DISTRIBUTION OF PHTHALATE ESTERS IN A MARINE AQUATIC …rem-main.rem.sfu.ca/theses/MackintoshCheryl_2002_MRM295.pdf · benefited. Many thanks to my second supervisor, Dr. Margo Moore,

DISTRIBUTION OF PHTHALATE ESTERS

IN A MARINE FOOD WEB

by

Cheryl Mackintosh

B.Sc., University of British Columbia, 1996

A PROJECT SUBMITTED IN PARTIAL FULFILMENT OF THE

REQUIREMENTS FOR THE DEGREE OF MASTER OF RESOURCE

MANAGEMENT

in the School of Resource and Environmental Management

Report No. 295

© Cheryl Mackintosh 2002

Simon Fraser University

APRIL 2002

All rights reserved. This work may not be reproduced in whole or in part, by photocopy or other

means, without the permission of the author.

ii

APPROVAL NAME: Cheryl Mackintosh DEGREE: Master of Resource Management TITLE OF PROJECT: Distribution of Phthalate Esters in a Marine Food Web REPORT NO.: 295 EXAMINING COMMITTEE:

Dr. Frank A.P.C. Gobas Senior Supervisor

Associate Professor School of Resource and Environmental Management

Simon Fraser University

Dr. Margo Moore Associate Professor

Department of Biological Sciences Simon Fraser University

Date Approved:_______________________

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ABSTRACT

Phthalate esters (PEs) are widely used chemicals, with over 4 million tonnes being produced

worldwide each year. PEs exhibit octanol-water partition coefficients (Kow) ranging from

101.8 for dimethyl phthalate to 1010.6 for di-iso-decyl phthalate. Because of their

hydrophobicity, some congeners have the potential to bioconcentrate and biomagnify in

marine and aquatic food chains. There are currently no reported field studies on phthalate

ester bioaccumulation. To investigate PE bioaccumulation in a marine food web, a field

study was conducted in False Creek Harbour, Vancouver, Canada. The study involved

collecting samples of seawater, sediment and eighteen marine species. Samples were

analyzed by GC-LRMS for eight individual phthalate congeners (i.e., dimethyl, diethyl, di-

iso-butyl, di-n-butyl, butyl-benzyl, di(2-ethylhexyl), di-n-octyl, di-n-nonyl), and by LC-

ESI/MS for five isomeric mixtures (i.e., di-iso-hexyl (C6), di-iso-heptyl (C7), di-iso-octyl

(C8), di-iso-nonyl (C9), di-iso-decyl (C10)). Environmental concentrations were

determined and corresponding fugacities were calculated. PE fugacities in the sediment were

greater than those in the freely dissolved water fraction. The degree of sediment-water

disequilibrium decreased with KOW from a factor of 17,700 for dimethyl phthalate to values

between 2.7 and 44 for the other twelve PEs. For the low KOW PEs (i.e., dimethyl and

diethyl) fugacities in the biota were between those in the sediment and water, and did not

exhibit a trend with trophic position in the food web. For the intermediate KOW PEs (i.e., di-

iso-butyl, di-n-butyl, benzyl-butyl, C6, and C7), fugacities in the biota were lower than those

in the sediment, comparable to those in the freely dissolved water fraction, and did not show

a statistically significant pattern with trophic position. For the high KOW PEs (i.e., di(2-

ethylhexyl), di-n-octyl, di-n-nonyl, C8, C9, C10), fugacity significantly declined with

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increasing trophic position, and fugacities in the media appeared to decline from sediment ≥

freely dissolved water ≅ prey species > predator species. These results suggest that PEs do

not biomagnify in the food web. Equilibrium partitioning between the organisms and the

water appears to occur for the low and intermediate KOW phthalates, while trophic dilution in

the food web occurs for the high KOW phthalates. Mean bioaccumulation factors (BAFs,

L/kg lipid) based on the “total” water concentration were generally below the Canadian

Environmental Protection Act (1999) bioaccumulation criteria of 100,000 L/kg lipid. BAFs

for butyl-benzyl, di(2-ethylhexyl), di-n-octyl, di-n-nonyl, C6, C7, C8, C9, and C10, based on

the “freely dissolved” water concentration, generally exceeded the CEPA criteria. Biota-

Sediment Accumulation Factors (BSAFs, kg OC/kg lipid) for the benthic species in False

Creek were generally less than one.

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ACKNOWLEDGEMENTS First off, I would like to sincerely thank my senior supervisor, Dr. Frank Gobas for his vast

knowledge in the field of environmental toxicology, his valuable guidance with the project,

and his continually positive attitude. I learned a great deal from him and am grateful for the

opportunities he provided for presenting my research at conferences. I also wish to thank Dr.

Michael Ikonomou from the Institute for Ocean Sciences for overseeing the chemical analysis

on the project and his expertise in analytical environmental chemistry, from which I greatly

benefited. Many thanks to my second supervisor, Dr. Margo Moore, for her insightful

comments on the project and thesis write-up. Thanks also to Tom Parkerton and Ken

Robillard, who provided comments throughout the project. There were several people who

were instrumental in assisting with the hands-on aspects of this research project. I am grateful

for the excellent efforts of Audrey Chong, Jing Hongwu, Jody Carlow, Natasha Hoover,

Zhongping Lin, and Linda White who conducted the chemical analysis for the project at the

Institute for Ocean Sciences. I would also like to thank several people for their assistance

with the field collections: Shane Cuff, John Wilcockson, Dave Swanston, Barry Kelly, Laura

McLean, Jon Arnot, Glenn Harris, Kim Chapman, and Elsie Sunderland. Thanks also to

Laurie Wilson of the Canadian Wildlife Service for providing the surf scoter bird samples. I

would like to thank Natural Sciences and Engineering Research Council of Canada (NSERC)

for scholarship funding. Funding for the project was received from the American Chemistry

Council, Environment and Health Canada through the Toxic Substances Research Initiative

(TSRI), and from NSERC.

I would also like to thank my partner Daryl, my family, the “TOX” group, and my volleyball

teammates for helping make these last four years rich and memorable. Finally, I would like to

dedicate this work to the memory of my father Ted, who supported and encouraged me in all

my endeavors.

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TABLE OF CONTENTS APPROVAL.....................................................................................................................................................II ABSTRACT................................................................................................................................................... III ACKNOWLEDGEMENTS ............................................................................................................................ V TABLE OF CONTENTS ............................................................................................................................... VI LIST OF FIGURES ......................................................................................................................................... X LIST OF TABLES.......................................................................................................................................XVII DEFINITIONS...........................................................................................................................................XXIII

1. INTRODUCTION...........................................................................................................................................1

2. METHODS ......................................................................................................................................................8

2.1. FIELD SAMPLING METHODS ....................................................................................................................8 2.1.1. Study Site and Design....................................................................................................................8 2.1.2. Preparation of Field Sampling Equipment..................................................................................11 2.1.3. Sediment Sample Collection........................................................................................................11 2.1.4. Water Sample Collection.............................................................................................................12 2.1.5. Biota Sample Collection..............................................................................................................13

2.2. ANALYTICAL METHODS FOR DETERMINING PHTHALATE ESTER CONCENTRATIONS IN ENVIRONMENTAL SAMPLES.........................................................................................................................................................17

2.2.1. Materials .....................................................................................................................................17 2.2.2. Preparation of Glassware and Reagents.....................................................................................18 2.2.3. Extraction and Cleanup of Sediment and Biota Samples ............................................................18 2.2.4. Extraction and Cleanup of Seawater Samples ............................................................................20 2.2.5. Quantification of Suspended Particulate Matter in the Seawater Samples.................................22 2.2.6. GC/MS Analysis of Environmental Samples ...............................................................................25 2.2.7. LC/ESI-MS Analysis of Environmental Samples .........................................................................25 2.2.8. Optimization of ESI-MS Parameters ...........................................................................................27 2.2.9. LC/ESI-MS/MS Analysis of Environmental Samples...................................................................27 2.2.10. MS Calibration, Recovery and Procedural Blanks .....................................................................28 2.2.11. Quantitation of Phthalate Esters in Environmental Samples ......................................................29 2.2.12. Quantification of Diisodecyl Phthalate (C10) in Biota Samples.................................................30

2.3. QUALITY ASSURANCE AND CONTROL OF DATA (QA/QC) ....................................................................32 2.3.1. Sediment & Biota Concentration Data .......................................................................................32 2.3.2. Seawater Concentration Data.....................................................................................................36 2.3.3. Summary of the Sediment, Biota and Seawater Data Quality .....................................................43

2.4. MEASUREMENTS OF ORGANIC CARBON & LIPID CONTENTS IN SEDIMENT AND BIOTA SAMPLES .........45 2.4.1. Organic Carbon Content Analysis ..............................................................................................45 2.4.2. Lipid Content Determination ......................................................................................................47

2.5. DATA ANALYSIS AND NORMALIZATIONS ..............................................................................................47 2.5.1. Analysis of Concentration Distributions .....................................................................................47 2.5.2. Sediment Organic Carbon Normalization...................................................................................48 2.5.3. Biota Lipid Normalizations .........................................................................................................48 2.5.4. Fugacity Calculations .................................................................................................................50 2.5.5. Trophic Position Calculation ......................................................................................................51

3. RESULTS & DISCUSSION.........................................................................................................................57

3.1. SEDIMENT CONCENTRATIONS OF PHTHALATE ESTERS ..........................................................................57 3.1.1. Concentration Summary..............................................................................................................57 3.1.2. Spatial Variability .......................................................................................................................61

3.2. SEAWATER CONCENTRATIONS OF PHTHALATE ESTERS.........................................................................63 3.2.1. “Total” Seawater Concentration Summary ................................................................................63 3.2.2. Spatial Variability .......................................................................................................................64 3.2.3. Ratio of Seawater Concentrations to Aqueous Solubilities .........................................................65 3.2.4. Distribution of Phthalate Ester Internal Standards between the Glass Fibre Filter and C18 Extraction Disks ........................................................................................................................................66

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3.2.5. Distribution of Seawater Borne Phthalate Esters between the Glass Fibre Filter and C18 Extraction Disks ........................................................................................................................................68 3.2.6. Summary of the “Total”, “C18”, and “Freely Dissolved” Water Concentrations......................75 3.2.7. Chemical Fugacities in the Water ...............................................................................................77

3.3. SEDIMENT - WATER DISTRIBUTION OF PHTHALATE ESTERS..................................................................78 3.4. BIOTA CONCENTRATIONS OF PHTHALATE ESTERS ................................................................................82

3.4.1. Biota Concentration Overview....................................................................................................82 3.4.2. Spatial Variability .......................................................................................................................83 3.4.3. Distribution of Phthalate Esters in Sediment, Seawater, and Biota and Chemical Transfer through the Food Web ...............................................................................................................................86 3.4.4. Summary of Food Chain Bioaccumulation Results...................................................................121 3.4.5. Discussion .................................................................................................................................123

3.5. BIOTA - WATER DISTRIBUTION OF PHTHALATE ESTERS .....................................................................131 3.5.1. Overview ...................................................................................................................................131 3.5.2. Bioaccumulation Factors (BAFs)..............................................................................................132 3.5.3. Chemical Distribution in the Food Chain .................................................................................156 3.5.4. Relationship between the Lipid BAFs, based on the “Total” water concentration, and the Octanol – Seawater Partition Coefficient................................................................................................158 3.5.5. Relationship between the Lipid BAFs, based on the “Freely Dissolved” water concentration, and the Octanol – Seawater Partition Coefficient...................................................................................163

3.6. BIOTA - SEDIMENT DISTRIBUTION OF PHTHALATE ESTERS.................................................................166 3.6.1. Overview ...................................................................................................................................166 3.6.2. Biota - Sediment Accumulation Factors (BSAFs) .....................................................................166 3.6.3. Relationship Between the BSAF in Benthic Species and the Octanol-Seawater Partition Coefficient …...........................................................................................................................................174

REFERENCES................................................................................................................................................178

APPENDIX A: BACKGROUND INFORMATION ON PHTHALATE ESTERS...................................195

1. INTRODUCTION ..................................................................................................................................1 2. METHODS.............................................................................................................................................8

2.1. Field Sampling Methods................................................................................................................8 LATIN NAME...................................................................................................................................................14

2.2. Analytical Methods for Determining Phthalate Ester Concentrations in Environmental Samples 17 2.3. Quality Assurance and Control of Data (QA/QC) ......................................................................32 2.4. Measurements of Organic Carbon & Lipid Contents in Sediment and Biota Samples ...............45 2.5. Data Analysis and Normalizations..............................................................................................47

3. RESULTS & DISCUSSION.................................................................................................................57 3.1. Sediment Concentrations of Phthalate Esters .............................................................................57 3.2. Seawater Concentrations of Phthalate Esters.............................................................................63 3.3. Sediment - Water Distribution of Phthalate Esters .....................................................................78 3.4. Biota Concentrations of Phthalate Esters ...................................................................................82 3.5. Biota - Water Distribution Of Phthalate Esters ........................................................................131 3.6. Biota - Sediment Distribution Of Phthalate Esters ...................................................................166

REFERENCES.............................................................................................................................................178 I) NORMALITY TESTS ON DISTRIBUTIONS OF PHTHALATE ESTER CONCENTRATION DATA ...............................................................................................................................................................287

II) STATISTICAL TESTS ON THE SPATIAL DISTRIBUTION OF PHTHALATE ESTERS IN FALSE CREEK HARBOUR .........................................................................................................................287

III) STATISTICAL TESTS ON THE DISTRIBUTION OF PHTHALATE ESTERS IN THE ENVIRONMENTAL MEDIA AND SPECIES OF FALSE CREEK HARBOUR....................................287

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I) MEAN PHTHALATE ESTER CONCENTRATIONS AND FUGACITIES IN SEDIMENT, SEAWATER AND BIOTA FROM FALSE CREEK HARBOUR.............................................................310

II) COMPARISON OF REPORTED PHTHALATE ESTER CONCENTRATIONS IN VARIOUS LOCATIONS THROUGHOUT THE WORLD TO OBSERVED CONCENTRATIONS IN FALSE CREEK HARBOUR.......................................................................................................................................310

III) MEAN BIOACCUMULATION FACTORS..................................................................................310

IV) MEAN BIOTA-SEDIMENT ACCUMULATION FACTORS.....................................................310

APPENDIX B: TROPHODYNAMIC INTERACTIONS AND LIFE HISTORY INFORMATION ON SELECTED RESIDENT MARINE SPECIES IN SOUTHWESTERN BRITISH COLUMBIA............210


2.1. Field Sampling Methods................................................................................................................8 LATIN NAME...................................................................................................................................................14

2.2. Analytical Methods for Determining Phthalate Ester Concentrations in Environmental Samples 17 2.3. Quality Assurance and Control of Data (QA/QC) ......................................................................32 2.4. Measurements of Organic Carbon & Lipid Contents in Sediment and Biota Samples ...............45 2.5. Data Analysis and Normalizations..............................................................................................47


REFERENCES.............................................................................................................................................178 I) NORMALITY TESTS ON DISTRIBUTIONS OF PHTHALATE ESTER CONCENTRATION DATA ...............................................................................................................................................................287

II) STATISTICAL TESTS ON THE SPATIAL DISTRIBUTION OF PHTHALATE ESTERS IN FALSE CREEK HARBOUR .........................................................................................................................287

III) STATISTICAL TESTS ON THE DISTRIBUTION OF PHTHALATE ESTERS IN THE ENVIRONMENTAL MEDIA AND SPECIES OF FALSE CREEK HARBOUR....................................287

I) MEAN PHTHALATE ESTER CONCENTRATIONS AND FUGACITIES IN SEDIMENT, SEAWATER AND BIOTA FROM FALSE CREEK HARBOUR.............................................................310

II) COMPARISON OF REPORTED PHTHALATE ESTER CONCENTRATIONS IN VARIOUS LOCATIONS THROUGHOUT THE WORLD TO OBSERVED CONCENTRATIONS IN FALSE CREEK HARBOUR.......................................................................................................................................310

III) MEAN BIOACCUMULATION FACTORS..................................................................................310

IV) MEAN BIOTA-SEDIMENT ACCUMULATION FACTORS.....................................................310

APPENDIX C: DIETARY MATRIX FOR CALCULATION OF TROPHIC POSITIONS ...................267

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APPENDIX D: QUALITY ASSURANCE AND CONTROL OF DATA (QA/QC) - TABLES AND FIGURES FROM SECTION 2.4...................................................................................................................270

APPENDIX E:STATISTICAL ANALYSES ON PHTHALATE ESTER CONCENTRATION DATA 287

I. NORMALITY TESTS ON DISTRIBUTIONS OF PHTHALATE ESTER CONCENTRATION DATA…………….….288 SEDIMENT CONCENTRATION DATA..............................................................................................289

WATER CONCENTRATION DATA....................................................................................................290 BIOTA CONCENTRATION DATA .....................................................................................................291

II. STATISTICAL TESTS ON THE SPATIAL DISTRIBUTION OF PHTHALATE ESTERS IN FALSE CREEK HARBOUR. ……………………………………………………………………………………………………………...298

SEDIMENT CONCENTRATION DATA .............................................................................................299 BIOTA CONCENTRATION DATA ......................................................................................................300

III. STATISTICAL TESTS ON THE DISTRIBUTION OF PHTHALATE ESTERS IN THE ENVIRONMENTAL MEDIA AND SPECIES OF FALSE CREEK HARBOUR………………………………………………………………………..305

APPENDIX F: DATA TABLES FROM SECTION 3 (RESULTS & DISCUSSION) ..............................310


2.1. Field Sampling Methods................................................................................................................8 2.2. Analytical Methods for Determining Phthalate Ester Concentrations in Environmental Samples 17 2.3. Quality Assurance and Control of Data (QA/QC) ......................................................................32 2.4. Measurements of Organic Carbon & Lipid Contents in Sediment and Biota Samples ...............45 2.5. Data Analysis and Normalizations..............................................................................................47


REFERENCES.............................................................................................................................................178 APPENDIX G: ORIGINAL RAW DATA OF PHTHALATE ESTER CONCENTRATIONS IN SEDIMENT, SEAWATER AND MARINE BIOTA SAMPLES FROM FALSE CREEK HARBOUR..........................................................................................................................................................................349

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LIST OF FIGURES Chapter 1 Introduction FIGURE 1.1. GENERALIZED PHTHALATE ESTER CHEMICAL STRUCTURE................................................................2 FIGURE 1.2. FUGACITY “F” ANALYSIS OF ALTERNATIVE HYPOTHESES OF CHEMICAL MOVEMENT THROUGH A

FOOD CHAIN. ...............................................................................................................................................5 Chapter 2 Methods FIGURE 2.1. MAP OF FIELD STUDY SITE: FALSE CREEK HARBOUR, VANCOUVER, BRITISH COLUMBIA, SHOWING

LOCATIONS OF FOUR SAMPLING STATIONS (λ): “NORTH CENTRAL”, “MARINA – SOUTH”, “CAMBIE BRIDGE” AND “EAST BASIN”. ....................................................................................................................10

FIGURE 2.2. FIELD SAMPLING EQUIPMENT..........................................................................................................12 A) PETIT PONAR SEDIMENT GRAB SAMPLER, AND B) SEAWATER COLLECTION APPARATUS. .............................12 FIGURE 2.3. GENERALIZED TROPHIC LINKAGES BETWEEN EIGHTEEN MARINE ORGANISMS COLLECTED FROM

FALSE CREEK HARBOUR AND THE SPECIES TROPHIC POSITIONS (SEE SECTION 2.5.5). ..............................16 FIGURE 2.4. WATER EXTRACTION APPARATUS CONSISTING OF FMI VALVELESS LABORATORY PUMP AND

THREE 47MM STAINLESS STEEL IN-LINE FILTER HOLDERS HOUSING A GLASS FIBRE FILTER (0.45μM DIAMETER PORE SIZE) IN HOLDER #1, AND AN OCTADECYL (C18) EMPORE EXTRACTION DISK IN HOLDERS #2 AND #3. .................................................................................................................................................21

