
6.6.3 Circuit Board Manufacturing 206
6.6.4 Paints 208
6.6.5 Adhesives 209
6.6.6 Chemical Intermediates 211
6.6.7 Surface Coating Operations 212
6.6.8 Textile Industry 213
6.6.9 Auxiliary Blowing Agent for Polyurethane
Foam 213
6.6.10 Cleaning Movie Film 214
6.6.11 Septic Tank Cleaners 214
6.6.12 Home Products 215
6.6.13 Flushing Hydraulic Systems 215
6.6.14 Miscellaneous 215
6.7 Conclusion 216
References 216
Chapter 7 CFC-113
7.1 Introduction 225
7.2 Production of CFC-113 226
7.3 Formulations 227
7.4 Stabilizers 228
7.5 Applications 231
7.5.1 Metal Cleaning in the Electronics Industry 232
7.5.2 Production of Foam Products 233
7.5.3 Scouring Agent 234
7.5.4 Production of Chlorotrifluoroethylene (CTFE) 234
7.5.5 Precision Cleaning 234
7.5.6 Optical Industry 237
7.5.7 Dry Cleaning 237
7.5.8 Refrigerants 238
7.5.9 Tracers 238
7.5.10 Measuring Residue in Oxygen and
Refrigeration Systems 239
7.5.11 Miscellaneous Applications 239
7.6 Conclusion 240
References 240
xii Contents
Chapter 8 A Forensic History of Dry Cleaning
8.1 Introduction 247
8.2 Dry Cleaning Chemicals 247
8.2.1 Detergents 249
8.2.2 Bleaches 252
8.2.3 Sizing 253
8.2.4 Flame Retardants 253
8.2.5 Spotting Agents 253
8.2.6 Fabric Conditioners and Stain Repellents 255
8.2.7 Dry Cleaning Solvents 255
8.2.8 Dry Cleaning Solvent Stabilizers 266
8.2.9 Dry Cleaning Solvent Impurities 267
8.3 Categories of Dry Cleaning Equipment 267
8.3.1 First Generation 268
8.3.2 Second Generation (Vented Dry to Dry) 269
8.3.3 Third Generation Closed Loop (Non-vented)
Dry to Dry Machines 270
8.3.4 Fourth Generation Closed Loop (Non-vented)
Dry to Dry Machines 271
8.3.5 Fifth Generation Closed Loop (non-vented) 272
8.3.6 European Dry Cleaning Machines 272
8.3.7 Coin Operated Dry Cleaning Machines 272
8.3.8 Carbon Dioxide Machines 274
8.3.9 Wet-Cleaning Machines 275
8.4 Components of Dry Cleaning Equipment 275
8.4.1 Filters 276
8.4.2 Solvent Recovery Equipment 282
8.5 Conclusion 286
References 286
Chapter 9 A Forensic History of Degreasing with Chlorinated Solvents
9.1 Introduction 292
9.2 Vapor Degreasing Solvents 293
9.2.1 Perchloroethylene 293
9.2.2 Trichloroethylene 293
9.2.3 Methyl Chloroform 294
9.2.4 Carbon Tetrachloride 294
9.2.5 CFC-113 294
9.2.6 Other Solvents 295
9.3 Vapor Degreasers 295
9.3.1 Conventional Vapor Degreaser 296
9.3.2 Vapor–Distillate Spray Degreaser 296
9.3.3 Vapor–Spray–Vapor Degreaser 297
Contents xiii
9.3.4 Liquid–Vapor Degreaser 297
9.3.5 Two-Chamber Immersion Degreaser 299
9.3.6 Ultrasonic Vapor Degreaser 299
9.3.7 Conveyorized Degreaser 301
9.3.8 Cross-Rod Degreaser 301
9.3.9 Monorail Degreaser 301
9.3.10 Vibra Degreaser 302
9.3.11 Ferris Wheel Degreaser 302
9.3.12 Belt and Strip Degreaser 302
9.3.13 Circuit Board Degreaser 303
9.3.14 Closed System Degreaser 303
9.4 Vapor Degreasing Equipment 303
9.4.1 Freeboard 304
9.4.2 Water Jacket 305
9.4.3 Cooling Coils 305
9.4.4 Carbon Adsorbers 306
9.4.5 Water Separator 306
9.4.6 Distillation Still 307
9.4.7 Heat Source 308
9.5 Cold Cleaning 309
9.6 Forensic Opportunities 311
9.6.1 Water Separators 313
9.6.2 Spent Solvent and Distillation Sludge 314
9.7 Conclusion 318
References 318
Chapter 10 Forensic Investigations of Dry Cleaners
10.1 Introduction 325
10.2 Forensic Methodology 326
10.3 Collection of Operational Information 326
10.3.1 Regulatory Documentation 327
10.3.2 Dry Cleaning Equipment 327
10.3.3 Drain and Sewer Information 328
10.3.4 Solvent Consumption 329
10.3.5 Chronology of Facility Renovations 330
10.3.6 Solvent Delivery Location(s) and Protocol 330
10.3.7 Solvent Mileage Records 330
10.3.8 Historical Dumpster Locations 332
10.3.9 Depth to Groundwater 332
10.3.10 Evidence of DNAPL 332
10.3.11 Dendroecology Assessment 332
10.4 Identification of Potential Background Sources 333
10.5 Site Specific Sources 334
10.5.1 Florida Study 334
