Bioaccumulation in Marine Organisms: Effect of Contaminants from Oil Well Produced Water

BIOACCUMULATION IN MARINE ORGANISMS

Effect of Contaminants from Oil Well Produced Water

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BIOACCUMULATION IN

MARINE ORGANISMS

Effect of Contaminants

from Oil Well Produced Water

JERRY M. NEFF, Ph.D.

Battelle, Coastal Resources and Environmental Management,

Duxbury, Massachusetts 02332, USA

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Contents

Preface ................................................. xi

Acknowledgements ................................................ xv

CHAPTER 1: PRODUCED WATER .................................. 1

1.1 Composition of Produced Water ............................... 1

1.1.1 Sources and Treatment of Produced Water ................. 1

1.1.2 Naturally-Occurring Chemicals in Produced Water .......... 2

1.1.3 Production Chemicals in Produced Water .................. 16

1.2 Volumes of Produced Water Discharged to the Ocean .............. 18

1.3 Fate of Chemicals from Produced Water in the Ocean .............. 19

1.3.1 Modeled Dilution of the Produced Water Plume ............. 19

1.3.2 Fate of Chemicals in Produced Water Plumes .............. 22

1.3.3 Degradation of Produced Water Chemicals in the Ocean ...... 27

1.4 Toxicity of Produced Water .................................. 30

1.4.1 Toxicity of Whole Produced Water ....................... 30

1.4.2 Causes of Produced Water Toxicity ...................... 33

1.4.3 Toxicity of Produced Water Additives .................... 34

CHAPTER 2: BIOACCUMULATION MECHANISMS ................... 37

2.1 Introduction .............................................. 37

2.2 Bioavailability ............................................ 37

2.2.1 Definitions ......................................... 37

2.2.2 Metals ............................................ 38

2.2.3 Organic Chemicals ................................... 42

2.3 Bioaccumulation .......................................... 43

2.4 Bioconcentration .......................................... 44

2.4.1 Definitions ......................................... 44

2.4.2 Nonpolar Organic Chemicals ........................... 44

vi Bioaccumulation in Marine Organisms

2.5

2.4.3

2.4.4

Ionizable Organic Chemicals ...........................

Metals ............................................

Biomagnification ..........................................

2.5.1 Definitions .........................................

2.5.2 Organic Chemicals ...................................

2.5.3 Metals ............................................

46

47

50

50

51

54

CHAPTER 3" ARSENIC IN THE OCEAN .............................