FIGURE 2.5. SUMMARY OF THE EXTRACTION AND ANALYTICAL PROCEDURES FOR THE ANALYSIS OF PHTHALATE ESTERS IN SEDIMENT, BIOTA AND SEAWATER SAMPLES. (POLYCHLORINATED BIPHENYLS (PCBS) WERE EXTRACTED CONCURRENTLY). ...................................................................................................................24

FIGURE 2.6. MEAN PHTHALATE ESTER CONCENTRATIONS (NG/G) IN SODIUM SULFATE PROCEDURAL BLANKS FOR SEDIMENT AND BIOTA ANALYSIS. ERROR BARS REPRESENT ONE STANDARD DEVIATION...................33

FIGURES 2.7 - 2.10 (SEE APPENDIX D LISTINGS) FIGURE 2.11. MEAN TOTAL RECOVERIES (%) OF INTERNAL STANDARDS IN SPIKED WELL WATER BLANKS AND

FALSE CREEK SEAWATER SAMPLES USING GC/MS ANALYSIS. BARS INDICATE FRACTIONS ON THE GLASS FIBRE FILTER (GF) AND C18 EXTRACTION DISKS (C18). ERROR BARS INDICATE ONE STANDARD DEVIATION. ................................................................................................................................................38

FIGURE 2.12. MEAN CONCENTRATIONS (NG/L) OF PHTHALATE ESTERS IN WELL WATER BLANKS. ERROR BARS REPRESENT ONE STANDARD DEVIATION. ....................................................................................................40

FIGURES 2.13 (SEE APPENDIX D LISTINGS) FIGURE 2.14. ILLUSTRATION OF THE PARTICULATE ORGANIC CARBON (POC) – BOUND CHEMICAL (LARGE

DIAMETER SUSPENDED MATTER “LDSM”), DISSOLVED ORGANIC CARBON (DOC) – BOUND CHEMICAL (SMALL DIAMETER SUSPENDED MATTER “SDSM”), AND THE FREELY DISSOLVED CHEMICAL FRACTION IN THE WATER PHASE AND THE THREE WATER CONCENTRATIONS REPORTED IN THE STUDY...................43

Chapter 3 Results & Discussion FIGURE 3.1A & B. PHTHALATE ESTER CONCENTRATIONS IN FALSE CREEK HARBOUR SEDIMENTS, EXPRESSED

ON A DRY WEIGHT BASIS (NG/G DRY SEDIMENT) (A), AND ON AN ORGANIC CARBON NORMALIZED BASIS (NG/G ORGANIC CARBON) (B). ....................................................................................................................59

FIGURE 3.1.C & D. PHTHALATE ESTER FUGACITIES (NPA) IN FALSE CREEK HARBOUR SEDIMENTS (C), AND COMPARISON OF PHTHALATE ESTER CONCENTRATION (NG/N OC) AND FUGACITY (NPA) PROFILES IN FALSE CREEK HARBOUR SEDIMENTS (D)...................................................................................................60

FIGURE 3.2. SPATIAL VARIABILITY......................................................................................................................62 FIGURE 3.3. TOTAL CONCENTRATIONS (MEAN ± STANDARD DEVIATIONS, NG/L) OF PHTHALATE ESTERS IN

SEAWATER SAMPLES FROM FALSE CREEK HARBOUR. (NUMBER OF SAMPLES FOR WHICH WATER CONCENTRATION EXCEEDED THE MDL, IN BRACKETS). .............................................................................64

FIGURE 3.4. RATIO OF THE SEAWATER CONCENTRATIONS (CW, NG/L) TO THE AQUEOUS SOLUBILITIES (SW, NG/L) OF PHTHALATE ESTERS, FOR THE TOTAL SEAWATER CONCENTRATION AND THE FREELY DISSOLVED SEAWATER CONCENTRATION, AS A FUNCTION OF THE OCTANOL - SEAWATER PARTITION COEFFICIENT. .66

FIGURE 3.5. MEAN OBSERVED FRACTIONS (± STANDARD DEVIATION) OF SPIKED PHTHALATE ESTER INTERNAL STANDARDS ON THE GLASS FIBRE FILTER AND C18 EXTRACTION DISKS IN FALSE CREEK HARBOUR

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SEAWATER SAMPLES, AND THE MODEL-FITTED FREELY DISSOLVED (FDW MODEL) AND PARTICULATE-BOUND (PB MODEL) FRACTIONS, DETERMINED FROM EQUATION 3.3. ......................................................68

FIGURE 3.6. MEAN OBSERVED FRACTIONS (± STANDARD DEVIATIONS) OF SEAWATER-BORNE PHTHALATE ESTERS ON THE C18 EXTRACTION DISKS IN SEAWATER SAMPLES FROM FALSE CREEK HARBOUR, THE 2-PHASE MODEL-FITTED FREELY DISSOLVED FRACTION (EQN. 3.3) AND THE 3-PHASE MODEL-FITTED C18 FRACTION (SDSM-BOUND + FDW) (EQN. 3.4) AND FREELY DISSOLVED FRACTION (EQN. 3.5).................................73

FIGURE 3.7. FRACTION OF PHTHALATE ESTERS BOUND TO LARGE DIAMETER SUSPENDED MATTER (LDSM) ( ), BOUND TO SMALL DIAMETER SUSPENDED MATTER ( ), AND FREELY DISSOLVED ( ) IN FALSE CREEK HARBOUR SEAWATER, DETERMINED FROM THE 3-PHASE SORPTION MODEL (EQN. 3.5). THE Y-AXIS ON THE RIGHT PANEL IS EXPRESSED ON A LOGARITHMIC SCALE. ........................................................74

FIGURE 3.8. MEAN PHTHALATE ESTER CONCENTRATIONS (± STANDARD DEVIATIONS, NG/L) IN FALSE CREEK HARBOUR SEAWATER. “TOTAL” CONCENTRATIONS INCLUDE CHEMICAL BOUND TO LARGE AND SMALL DIAMETER SUSPENDED MATTER (LDSM, SDSM) AND FREELY DISSOLVED CHEMICAL. “C18” CONCENTRATIONS INCLUDE SDSM-BOUND AND FREELY DISSOLVED CHEMICAL. THE THIRD BAR REPRESENTS MODEL ESTIMATES OF THE “FREELY DISSOLVED” CHEMICAL CONCENTRATION. ...................76

FIGURE 3.9. MEAN “TOTAL”, “C18”, AND “FREELY DISSOLVED” FUGACITIES (± STANDARD DEVIATIONS, PA) IN FALSE CREEK HARBOUR SEAWATER. “TOTAL” FUGACITIES INCLUDE CHEMICAL BOUND TO LARGE AND SMALL DIAMETER SUSPENDED MATTER (LDSM, SDSM) AND FREELY DISSOLVED CHEMICAL. “C18” FUGACITIES INCLUDE SDSM-BOUND AND FREELY DISSOLVED CHEMICAL. THE THIRD BAR REPRESENTS ESTIMATES OF THE FUGACITY BASED ON “FREELY DISSOLVED” CONCENTRATIONS...................................78

FIGURE 3.10. OBSERVED SEDIMENT-WATER PARTITION COEFFICIENTS (LOG KOC, L/KG OC), BASED ON THE TOTAL WATER CONCENTRATION “TOT”, AND THE FREELY DISSOLVED WATER CONCENTRATION “FD”, AND THE PREDICTED SEDIMENT-WATER EQUILIBRIUM COEFFICIENT (L/KG OC), BASED ON SETH ET AL. 1999. ..........................................................................................................................................................81

FIGURE 3.11. MEAN LIPID CONCENTRATIONS (± STANDARD DEVIATIONS, NG/G LIPID WT.) OF PHTHALATE ESTERS IN MARINE BIOTA SAMPLES FROM THREE SAMPLING STATIONS (“NC” = NORTH CENTRAL, “MA” = MARINA, AND “EB” = EAST BASIN) IN FALSE CREEK HARBOUR. SPECIES PRESENTED ARE: A) PLANKTON, B) GREEN ALGAE, C) GEODUCK CLAMS, D) PACIFIC OYSTERS, AND E) STRIPED SEAPERCH. STARRED BARS (*) INDICATE STATISTICALLY SIGNIFICANT DIFFERENCES IN CONCENTRATION BETWEEN 1 STATION AND THE OTHER 2 (SINGLE STAR PER CHEMICAL), OR BETWEEN 2 SPECIFIC STATIONS (TWO STARS PER CHEMICAL). .........................................................................................................................................86

FIGURE 3.12. CONCENTRATIONS OF DIMETHYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP), LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM). .............88

FIGURE 3.13. FUGACITIES (NPA) OF DIMETHYL PHTHALATE IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR................................89

FIGURE 3.14. CONCENTRATIONS OF DIETHYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM)........90

FIGURE 3.15. FUGACITIES (NPA) OF DIETHYL PHTHALATE IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR................................91

FIGURE 3.16. LOG FUGACITY (NPA) VERSUS TROPHIC POSITION FOR DIMETHYL PHTHALATE (LEFT) AND DIETHYL PHTHALATE (RIGHT). ..................................................................................................................92

FIGURE 3.17. CONCENTRATIONS OF DI-ISO-BUTYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM)........95

FIGURE 3.18. FUGACITIES (NPA) OF DI-ISO-BUTYL PHTHALATE IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR. ...................96

FIGURE 3.19. CONCENTRATIONS OF DI-N-BUTYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM)........97

FIGURE 3.20. FUGACITIES (NPA) OF DI-N-BUTYL PHTHALATE IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK. HARBOUR...............................98

FIGURE 3.21. CONCENTRATIONS OF BUTYLBENZYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM)...................................................................................................................................................99

FIGURE 3.22. FUGACITIES (NPA) OF BUTYLBENZYL PHTHALATE IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR. .................100

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FIGURE 3.23. CONCENTRATIONS OF DI-ISO-HEXYL PHTHALATE (C6) IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM).................................................................................................................................................101

FIGURE 3.24. FUGACITIES (NPA) OF DI-ISO-HEXYL PHTHALATE (C6) IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK. HARBOUR. ................102

FIGURE 3.25. CONCENTRATIONS OF DI-ISO-HEPTYL PHTHALATE (C7) IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM).................................................................................................................................................103

FIGURE 3.26. FUGACITIES (NPA) OF DI-ISO-HEPTYL PHTHALATE (C7) IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK. HARBOUR. ................104

FIGURE 3.27. FUGACITY (NPA) VERSUS TROPHIC POSITION FOR DI-ISO-BUTYL PHTHALATE (TOP LEFT), DI-N-BUTYL PHTHALATE (TOP RIGHT), BENZYLBUTYL PHTHALATE (MIDDLE), DI-ISO-HEXYL PHTHALATE (C6) (BOTTOM LEFT), AND DI-ISO-HEPTYL PHTHALATE (C7) ( BOTTOM RIGHT). ..............................................105

FIGURE 3.28. CONCENTRATIONS OF DI(2-ETHYLHEXYL) PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM).................................................................................................................................................108

FIGURE 3.29. FUGACITIES (NPA) OF DI(2-ETHYLHEXYL) PHTHALATE IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR. .................109

FIGURE 3.30. CONCENTRATIONS OF DI-N-OCTYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM)......110

FIGURE 3.31. FUGACITIES (NPA) OF DI-N-OCTYL PHTHALATE IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR..............................111

FIGURE 3.32. CONCENTRATIONS OF DI-ISO-OCTYL PHTHALATE (C8) IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM).................................................................................................................................................112

FIGURE 3.33. FUGACITIES (NPA) OF DI-ISO-OCTYL PHTHALATE (C8) IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR. .................113

FIGURE 3.34. CONCENTRATIONS OF DI-N-NONYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM)......114

FIGURE 3.35. FUGACITIES (NPA) OF DI-N-NONYL PHTHALATE IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR..............................115

FIGURE 3.36. CONCENTRATIONS OF DI-ISO-NONYL PHTHALATE (C9) IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM).................................................................................................................................................116

FIGURE 3.37. FUGACITIES (NPA) OF DI-ISO-NONYL PHTHALATE (C9) IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR. .................117

FIGURE 3.38. CONCENTRATIONS OF DI-ISO-DECYL PHTHALATE (C10) IN MARINE BIOTA FROM FALSE CREEK HARBOUR EXPRESSED IN WET WEIGHT (NG/G WET WT.) (TOP) AND LIPID WEIGHT (NG/G LIPID WT.) (BOTTOM).................................................................................................................................................118

FIGURE 3.39. FUGACITIES (NPA) OF DI-ISO-DECYL PHTHALATE (C10) IN MARINE BIOTA (λ), SEDIMENT (ν), AND TOTAL (▬), C18 ( ), AND FREELY DISSOLVED ( ) WATER FROM FALSE CREEK HARBOUR. .................119

FIGURE 3.40. LOG FUGACITY (NPA) VERSUS TROPHIC POSITION FOR DI(2-ETHYLHEXYL) PHTHALATE (TOP LEFT), DI-N-OCTYL PHTHALATE (TOP RIGHT), DI-ISO-OCTYL PHTHALATE (C8) (MIDDLE LEFT) AND DI-N-NONYL PHTHALATE (MIDDLE RIGHT). AND DI-ISO-NONYL PHTHALATE (C9) (BOTTOM LEFT), AND DI-ISO-DECYL PHTHALATE (C10) (BOTTOM RIGHT). ............................................................................................120

FIGURE 3.41. FUGACITY VERSUS TROPHIC POSITION FOR INDIVIDUAL PHTHALATE ESTERS (DMP, DEP, DIBP, AND DBP (TOP), BBP, DEHP, DNOP, AND DNNP (BOTTOM)) IN MARINE BIOTA FROM FALSE CREEK HARBOUR.................................................................................................................................................122

FIGURE 3.42. FUGACITY VERSUS TROPHIC POSITION FOR PHTHALATE ESTER ISOMERIC MIXTURES (C6, C7, C8, C9, AND C10) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ...........................................................123

FIGURE 3.43. CHEMICAL UPTAKE AND ELIMINATION ROUTES IN FISH .............................................................124 FIGURE 3.44. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID

WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DIMETHYL PHTHALATE IN FALSE CREEK MARINE BIOTA. THE BAFS ARE CALCULATED FROM “TOTAL” (▬), “C18” (σ), AND “FREELY DISSOLVED” (○) WATER

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CONCENTRATIONS. THE CEPA BIOACCUMULATION CRITERION ( — ― ), AND OCTANOL-SEAWATER PARTITION COEFFICIENT (⎯) ARE PRESENTED. ERROR BARS REPRESENT ONE STANDARD DEVIATION.....134

FIGURE 3.45. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DIETHYL PHTHALATE IN FALSE CREEK MARINE BIOTA. THE BAFS ARE CALCULATED FROM “TOTAL” (▬), “C18” (σ), AND “FREELY DISSOLVED” (○) WATER CONCENTRATIONS. THE CEPA BIOACCUMULATION CRITERION ( — ― ), AND OCTANOL-SEAWATER PARTITION COEFFICIENT (⎯) ARE PRESENTED. ERROR BARS REPRESENT ONE STANDARD DEVIATION.....135

FIGURE 3.46. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-ISO-BUTYL PHTHALATE IN FALSE CREEK MARINE

BIOTA. THE BAFS ARE CALCULATED FROM “TOTAL” (▬), “C18” (σ), AND “FREELY DISSOLVED” (○) WATER CONCENTRATIONS. THE CEPA BIOACCUMULATION CRITERION ( — ― ), AND OCTANOL-SEAWATER PARTITION COEFFICIENT (⎯) ARE PRESENTED. ERROR BARS REPRESENT ONE STANDARD DEVIATION. ..............................................................................................................................................138

FIGURE 3.47. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-N-BUTYL PHTHALATE IN FALSE CREEK MARINE BIOTA. THE BAFS ARE CALCULATED FROM “TOTAL” (▬), “C18” (σ), AND “FREELY DISSOLVED” (○) WATER CONCENTRATIONS. THE CEPA BIOACCUMULATION CRITERION ( — ― ), AND OCTANOL-SEAWATER PARTITION COEFFICIENT (⎯) ARE PRESENTED. ERROR BARS REPRESENT ONE STANDARD DEVIATION.....139

FIGURE 3.48. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR BUTYLBENZYL PHTHALATE IN FALSE CREEK MARINE


FIGURE 3.49. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-ISO-HEXYL PHTHALATE IN FALSE CREEK MARINE BIOTA. THE BAFS ARE CALCULATED FROM “TOTAL” (▬), “C18” (σ), AND “FREELY DISSOLVED” (○) WATER CONCENTRATIONS. THE CEPA BIOACCUMULATION CRITERION ( — ― ), AND OCTANOL-SEAWATER PARTITION COEFFICIENT (⎯) ARE PRESENTED. ERROR BARS REPRESENT ONE STANDARD DEVIATION.....143

FIGURE 3.50. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-ISO-HEPTYL PHTHALATE IN FALSE CREEK MARINE


FIGURE 3.51. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-2-ETHYLHEXYL PHTHALATE IN FALSE CREEK MARINE


FIGURE 3.52. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-N-OCTYL PHTHALATE IN FALSE CREEK MARINE BIOTA. THE BAFS ARE CALCULATED FROM “TOTAL” (▬), “C18” (σ), AND “FREELY DISSOLVED” (○) WATER CONCENTRATIONS. THE CEPA BIOACCUMULATION CRITERION ( — ― ), AND OCTANOL-SEAWATER PARTITION COEFFICIENT (⎯) ARE PRESENTED. ERROR BARS REPRESENT ONE STANDARD DEVIATION.....149

FIGURE 3.53. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-N-NONYL PHTHALATE IN FALSE CREEK MARINE BIOTA. THE BAFS ARE CALCULATED FROM “TOTAL” (▬), “C18” (σ), AND “FREELY DISSOLVED” (○) WATER CONCENTRATIONS. THE CEPA BIOACCUMULATION CRITERION ( — ― ), AND OCTANOL-SEAWATER PARTITION COEFFICIENT (⎯) ARE PRESENTED. ERROR BARS REPRESENT ONE STANDARD DEVIATION.....150

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FIGURE 3.54. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-ISO-OCTYL (C8) PHTHALATE IN FALSE CREEK MARINE


FIGURE 3.55. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-ISO-NONYL (C9) PHTHALATE IN FALSE CREEK MARINE


FIGURE 3.56. BIOACCUMULATION FACTORS EXPRESSED ON A WET WEIGHT (L/KG WET WT.) (TOP), AND LIPID WEIGHT (L/KG LIPID WT.) (BOTTOM) BASIS FOR DI-ISO-DECYL (C10) PHTHALATE IN FALSE CREEK MARINE


FIGURE 3.57. LIPID BASED BIOACCUMULATION FACTORS (L/KG LIPID WT.) PLOTTED AS LOGARITHMS VERSUS TROPHIC POSITION FOR INDIVIDUAL PHTHALATE ESTERS (DMP, DEP, DIBP, AND DBP (TOP), BBP, DEHP, DNOP, AND DNNP (BOTTOM)) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ..................................157

FIGURE 3.58. LIPID BASED BIOACCUMULATION FACTORS (L/KG LIPID WT.) PLOTTED AS LOGARITHMS VERSUS TROPHIC POSITION FOR PHTHALATE ESTER ISOMERIC MIXTURES (C6, C7, C8, C9, AND C10) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ....................................................................................................158

FIGURE 3.59A. LIPID NORMALIZED BIOACCUMULATION FACTORS, BASED ON “TOTAL” WATER CONCENTRATIONS, OF PHTHALATE ESTERS IN MARINE BIOTA FROM FALSE CREEK HARBOUR VERSUS THE OCTANOL - SEAWATER PARTITION COEFFICIENT. THE CEPA CRITERIA (⎯) AND BAFLIPID = KOW LINE (▬) ARE PRESENTED........................................................................................................................................161

FIGURE 3.59B. LIPID NORMALIZED BIOACCUMULATION FACTORS, BASED ON “TOTAL” WATER CONCENTRATIONS, OF PHTHALATE ESTERS IN MARINE BIOTA FROM FALSE CREEK HARBOUR VERSUS THE OCTANOL - SEAWATER PARTITION COEFFICIENT. THE CEPA CRITERIA (⎯) IS PRESENTED. ..................162