3.1

3.2

3.3

3.4

3.5

3.6

57

Arsenic in Seawater ........................................ 57

Arsenic in Marine Sediments ................................. 60

Bioaccumulation and Biotransformation of Arsenic ................ 62

Concentrations of Arsenic in Tissues of Marine Organisms .......... 68

Toxicity of Arsenic to Marine Organisms ........................ 72

Environmental Effects of Arsenic in Produced Water ............... 76

CHAPTER 4: BARIUM IN THE OCEAN ............................. 79

4.1 Barium in Seawater ........................................ 79

4.2 Barium in Marine Sediments ................................. 81

4.3 Bioaccumulation of Barium by Marine Organisms ................. 82

4.4 Concentrations of Barium in Tissues of Marine Organisms .......... 83

4.5 Toxicity of Barium to Marine Organisms ........................ 84

4.6 Environmental Effects of Barium in Produced Water ............... 86

CHAPTER 5" CADMIUM IN THE OCEAN ........................... 89

5.1

5.2

5.3

5.4

5.5

5.6

Cadmium in Seawater ...................................... 89

Cadmium in Marine Sediments ............................... 92

Bioaccumulation of Cadmium by Marine Organisms ............... 93

Concentrations of Cadmium in Tissues of Marine Organisms ......... 97

Toxicity of Cadmium to Marine Organisms ...................... 100

Environmental Effects of Cadmium in Produced Water ............. 102

CHAPTER 6: MERCURY IN THE OCEAN ............................ 103

6.1

6.2

6.3

6.4

6.5

6.6

Mercury in Seawater ....................................... 103

Mercury in Marine Sediments ................................ 108

Bioaccumulation of Mercury by Marine Organisms ................ 112

Concentrations of Mercury in Tissues of Marine Organisms .......... 117

Toxicity of Mercury to Marine Organisms ....................... 125

Environmental Effects of Mercury in Produced Water .............. 129

Contents vii

CHAPTER 7: CHROMIUM IN THE OCEAN ............ .............. 131

7.1

7.2

7.3

7.4

7.5

7.6

Chromium in Seawater ...................................... 131

Chromium in Marine Sediments ............................... 133

Bioaccumulation of Chromium by Marine Organisms .............. 135

Concentrations of Chromium in Tissues of Marine Organisms ........ 137

Toxicity of Chromium to Marine Organisms ..................... 141

Environmental Effects of Chromium in Produced Water ............. 142

CHAPTER 8: COPPER IN THE OCEAN .............................. 145

8.1

8.2

8.3

8.4

8.5

8.6

Copper in Seawater ........................................ 145

Copper in Marine Sediments ................................. 148

Bioaccumulation of Copper by Marine Organisms ................. 150

Concentrations of Copper in Tissues of Marine Organisms .......... 153

Toxicity of Copper to Marine Organisms ........................ 157

Environmental Effects of Copper in Produced Water ............... 159

CHAPTER 9: LEAD IN THE OCEAN ................................ 161

9.1

9.2

9.3

9.4

9.5

9.6

Lead in Seawater .......................................... 161

Lead in Marine Sediments ................................... 164

Bioaccumulation of Lead by Marine Organisms ................... 166

Concentrations of Lead in Tissues of Marine Organisms ............ 167

Toxicity of Lead to Marine Organisms .......................... 170

Environmental Effects of Lead in Produced Water ................. 173

CHAPTER 10: ZINC IN THE OCEAN ............................... 175

10.1 Zinc in Seawater .......................................... 175

10.2 Zinc in Marine Sediments ................................... 177

10.3 Bioaccumulation of Zinc by Marine Organisms ................... 179

10.4 Concentrations of Zinc in Tissues of Marine Organisms ............. 182

10.5 Toxicity of Zinc to Marine Organisms .......................... 186

10.6 Environmental Effects of Zinc in Produced Water ................. 188

CHAPTER 11: RADIUM ISOTOPES IN THE OCEAN ................... 191

11.1 Radium in Seawater ........................................ 191

11.2 Radium in Marine Sediments ................................. 194

11.3 Bioaccumulation of Radium by Marine Organisms ................ 195

11.4 Concentrations of Radium in Tissues of Marine Organisms .......... 198

11.5 Toxicity of Radium to Marine Organisms ........................ 199

11.6 Environmental Effects of Radium in Produced Water ............... 200

viii Bioaccumulation in Marine Organisms

CHAPTER 12: PHENOLS IN THE OCEAN ........................... 203

12.1 Phenols in Seawater ........................................ 203

12.2 Phenols in Marine Sediments ................................. 206

12.3 Bioaccumulation of Phenols by Marine Organisms ................ 207

12.4 Concentrations of Phenols in Tissues of Marine Organisms .......... 209

12.5 Toxicity of Phenols to Marine Organisms ........................ 210

12.6 Environmental Effects of Phenols in Produced Water ............... 213

CHAPTER 13: DI(2-ETHYLHEXYL)PHTHALATE IN THE OCEAN ....... 215

13.1 Di(2-ethylhexyl)phthalate in Seawater .......................... 215

13.2 Di(2-ethylhexyl)phthalate in Marine Sediments ................... 218

13.3 Bioaccumulation of Di(2-ethylhexyl)phthalate by Marine Organisms ... 219

13.4 Concentrations of Di(2-ethylhexyl)phthalate in Tissues of

Marine Organisms ......................................... 220

13.5 Toxicity of Di(2-ethylhexyl)phthalate to Marine Organisms .......... 221

13.6 Environmental Effects of Di(2-ethylhexyl)phthalate in Produced Water... 223

CHAPTER 14: MONOCYCLIC AROMATIC HYDROCARBONS

IN THE OCEAN .................................... 225

14.1 Monocyclic Aromatic Hydrocarbons in Seawater .................. 225

14.1.1 Sources of Monocyclic Aromatic Hydrocarbons in the Ocean .. 225

14.1.2 Concentrations of Monocyclic Aromatic Hydrocarbons