FIGURE 3.60. LIPID NORMALIZED BIOACCUMULATION FACTORS, BASED ON “FREELY DISSOLVED” WATER CONCENTRATIONS, OF PHTHALATE ESTERS IN MARINE BIOTA FROM FALSE CREEK HARBOUR VERSUS THE OCTANOL - SEAWATER PARTITION COEFFICIENT. THE CEPA CRITERIA (⎯) AND BAFLIPID = KOW LINE (▬) ARE PRESENTED........................................................................................................................................165

FIGURE 3.61. BIOTA - SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF DIMETHYL PHTHALATE (TOP), AND DIETHYL PHTHALATE (BOTTOM) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ERROR BARS REPRESENT ONE STANDARD DEVIATION. ..................................................................................................168

FIGURE 3.62. BIOTA - SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF DI-ISO-BUTYL PHTHALATE (TOP), AND DI-N-BUTYL PHTHALATE (BOTTOM) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ERROR BARS REPRESENT ONE STANDARD DEVIATION. .........................................................................................169

FIGURE 3.63. BIOTA - SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF BUTYLBENZYL PHTHALATE (TOP), AND DI(2-ETHYLHEXYL) PHTHALATE (BOTTOM) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ERROR BARS REPRESENT ONE STANDARD DEVIATION. .............................................................................170

FIGURE 3.64. BIOTA - SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF DI-N-OCTYL PHTHALATE (TOP), AND DI-N-NONYL PHTHALATE (BOTTOM) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ERROR BARS REPRESENT ONE STANDARD DEVIATION. .........................................................................................171

FIGURE 3.65. BIOTA - SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF DI-ISO-HEXYL (C6) PHTHALATE (TOP), AND DI-ISO-HEPTYL (C7) PHTHALATE (BOTTOM) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ERROR BARS REPRESENT ONE STANDARD DEVIATION............................................................172

FIGURE 3.66. BIOTA - SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF DI-ISO-OCTYL (C8) PHTHALATE (TOP), AND DI-ISO-NONYL (C9) PHTHALATE (BOTTOM) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ERROR BARS REPRESENT ONE STANDARD DEVIATION............................................................173

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FIGURE 3.67. BIOTA - SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF DI-ISO-OCTYL (C8) PHTHALATE (TOP), AND DI-ISO-NONYL (C9) PHTHALATE (BOTTOM) IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ERROR BARS REPRESENT ONE STANDARD DEVIATION..........................................................1734

FIGURE 3.68 BIOTA - SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) ON A LOGARITHMIC SCALE VERSUS LOG OCTANOL - SEAWATER PARTITION COEFFICIENTS FOR PHTHALATE ESTERS IN BENTHIC MARINE BIOTA FROM FALSE CREEK HARBOUR. ......................................................................................177

Appendix A FIGURE A.1. CHEMICAL STRUCTURES OF SIX PHTHALATE ESTER CONGENERS.................................................199 FIGURE A.2. MEAN WET WEIGHT BIOCONCENTRATION FACTORS (L/KG WET WT.) OF PHTHALATE ESTERS AS A

FUNCTION OF LOG KOW FROM LABORATORY STUDIES REVIEWED BY STAPLES ET AL. 1997A. “PARENT” BCFS REFER TO PARENT PHTHALATE ESTERS. “TOTAL” BCFS REFER TO THE PARENT COMPOUND AND RADIOLABELED METABOLITES..................................................................................................................205

Appendix B FIGURE B.1. SUMMARY OF TROPHIC INTERACTIONS BETWEEN SELECTED MARINE SPECIES IN SOUTHWESTERN

BRITISH COLUMBIA............................................................................................................................263 Appendix D FIGURE D.2.7A. PROCEDURAL BLANK CONCENTRATIONS, MDLS AND SAMPLE CONCENTRATIONS IN 8 BIOTA

BATCHES FOR: DIMETHYL PHTHALATE (TOP LEFT); DIETHYL PHTHALATE (TOP RIGHT); DI-ISO-BUTYL PHTHALATE (BOTTOM LEFT); AND DI-N-BUTYL PHTHALATE (BOTTOM RIGHT). ........................................272

FIGURE D.2.7B. PROCEDURAL BLANK CONCENTRATIONS, MDLS AND SAMPLE CONCENTRATIONS IN 8 BIOTA BATCHES FOR: BENZYLBUTYL PHTHALATE (TOP LEFT); DI-2-ETHYLHEXYL PHTHALATE (TOP RIGHT); DI-N-OCTYL PHTHALATE (BOTTOM LEFT); AND DI-N-NONYL PHTHALATE (BOTTOM RIGHT). ............................273

FIGURE D.2.7C. PROCEDURAL BLANK CONCENTRATIONS, MDLS AND SAMPLE CONCENTRATIONS IN 8 BIOTA BATCHES FOR: DIISOHEXYL PHTHALATE (C6) (TOP LEFT); DIISOHEPTYL PHTHALATE (C7) (TOP RIGHT); DIISOOCTYL PHTHALATE (C8) (BOTTOM LEFT); AND DIISONONYL PHTHALATE (C9) (BOTTOM RIGHT). ...274

FIGURE D.2.8. BLANK-CORRECTED SEDIMENT CONCENTRATIONS IN RELATION TO THE METHOD DETECTION LIMITS (MDLS) (▬) (I.E., 3 STANDARD DEVIATIONS) FOR EACH PHTHALATE ESTER (NG/G DRY WEIGHT). SEDIMENT SAMPLES ARE DIVIDED INTO TWO CATEGORIES: CONCENTRATIONS > MDL ( ), AND CONCENTRATIONS < MDL (ς)..................................................................................................................275

FIGURE D.2.9A. BLANK-CORRECTED BIOTA CONCENTRATIONS IN RELATION THE 10TH, 50TH AND 90TH PERCENTILES OF THE BATCH MDLS FOR: DIMETHYL PHTHALATE (TOP); AND DIETHYL PHTHALATE (BOTTOM). DATA ARE CLASSIFIED INTO THREE CATEGORIES: DATA > MDL ( ), DATA < MDL (ς), AND DATA < MDL, BUT WITHIN THE RANGE OF OTHER DATA ( )...................................................................276

FIGURE D.2.9B. BLANK-CORRECTED BIOTA CONCENTRATIONS IN RELATION THE 10TH, 50TH AND 90TH PERCENTILES OF THE BATCH MDLS FOR: DIISOBUTYL PHTHALATE (TOP); AND DI-N-BUTYL PHTHALATE (BOTTOM). DATA ARE CLASSIFIED INTO THREE CATEGORIES: DATA > MDL ( ), DATA < MDL (ς), AND DATA < MDL, BUT WITHIN THE RANGE OF OTHER DATA ( )...................................................................277

FIGURE D.2.9C. BLANK-CORRECTED BIOTA CONCENTRATIONS IN RELATION THE 10TH, 50TH AND 90TH PERCENTILES OF THE BATCH MDLS FOR: BUTYLBENZYL PHTHALATE (TOP); AND DI-2-ETHYLHEXYL PHTHALATE (BOTTOM). DATA ARE CLASSIFIED INTO THREE CATEGORIES: DATA > MDL ( ), DATA < MDL (ς), AND DATA < MDL, BUT WITHIN THE RANGE OF OTHER DATA ( ). ....................................................278

FIGURE D.2.9D. BLANK-CORRECTED BIOTA CONCENTRATIONS IN RELATION THE 50TH AND 90TH PERCENTILES OF THE BATCH MDLS FOR: DI-N-OCTYL PHTHALATE (TOP); AND DI-N-NONYL PHTHALATE (BOTTOM). DATA ARE CLASSIFIED INTO THREE CATEGORIES: DATA > MDL ( ), DATA < MDL (ς), AND DATA < MDL, BUT WITHIN THE RANGE OF OTHER DATA ( )..................................................................................................279

FIGURE D.2.9E. BLANK-CORRECTED BIOTA CONCENTRATIONS IN RELATION THE 50TH AND 90TH PERCENTILES OF THE BATCH MDLS FOR: DIISOHEXYL PHTHALATE (C6) (TOP); AND DIISOHEPTYL PHTHALATE (C7) (BOTTOM). DATA ARE CLASSIFIED INTO THREE CATEGORIES: DATA > MDL ( ), DATA < MDL (ς), AND DATA < MDL, BUT WITHIN THE RANGE OF OTHER DATA ( )...................................................................280

FIGURE D.2.9F. BLANK-CORRECTED BIOTA CONCENTRATIONS IN RELATION THE 10TH, 50TH AND 90TH PERCENTILES OF THE BATCH MDLS FOR: DIISOHEXYL PHTHALATE (C6) (TOP); AND DIISOHEPTYL PHTHALATE (C7)

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(BOTTOM). DATA ARE CLASSIFIED INTO THREE CATEGORIES: DATA > MDL ( ), DATA < MDL (ς), AND DATA < MDL, BUT WITHIN THE RANGE OF OTHER DATA ( )...................................................................281

FIGURE D.2.9G. BLANK-CORRECTED BIOTA CONCENTRATIONS IN RELATION TO THE MDL FOR DIISODECYL PHTHALATE (C10). CONFIRMED DATA > MDL ( ), DATA ESTIMATED BY THE APPLICATION OF A RATIO ( ), AND DATA < MDL (ς) ARE PRESENTED. ............................................................................................282

FIGURE D.2.10. MEAN RECOVERIES OF INTERNAL STANDARDS IN SPIKED SEDIMENT SAMPLES AND SODIUM SULFATE BLANKS ANALYZED BY GC/MS (A), AND BY LC-ESI/MS (B), AND IN BIOTA SAMPLES AND SODIUM SULFATE BLANKS ANALYZED BY GC/MS (C), AND BY LC-ESI/MS (D). ERROR BARS REPRESENT ONE STANDARD DEVIATION. .....................................................................................................................283

FIGURE D.2.13A. WELL WATER BLANKS, METHOD DETECTION LIMITS (MDLS), AND SEAWATER SAMPLE CONCENTRATIONS (NG/L) IN 4 BATCHES FOR DIMETHYL PHTHALATE (TOP LEFT), DIETHYL PHTHALATE (TOP RIGHT), DI-ISO-BUTYL PHTHALATE (BOTTOM LEFT), AND DI-N-BUTYL PHTHALATE (BOTTOM RIGHT)..................................................................................................................................................................284

FIGURE D.2.13B. WELL WATER BLANKS, METHOD DETECTION LIMITS (MDLS), AND SEAWATER SAMPLE CONCENTRATIONS (NG/L) IN 4 BATCHES FOR BUTYL-BENZYL PHTHALATE (TOP LEFT), DI(2-ETHYLHEXYL) PHTHALATE (TOP RIGHT), DI-N-OCTYL PHTHALATE (BOTTOM LEFT), AND DI-N-NONYL PHTHALATE (BOTTOM RIGHT). .....................................................................................................................................285

FIGURE D.2.13C. WELL WATER BLANKS, METHOD DETECTION LIMITS (MDLS), AND SEAWATER SAMPLE CONCENTRATIONS (NG/L) IN 4 BATCHES FOR DIISOHEXYL PHTHALATE (C6) (TOP LEFT), DIISOHEPTYL PHTHALATE (C7) (TOP RIGHT), DIISOOCTYL PHTHALATE (C8) (BOTTOM LEFT), AND DIISONONYL PHTHALATE (C9) (BOTTOM MIDDLE), AND DIISODECYL PHTHALATE (C10) (BOTTOM RIGHT)...................286

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LIST OF TABLES

Chapter 1 Introduction TABLE 1.1. MOLECULAR WEIGHTS (G/MOL), LE BAS MOLAR VOLUMES (CM3/MOL), AQUEOUS SOLUBILITIES

(MG/L), AND LOG OCTANOL – SEAWATER PARTITION COEFFICIENTS1 OF 13 SELECTED PHTHALATE ESTERS, AS REPORTED IN COUSINS & MACKAY (2000). ..............................................................................3

Chapter 2 Methods TABLE 2.1. TROPHIC CATEGORY, COMMON NAME, LATIN NAME, SAMPLE SIZE, MEAN LENGTH (CM), MEAN

WET WEIGHT (G) AND SAMPLING METHODS FOR EIGHTEEN MARINE ORGANISMS COLLECTED FROM FALSE CREEK HARBOUR, VANCOUVER, BRITISH COLUMBIA.....................................................................14

TABLE 2.2. COMPOSITION OF PHTHALATE ESTER (PE) AND POLYCHLORINATED BIPHENYL (PCB) STANDARDS, AND AMOUNTS (NG) ADDED TO SEDIMENT AND BIOTA SAMPLES. .............................................................20

TABLE 2.3. MEAN PERCENTAGE OF C10 IN THE TOTAL PEAK (C10 + INTERFERENCE), THE COEFFICIENT OF VARIATION (%), SAMPLE SIZE (N), AND NUMBER OF SAMPLES WITH NON-DETECT C10 CONCENTRATIONS FOR BIOTA SAMPLES CONFIRMED USING LC/ESI-MS/MS.........................................................................31

TABLE 2.4. (SEE APPENDIX D LISTINGS) TABLE 2.5. MEAN CONCENTRATIONS (NG/G) OF PHTHALATE ESTERS IN SODIUM SULFATE PROCEDURAL BLANKS

FOR BIOTA AND SEDIMENT ANALYSIS, 3 STANDARD DEVIATIONS OF THE BLANKS, AND METHOD DETECTION LIMITS DEFINED AS THE MEAN BLANK CONCENTRATION + 3 STANDARD DEVIATIONS. ........35

TABLE 2.6. MEAN (+/- STANDARD DEVIATION) RECOVERIES OF INTERNAL STANDARDS FROM SPIKED FALSE CREEK SEDIMENT AND BIOTA SAMPLES AND SODIUM SULFATE BLANKS (%) ...........................................36

TABLE 2.7. MEAN (+/- STANDARD DEVIATION) INTERNAL STANDARD RECOVERIES FOR FALSE CREEK SEAWATER SAMPLES AND WELL WATER BLANKS (%) ..............................................................................37

TABLE 2.8. (SEE APPENDIX D LISTINGS) TABLE 2.9. MINIMUM AND MAXIMUM METHOD DETECTION LIMITS (MDLS) IN NG/L AMONG 4 BATCHES OF

WATER SAMPLES. MDLS REPRESENT THE MEAN PE CONCENTRATION IN THE BATCH BLANKS + 3 STANDARD DEVIATIONS..............................................................................................................................41

TABLE 2.10. NUMBER OF SAMPLES WITH DETECTABLE CONCENTRATIONS ABOVE THE METHOD DETECTION LIMITS (MDLS)..........................................................................................................................................44

TABLE 2.11. MEAN LIPID CONTENTS (%, G LIPID/ G WET TISSUE) AND ORGANIC CARBON CONTENTS (% DRY WEIGHT AND % WET WEIGHT) (± STANDARD DEVIATION) IN BIOTA TISSUES THAT WERE ANALYZED FOR PHTHALATE ESTERS. ..................................................................................................................................49

TABLE 2.12. LATIN NAME, COMMON NAME, TROPHIC POSITION, PREY ITEMS AND THEIR DIETARY PROPORTIONS, AND PREDATORS OF KEY RESIDENT MARINE SPECIES IN THE GEORGIA BASIN ECOSYSTEM....................................................................................................................................................................53

TABLE 2.13. SUMMARY OF TROPHIC POSITIONS FOR SPECIES COLLECTED FROM FALSE CREEK .........................56 Chapter 3 Results & Discussion TABLE 3.1. - 3.4. (SEE APPENDIX F LISTINGS) TABLE 3.5. MEAN FRACTIONS OF INTERNAL STANDARDS ON THE GLASS FIBRE FILTER (GF) AND C18

EXTRACTION DISKS (C18) IN WELL WATER BLANKS AND FALSE CREEK SEAWATER SAMPLES (%). .........67 TABLE 3.6. MEAN OBSERVED FRACTIONS (%) (± STANDARD DEVIATIONS) OF SEAWATER BORNE PHTHALATE

ESTERS ON THE GLASS FIBRE FILTER (GF) AND C18 EXTRACTION DISKS (C18) IN WELL WATER BLANKS AND FALSE CREEK SEAWATER SAMPLES. ..................................................................................................71

TABLE 3.7. MEAN FRACTIONS (%) OF PHTHALATE ESTERS BOUND TO LARGE AND SMALL DIAMETER SUSPENDED MATTER (LDSM, SDSM) AND FREELY DISSOLVED IN FALSE CREEK HARBOUR SEAWATER, DETERMINED FROM THE 3-PHASE SORPTION MODEL (EQN 3.5).................................................................72

TABLE 3.8. (SEE APPENDIX F LISTINGS) TABLE 3.9. OBSERVED AND PREDICTED SEDIMENT-WATER PARTITION COEFFICIENTS (OBS KOC AND PRED

KOC, L/KG OC) BASED ON THE FREELY DISSOLVED WATER CONCENTRATION, AND THE RATIO BETWEEN THE OBSERVED AND PREDICTED PARTITION COEFFICIENTS. ......................................................................81

TABLE 3.10 - 3.16. (SEE APPENDIX F LISTINGS) TABLE 3.17. STATISTICAL RESULTS OF REGRESSION: FUGACITY VERSUS TROPHIC POSITION (TP) ..................121 TABLE 3.18 - 3.30. (SEE APPENDIX F LISTINGS)

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TABLE 3.31. STATISTICAL RESULTS OF REGRESSION: LOG BAF (L/KG LIPID WT.) VERSUS TROPHIC POSITION 156 Appendix A TABLE A.1. PHTHALATE ESTER (PE) END USE PRODUCTS1...............................................................................196 TABLE A.2. PRODUCTION (PRDN), IMPORTS (IMP), AND CONSUMPTION (CONS) OF PHTHALATE ESTERS BY

REGION (KTONNES PER YEAR) (PARKERTON AND KONKEL 2000). ...........................................................197 TABLE A.3. PHYSIOCHEMICAL PROPERTIES OF 13 SELECTED PHTHALATE ESTERS AS REPORTED IN COUSINS &

MACKAY (2000): MOLECULAR WEIGHT (G/MOL), LE BAS MOLAR VOLUME (CM3/MOL), AQUEOUS SOLUBILITY (MG/L), VAPOUR PRESSURE (PA), LOG OCTANOL – SEAWATER PARTITION COEFFICIENT, HENRY’S LAW CONSTANT (PA-M3/MOL), AND FUGACITY CAPACITY IN WATER (MOL/ PA-M3)................200

TABLE A.4. “TOTAL1” AND “PARENT2” BICONCENTRATION FACTORS (L/KG WET WT.) AND WATER EXPOSURE CONCENTRATIONS (UG/L), FROM REPORTED PHTHALATE ESTER BIOCONCENTRATION STUDIES, EXPRESSED AS THE MEAN AND/OR (RANGE) FOR EACH TAXA. ................................................................202

Appendix B TABLE B.1 SPECIES NAME, PREY ITEMS, DIETARY PROPORTIONS, AND PREDATORS FOR SELECTED RESIDENT

MARINE SPECIES IN SOUTHWESTERN BRITISH COLUMBIA .................................................................259 TABLE B.2. SUMMARY OF SPAWNING AND REPRODUCTIVE SCHEDULES OF SELECTED MARINE SPECIES IN

SOUTHWESTERN BRITISH COLUMBIA.................................................................................................265 Appendix C TABLE C.2.1. DIETARY COMPOSITION AND TROPHIC POSITIONS OF 21 PREDATOR SPECIES1 / ORGANISMS IN THE

GEORGIA BASIN ECOSYSTEM. PREY SPECIES, AND THEIR CORRESPONDING TROPHIC POSITIONS AND DIETARY PROPORTIONS ARE IDENTIFIED............................................................................................268

TABLE C.2.2. IDENTIFICATION OF THE PREDATOR SPECIES PRESENTED IN TABLE C.2.1 (DIETARY MATRIX) AND THEIR CALCULATED TROPHIC POSITIONS. SPECIES / ORGANISMS IN BOLD TYPE ARE REPORTED ON IN THE CURRENT STUDY.................................................................................................................................269

Appendix D TABLE D.2.4. MEAN PHTHALATE ESTER CONCENTRATIONS (NG/G) IN SODIUM SULFATE PROCEDURAL BLANKS

FOR BIOTA AND SEDIMENT ANALYSIS AND (LOWER – UPPER STANDARD DEVIATIONS)..........................271 TABLE D.2.8. GEOMETRIC MEAN CONCENTRATIONS (NG/L) OF PHTHALATE ESTERS IN 12 WELL WATER

BLANKS AND (LOWER – UPPER STANDARD DEVIATIONS)........................................................................271 Appendix E TABLE E.2.1. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL

PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN SODIUM SULFATE BLANKS USED IN SEDIMENT ANALYSIS. ...................................................................................................289

TABLE E.2.2. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR SEDIMENT SAMPLES. ...............................................................................................................289

TABLE E.2.3. RESULTS OF SHAPIRO-WILK NORMALITY TEST ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN WELL WATER BLANKS....................290

TABLE E.2.4. RESULTS OF SHAPIRO-WILK NORMALITY TEST ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK SEAWATER SAMPLES.290

TABLE E.2.5. RESULTS OF KOLMOGOROV-SMIRNOV NORMALITY TEST ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN SODIUM SULFATE BLANKS USED IN THE BIOTA ANALYSIS......................................................................................................................................291

TABLE E.2.6. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR PLANKTON SAMPLES. ..............................................................................................................291

TABLE E.2.7. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR GREEN ALGAE SAMPLES. ........................................................................................................292

xix

TABLE E.2.8. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR GEODUCK CLAM SAMPLES......................................................................................................292

TABLE E.2.9. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR BLUE MUSSEL SAMPLES..........................................................................................................293

TABLE E.2.10. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR PACIFIC OYSTER SAMPLES. .....................................................................................................293

TABLE E.2.11. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR DUNGENESS CRAB SAMPLES. ..................................................................................................294

TABLE E.2.12. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR MINNOW SAMPLES. .................................................................................................................294

TABLE E.2.13. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR STRIPED SEAPERCH SAMPLES..................................................................................................295

TABLE E.2.14. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR PACIFIC STAGHORN SCULPIN SAMPLES. ..................................................................................295

TABLE E.2.15. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR WHITESPOTTED GREENLING SAMPLES. ...................................................................................296

TABLE E.2.16. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR SPINY DOGFISH LIVER SAMPLES. ............................................................................................296

TABLE E.2.17. RESULTS OF KOLMOGOROV-SMIRNOV AND SHAPIRO-WILK NORMALITY TESTS ON ORIGINAL PHTHALATE ESTER CONCENTRATIONS AND LOG TRANSFORMED CONCENTRATIONS IN FALSE CREEK HARBOUR SPINY DOGFISH MUSCLE SAMPLES. ........................................................................................297

TABLE E.3.1A. RESULTS OF ANOVA TESTS FOR DIFFERENCES IN THE ORGANIC CARBON NORMALIZED CONCENTRATIONS (NG/G OC) OF PHTHALATE ESTERS IN THE SEDIMENTS OF FOUR FALSE CREEK HARBOUR SAMPLING STATIONS...............................................................................................................299

TABLE E.3.1B. TUKEY TEST RESULT MATRIX FOR DIFFERENCES IN CONCENTRATIONS (NG/G OC) OF PHTHALATE ESTERS IN SEDIMENTS FROM FOUR SAMPLING STATIONS IN FALSE CREEK HARBOUR.........299

TABLE E.3.2A. RESULTS OF ANOVA TESTS FOR DIFFERENCES IN THE LIPID NORMALIZED CONCENTRATIONS (NG/G LIPID) OF PHTHALATE ESTERS IN PLANKTON SAMPLES FROM THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR. ....................................................................................................................................300

TABLE E.3.2B. TUKEY TEST RESULT MATRIX FOR DIFFERENCES IN CONCENTRATION (NG/G LIPID) OF PHTHALATE ESTERS IN PLANKTON SAMPLES FROM THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR.................................................................................................................................................300

TABLE E.3.3A. RESULTS OF ANOVA TESTS FOR DIFFERENCES IN THE LIPID NORMALIZED CONCENTRATIONS (NG/G LIPID) OF PHTHALATE ESTERS IN GREEN ALGAE SAMPLES FROM THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR. .........................................................................................................................301

TABLE E.3.3B. TUKEY TEST RESULT MATRIX FOR DIFFERENCES IN CONCENTRATION (NG/G LIPID) OF INDIVIDUAL PHTHALATE ESTERS IN GREEN ALGAE SAMPLES FROM THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR. ....................................................................................................................................301

TABLE E.3.4A. RESULTS OF ANOVA TESTS AND TWO-TAILED T-TESTS FOR DIFFERENCES IN THE LIPID NORMALIZED CONCENTRATIONS (NG/G LIPID) OF PHTHALATE ESTERS IN GEODUCK CLAMS SAMPLES FROM TWO OR THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR. ................................................302

TABLE E.3.4B. TUKEY TEST / T-TEST RESULT MATRIX FOR DIFFERENCES IN CONCENTRATIONS (NG/G LIPID) OF PHTHALATE ESTERS IN GEODUCK CLAM SAMPLES FROM THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR.................................................................................................................................................302

TABLE E.3.5A. RESULTS OF ANOVA TESTS FOR DIFFERENCES IN THE LIPID NORMALIZED CONCENTRATIONS (NG/G LIPID) OF PHTHALATE ESTERS IN PACIFIC OYSTER SAMPLES FROM THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR. .........................................................................................................................303

xx

TABLE E.3.5B. TUKEY TEST RESULT MATRIX FOR DIFFERENCES IN CONCENTRATION (NG/G LIPID) OF PHTHALATE ESTERS IN PACIFIC OYSTER SAMPLES FROM THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR.................................................................................................................................................303

TABLE E.3.6. RESULTS OF ANOVA TESTS FOR DIFFERENCES IN THE LIPID NORMALIZED CONCENTRATIONS (NG/G LIPID) OF PHTHALATE ESTERS IN BLUE MUSSEL SAMPLES FROM THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR. .........................................................................................................................304

TABLE E.3.7. RESULTS OF ANOVA TESTS FOR DIFFERENCES IN THE LIPID NORMALIZED CONCENTRATIONS (NG/G LIPID) OF PHTHALATE ESTERS IN STRIPED SEAPERCH SAMPLES FROM THREE SAMPLING STATIONS IN FALSE CREEK HARBOUR. .....................................................................................................................304

TABLE E.3.8. RESULTS OF ANOVA AND TUKEY TESTS ON DIFFERENCES IN THE CHEMICAL FUGACITIES BETWEEN THE FREELY DISSOLVED WATER FRACTION AND THE SEDIMENT OR MARINE BIOTA SPECIES. LEVEL OF SIGNIFICANCE IS 0.05 (* VALUES INDICATE Q<0.10). ..............................................................306

TABLE E.3.9. RESULTS OF ANOVA AND TUKEY TESTS ON DIFFERENCES IN THE CHEMICAL FUGACITIES BETWEEN THE SEDIMENT AND MARINE BIOTA SPECIES. LEVEL OF SIGNIFICANCE IS 0.05 (* VALUES INDICATE Q<0.10). ...................................................................................................................................307

TABLE E.3.10. RESULTS OF ANOVA AND TUKEY TESTS ON DIFFERENCES IN THE CHEMICAL FUGACITIES BETWEEN THE DOGFISH (MUSCLE) AND OTHER MARINE BIOTA SPECIES. LEVEL OF SIGNIFICANCE IS 0.05 (* VALUES INDICATE Q<0.10). .................................................................................................................308

TABLE E.3.11. RESULTS OF ANOVA AND TUKEY TESTS ON DIFFERENCES IN THE CHEMICAL FUGACITIES BETWEEN THE DOGFISH (LIVER) AND OTHER MARINE BIOTA SPECIES. LEVEL OF SIGNIFICANCE IS 0.05 (* VALUES INDICATE Q<0.10). .....................................................................................................................309

Appendix F TABLE F.3.1. MEAN CONCENTRATIONS (NG/G) AND (LOWER - UPPER STANDARD DEVIATIONS), EXPRESSED IN

DRY WEIGHTS (NG/G DRY WT.) AND ORGANIC CARBON WEIGHTS (NG/G OC), AND CORRESPONDING FUGACITIES (PA), OF PHTHALATE ESTERS IN FALSE CREEK HARBOUR SEDIMENTS.................................311

TABLE F.3.2.A. REPORTED UPPER AND LOWER CONCENTRATION RANGES OR MEAN CONCENTRATIONS (NG/G DRY WEIGHT) OF PHTHALATE ESTERS IN SEDIMENTS FOR VARIOUS LOCATIONS IN THE WORLD.............313

TABLE F.3.2.B. REPORTED UPPER AND LOWER CONCENTRATION RANGES OR MEANS (NG/G ORGANIC CARBON) OF PHTHALATE ESTERS IN SEDIMENTS FOR VARIOUS LOCATIONS IN THE WORLD. ..................................314

TABLE F.3.3. MEAN TOTAL CONCENTRATIONS (NG/L) AND (LOWER - UPPER STANDARD DEVIATIONS) OF PHTHALATE ESTERS IN FALSE CREEK HARBOUR SEAWATER, AND NUMBER OF SAMPLES FOR WHICH WATER CONCENTRATION EXCEEDED THE MDL (N). ...............................................................................315

TABLE F.3.8A. MEAN “TOTAL”, “C18”, AND “FREELY DISSOLVED” CONCENTRATIONS (± STANDARD DEVIATION, NG/L) OF PHTHALATE ESTERS IN FALSE CREEK HARBOUR SEAWATER. ...............................315

TABLE F.3.8B. MEAN “TOTAL”, “C18”, AND “FREELY DISSOLVED” FUGACITIES (± STANDARD DEVIATION, PA) OF PHTHALATE ESTERS IN FALSE CREEK HARBOUR SEAWATER. .............................................................316

TABLE F.3.4. REPORTED UPPER AND LOWER CONCENTRATION RANGES OR MEANS (NG/L) OF PHTHALATE ESTERS IN MARINE WATER AND FRESHWATER FOR VARIOUS LOCATIONS IN THE WORLD......................317

TABLE F.3.10. MEAN WET WEIGHT CONCENTRATIONS (NG/G WET WT.) AND LOWER - UPPER STANDARD DEVIATIONS OF INDIVIDUAL PHTHALATE ESTERS IN MARINE BIOTA FROM FALSE CREEK HARBOUR .....318

TABLE F.3.11. MEAN WET WEIGHT CONCENTRATIONS (NG/G WET WT.) AND LOWER - UPPER STANDARD DEVIATIONS OF PHTHALATE ESTER ISOMERIC MIXTURES IN MARINE BIOTA FROM FALSE CREEK HARBOUR.................................................................................................................................................320

TABLE F.3.12. MEAN LIPID WEIGHT CONCENTRATIONS (NG/G LIPID) AND LOWER - UPPER STANDARD DEVIATIONS OF INDIVIDUAL PHTHALATE ESTERS IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ....322

TABLE F.3.13. MEAN LIPID WEIGHT CONCENTRATIONS (NG/G LIPID) AND LOWER - UPPER STANDARD DEVIATIONS OF PHTHALATE ESTER ISOMERIC MIXTURES IN MARINE BIOTA FROM FALSE CREEK HARBOUR.................................................................................................................................................324

TABLE F.3.14. MEAN FUGACITIES (PA) AND LOWER - UPPER STANDARD DEVIATIONS OF INDIVIDUAL PHTHALATE ESTERS IN MARINE BIOTA FROM FALSE CREEK HARBOUR. .................................................326

TABLE F.3.15. MEAN FUGACITIES (PA) AND LOWER - UPPER STANDARD DEVIATIONS OF PHTHALATE ESTER ISOMERIC MIXTURES IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ................................................328

TABLE F.3.16. REPORTED LOWER AND UPPER CONCENTRATION RANGES OR SINGLE OBSERVATIONS (NG/G WET WEIGHT) OF PHTHALATE ESTERS IN BIOLOGICAL SAMPLES FROM VARIOUS LOCATIONS IN THE WORLD.331

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TABLE F.3.18. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DIMETHYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................333

TABLE F.3.19. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DIETHYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................334

TABLE F.3.20. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-ISO-BUTYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................335

TABLE F.3.21. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-N-BUTYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................336

TABLE F.3.22. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF BUTYLBENZYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................337

TABLE F.3.23. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-(2-ETHYLHEXYL) PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................338

TABLE F.3.24. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-N-OCTYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................339

TABLE F.3.25. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-N-NONYL PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................340

TABLE F.3.26. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-IOS-HEXYL (C6) PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................341

TABLE F.3.27. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-IOS-HEPTYL (C7) PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................342

TABLE F.3.28. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-ISO-OCTYL (C8) PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................343

TABLE F.3.29. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-ISO-NONYL (C9) PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................344

TABLE F.3.30. MEAN WET WEIGHT (L/KG WET WT.) AND LIPID WEIGHT (L/KG LIPID) BIOACCUMULATION FACTORS AND (LOWER – UPPER STANDARD DEVIATIONS) OF DI-ISO-DECYL (C10) PHTHALATE IN MARINE BIOTA FROM FALSE CREEK HARBOUR USING “TOTAL”, “C18” AND “FREELY DISSOLVED” WATER CONCENTRATIONS, EXPRESSED IN LOGARITHMS......................................................................................345

TABLE F.3.32. BIOTA – SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF DIMETHYL, DIETHYL, DI-ISO-BUTYL, AND DI-N-BUTYL PHTHALATE ESTERS IN MARINE BIOTA FROM FALSE CREEK HARBOUR....346

xxii

TABLE F.3.33. BIOTA – SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF BUTYLBENZYL, DI(2-ETHYLHEXYL), DI-N-OCTYL, AND DI-N-NONYL PHTHALATE ESTERS IN MARINE BIOTA FROM FALSE CREEK HARBOUR.................................................................................................................................................347

TABLE F.3.34. BIOTA – SEDIMENT ACCUMULATION FACTORS (KG OC / KG LIPID) OF DI-ISO-HEXYL (C6), DI-ISO-HEPTYL (C7) DI-ISO-OCTYL (C8), DI-ISO-NONYL (C9), AND DI-ISO-DECYL (C10) PHTHALATE ESTER ISOMERIC MIXTURES IN MARINE BIOTA FROM FALSE CREEK HARBOUR. ................................................348

Appendix G TABLE G.1. STATION LOCATION, SAMPLE ID, SAMPLING DATE, ORGANIC CARBON CONTENT (TOC), INTERNAL

STANDARD RECOVERY FOR GC-MS AND LC-ESI/MS ANALYSIS, AND BLANK AND RECOVERY CORRECTED PHTHALATE ESTER CONCENTRATIONS (NG/G DRY WT.) IN SEDIMENT SAMPLES FROM FALSE CREEK HARBOUR. ..............................................................................................................................350

TABLE G.2. STATION LOCATION, SAMPLE ID, SAMPLING DATE, CONCENTRATION OF LARGE AND SMALL DIAMETER SUSPENDED MATTER (LDSM & SDSM) (MG/L) IN THE SEAWATER, INTERNAL STANDARD RECOVERY FOR GC-MS AND LC-ESI/MS ANALYSIS, AND BLANK AND RECOVERY CORRECTED PHTHALATE ESTER CONCENTRATIONS (NG/L) IN SEAWATER SAMPLES FROM FALSE CREEK HARBOUR.

...........................................................................................................................................................351 TABLE G.3. SPECIES, LATIN NAME, SAMPLE ID1, SAMPLING DATE, LIPID CONTENT (% WET WT.), TOTAL

ORGANIC CARBON CONTENT (TOC) (% DRY WT.), INTERNAL STANDARD RECOVERY FOR GC-MS AND LC-ESI/MS ANALYSIS, AND BLANK AND RECOVERY CORRECTED PHTHALATE ESTER CONCENTRATIONS (NG/G WET WT.) IN BIOTA SAMPLES FROM FALSE CREEK HARBOUR..................................................352

xxiii

DEFINITIONS 1) Octanol-Water Partition Coefficient “KOW” refers to the ratio of the concentration of

a chemical in octanol (a surrogate for lipids) to its concentration in water, at

equilibrium. It is a measure of the hydrophobicity of the chemical, and indicates the

potential of a chemical to partition into the lipid tissue of organisms, and bioconcentrate

(Mackay 1991, Connell 1990).

2) Fugacity (f) is equivalent to chemical activity. It is the pressure a chemical exerts in a

particular medium and is expressed in units of Pascal. It is a function of the

concentration of a chemical in a medium (C in units of mol/m3), and the fugacity

capacity of that medium for that particular chemical (Z in units of Pa ⋅ m3/mol), i.e.,

f = C / Z (Mackay 1991).

3) Fugacity Capacity (Z) is a measure of the solubility of a particular chemical in a

particular medium. It is defined as the amount of chemical that can be absorbed in a

medium to increase the partial pressure in that medium by 1 Pascal, and is expressed in

units of Pa⋅m3/mol (Mackay 1991).

4) Equilibrium Partitioning refers to a situation of chemical equilibrium, where the

fugacities of a chemical in two or more media in the (eco)system are equal (Mackay

1982, 1991, Gobas et al. 1993).

5) Bioconcentration refers to the process of accumulation of a chemical substance in an

organism, resulting from exposure of the organism to the substance in the water,

typically under laboratory conditions. The driving force of bioconcentration is

equilibrium partitioning of a substance between the organism and ambient water

(Mackay 1982, Clark et al. 1990, Gobas et al. 1993).

6) Bioconcentration Factor (BCF) is the ratio of the chemical concentration in the

organism to that in the water, under water-only exposure conditions, and may be

xxiv

expressed in units of L/kg wet weight of L/kg lipid weight (Mackay 1982, Connell

1990).

7) Biomagnification refers to a process of accumulation of a chemical substance in an

organism due to dietary exposure and absorption of the chemical. The driving force of

biomagnification is a fugacity gradient in the gastrointestinal tract of an organism,

where fGIT > forganism (Gobas et al. 1993, Gobas et al. 1999).

8) Bioaccumulation refers to the process of accumulation of a chemical substance in an

organism, resulting from chemical uptake through all routes of exposure (e.g. dietary

absorption, transport across the respiratory surface, dermal absorption, and inhalation),

and typically takes place under field conditions (Gobas and Morrison 1998, Clark et al.

1990).

9) Bioaccumulation Factor (BAF) is the ratio of the chemical concentration in the

organism to that in the water, as the result of all routes of chemical exposure (e.g., water

and diet), and is may be expressed in units of L/kg wet weight (Connell 1990).

10) Biota – Sediment Accumulation Factor (BSAF) is the ratio of the chemical

concentration in the organism to that in the sediment. When normalized to organic

carbon content in the sediment and lipid content in the organism, it is expressed in units

of kg OC/ kg lipid (Morrison et al. 1996).

11) Biomagnification in the food chain refers to the process of chemical accumulation in

the food chain, where the chemical fugacities in the organisms increase at each trophic

level, due to biomagnification (dietary uptake) (Clark et al. 1990, Gobas 1993, Gobas et

al. 1993, Gobas et al. 1999).

12) Trophic Dilution refers to a process where the chemical fugacities in organisms

decrease at higher trophic levels in the food chain, generally due to metabolic

transformation of the chemical within organisms.