in Seawater ........................................ 228

14.2 Monocyclic Aromatic Hydrocarbons in Marine Sediments ........... 231

14.3 Degradation of Monocyclic Aromatic Hydrocarbons in

Water and Sediments ....................................... 232

14.4 Bioaccumulation of Monocyclic Aromatic Hydrocarbons

by Marine Organisms ....................................... 233

14.5 Concentrations of Monocyclic Aromatic Hydrocarbons

in Tissues of Marine Organisms ............................... 235

14.6 Toxicity of Monocyclic Aromatic Hydrocarbons to Marine Organisms .. 237

14.7 Environmental Effects of Monocyclic Aromatic Hydrocarbons

in Produced Water ......................................... 239

CHAPTER 15: POLYCYCLIC AROMATIC HYDROCARBONS

IN THE OCEAN .................................... 241

15.1 Sources of Polycyclic Aromatic Hydrocarbons in the Marine Environment . 241

15.1.1 Formation of Polycyclic Aromatic Hydrocarbons ............ 241

15.1.2 Petrogenic Polycyclic Aromatic Hydrocarbons .............. 243

15.1.3 Pyrogenic Polycyclic Aromatic Hydrocarbons .............. 247

Contents ix

15.2 Polycyclic Aromatic Hydrocarbons in Seawater ................... 254

15.3 Polycyclic Aromatic Hydrocarbons in Marine Sediments ............ 262

15.3.1 Sorption of Polycyclic Aromatic Hydrocarbons to Sediments ... 262

15.3.2 Concentration of Polycyclic Aromatic Hydrocarbons in Sediments 266

15.4 Degradation of Polycyclic Aromatic Hydrocarbons ................ 269

15.4.1 Photooxidation ...................................... 269

15.4.2 Microbial Degradation ................................ 271

15.5 Bioaccumulation of Polycyclic Aromatic Hydrocarbons by

Marine Organisms ......................................... 277

15.5.1 Uptake of Polycyclic Aromatic Hydrocarbons by

Marine Organisms ................................... 277

15.5.2 Metabolism of Polycyclic Aromatic Hydrocarbons

by Marine Organisms ................................. 281

15.5.3 Net Bioaccumulation and Trophic Transfer of Polycylic

Aromatic Hydrocarbons by Marine Organisms .............. 288

15.6 Concentrations of Polycyclic Aromatic Hydrocarbons in Tissues

of Marine Organisms ....................................... 293

15.7 Toxicity of Polycyclic Aromatic Hydrocarbons to Marine Organisms... 299

15.7.1 Toxicity of Unmodified PAHs .......................... 299

15.7.2 Phototoxicity of PAHs ................................ 304

15.7.3 Causes of Toxicity of Complex Mixtures Containing PAHs .... 308

15.7.4 Mutagenicity and Carcinogenicity of PAHs ................ 310

15.7.5 Human Toxicity of PAHs in Seafoods .................... 311

15.8 Environmental Effects of Polycyclic Aromatic Hydrocarbons

in Produced Water ......................................... 313

REFERENCES .................................................. 319

INDEX ........................................................ 439

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Preface

Large amounts of organic and inorganic chemicals enter estuarine and coastal marine

environments from natural and anthropogenic sources. Human activities have increased

the flux of many naturally occurring chemicals, such as metals, naturally occurring

radioactive materials (NORM), and petroleum hydrocarbons, to the ocean. On the other

hand, many industrial, domestic, and agricultural activities are the sole sources of an

ever-increasing number of synthetic organic chemicals in the ocean.

Some of these chemicals enter the marine environment in forms and concentrations

that may be harmful to marine organisms and ecosystems, or to consumers, including

humans, of foods from the sea. A chemical must be in a bioavailable form in order to

produce toxic responses in marine organisms or their consumers. A chemical is bioavail￾able if it is in a form that can move through or bind to the surface coating (e.g., skin, gill

epithelium, gut epithelium, cell membrane) of an organism and thereby elicit biological

responses. Bioavailable chemicals may accumulate to high, potentially toxic concentra￾tions in the tissues of marine organisms or their consumers if they have a higher affinity

for some tissue compartment (e.g., lipids) than for the ambient water, or if they bind to

tissue components.

Naturally occurring, bioavailable chemicals are bioaccumulated by marine organ￾isms, often to concentrations much higher than those in the ambient seawater. Con￾centrations of these chemicals in tissues of marine organisms often are in equilibrium

with the natural concentrations in seawater. Thus, the tissues of marine organisms con￾tain natural background concentrations of many naturally-occurring chemicals, such as

most metals and metalloids. These background body burdens of chemicals probably are

not toxic to the marine organisms. However, increased inputs to the marine environment

of some of these chemicals from man's activities can result in increases in the concen￾trations of the chemicals in seawater and enhanced bioaccumulation in the tissues of

marine organisms, possibly to concentrations that are toxic to the organisms themselves

or their consumers, including man.

xi

xii Bioaccumulation in Marine Organisms

Several solid and liquid wastes are generated during the exploration, development,

and production phases of oil and gas activities in coastal and offshore marine waters.

Some of these wastes are discharged intentionally to the ocean. In U.S. territorial waters,

discharges to the ocean from offshore oil rigs and platforms are regulated by National

Pollution Elimination System (NPDES) permits that are issued by the U.S.

Environmental Protection Agency (EPA) or a state environmental protection agency des￾ignated by EPA. NPDES permit limitations and requirements are intended to protect the

local receiving water environment and its uses from harm attributable to the permitted

discharges.