1

1. INTRODUCTION

Phthalates esters (PEs, Figure 1.1) are widely used as plasticizers in polyvinyl

chloride (PVC), polyvinyl acetates, cellulosics and polyurethanes. Additionally, they

have several other non-plasticizer applications including use in lubricating oils,

automobile parts, paints, glues, insect repellents, photographic films, perfumes, and food

packaging (e.g. paperboard and cardboard) (Pierce et al. 1980). Current North American

production of phthalate esters is approximately 650,000 tonnes/year, while the global

production level is approximately 4,300,000 tonnes/year (Furtmann 1996, Parkerton and

Konkel 2000). Industrial formulations of phthalate esters include a large number of

congeners, which vary in alkyl chain length and branching and range in molecular weight

from 194 to over 600 g/mol. Phthalate esters are hydrophobic chemicals with octanol-

seawater partition coefficients (KOW’s) ranging between 101.8 for dimethyl phthalate to

1010.6 for diisodecyl phthalate (Table 1.1, Staples et al. 1997a, Cousins and Mackay

2000). Due to their hydrophobicity, phthalate esters are often assumed to have a high

potential to bioconcentrate and bioaccumulate in biological organisms. A large number

of laboratory studies have investigated the bioconcentration of phthalate esters in various

fish species, algae, macrophytes, polychaetes, molluscs, crustaceans and aquatic insects

(Staples et al. 1997a). These studies indicate that phthalate esters may bioconcentrate in

several taxa. However, quantification of reliable bioconcentration factors (BCFs) in most

reported studies has been problematic due to several experimental artifacts, including the

use of radiolabeled compounds, and conducting experiments at exposure concentrations

in excess of the aqueous solubility of the test substance. Hence, the reported BCF values

2

may not accurately characterize the bioaccumulation potential of phthalate esters. In fish

and certain invertebrate species, the BCFs that have been reported for certain phthalate

ester congeners are less than expected from their Kow. The lower than expected BCFs of

these substances have been linked to an organism’s ability to metabolize phthalate ester

congeners. Bioavailability in the water phase has also been identified as another

important factor affecting the measured BCFs in laboratory experiments. However, its

role has never been determined or quantified. In terms of the environmental fate of

phthalate esters, it has been suggested that these substances do not bioaccumulate in the

food chain (Staples et al. 1997a, Macek et al. 1979, Belise et al. 1975). However, field

studies to confirm this do not exist. Additionally, the majority of the data collected on

the bioaccumulation of phthalate esters refers to a small number of congeners. Data on

DEHP are abundant, whereas similar data for other congeners are sparse or non-existent.

Figure 1.1. Generalized Phthalate Ester Chemical Structure

O

O

C

C R′

R

O

O

3

Table 1.1. Molecular Weights (g/mol), Le Bas Molar Volumes (cm3/mol), Aqueous

Solubilities (mg/L), and Log Octanol – Seawater Partition Coefficients1 of 13

Selected Phthalate Esters, as Reported in Cousins & Mackay (2000).

Phthalate Ester Molecular

Weight (g/mol)

Le Bas Molar Volume

(cm3/mol)

AQ Solubility (mg/L)

Salinity Corrected Log Kow1

Dimethyl DMP 194.2 206.4 5220 1.80 Diethyl DEP 222.2 254.0 591 2.77

Diisobutyl DiBP 278.4 342.8 9.9 4.58 Di-n-butyl DnBP 278.4 342.8 9.9 4.58

Butyl Benzyl BBP 312.4 364.8 3.8 5.03 Di(2-ethylhexyl) DEHP 390.6 520.4 2.5 ·10-3 8.20

Di-n-octyl DnOP 390.6 520.4 2.5 ·10-3 8.20 Di-n-nonyl DnNP 418.6 564.8 6.0 ·10-4 9.11 Diisohexyl C6 334.4 431.6 5.0 ·10-2 6.69 Diisoheptyl C7 362.4 476.0 1.1 ·10-2 7.44 Diisooctyl C8 390.6 520.4 2.5 ·10-3 8.20 Diisononyl C9 418.6 564.8 6.0 ·10-4 9.11 Diisodecyl C10 446.7 609.2 1.3 ·10-4 10.6

1 See Appendix A for calculation of the salinity corrected KOW.

The degree of bioaccumulation of phthalate esters is of considerable legal and

regulatory importance. Both international legislation (UNECE Convention on Long on

Long Range Transboundary Air Pollution (1979) and its Protocol Persistent Organic

Pollutants, 1998), as well as domestic legislation in Canada (Canadian Environmental

Protection Act, 1999), the US (Toxic Substances Control Act, 1976; US EPA, 1998), and

Europe (UNECE, 1998) include provisions for eliminating substances from commerce

that are “bioaccumulative”, “persistent” and “toxic”. Under the Canadian Environmental

Protection Act (CEPA), chemicals are considered “bioaccumulative” if they exhibit

bioaccumulation factors (BAFs) or, alternatively, bioconcentration factors (BCFs) greater

than 5,000 L/kg wet weight or 100,000 L/kg lipid weight in aquatic organisms. In the

absence of a BAF or BCF, substances with octanol-water partition coefficients (KOW’s)

4

greater than 105 are classified as bioaccumulative. While certain phthalate esters meet

this hydrophobic criterion (Table 1.1), there is no evidence from field studies to support

categorizing the substances as bioaccumulative.

Since phthalate esters are hydrophobic chemicals, the research hypothesis is that

they will biomagnify in the food web (see preface pages for “definitions”).

Biomagnification occurs when organisms accumulate contaminants through dietary

sources, and are generally unable to metabolise the contaminants (Gobas et al. 1993,

Clark et al. 1990, and Gobas 1993). Biomagnification in the food web is defined to

occur if the fugacities of the test chemical increase at higher trophic levels in the food

chain, i.e., fpredator > fprey (Figure 1.2). Trophic dilution is an alternative hypothesis. It is

defined to occur if fugacities decline with increasing trophic position, i.e., fpredator < fprey

(Figure 1.2). The lack of a fugacity increase or decrease in the food-chain (i.e., the null

hypothesis), where the fugacities in the predator and prey are equal to those in the water,

indicates that equilibrium partitioning of a substance between the lipid tissue of

organisms and the water is occurring, i.e., fpredator ≅ fprey ≅ fwater (Figure 1.2, Mackay 1982,

1991, Gobas et al. 1993).

5

Food Web Biomagnification Trophic Dilution Equilibrium Partitioning fwater < fbiota fwater > fbiota fwater ≅ fbiota

fprey1 < fprey2 < fpredator fprey1 > fprey2 > fpredator fprey1 ≅ fprey2 ≅ fpredator Figure 1.2. Fugacity “f” Analysis of Alternative Hypotheses of Chemical Movement

through a Food Chain.

The main purpose of this study is to determine the degree of food web

bioaccumulation of phthalate esters. To test the alternative hypotheses of food web

biomagnification versus trophic dilution versus equilibrium partitioning, a food web

bioaccumulation field study was conducted in False Creek Harbour, Vancouver, British

Columbia, Canada. The bioaccumulation behaviour of eight individual phthalate ester

congeners (dimethyl (DMP), diethyl (DEP), di-iso-butyl (DiBP), di-n-butyl (DBP), butyl

benzyl (BBP), di 2-ethylhexyl (DEHP), di-n-octyl (DnOP), and di-n-nonyl (DNP)), and

five isomeric mixtures (di-iso-hexyl (C6), di-iso-heptyl (C7), di-iso-octyl (C8), di-iso-

nonyl (C9), and di-iso-decyl (C10)) was investigated in this study (Table 1.1 and A.3 in

Appendix A). The author conducted a review of the literature on phthalate esters, related

to their production and use, chemical properties, bioaccumulation/ bioconcentration, and

fsediment

fpredator

fprey1

fwater

fprey2

fpredator

fprey1

fwater

fprey2

Biomagnification Trophic Dilution Equilibrium Partitioning

OO O

OO O

fpredator

fprey1

fwater

fprey2

OO O

6

ecological effects, which is presented in Appendix A. To ascertain the trophodynamic

interactions and life history strategies of many of the key resident species in the

southwestern British Columbia marine ecosystem, the author conducted an analysis of the

relevant fisheries literature (Appendix B). Based on this information, a trophic position

model was applied to quantify the positions of the species in the food web (Vander

Zanden and Rasmussen 1996, Section 2.5.5 and Appendix C). These trophic positions

were used as the basis for assessing chemical movement in the food web. In addition to

the scientific aspects of this research, the results are applied in a management context by

comparing the observed bioaccumulation factors (BAFs) to the CEPA (1999)

bioaccumulation criteria.

This study was conducted in collaboration between Simon Fraser University

(SFU) and the Institute for Ocean Sciences (IOS). The methods of this study involved (i)

collecting environmental samples, conducted by the author (Section 2.1), (ii) filtering the

seawater samples and measuring suspended particulate matter, conducted by the author

(Section 2.2.4 and 2.2.5), (iii) chemical extraction and analysis of the samples, conducted

at IOS by Audrey Chong and Jody Carlow (laboratory equipment cleaning and sample

preparations and extractions), and Hongwu Jing, Zhongping Lin, and Natasha Hoover

(GC-MS and LS-ESI/MS machine analysis) (Section 2.2), (iv) measurements of organic

carbon and lipid contents in the sediment and biota samples, conducted at IOS by Linda

White (organic carbon contents), Audrey Chong and Jody Carlow (lipid contents)

(Section 2.4), (v) assessing data quality (QA/QC), conducted by the author (Section 2.3),

(vi) statistically analyzing the data, conducted by the author (Section 2.5), and (vii)

7

conducting a fugacity analysis of the concentration data, conducted by the author

(Section 2.5.4). The work at IOS was done under a grant to Dr. Frank Gobas, SFU.

8

2. METHODS

Overview: The methods section is divided into five parts describing the (i) field

sampling, (ii) chemical analysis, (iii) methods for quality assurance and control (QA/QC)

of data, (iv) supporting data measurement, and (v) methods related to the data analysis.

As stated in the Introduction, the chemical analysis and organic carbon and lipid content

measurements were conducted at the Institute for Ocean Sciences by Audrey Chong,

Jody Carlow, Hongwu Jing, Zhongping Lin, Natasha Hoover, and Linda White.

However, for completeness and because of their importance, I have included a

description of the methods related to the chemical analysis and supporting data

measurement in the Methods section. Additionally, as part of the overall study, the

methods that were developed for the chemical analysis of phthalate esters involved the

concurrent extraction and analysis of polychlorinated biphenyls (PCBs). Therefore

standards of both PEs and PCBs were added to the environmental samples, and are

described in the methods section. However, all concentration results relating to PCBs in

the environmental samples will be reported in Gobas et al. (in preparation).

2.1. Field Sampling Methods

2.1.1. Study Site and Design

To assess the extent of phthalate ester bioaccumulation in a marine food web, a

field study was conducted in False Creek Harbour, a residential/ industrial embayment

located in downtown Vancouver, Canada (Figure 2.1.). False Creek is part of the Strait

of Georgia, where the mean summer temperature is 10.9°C, average salinity is 30 ppt,

and precipitation ranges from 90 to 200 cm/year. False Creek is shallow (i.e., mean

9

depth is ~ 20ft), and relatively well mixed. Within False Creek, three sampling stations

were selected to assess spatial variability: “North-Central” (49°16'13”N 123°07'40”W),

“Marina-South” (49°16'09”N 123°07'15”W), and “East-Basin” (49°16'28”N

123°06'18”W). Supplementary sediment and water samples were also collected from a

fourth station: “Cambie Bridge” (49°16' 18"N 123°07' 04"W). From each station, three

independent samples of each media and species (i.e., sediment, water, and eighteen

marine organisms) were collected to determine sampling and analytical variability. A

limited number of samples of sediment (n=8), mussel (n=8), clam (n=3), and oyster (n=3)

samples were collected from False Creek during a pilot study in July of 1998, and were

used for analytical method development. The remainder of the sediment and biota

samples, including the surf scoter samples from the Canadian Wildlife Service, were

collected from May to October 1999, and were pooled with the 1998 samples. Water

samples were collected in July of 2000, since they required additional time for sample

filtration and extraction.

Figure 2.1. Map of field study site: False Creek Harbour, Vancouver, British Columbia, showing locations of four sampling stations

(λ): “North Central”, “Marina – South”, “Cambie Bridge” and “East Basin”.

11

2.1.2. Preparation of Field Sampling Equipment

Due to their widespread use, phthalate esters are commonly found in both sampling

and analytical equipment, as well as in laboratory air and reagents. Consequently, reducing

and determining the background contamination of samples is crucial for ensuring that

environmental data on phthalate esters are acceptable, accurate and of high quality. Thus,

several preparatory steps for cleaning field equipment were included in the protocol. All

sampling equipment was made of glass or stainless steel. Glass vials (125 mL, 250 mL, 4L)

were washed with lab grade detergent, rinsed twice with distilled hexane, iso-octane, and

dichloromethane, and then heated in a muffler oven at 400°C for at least 10 hours. After

baking, the vials were re-rinsed three times with distilled acetone, hexane, iso-octane, and

dichloromethane, and then covered with clean aluminum foil and solvent rinsed metal lids.

Aluminum foil was rinsed with distilled acetone and distilled hexane and then heated at

350°C for 10 hours. Stainless steel sampling tools (e.g., spoons, knives, trays, and buckets)

were cleaned following the procedures for the glass vials, and were wrapped with aluminum

foil prior to sampling. The petit ponar sediment grab sampler was washed with lab-grade

detergent and then rinsed three times with distilled acetone, hexane and dichloromethane.

2.1.3. Sediment Sample Collection

Surficial sediment samples were collected using a petit ponar grab sampler and

transferred onto clean aluminum foil (Figure 2.2). The top 0.5 to 1.0 cm, representing the

“active layer”, was removed with a metal spoon and transferred into a pre-cleaned glass vial,

which was covered with aluminum foil and sealed with a metal lid. Vials were immediately

placed on ice and were then kept at - 20°C in the dark prior to analysis.

12

12 ft.stainless steelextractablepole

Foil lined corkwith monofilament

line attached

4L amberglass bottle

Stainlesssteel wire

attachment

Stainlesssteel

connectingclamp

B)

2.1.4. Water Sample Collection

Water samples were collected in 4L amber glass bottles from mid-ocean depth (~10-

12 ft) using a 12-foot extendible stainless steel pole (Figure 2.2). After collection, the

bottles were sealed with a foil-lined lid, placed on ice, and then transferred to a 4°C

refrigerator in the laboratory. Well water, used for procedural blanks, was collected from

Lynn Headwater Regional Park, North Vancouver. From each sample or blank, 1L of

seawater or well water was quantitatively measured and spiked with 100ng of each DMP-d4,

DBP-d4, and DnOP-d4, 1.2ng of each 13C-PCB 52, 13C-PCB 128, 13C-PCB 209, and 5mL

HPLC grade methanol 1hr prior to extraction. The sample extraction occurred within 12

hours of collection, and is explained in the analytical methods section (2.2.4).

Figure 2.2. Field Sampling Equipment.

A) Petit Ponar Sediment Grab Sampler,

and B) Seawater Collection Apparatus.

A)

13

2.1.5. Biota Sample Collection

Eighteen marine organisms (Table 2.1, Figure 2.3) from various trophic levels in the

food chain were collected from False Creek Harbour. These species represent both the

benthic and pelagic food webs, and exhibit a variety of feeding strategies, sizes, and life-

histories. For example, primary producers (e.g., plankton and algae) as well as both filter

feeders (e.g. blue mussels (Mytilus edulis)) and deposit feeders (e.g., geoduck clams

(Panope abrupta)) were collected. The fish that were collected range from rapidly

maturing, short-lived species with high fecundity rates such as the striped seaperch

(Embiotoca lateralis), to slow growing and long-lived species such as the spiny dogfish

(Squalus acanthias), whose gestation period lasts two years and natural life expectancy is

greater than 50 years. Additionally, the selected species were “resident” or non-migratory,

so that the False Creek sediment and water concentrations represented the phthalate ester

levels to which the organisms were being exposed. The only exception was the dogfish,

which inhabit larger range sizes and move inshore with the tide to forage. The selected

species were also relatively abundant and widespread in False Creek, which facilitated

collection. The methods of collection are described in Table 2.1. Plankton samples were

collected in pre-cleaned 250mL glass vials. All other biota samples were wrapped in

solvent- rinsed aluminum foil and frozen at - 20°C, prior to analysis.

Table 2.1. Trophic Category, Common Name, Latin Name, Sample Size, Mean Length (cm), Mean Wet Weight (g) and

Sampling Methods for Eighteen Marine Organisms Collected from False Creek Harbour, Vancouver, British Columbia

Trophic Group

Common Name Latin Name Sample Size

Mean Length (Range) (cm)

Mean Weight (Range) (g)

Sampling / Collection Methods

Green Algae Enteromorpha intestinalis

9 NA NA Collected from shore at low tide

Nereocystis luetkeana 1 Collected from water Brown Algae Fucus gardneri 1

NA NA Collected from shore at low tide

Primary Producers

Phytoplankton1 9 NA NA Plankton tow net - 236 μm mesh size Blue Mussels Mytilus edulis 9 Collected from pilings during low tide

Pacific Oysters Crassostrea gigas 9 Collected off rocks during low tide Geoduck Clams Panope abrupta 9 Dug up from mud shore during low tide Manila Clams Tapes philippinarum 5

NA Individual shellfish were

pooled to obtain

samples of ≥ 10g.

Dug up from mud shore during low tide

Dungeness Crabs Cancer magister 9 12.4 (9.3 – 16.0)

carapace width

252 (102 – 514)

Stainless steel crab traps and bait

Benthic Invertebrates

Purple Starfish Pisaster ochraccus 3 NA NR Collected from rocks and pilings during low tide

Forage Fish Minnows 16 Shiner Perch Cymatogaster aggregata 6 Pacific Staghorn

Sculpin Leptocottus armatus 3

Cutthroat Trout Salmo clarki clarki 2 Three Spine

Stickleback Gasterosteus aculeatus 2

Whitespotted Greenling

Hexogrammos stelleri 2

Starry Flounder Platichthys stellatus 1

Individuals

ranged in size from approx. 2.5 – 10 cm

Individuals were pooled

to obtain samples of ≥ 5g; individual

minnows ranged from

approx. 1 – 20g

Beach seining net – ¼ inch mesh size

Trophic Group

Common Name Latin Name Sample Size

Mean Length (Range) (cm)

Mean Weight (Range) (g)

Sampling / Collection Methods

Pacific Herring Clupea harengus pallasi 2 11 - 18 45 – 160 Herring gill nets – 1 inch mesh size Forage Fish Cont’d Surf Smelt Hypomesus pretiosus

pretiosus 1 15 30

Northern Anchovy

Engraulis mordax mordax

1 13 28 Herring gill nets – 1 inch mesh size

Pile Perch Rhacochilus vacca 3 14.1 (13.5 – 15.0)

54 (49 – 60)

Striped Seaperch Embiotoca lateralis 9 14.2 (12.5 – 17.5)

73 (49 – 174)

Beach seine net – ¼ inch mesh size AND Herring gill nets – 2 inch mesh size

Pacific Staghorn Sculpin

Leptocottus armatus 9 17.4 (12.0 – 29.5)

106 (22 – 344)

Stainless steel prawn traps & bait

English Sole Pleuronectes ventulus 1 15 74 Starry Flounder2 Platichthys stellatus 1 15 (11 – 22) NR

Sinking gill net – 2 inch mesh size

Whitespotted Greenling

Hexogrammos stelleri 9 20 (18.5 – 21.5)

126 ( 100 – 141)

Stainless steel prawn traps & bait

Predatory Fish

Spiny Dogfish Squalus Acanthias 13 82 (61 – 104) ca. 2000 Long-line fishing Marine bird Surf Scoters Melanitta perspicillata 10 NA NR Collected by the Canadian Wildlife

Service 1Plankton sample was a composite of phytoplankton and zooplankton, as well as other pelagic invertebrates and algae; 2The starry flounder sample was pooled from 3 individuals; NA = not applicable; NR = not reported / recorded.

Figure 2.3. Generalized Trophic Linkages Between Eighteen Marine Organisms Collected from False Creek Harbour and the Species

Trophic Positions (see Section 2.5.5).

17

2.2. Analytical Methods for Determining Phthalate Ester Concentrations in Environmental Samples

2.2.1. Materials

Standards of the individual phthalates: dimethyl phthalate (DMP), diethyl phthalate

(DEP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP) and di(2-ethylhexyl)

phthalate (DEHP) were purchased from Aldrich (Milwaukee, WI) and di-n-octyl phthalate

(DnOP) from American Biorganics (Niagara Falls, NY). Standards of phthalate isomeric

mixtures (C6H4(COOR)2: R = C6 to C10): JAYFLEX DHP (mixture of C6 isomers),

JAYFLEX77 (mixture of C7 isomers) and Diisodecyl phthalate (mixture of C10 isomers)

were obtained from Exxon Chemical (New Milford, CT). Diisooctyl phthalate (mixture of

C8 isomers) was purchased from Aldrich, and diisononyl phthalate (mixture of C9 isomers)

was obtained from Aritech Chemical (Pittsburgh, PA). The isotope-labeled compounds: d4-

DEP, d4-DBP and d4-BBP used as method internal standards (IS); and d4-DEP and d4-BBP

used as method performance standards (PS), were purchased from Cambridge Isotope

Laboratories (Andover, MA). Individual standard stock solutions were prepared at various

concentrations in toluene and the spiking solutions were prepared in acetone. The calibration

solutions were diluted from the stock solutions with methanol. Isotope-labeled PCBs were

purchased from Cambridge Isotope Laboratories and the compounds: 13C-PCB 28, 13C-PCB

105, 13C-PCB 118, 13C-PCB 156, 13C-PCB 15, d5-PCB 38, 13C-PCB 77, 13C-PCB 126, 13C-

PCB 169, 13C-PCB 52, 13C-PCB 101, 13C-PCB 128, 13C-PCB 180, 13C-PCB 194, 13C-PCB

208, and 13C-PCB 209 were used as internal standards (IS); and 13C-PCB 111 was used as a

performance / external standard (PS). The PCB-labeled stock solutions were prepared in n-

nonane, and were diluted in toluene to prepare spiking solutions for the biota and sediment

18

samples, or in methanol for spiking water samples. All solutions were kept at 4oC in the

dark. Solvents were “distilled-in-glass” grade (Caledon, ON, Canada) and reagent water

was high-purity HPLC grade (Burdick and Jackson, MI). Alumina (Neutral) was purchased

from ICN Biomedicals (Germany). Sodium acetate and anhydrous sodium sulfate (granular)

were purchased from Aldrich.

2.2.2. Preparation of Glassware and Reagents

Since, solvents were found to be the dominant source of background PE

contamination, all solvents used were doubly distilled. Laboratory glassware was detergent

washed, rinsed with water, then with doubly-distilled acetone, hexane, iso-octane, and

dichloromethane, respectively, baked at 400oC for at least 10 hours and stored in clean

aluminum foil. Mortars and pestles were cleaned using the same procedure as that for

glassware but were baked at 150 o C for 10 hours. As part of the QA/QC protocol, solvent

rinses were collected, processed in the same manner as real samples, and then analyzed by

GC/MS to ensure that background contamination levels of phthalates did not exceed the

machine detection limit. Alumina and sodium sulfate were baked at 200o C and 450o C,

respectively, for at least 24 hours, cooled and stored in a desiccator. Other materials such as

Teflon stoppers, GC septa and caps of sample vials, which decompose at elevated

temperatures, were washed extensively with 1:1 dichloromethane/hexane (DCM/Hex).

2.2.3. Extraction and Cleanup of Sediment and Biota Samples

The sediment and biota sample extraction procedure is summarized in Figure 2.5.

Approximately 2 g of sediment or 5 g biota sample was weighed and spiked with 100 ng of

PE surrogate internal standards (i.e., DMP-d4, DBP-d4, and DnOP-d4), and 25 μl of prepared

Non-ortho PCB internal standard (i.e., 13C-PCB 28, 13C-PCB 105, 13C-PCB 118, and 13C-

19

PCB 156), 25 μl of prepared Mono-ortho PCB internal standard (i.e., 13C-PCB 15, d5-PCB

38, 13C-PCB 77, 13C-PCB 126, and 13C-PCB 169), and 25 μl of prepared Di-ortho PCB

internal standard (i.e., 13C-PCB 52, 13C-PCB 101, 13C-PCB 128, 13C-PCB 180, 13C-PCB

194, 13C-PCB 208, and 13C-PCB 209) (Table 2.2). The sample was then blended with 15 to

20 g of pre-baked sodium sulfate, and ground with mortar and pestle to a free-flowing

powder. The homogenate was placed in a flask, extracted with 50 mL of 1:1 (v/v)

DCM/Hex in a Branson 5210 ultrasonic water-bath (Branson Ultrasonics Co., CT) for 10

min, and shaken on a shaker table (Eberbach Co., MI) for 10 min. Once the suspended

particles settled, the supernatant was removed. The extraction was repeated twice more with

fresh solvent. The combined extracts were concentrated to ca. 5 mL under a gentle stream

of high-purity nitrogen. The concentrate was quantitatively transferred onto a 350 mm x 10

mm i.d. glass column packed with 15 g deactivated alumina (activated with 15% HPLC

water, w/w) and capped with 1-2 cm of anhydrous Na2SO4.

To prepare samples for GC/MS analysis, the column was eluted with three

consecutive 30 ml fractions of (1) hexane; (2) 1:9 DCM/Hex; and (3) 1:1 DCM/Hex. The

first fraction, containing the polychlorinated biphenyls (PCBs) in hexane was evaporated to

near dryness under a stream of nitrogen and then re-dissolved in 5 mL 1:1 DCM/Hex. The

concentrate was eluted over an acid-base silica column with 60 mL of 1:1 DCM/Hex. The

eluent was then evaporated to near dryness and re-dissolved in 5 mL of hexane. This

concentrate was quantitatively transferred to a dry alumina column, which was eluted with

(1) 25 mL of hexane, which was discarded, and (2) 60 mL of 1:1 DCM/Hex. The eluent

from the second fraction was blown down to 100 μL under a gentle stream of nitrogen, and

then spiked with 30 μL of the PCB recovery standard solution (i.e., 13C-PCB 111, Table

20

2.2), and analyzed by GC-High Resolution Mass Spectrometer (GC/HRMS). The analytical

methods and results for the PCBs will be reported in Gobas and Maldonado (in preparation).

The third fraction eluent (in the 1:1 DCM/Hexane), contained the phthalate esters. It was

concentrated to ca. 100 μL under a stream of nitrogen and spiked with 50 ng of the phthalate

recovery standards (i.e., DEP-d4 and BBP-d4, Table 2.2) before GC-MS/LRMS analysis.

After running the sample on the GC-MS, the extract was then evaporated to near dryness,

reconstituted in 300μL of doubly distilled methanol, and analyzed by LC/ESI-MS.

Table 2.2. Composition of Phthalate Ester (PE) and Polychlorinated Biphenyl (PCB)

Standards, and Amounts (ng) Added to Sediment and Biota Samples.

Standard Compounds Amount (ng) of Each Compound

PE Internal DMP-d4, DBP-d4, DnOP-d4 100 PE External / Recovery DEP-d4, BBP-d4 50 PCB non ortho Internal

Standard 13C-PCB 28, 13C-PCB 105, 13C-PCB 118,

13C-PCB 156 ca. 1

PCB mono ortho Internal Standard

13C-PCB 15, d5-PCB 38, 13C-PCB 77, 13C-PCB 126, 13C-PCB 169

ca. 1

PCB di ortho Internal Standard

13C-PCB 52, 13C-PCB 101, 13C-PCB 128, 13C-PCB 180, 13C-PCB 194, 13C-PCB 208,

13C-PCB 209

ca. 1

PCB External / Recovery Standard

13C-PCB 111 ca. 2

2.2.4. Extraction and Cleanup of Seawater Samples

An overview of the procedure for extraction of the water samples is presented in

Figure 2.5. The water extraction apparatus consisted of an FMI valveless pump, which

pumped water at a flow rate of 8-10 ml/min through a 47mm glass fiber filter (0.45μm

diameter pore size, from Gelman Laboratory, Pall Corporation, Ann Arbor, Michigan), and

two independent 47mm Octadecyl (C18) extraction disks, which were housed in 47mm

21

stainless steel in-line filter holders (from Gelman Laboratory, Pall Corporation, Ann Arbor,

Michigan) (Figure 2.4). The C18 disks were from 3M (St. Paul, MN), and the typical

composition is 90 % octadecyl bonded silica particles and 10% matrix PTFE by weight

(Hagen et al. 1990). Extensive cleaning of these discs prior to extraction by subsequent

15min sonications in iso-octane, doubly distilled toluene, and 1:1 DCM/hexane was required

to remove phthalate ester residues from the commercial membranes. The final extract from

the sonications was checked by GC to confirm that residual phthalate levels were negligible.

Figure 2.4. Water Extraction Apparatus Consisting of FMI Valveless Laboratory Pump and

Three 47mm Stainless Steel In-line Filter Holders Housing a Glass Fibre Filter (0.45μm

diameter pore size) in Holder #1, and an Octadecyl (C18) Empore Extraction Disk in Holders

#2 and #3.

Porcelainlab pump

Stainless steel filterholders containing:

Glass fibre filter

C18 Emporeextraction disks

1Lwater

samplein glassbottle

Inflow

Outflow

22

After filtration of the 1L seawater sample (to which the internal standards had been

added) at the Simon Fraser laboratory, the glass fibre filter and C18 disks were removed from

the system and collected separately in glass vials containing 15 mL 1:1 DCM/Hex. These

vials were refrigerated at 4°C and transferred to the IOS lab. The filter and disks were then

extracted independently by 3 subsequent 5 min sonications with 20mL 1:1 DCM/hexane.

These extracts were combined and concentrated to 3-5mL under a gentle stream of high

purity nitrogen, which was then quantitatively transferred to a neutral alumina column for

cleanup. The alumina column was packed with 15g deactivated alumina (15% H20, w/w),

topped with a 2cm layer of anhydrous Na2SO4 . Prior to introducing the extract, 15-20mL

doubly distilled hexane was run through the column. The sample was then loaded on the

column, which was then eluted with 3 consecutive 30mL fractions of (1) hexane, (2) 1:9

DCM/Hex, and (3) 1:1 DCM/Hex. The third fraction was collected and concentrated to

100μL and spiked with 50ng of the recovery standards (i.e., DEP-d4 and BBP-d4). The

sample vial was capped with clean aluminum foil lined septa and analyzed by GC-MS. After

GC-MS analysis, the samples were evaporated to near dryness under a gentle stream of high

purity nitrogen, re-dissolved in 300μL of doubly distilled methanol, and then analyzed by

LC/ESI-MS.

2.2.5. Quantification of Suspended Particulate Matter in the Seawater

Samples

Suspended particulate matter was found on both the glass fiber filter and C18

extraction disk(s). Particulate matter amounts were quantified by pumping the remaining 3L

of each seawater sample through the filtration system (at SFU) and subtracting the pre-

filtered dry weights from the post-filtered dry weights of the glass fibre filter and C18 disks.

23

Particulate matter present on the glass fibre filter was greater than 0.45μm in diameter and

was operationally defined “large diameter suspended matter” (LDSM). The particulate

matter measured on the C18 disk was fine-grain material and was operationally defined as

“small diameter suspended matter” (SDSM).

Figure 2.5. Summary of Sediment, Biota and Water Sample Extraction Procedures for Phthalate Ester Analysis (Polychlorinated

Biphenyls were Extracted Concurrently).

25

2.2.6. GC/MS Analysis of Environmental Samples

Low-resolution gas chromatography with detection by mass spectrometry (GC/MS)

was used for the quantification of the individual phthalate esters (i.e., DMP, DEP, DiBP,

DnBP, BBP, DEHP, DnOP, DnNP) in the marine samples. GC/MS analysis was carried out

on a Finnigan Voyager GC/MS system (Manchester, UK) at the IOS laboratory. The mass

spectrometer was operated at 70 eV in the EI mode with a resolution of approximately 1000.

Data were acquired in the selected ion recording mode (m/z 163 for DMP and m/z 149 for

all other phthalates) and processed using Masslab software (version 1.4). The dwell time

was 100 ms, with a delay time of 10 ms. The mass spectrometer was coupled to a Finnigan

8000 Series gas chromatograph. A J & W DB-5 fused silica capillary column (30 m x 0.25

mm, 0.1 μm film thickness) was used for separation. The injection port, GC/MS interface

and ion source temperature were kept at a constant temperature of 250oC. Splitless

injections of 1 μL were analyzed by programming the column temperature to go from 100oC

(held for 1 min) to 180 at 5oC/min, then to 240oC at 10oC/min, and to 280oC at 10oC/ min

(held for 10 min). Helium was used as the carrier gas at a flow rate of 1 mL/min.

2.2.7. LC/ESI-MS Analysis of Environmental Samples

Liquid chromatography with electron spray ionization was applied at the IOS

laboratory to quantify the concentrations of isomeric commercial mixtures of phthalate

esters in the marine samples (i.e., C6, C7, c8, C9, and C10) (see Lin et al. in preparation).

The eluent was delivered by a Beckman Model 126 programmable solvent system controlled

by a Beckman System Gold software (version 8.1) (Beckman, Fullerton, CA).

Chromatographic separations were performed on a 250mm x 2mm I.D. stainless steel C8

analytical column packed with 5μm Spherclone (Phenomenex, Torrance, CA). An OPTI-

26

SOLV Mini-Filter (Chromatographic Specialties Inc., ON) was used to protect the analytical

column. For the determination of individual phthalates, gradient elution was applied using

an eluent that contained mobile phase A (60:40 methanol/water with 0.5mM sodium acetate)

and mobile phase B (pure methanol with 0.5mM sodium acetate). The solvent composition

was held for 5 min at 60% A, and then linearly programmed to 100% A at 12 min, and then

to 30 % A in 33 min. For the determination of phthalate ester isomeric mixtures, the eluent

used was 90:10 methanol/water with 0.5mM sodium acetate, which was held constant

throughout the analysis. The injection volume was 3μL, and the mobile phase flow rate was

0.22mL/min. To be compatible with ESI, a splitter was used to feed about 50μL/min of

eluent into the sprayer. The flow-split ratio was regulated by adjusting the length and

diameter of two capillary tubes.

Mass analysis was performed using a VG Quattro triple-quadrupole mass

spectrometer equipped with a pneumatically assisted electrospray source (Micromass,

Manchester, UK). The source temperature was 150o C, and nitrogen was used as the bath

and nebulizing gas (250, 16L/hr, respectively). Typical electrospray ionization conditions

were as follows: electrospray capillary voltage, 3.7kV; high-voltage lens (counter electrode),

150V; skimmer cone voltage, 27V; focus (second skimmer) voltage, 20V. The tuning

conditions were optimized by performing flow-injection analysis of a solution of stable

isotope-labeled benzyl butyl phthalate (ring-d4). The mass spectrometer was operated in the

positive ion mode. Mass spectra were scanned in the m/z range of 50 to 500 at the rate of

5s/scan, with an inter-scan delay of 10ms. A dwell time of 200ms per Dalton was used for

selected ion monitoring LC-MS experiments. For quantitative analysis, the mass

spectrometer was operated under single ion recording (SIR) mode, and was monitored for

27

m/z of 357, 385, 413, 441 and 469 for C6, C7, C8, C9 and C10, respectively as well as m/z

417 for the internal standard DnOP-d4. Data were processed using the Masslynx software

(version 2.1). Peak areas were obtained from the Masslynx data system by interactive

processing, where the peak baselines were operator defined.

2.2.8. Optimization of ESI-MS Parameters

Optimization of ESI-MS parameters was carried out by flow injection analysis (FIA)

experiments. For FIA/ESI-MS, 20μL of phthalate standard solution was directly injected

into the flow of the mobile phase at a flow rate of 20μL/min. The MS was operated in full

scan mode under positive ion mode covering the mass range m/z 50 to 500. In negative ion

mode, all phthalates tested did not show detectable signals. After preliminary tuning and

signal optimization with FIA, the final optimization was accomplished with the LC column

in place because, under chromatographic conditions, the system performance is

compromised by i) the presence and condition of the LC column, ii) ionic strength additives,

and iii) variable solvent compositions from gradient elution. The quantitative linearity of the

LC/ESI-MS response was tested for the concentration ranges of 0.0028 to 42.8 ng/μL for the

individual phthalates, and 0.0428 to 55.1 ng/μL for phthalate ester isomeric mixtures.

2.2.9. LC/ESI-MS/MS Analysis of Environmental Samples

To investigate the potential co-elution of sample matrix interferences with the

phthalate ester isomers, tandem mass spectrometry (MS-MS) (at the IOS lab) was used for

confirmation. The VG Quattro MS machine was operated in multiple reaction monitor

(MRM) mode to produce collision-induced dissociation (CID). To optimize the response

under MS-MS conditions, different modifiers (i.e., Na+, Li+, K+, H+, and NH4+),

concentrations of modifiers, and analytical/ monitoring conditions (i.e., collision energies,

28

and the collision gas pressures) were investigated and will be reported on in Ikonomou et al.,

in preparation. Lithium (Li+) was used as a solvent modifier because it had a higher overall

sensitivity, and produced ESI-MS/MS spectra with several major daughter ions, and higher

daughter to parent ion ratios, relative to the other molecular adducts. Argon was used as

collision gas, with a pressure of about 2·10-4 mbar in the analyzer vacuum. Typical

conditions used for lithiated ions were: collision energy 75 eV, cone voltage 33 V, capillary

4.23 kV, HV lens 320V. Under MS-MS conditions, the Li+ adduct produced two major

common daughter ions, i.e., m/z 155 and 173, from the phthalate ester isomeric mixtures

(C6, C7, C8, C9, and C10). Specific ions were also formed for each isomer: diisodecyl

(C10) ions with m/z 453 (parent), 313 and 165 (daughters); diisononyl (C9) ions with m/z

425 (parent), 299, and 151 (daughters); diisooctyl (C8) ions with m/z 397 (parent), 285 and

137 (daughters); Jayflex 77 (C7) ions with m/z 369 (parent), 271 and 123 (daughters); and

Jayflex DHP (C6) ions with m/z 341 (parent), 257 and 109 (daughters).

2.2.10. MS Calibration, Recovery and Procedural Blanks

Prior to sample analysis, calibration curves were constructed to verify the linearity of

the MS response for all native phthalate esters covering the concentration range of 0.3pg/μL

to 2000pg/μL (GC/MS), and 7pg/μL to 4000pg/μL (LC-ESI/MS). Machine detection limits

were assessed by analyzing the lowest concentration standard solution (i.e., 0.3 pg/μL for

GC/MS, and 7pg/μL for LC-ESI/MS), and repeating this analysis periodically.

Additionally, a calibration standard was run at the beginning and end of each batch of

sample runs. For GC-MS analysis, this standard calibration solution contained the

individual phthalate test chemicals at concentrations of ca. 100pg/μL, as well as the internal

standards and recovery standards at concentrations of ca. 500pg/μL. The LC-ESI/MS batch

29

calibration solution contained both the individual test chemicals and isomeric mixtures at

concentrations of ca. 400 – 900pg/μL, and the internal and recovery standards at

concentrations of ca. 250pg/μL.

To determine the recovery of the test chemicals throughout the extraction and clean

up process, each sample and blank was spiked with 100ng of the internal standards (i.e.,

DMP-d4, DBP-d4 and DnOP-d4) prior to extraction. Recovered amounts were quantified by

mass spectrometry, and used to correct the data for chemical loss and variance in machine

sensitivity. 50ng of each external/ recovery standards (i.e., DEP-d4 and BBP-d4) were added

prior to machine analysis to correct for variance in the sample injection and the sensitivity of

the MS detector. Procedural blanks for the sediment and biota consisted of 10-20g of pre-

baked sodium sulfate; those for the seawater consisted of 1L of well water.

2.2.11. Quantitation of Phthalate Esters in Environmental Samples

Quantification was achieved by generation of relative response factors (RRFs) for

each analyte, which relate peak area-to-mass ratios for two compounds, “i" and “j” (e.g., the

internal standard and the recovery standard, or the test analyte and the internal standard)

(Equation 2.1):

RRFi/j = (Peak Areai / Massi) (2.1) (Peak Areaj / Massj)

Relative response factors were determined from analyzing a standard calibration solution

(with known amounts each analyte) before and after batch analysis, and using the mean of

these two calibration runs for quantitation. RRFs for the recovery standards (RS) (DEP-d4

and BBP-d4) in the calibration solution were set to a value of one. RRFs for the internal

standards (IS) (i.e., DMP-d4, DBP-d4, and DnOP-d4) in the calibration solution were

determined from peak area-to-mass ratios with the recovery standard (RS) that was most

30

similar in molecular weight (i.e., DMP-d4 from DEP-d4; and DBP-d4 and DnOP-d4 from

BBP-d4) (i.e., RRFIS/RS). Relative response factors for the native phthalates (PE) in the

calibration solution were determined from peak area-to-mass ratios with the internal

standard most similar in molecular weight (i.e., DMP and DEP from DMP-d4; DiBP, DBP,

BBP, C6 and C7 from DBP-d4; and DEHP, DnOP, DnNP, C8, C9, and C10 from DnOP-d4)

(i.e., RRFPE/IS).