Effluent standards for produced water destined for ocean disposal focus primarily on

limiting the concentration of petroleum (usually measured as total oil and grease) in the

treated effluent. The oil and gas industry treats produced water through a treatment sys￾tem designed to remove oil and grease from the wastewater stream to concentrations

below the NPDES limits. The Final NPDES General Permit for the westem portion of

the outer continental shelf of the Gulf of Mexico (GMG290000) states that produced

water discharges must contain less than a daily maximum of 42 mg/L and a monthly

average of 29 mg/L total oil and grease (57 FR 224:54642, November 19, 1992 and 58

FR 231:63964, December 3, 1993). Modem produced water treatment systems are capa￾ble of generating an effluent that meets these requirements.

Monitoring requirements in the Gulf of Mexico General Permit include periodic

measurements of produced water discharge rates, toxicity of the effluent to marine

organisms, level of radioactivity from 226radium and 228radium in the effluent, and bioac￾cumulation of selected contaminants in marine animals in the receiving water environ￾ment. Flow and radium radioactivity are reported to EPA in the periodic Discharge

Monitoring Report (DMR). The no observed toxic effects concentration of the effluent,

as determined with a 7-day rapid chronic toxicity test, must be equal to or greater than

the critical dilution concentration determined according to a mathematical formula in the

permit.

The original permit required that a site-specific bioaccumulation monitoring study be

performed at all existing facilities that discharge more than 4,600 barrels/day (731,000

liters/day) of treated produced water to the ocean. The permit was subsequently modi￾fied to enable operators to participate in an EPA-approved, industry-wide bioaccumula￾tion monitoring study. Twice each year, three species of marine animals, a crustacean,

mollusk, and nektonic fish, were collected within 100 m down-current from the pro￾duced water discharge (Offshore Operators Committee, 1997a,b). Their edible tissues

were analyzed for three metals (arsenic, cadmium, and mercury), three monocyclic aro￾matic hydrocarbons (benzene, toluene, and ethylbenzene), two polycyclic aromatic

hydrocarbons (fluorene and benzo[a]pyrene), bis(2-ethylhexyl)phthalate, phenol, and

the naturally-occurring radium isotopes, 226Ra and 228Ra.

A part of the monitoring study was a review of the scientific literature on bioaccu￾mulation of the metals and organic chemicals of concern to EPA by marine organisms

(Neff, 1997a). That review has been updated and expanded as this book. The objective

of this book is to critically summarize and interpret the scientific literature dealing with

the bioaccumulation and ecotoxicology of metals, NORM, and selected organic chemi￾cals by marine organisms and their consumers, with particular emphasis on chemicals

commonly found in treated produced water from oil and gas wells. The book also

includes a summary of the range of concentrations of selected metals, NORM, and

Preface xiii

organic chemicals in the tissues of marine organisms from estuarine and marine waters

of the world. These summaries are based on data tables compiled by Neff (1997a). The

summary tables of tissue residues of selected metals and organic compounds in tissues

of marine organisms are not reproduced in this book but are available upon request at

[email protected].

This book is in three parts. The first part deals with the sources, volumes, composi￾tion, and fates in the marine environment of produced water. Emphasis is placed on a

summary of the available information on the chemical composition of produced waters

from wells world-wide. The second part of the review is a summary of our current under￾standing of the process of bioaccumulation of chemicals by freshwater and marine

organisms. The final section of the book is a discussion of the environmental fates and

biological effects of potentially toxic chemicals that have been identified at elevated

(significantly higher than concentrations in ambient seawater) concentrations in pro￾duced water from different sources.

The second part of this book begins with a brief discussion of the mechanisms of

bioaccumulation and food chain transfer of metal and organic contaminants in the

marine environment. The focus of this evaluation is on the bioaccumulation and food

chain transfer in the marine environment of the metals and organic chemicals of envi￾ronmental concern in produced water. The published scientific literature on the concen￾trations of several of these chemicals in the tissues of marine organisms from throughout

the world is summarized. A discussion is included in the third part of the book on the

physical/chemical behavior in the ocean and toxicity to marine organisms of each chem￾ical evaluated. Integration of information about the physical/chemical behavior, bioac￾cumulation, and toxicity of each compound of concern allows conclusions to be made

about its potential to cause harm (its ecological risk) to marine organisms and ecosys￾tems, and human consumers of fishery products, at the concentrations commonly found

in marine environments. Finally, an evaluation is made of the importance of produced

water as a source of chemical residues in the tissues of marine animals living near off￾shore oil and gas platforms.

The current scientific literature on the various topics covered in this book was

accessed through detailed, computerized literature searches. The focus of the literature

searches was on the most recent publications on the topics of interest. Many chemical

analyses of concentrations of metals and organic chemicals in marine environmental

matrices (seawater, sediments, tissues of marine organisms) performed before about

1980 were inaccurate or insensitive because of inadequate analytical methods and fre￾quent lack of consideration of problems of laboratory contamination and matrix inter￾ferences from the salts in produced water and seawater. Therefore, the most recent

available analytical data were used whenever possible.

JERRY M. NEFF

Battelle

November 2001

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