These relative response factors derived from the standard calibration solution were

then applied to quantify internal standard recoveries and amounts of phthalate esters in the

environmental samples and procedural blanks. The percent recovery was determined by

quantification of internal standard amounts (i.e., DMP-d4, DBP-d4 and DnOP-d4) in the

marine samples and blanks (Equation 2.2a):

MassIS = (Peak AreaIS / RRFIS/RS ) (2.2a) (Peak AreaRS / Mass SpikedRS)

RecoveryIS = MassIS Mass SpikedIS

To quantify the native phthalate ester amounts in each sample and blank, the RRFPE/IS was

then used (Equation 2.2b):

MassPE = (Peak AreaPE / RRFPE/IS ) (2.2b) (Peak AreaIS / Mass SpikedIS)

2.2.12. Quantification of Diisodecyl Phthalate (C10) in Biota Samples

While LC/ESI-MS/MS confirmation revealed no interferences for C6-C9 phthalate

isomers, a significant interference contributed the C10 response in the biological tissue

samples. As a result, MS-MS confirmation using Li+ was required for quantification of

diisodecyl phthalate (C10) in the biological samples. Approximately 50% of the biota

31

samples were confirmed using LC/ESI-MS/MS. The ratio of C10 to the total peak area (i.e.,

C10 + interference) was determined for these samples and ranged from approximately 70%

of the mass response for green algae and plankton samples to approximately 0.1% in fish

tissue samples (Table 2.3). To estimate the C10 concentration in samples that were not

confirmed with MS-MS, the mean fraction of C10 in the total peak area for each specific

species was applied to the unconfirmed LC-MS concentration data (which included C10

plus the interference). These concentration data are reported in Section 3.4 (Biota

Concentration Results).

Table 2.3. Mean Percentage of C10 in the Total Peak (C10 + Interference), the

Coefficient of Variation (%), Sample size (n), and Number of Samples with Non-Detect

C10 Concentrations for Biota Samples Confirmed using LC/ESI-MS/MS

Species Mean % of C10 in the Total Peak

Coefficient of Variation (%)

Samples Confirmed (n)

ND1 Samples for C10

Green Algae 72.7 18.8 3 0 Brown Algae 4.7 2 0

Plankton 65.4 17.5 5 1 Mussels 0.9 47.0 4 0 Oysters 2.0 55.1 6 0

M. Clams 1.4 5.2 2 0 G. Clams 5.0 34.2 3 0 Starfish 0.2 2 0 D. Crabs 0.3 26.9 4 1 Minnows 2.6 94.4 7 4 P. Perch ND 2 2 S. Perch 33.4 74.1 7 3

Forage Fish ND 2 2 Sculpin 0.5 5 3

Greenling 0.4 8.3 6 3 Dogfish - Liver 0.1 27.2 5 3

Dogfish - Muscle 0.6 12.9 5 3 Dogfish - Embryo 0.2 70.7 2 0 S. Scoter (Bird) 2.5 70.2 9 0

1Number of samples with “Non-Detectable” (ND) concentrations of C10.

32

2.3. Quality Assurance and Control of Data (QA/QC)

After quantitation, data quality was evaluated. Each sample was corrected for

background contamination of phthalate esters and chemical loss during sample extraction,

and then screened against method detection limits (MDLs). Certain tables and figures for

this section are presented in Appendix D “Data QA/QC”.

2.3.1. Sediment & Biota Concentration Data

2.3.1.1. Sodium Sulfate Blanks for Sediment & Biota Sample

Analysis

To assess the background contamination of phthalate esters, two or three sodium

sulfate blanks were included in each batch of sediment and biota samples (4-6 samples). All

samples were blank-corrected by subtracting the mean concentration of phthalate esters in

the blanks from each sample in the batch, prior to recovery correction. (In cases of batches

with one high blank, the highest blank was used for the correction. This was necessary for

only four out of thirty-five biota batches).

For GC-MS analysis, mean concentrations of phthalate esters in the sodium sulfate

blank ranged from 0.07 ng/g for DOP to 5.05 ng/g for DBP for biota analysis (n=85), and

from 0.24 to 10.06 ng/g for DMP and DBP, respectively, for sediment analysis (n=20). For

LC-ESI/MS, the mean concentrations of phthalate ester isomers in the blanks ranged from

0.12 to 3.46 ng/g (biota blanks, n=46), and from 0.28 to 8.62 ng/g (sediment blanks, n=14)

for C6 and C8, respectively, (Figure 2.6 and Table D.2.4 in Appendix D).

33

Figure 2.6. Mean Phthalate Ester Concentrations (ng/g) in Sodium Sulfate Procedural

Blanks for Sediment and Biota Analysis. Error bars represent one standard deviation.

2.3.1.2. Method Detection Limits for Sediment & Biota Concentration

Data

To ensure that background contamination did not contribute to the reported

environmental concentrations, method detection limits (MDLs) were determined. MDLs

were defined as 3 standard deviations above the mean blank concentration. (When data are

blank corrected, the MDL is simply equal to 3 standard deviations). The MDLs were

determined on a per-batch basis for the biota samples, and by using all the procedural blanks

for sediment samples (n=18), since sediment blanks were consistent between batches. Batch

MDLs were used for the biota data because of inter-batch variability in the blanks (i.e.,

background contamination was usually reduced in later batches). Inter-batch variability in

the blanks was an issue for the biota data because environmental concentrations of phthalate

0.01

0.1

1

10

100

DMP

DEP

DIBP DB

PBB

PDE

HPDO

PDN

P C6 C7 C8 C9 C10

Phthalate Ester

Con

cent

ratio

n (n

g/g

NaS

O4)

SedimentBiota

34

esters were typically lower in the biota samples, relative to the sediment samples. The

batch-based MDL method is demonstrated for eight representative biota batches in Figure

D.2.7 (Appendix D). Figure D.2.7 shows that, with the exception of DMP, DEP, DiBP, and

C6, there is variability in the blank concentrations between batches, particularly for DnBP,

DEHP, and C8.

The sediment and biota MDLs are presented in Table 2.5. Since the biota MDLs

were calculated on a per-batch basis, the mean variability (i.e., 3 standard deviations) and

the mean MDLs (i.e., mean blank concentrations + mean 3 standard deviations), for 35 biota

batches, are reported in the table. All sediment and biota samples were compared to the

MDL. The concentration data is presented with the MDLs in Figures D.2.8 (Sediment), and

D.2.9 (Biota) (Appendix D). (The data in these figures are blank-corrected, so the MDLs are

equivalent to 3 standard deviations). Concentrations that were greater than the MDL were

used in further analysis and reporting. Concentrations that were greater than the average

blank level, but did not meet the MDL, were always excluded for the sediment data, and

usually excluded for the biota data. Biota concentrations that did not meet the batch MDL,

but were within the range of data from other batches that met the MDL for that particular

congener and species, were included in the analysis (see Figure D.2.9). Again, because the

biota MDLs were calculated on a per-batch basis, the 10th, 50th, and 90th percentiles of the

batch MDLs are presented in Figure D.2.9.

35

Table 2.5. Mean Concentrations (ng/g) of Phthalate Esters in Sodium Sulfate

Procedural Blanks for Biota and Sediment Analysis, 3 Standard Deviations of the

Blanks, and Method Detection Limits Defined as the Mean Blank Concentration + 3

Standard Deviations.

Biota Analysis Sediment Analysis Phthalate Ester Mean 3 Stdev1 MDL1 Mean 3 Stdev MDL DMP 0.11 0.04 0.15 0.24 0.44 0.68 DEP 1.13 0.38 1.51 2.99 4.75 7.74 DIBP 0.33 0.14 0.47 0.54 0.54 1.08 DBP 5.05 1.77 6.82 10.1 12.2 22.3 BBP 0.8 0.31 1.11 2.27 4.8 6.07

DEHP 2.14 0.92 3.06 8.83 15.6 24.4 DOP 0.07 0.02 0.09 0.8 2.17 2.97

GC-MS

DNP 0.08 0.02 0.1 0.5 1.07 1.57 C6 0.12 0.04 0.16 0.28 0.28 0.56 C7 0.39 0.14 0.53 0.79 1.92 2.71 C8 3.46 3.02 6.48 8.62 32.5 41.1 C9 0.85 0.19 1.04 1.6 2.83 4.43

LC-ESI/MS

C10 1.19 0.4 1.59 1.54 3.08 4.62 1The mean “3 standard deviations” of the blanks in 35 biota batches is presented and used for determining the mean MDL1.

2.3.1.3. Recovery of Internal Standards in Sediment & Biota Samples

To correct for chemical loss during the extraction procedure, and changes in machine

sensitivity, deuterated internal standards (IS) (i.e., DMP-d4, DBP-d4, DOP-d4) were added to

all samples prior to extraction. The fraction of IS recovered gives an indication of the

efficiency of extraction. The recoveries for the sediment and biota samples are presented in

Table 2.6. Mean IS recoveries from spiked False Creek sediments ranged from 82 to 95%

(GC/MS) and from 79 to 101% (LC-ESI/MS) for DMP-d4 and DOP-d4 respectively. Those

for spiked sodium sulfate sediment blanks ranged from 72 to 78% (GC-MS), and 80 to

100% (LC-ESI/MS) for DMP-d4 and DOP-d4 respectively. Mean IS recoveries in biota

36

samples were 84, 91, and 71% (GC/MS), and 76, 99 and 90% (LC-ESI/MS), and in sodium

sulfate blanks were 82, 89, and 88% (GC/MS) and 80, 96, 100% (LC-ESI/MS). The

relatively low recovery for DOP-d4 in some biological samples analyzed by GC/MS (e.g.,

dogfish liver and crab hepatopancreas) coincided with high lipid contents in those tissues. If

the recovery of any surrogate standard (i.e., IS) was outside the range of 50 to 130%, the

sample was re-processed and reanalyzed, or the data were excluded from further analysis.

Table 2.6. Mean (+/- standard deviation) Recoveries of Internal Standards from Spiked

False Creek Sediment and Biota Samples and Sodium Sulfate Blanks (%)

Media Analysis Material DMP-d41 DBP-d4 DOP-d4

False Creek 82 +/- 12 89 +/- 12 95 +/- 19 GC/MS Na2SO4 Blanks 72 +/- 13 73 +/- 16 78 +/-21

False Creek 79 +/- 21 102 +/- 23 101 +/- 20

Sediment

LC-ESI/MS Na2SO4 Blanks 80 +/- 13 96 +/- 7 100 +/- 13

False Creek 84 +/- 15 91 +/- 15 71 +/- 23a GC/MS Na2SO4 Blanks 82 +/- 10 89 +/- 12 88 +/- 13

False Creek 76 +/- 18 99 +/- 9 90 +/- 24

Biota

LC-ESI/MS Na2SO4 Blanks 80 +/- 13 96 +/- 7 100 +/- 13

1DMP-d4 recoveries were not used for LC-ESI/MS for C6-C10 isomers

2.3.2. Seawater Concentration Data

2.3.2.1. Recovery of Internal Standards in Seawater Samples

Total water concentrations were determined by adding the measured amounts on the

glass fibre filter and C18 extraction disks, and then correcting this total concentration for

sample recovery. To determine the recovery of the test chemicals throughout the extraction

and clean up process, water samples were spiked with internal standards (i.e., DMP-d4,

DBP-d4 and DnOP-d4) approximately 1 hour prior to filtration; external standards (i.e., DEP-

d4 and BBP-d4) were added to sample extracts prior to machine injection. Total water

37

recoveries were determined by comparing the observed amounts of the internal standards on

both the glass fiber and C18 extraction disks to the amount of chemical spiked. Mean internal

standard recoveries were 70, 86 and 37% (GC/MS) and 54, 93 and 50% (LC-ESI/MS) in

seawater, and 70, 79 and 48% (GC/MS) and 58, 86, and 69% (LC-ESI/MS) in well water

(Table 2.7, Figure 2.11). The apparent drop in recovery from 80% for DBP to 40% for DOP

agreed with similar observations by Holadova and Hajslova (1995) and is believed to reflect

increased adsorption to the glass wall of the bottle due to the increase in KOW. Congeners for

which the observed recoveries were lower than 50% (DMP to BBP, and C6 to C7) were

excluded from the data set. Due to consistently lower recoveries for the higher molecular

weight phthalates (i.e., DEHP to DnNP, and C8 to C10), data for these PEs with recoveries

below 30% were excluded.

Table 2.7. Mean (+/- standard deviation) Internal Standard Recoveries for False Creek

Seawater Samples and Well Water Blanks (%)

Media Analysis Material DMP-d4 DBP-d4 DOP-d4

False Creek 70 +/- 20 86 +/- 28 37 +/- 12 GC/MS Well Water 70 +/- 32 79 +/- 36 48 +/- 22 False Creek 54 +/- 16* 93 +/- 33 50 +/- 16

Water

LC-ESI/MS Well Water 58 +/- 27* 86 +/- 38 69 +/- 31

*DMP-d4 recoveries were not used for LC-ESI/MS for C6-C10 isomers

38

Figure 2.11. Mean Total Recoveries (%) of Internal Standards in Spiked Well Water Blanks

and False Creek Seawater Samples using GC/MS Analysis. Bars indicate fractions on the

Glass Fibre Filter (GF) and C18 Extraction Disks (C18). Error bars indicate one standard

deviation.

Recoveries of the internal standards in the water appeared to follow a bilinear

relationship with Kow. Hence, a bilinear relationship was applied to determine the recovery

of each phthalate ester in each sample. The linear relationship, recovery (%) = mi * log

KOW + bi, was used to determine the recoveries of phthalates with log KOW’s between 1.61

and 4.45, where the slope (mi), and y-intercept (bi) were determined from the recoveries of

the internal standards in each sample. A second relationship was used to determine

recoveries for PEs with a log KOW between 4.45 and > 8.06. For the isomeric mixtures, the

linear relationships were based on the number of carbons (C) on each ester chain (i.e.,

recovery (%) = mi * C + bi). The first linear relationship was used to determine recoveries

0%

20%

40%

60%

80%

100%

120%

DMP-d4 DnBP-d4 DnOP-d4Internal Standard

Rec

over

y (%

)

C18 C18

GF GF

GF GFC18 C18

C18 C18

Well Water Blanks False Creek Seawater

39

for phthalates with 1 to 4 carbons on the ester chains; the second was used to determine

recoveries for phthalates with ester chains of 5 to 10 carbons.

2.3.2.2. Background Contamination of Seawater Samples

Each sample was also screened for contamination, where concentrations of a

particular congener in a sample were 25 to >100 times greater than those in the other

replicate samples from the same station. If both the glass fibre filter (GF) and C18 extraction

disks (C18) were contaminated for a particular congener, then that concentration was

discarded. If only one of the GF filter or the C18 disk was contaminated for a particular

congener, then a total concentration was determined from the chemical concentration on the

uncontaminated-disk. This calculation was based on the partitioning behaviour of the

substance between the two filter types.

2.3.2.3. Well Water Blanks for Seawater Sample Analysis

Water blanks consisted of 1L of well water. They were extracted at the same time,

and following the same procedures as the seawater samples (in batches of two or three

blanks per three seawater samples). After recovery correction, each water sample was then

blank-corrected by subtracting the mean response of the blanks in the batch from the

seawater observations. Mean phthalate ester concentrations in well water blanks ranged

from 2.16 ng/L for DOP to 128 ng/L for DBP, for GC/MS analysis, and from 3.50 ng/L for

C6 to 902 ng/L for C8 for LC/MS analysis (Figure 2.12 and Table D.2.8 in Appendix D).

40

Figure 2.12. Mean Concentrations (ng/L) of Phthalate Esters in Well Water Blanks. Error

bars represent one standard deviation.

2.3.2.4. Method Detection Limits for Seawater Concentration Data

Method detection limits (MDLs) for the water data were defined as 3 standard

deviations above the mean phthalate ester concentrations in the well water blanks. The

MDLs were determined on a per-batch basis due to inter-batch variability in the blanks. The

uncorrected sample concentrations (i.e., recovery corrected, but not blank corrected) are

compared to the MDLs in Figure D.2.13 (Appendix D). Concentrations that were greater

than the MDL were used in further analysis and reporting. Concentrations less than the

MDL were excluded from the data set. Table 2.8 presents the minimum and maximum

method detection limits of phthalate esters in 4 batches of water samples. For DMP, DEP,

DiBP, DBP, DEHP, DOP and C10, the range of observed method detection limits was

relatively small, indicating good reproducibility between the analyses. However, for BBP,

0.1

1

10

100

1000

DMP

DEP

DIBP DB

PBB

PDE

HPDO

PDN

P C6 C7 C8 C9 C10

Phthalate Ester

Con

cent

ratio

n (n

g/L)

41

DNP and C6, C7, C8 and C9, there were substantial differences between the MDLs among

batches of water samples due to the introduction of background contaminants throughout the

chemical extraction process.

Table 2.9. Minimum and Maximum Method Detection Limits (MDLs) in ng/L among 4

Batches of Water Samples. MDLs represent the mean PE concentration in the batch

blanks + 3 standard deviations.

Phthalate Ester Minimum MDL Maximum MDL DMP 3.32 4.32 DEP 39.3 51.6 DIBP 6.39 7.9 DBP 177 221 BBP 6.56 44.4

DEHP 397 544 DOP 6.01 15.3 DNP 4.31 34.9 C6 4.7 25.9 C7 8.3 61.2 C8 327 1,060 C9 199 534 C10 50 99.3

2.3.2.5. Determination of the “Total”, “C18”, and “Freely Dissolved”

Concentrations in the Seawater Samples, and the Chemical

Phases that they Represent

The chemical in the water phase can be divided into different fractions. It may occur

in the freely dissolved form, or associated with particulate matter. The particulate phase of

the water contains suspended material of varying sizes. For the purpose of this study, we

have divided this fraction into “large diameter suspended matter” (LDMS) (or particulate

organic carbon), operationally defined as particles > 0.45μm in diameter, and “small

42

diameter suspended matter” (SDSM) (or dissolved organic carbon), operationally defined as

solids < 0.45μm in diameter (Figure 2.14). Based on these different fractions of chemical in

the water, three concentrations were derived in this study: (1) the “total water concentration”

CW(tot) (ng/L), (2) the “C18 water concentration” CW(C18) (ng/L), and (3) the “freely dissolved

water concentration” CW(FD) (ng/L). The total water concentration was measured from

combining the observed PE amounts on the glass fibre filter, MGF (ng), and C18 extraction

disks, MC18 (ng), and represents all fractions or forms of the chemical in the water medium

(i.e., chemical bound to large diameter suspended matter (LDSM), and to small diameter

suspended matter (SDSM), and freely dissolved chemical), i.e.,

CW(tot) = (MGF + MC18) / VW (2.3)

Where VW (L) is the volume of filtered sample water.

The C18 water concentration represents the observed PE amounts on the C18

extraction disks, and was determined as:

CW(C18) = CW(tot)·fC18 (2.4)

Where fC18 is the mean fraction of total chemical concentration detected on the C18 disks.

The C18 concentration includes two fractions of the chemical: dissolved organic-bound (i.e.,

chemical bound to SDSM), and freely dissolved chemical, since the large diameter

suspended matter has been removed by the glass fibre filter. The “freely dissolved water”

concentration was estimated by fitting observed concentrations on the glass fibre and C18

extraction disks to a three phase partitioning model, as described in Section 3.2.

43

Figure 2.14. Illustration of the Particulate Organic Carbon (POC) – Bound Chemical (Large

Diameter Suspended Matter “LDSM”), Dissolved Organic Carbon (DOC) – Bound

Chemical (Small Diameter Suspended Matter “SDSM”), and the Freely Dissolved Chemical

Fraction in the Water Phase and the Three Water Concentrations Reported in the Study.

2.3.3. Summary of the Sediment, Biota and Seawater Data Quality

Table 2.10 gives an indication of the overall quality of all the data for both the

individual phthalate congeners and the isomeric mixtures. Generally, for the biota and

sediment data, more than 85% of the data meet the MDL screening requirements and

provide reportable concentrations. However, the quality of the water data was generally

lower, and varied between congeners. Specifically, the fraction of observed concentrations

exceeding the MDLs ranged between 100% for DMP to as low as 17% for C8. Low ambient

concentrations in certain samples and congeners, making background contamination a more

significant factor, is one cause for the low proportion of values exceeding the MDL. A

second factor causing a low proportion of the samples to exceed the MDL was the variation

ParticulateOrganicCarbon

DissolvedOrganicCarbon

FreelyDissolved

Total Water Concentration

C18 WaterConcentration

Freely DissolvedWater Concentration

(Model Estimated)

44

in the MDL between batches of samples, allowing water concentrations to exceed the MDL

in certain batches but not in others. The variation in the MDL is mainly due to differences

in the levels of background contamination between batches, as well as variability in these

background levels in the blanks within a batch.

Table 2.10. Number of Samples with Detectable Concentrations above the Method

Detection Limits (MDLs).

Media: Sediment n=17 GC ; n=13 LC

Water n=12

Biota n=155 GC ; n=141 LC

Data Points:

No. Samples Detected

Samples > MDL(%)


Samples > MDL(%)


Samples > MDL(%)

DMP 17 17 (100) 12 12 (100) 150 147 (96) DEP 17 15 (88) 12 11 (92) 154 150 (95) DiBP 17 17 (100) 12 8 (67) 152 146 (89) DBP 17 17 (100) 12 7 (58) 154 150 (88) BBP 17 17 (100) 12 11 (92) 150 149 (95)

DEHP 17 17 (100) 12 4 (33) 140 137 (90) DnOP 17 17 (100) 12 5 (42) 109 101 (88) DNP 17 17 (100) 12 4 (33) 84 78 (87) C6 13 11 (85) 12 5 (42) 81 80 (99) C7 13 12 (92) 12 5 (42) 82 76 (93) C8 13 12 (92) 12 2 (17) 128 120 (94) C9 13 12 (92) 12 3 (25) 76 68 (89) C10 13 12 (92) 12 2 (17) 56/812 51 (91)

1Certain biota data were excluded to low recoveries, interferences, and background contamination for DEHP, DnOP, DnNP, C6, C7, C8 and C9; 2An interference co-eluted with C10 in the biota samples for LC-ESI/MS analysis, MS-MS confirmation using a Li+ adduct was conducted on 81 biota samples.

45

2.4. Measurements of Organic Carbon & Lipid Contents in Sediment and Biota Samples

2.4.1. Organic Carbon Content Analysis

2.4.1.1. Sediment Samples

Organic carbon content analysis in the marine samples was conducted at IOS and the

methodology follow Van Iperen and Helder (1985). Approximately 500mg of dried

sediment was acidified in a clean crucible with 1N HCl to remove carbonates prior to

Carbon/Nitrogen analysis. The acidified sample was then dried in an oven at 70ºC for 2

hours followed by another 2 hours at 105ºC. The sample was then allowed to hydrate for

2.5 hours, prior to analysis. Subsamples of approximately 8–10mg were weighed into tin

cups for Carbon/Nitrogen analysis on a Leemans 440 Elemental Analyser. Acetanilide

standards, containing 71.09% Carbon and 10.36% Nitrogen, were included in the sediment

batches and sample duplicates were analyzed (pooled standard deviation for sample

duplicates was 0.23%, where n = 3 sample pairs). Organic carbon content was expressed on

a dry weight basis as g OC/ g dry sediment.

2.4.1.2. Algae

Green and brown algae samples were rinsed with double-milli-q (dmq) water to

remove sand, shell fragments and other inorganic substances that might contribute to the

total organic carbon content (TOC) measurement. Algae samples were dried overnight at

60°C to achieve a stable weight, homogenized, and then subsampled for TOC measurement.

A 2-3 mg sample was then analyzed in a Leeman's Elemental Analyzer, which was

46

calibrated with acetanilide. Organic carbon content was expressed on a dry weight basis as g

OC/ g wet algae. Moisture contents were determined in unwashed algae samples.

2.4.1.3. Plankton

Plankton samples were homogenized and subsampled with a clean spoon. Large

wood pieces, leaves, and non-planktonic material were removed, however, small pieces of

algae were included. The cleaned sample was filtered with double-milli-q water on acid-

washed, combusted 47mm - 0.8 μm nucleopore filters to remove salts. Samples were then

oven dried at 60°C until their weight was stable. Material was then further cleaned by

sieving it through a 1000μm mesh to remove more debris. The dried particulate material

was then homogenized with a mortar and pestle, transferred to a clean vial and acidified

with 4% HCl to remove inorganic carbon (i.e., CaC03). The homogenate was then

transferred to a combusted 25 mm nuclepore filter, rinsed three times with dmq water to

remove the acid, and oven dried at 60°C to a stable weight. A 2 - 3 mg sample was analyzed

in Leeman's Elemental Analyzer, which was standardized with acetanilide. Organic carbon

content was expressed on a wet weight basis as g OC/ g wet plankton.

2.4.1.4. Particulate Matter

Suspended solids were collected on the 47-mm diameter; 0.45-μm pore size, glass

fibre filters. The samples were fumed with concentrated HCl, to remove inorganic carbon,

and analyzed on the Leeman’s Elemental Analyzer. Organic carbon content was expressed

on a wet weight basis as g OC/ g wet particulate matter.

47

2.4.2. Lipid Content Determination

Lipid contents in the biota samples were measured at the IOS laboratory. For each

biota sample, 5g of wet tissue (muscle, or whole body) was weighed on an aluminum boat

and then transferred to a glass mortar where it was homogenized with 100g anhydrous

sodium sulfate. The homogenate was transferred to a 30cm x 30cm glass column, which

was packed with glass wool at the tip and a Turbovap was placed under the column. To

remove any remaining sample material, the aluminum weigh boat, mortar and pestle, funnel,

and spatula were rinsed three times with 1:1 DCM/Hexane. The column was then eluted

with 100mL 1:1 DCM/Hexane. The extract was then reduced to 1mL in the Turbovap and

quantitatively transferred with 1:1 DCM/Hex to another pre-weighed aluminum weigh boat.

The weigh boat and solvent were dried for several hours at 40oC in a vented oven, and then

cooled completely in a desiccator. The sample weight was determined, and lipid content

was calculated on a wet weight basis.

2.5. Data Analysis and Normalizations

2.5.1. Analysis of Concentration Distributions

All concentration data were tested for normality using Kolmogorov-Smirnov and

Shapiro-Wilk normality tests. The results of these tests are reported in Tables E.2.1 to

E.2.17 of Appendix E. In general, both the environmental concentrations and the blank

concentrations for all media and species were log-normally distributed. Therefore, data

were log transformed; geometric means and upper and lower standard deviations are

reported.

48

2.5.2. Sediment Organic Carbon Normalization

Sediment concentrations were measured on a dry weight basis, Cdry (ng/g dry

sediment). Organic carbon (OC) contents were measured for each individual sediment

sample (Table G.1, Appendix G), and organic carbon normalized concentrations COC (ng/g

organic carbon), were computed on a sample-specific basis, as:

COC = Cdry / φOC (2.5)

Where φOC is the fraction of organic carbon in the dry sediment material (g OC / g dry

sediment). In False Creek, the average organic carbon content of the sediments was 2.80%

(± 0.31%, n=12).

2.5.3. Biota Lipid Normalizations

Lipid contents were analyzed for each individual biota sample (Table G.3 of

Appendix G) and samples were lipid normalized on a sample specific basis. Lipid

normalized concentrations for the biota, Clipid (ng/g lipid tissue), with the exception of the

plankton and algae, were calculated as:

Clipid = Cwet / L (2.6)

Where Cwet (ng/g wet tissue) is the wet weight biota concentration and L is the lipid fraction

of the sampled tissue (g lipid / g wet tissue). The mean lipid contents for the species

collected from False Creek are reported in Table 2.11.

Plankton and algae samples were lipid and organic carbon normalized following:

Clipid = Cwet / [L + (0.35 * φOC)] (2.7)

Where φOC is the fraction of non-lipid organic carbon in the wet sample, (g OC / g wet

sample); and 0.35 is a proportionality constant recommended by Seth and others (1999) to

relate the sorbing properties of organic carbon to those of octanol. The rationale for

49

including the organic carbon contents in the normalization of the plankton and algae samples

is that these organisms possess low lipid contents, and relatively high organic carbon

contents (Table 2.11). Organic carbon serves as the organisms energy and carbon source,

and due to its relatively high content, is likely to serve as an important site for chemical

accumulation. The normalization of plankton and algae data is further discussed in the

Section 3.4 (Biota Discussion).

Table 2.11. Mean Lipid Contents (%, g lipid/ g wet tissue) and Organic Carbon

Contents (% dry weight and % wet weight) (± Standard Deviation) in Biota Tissues that

were Analyzed for Phthalate Esters.

Species Tissue Type Mean Lipid Content (± Stdev) (%)

Mean Organic Carbon Content

(± Stdev) (%) Plankton Whole Organism 0.09% (± 0.02) 40% (± 9)dry;

0.6% (± 0.2) wet Green Algae Whole Organism 0.20% (± 0.10) 34% (± 3) dry;

6.1% (± 1.5) wet Brown Algae Whole Organism 0.08% (± 0.02) 36% (± 3) dry;

6.3% (± 5.3) wet Geoduck Clams Whole Organism 0.7 (± 0.2) NA Manila Clams Whole Organism 1.2 (± 0.2) NA Blue Mussels Whole Organism 1.3 (± 0.1) NA

Pacific Oysters Whole Organism 2.1 (± 0.6) NA Dungeness Crab Hepatopancreas 8.0 (± 6.0) NA Purple Seastar Stomach Section 2.5 – 18 NA

Minnows Whole Body 2.1 (± 1.0) NA Striped Seaperch Muscle 0.17 (± 0.09) NA

Pile Perch Muscle 0.7 (± 0.9) NA Forage Fish Muscle 3.2 (± 1.3) NA

Whitespotted Greenling Muscle 0.6 (± 0.4) NA Pacific Staghorn Sculpin Muscle 0.3 (± 0.1) NA

English Sole Muscle 0.5 NA Spiny Dogfish Whole Embryos 6 – 28 NA Spiny Dogfish Liver 62 (± 10) NA Spiny Dogfish Muscle 8.3 (± 3.9) NA

Surf Scoter Liver 2.2 (± 0.6) NA

50

2.5.4. Fugacity Calculations

In addition to wet/dry weight and lipid/organic carbon weight concentrations, the

data are expressed in terms of fugacities such that the phthalate ester levels in the various

media and species can be compared on a common or “normalized” basis. Fugacity, f (Pa), is

related to concentration, C (mol/m3), through the linear relationship: f = C / Z; where Z is

the fugacity capacity of the medium (Pa m3 / mol) (see section 1.3). Fugacity capacities (Z)

were determined as:

Water ZW = 1/H (2.8) Sediment ZSED = KP * ρ * Zw ZSED = 0.35 * φOC * KOW * ρ * (1/H) (2.9) Algae and Plankton ZGA/PK = (L * KOW * ρ * Zw) + (φOC * 0.35 * KOW * ρ * Zw) + (W * Zw)

= (L * KOW * ρ * (1/H)) + (φOC * 0.35 * KOW * ρ * (1/H)) + (W * (1/H)) (2.10) Benthic Invertebrates, Fish and Birds ZBIO = Kb * ρ * Zw

= L * KOW * ρ * (1/H) (2.11)

Chemical fugacities in the various media were calculated following equations 2.12 to

2.15 (i.e., f = C/Z). In the equations, a proportionality constant of 0.35 was used to relate the

sorptive capacity of organic carbon to that of octanol, (Seth et al. 1999, and Mackay 1991).

For the water, three chemical concentrations were determined based on the different

chemical fractions in the water (Figure 2.14). Therefore, three chemical fugacities in the

water phase are presented: “fW(tot)” (based on the total water concentration); “fW(C18)” (based

51

on the C18 water concentration) and “fW(FD)” (based on the freely dissolved water

concentration).

Water fW = CW / (1/H) (2.12)

Sediment fsed = Csed / [0.35 * φOC * KOW * ρ * (1/H)] (2.13)

Algae and Plankton fGA/PK = CGA/PK / [L * KOW * (1/H)) + (φOC * 0.35 * KOW * (1/H)) + (W * (1/H))] (2.14) Benthic Invertebrates, Fish and Bird Tissues fBIO = CBIO / [L * KOW * ρ * (1/H)] (2.15) where H = Henry’s Law constant (mol / Pa m3) (Table 1.3)

Kp = particle – water partition coefficient Kb = biota – water partition coefficient ρ = density (kg/L) (sediment = 1.5 kg/L; biota = 1.0 kg/L) Zw = fugacity capacity of water (Pa m3 / mol) (Table 1.3) φOC = fraction of organic carbon in sediment / organism L = fraction of lipid in tissue W = moisture content (water fraction) of organism KOW = octanol – water partition coefficient (Table 1.3)

2.5.5. Trophic Position Calculation

Marine food webs tend to be complex and characterized by numerous linkages

between species. To explore the movement of phthalate esters through the marine food web,

it was necessary to determine the dietary interactions and quantify the relative trophic

positions of the species collected for the study. A literature review was conducted on the

species collected in this study, as well as other key species in the Georgia Basin/

Southwestern British Columbia food web (see Appendix B, Pauly and Christensen 1996,

Butler 1964, 1980, Cass et al. 1990, Dygert 1990, Forrester 1969, Hart 1973, Jamieson and

Francis 1986, Jones 1976, Ketchen 1996, Levy 1985, Miller 1967, Murie 1995, Nybakken

1997, Onate 1991, Pratasik 1993, Richards 1987, Ricketts et al. 1985, Robles 1987, Starr et

52

al. 1990, Taylor 1964, Vermeer and Ydenburg 1989). Table 2.12 summarizes the prey items

of these species, and their relative dietary proportions. Trophic positions were calculated

according to Equation 2.16, based on Vander Zanden and Rasmussen (1996), and are listed

in Table 2.13. The general trophic linkages of the study species, and their trophic positions,

were presented in Figure 2.3.

TPpredator = ( ∑ TPprey * pprey ) + 1 (2.16) = (TP1 * p1) + (TP2 * p2) + (TPi * pi) + 1 Where “TP” is the trophic position of the predator or prey, and “pi” is the proportion of prey

item i in the diet of the predator. The dietary matrix used for the calculation of trophic

position is presented in Tables C.2.1 and C.2.2 of Appendix C. Species at the base of the

food chain were assigned trophic positions according to Vander Zanden and Rasmussen

(1996). Additionally, certain organisms were lumped together into trophic guilds for the

purpose of the calculation.

53

Table 2.12. Latin Name, Common Name, Trophic Position, Prey Items and their

Dietary Proportions, and Predators of Key Resident Marine Species in the Georgia

Basin Ecosystem.

Species Latin Name

Species Common

Name

TP Prey Species and their Dietary Proportions

Predators Comments/ References

Herring 0.22 Seals Euphausiids 0.14 Sea Lions

Plankton (Zooplankton) 0.10 Shrimp 0.08 Crabs 0.07 Hake 0.07

Flatfish 0.06 Eulachon/Smelt 0.06

Octupus 0.03 Other fish 0.12

Squalus acanthias

Spiny Dogfish

4.07

Other Invertebrates 0.05

Jones 1976

Polychaetes (Benthic Inverts) ~ 0.45 Waterbirds Crustaceans – Crabs ~ 0.10 Large fish

Shrimps & Euphausiids ~ 0.19 Pelagic Invertebrates ~ 0.10

Small Forage Fish ~ 0.10 Pacific Herring ~ 0.05

Hexo-grammos stelleri

White-spotted

Greenling

3.81

Flatfish ~ 0.01

Hart 1973

Polychaetes (Benthic Inverts) 0.45 Bottom fish Brittle Stars (& Seastars) 0.20 Waterbirds

Clams 0.20 Sandlance (Sm. Forage Fish) 0.02

Clam siphons (Benthic Inverts) 0.02 Shrimp (& Euphausiids) 0.02

Amphipods (Benthic Inverts) 0.07

Parophrys vetulus

English Sole

3.74

Small Crabs 0.02

- benthic feeder- feeding stops during winter

Forrester 1969

Clams ~ 0.65 Octupus Other Bivalves ~ 0.10 Dogfish/shark

Shrimp ~ 0.10 Halibut Crustaceans (Pelagic Inverts) ~ 0.05 Sculpins Polychaetes (Benthic Inverts) ~ 0.05 Flounders

Fish (Sm. Forage Fish) ~ 0.05 Rockfish Waterbirds

Cancer magister

Dungeness Crab

3.55

Seals

- carnivore

Pauly and Christensen

1996

Water birds Nemertean & Priapulid worms (Benthic Inverts)

0.42 Bottom fish

Polychaetes (Benthic Inverts) 0.28

Platichthys stellatus

Starry Flounder

Clams 0.23

3.54

Small crabs 0.04

- benthic feeder- January to June feeding

stops Miller 1967

54

Species Latin Name

Species Common

Name



Brittle stars (& Seastars) 0.01 Amphipods (Benthic Inverts) 0.01

…Starry Flounder

Mysids (Pelagic Inverts) 0.01 Amphipods (Benthic Inverts) ~ 0.28 Waterbirds

Nereid worms (Benthic Inverts) ~ 0.17 Large fish Anchovies/Small Forage Fish ~ 0.20

Lingcod Larvae & Eggs ~ 0.05

Leptocottus armatus

Pacific Staghorn Sculpin

3.51

Pelagic Invertebrates ~ 0.25

Pauly & Christensen

1996; Wang 1986

Mussels 0.88 Other Bivalves 0.10

Melanitta perspi-cillata

Surf Scoter 3.49

Seastars 0.02

Vermeer & Ydenberg 1989

Mussels ~ 0.80 Waterbirds Clams (& Oysters) ~ 0.16 Seals

Snails ~ 0.02 Sea lions Chitons ~ 0.01

Barnacles ~ 0.01 Limpets < 0.01

Pisaster ochraceus

Purple seastar

3.47

Sea anemones < 0.01

- voracious predator

Ricketts et al.

1985

Crustaceans ~ 0.40 Fish Worms ~ 0.40 Starfish Shrimps ~ 0.10 Mollusks ~ 0.05

Cancer magister

Juvenile Dungeness

Crabs (Small Crabs)

3.37

Minnows / Larval Fish ~ 0.05


1996

Euphausiids (& Shrimps) ~ 0.10 Gulls Amphipods (Benthic Inverts) ~ 0.10 Diving ducks

Copepods (Zooplankton) ~ 0.25 Salmon Cladocerans (Zooplankton) ~ 0.25 Dogfish Decapods (Zooplankton) ~ 0.18 Sharks

Barnacles (Pelagic Inverts) Lingcod Polychaetes (Benthic Inverts) Seals Clam larvae (Pelagic Inverts) Sea lions

Shrimps (& Euphausiids) Whales Crabs (small) ~ 0.03

Eulochons (Sm. Forage Fish) ~ 0.07 Starry Flounder (Flatfish) ~ 0.02

Ronquil (Lg. Fish) < 0.01 Sandlance (Sm. Forage Fish)

Hake (Lg. Fish) Sculpins (Lg. Fish)

Clupea harengus pallasi

Pacific Herring

3.32

Rockfish (Lg. Fish)

- may filter feed when

other food is not available

- ceases feeding in winter prior to spawning

Hart 1973

Copepods (Zooplankton) ~ 0.70 Sculpins Amphipods (Benthic Inverts) ~ 0.10 Starry Flounder

Euphausiids (& Shrimps) ~ 0.10 Surfperch Comb jellies (Pelagic Inverts) ~ 0.05 Large fish

Hypomesus pretiosus pretiosus

Surf Smelt 3.18

Larval fish (& Minnows) ~ 0.03 Waterbirds


1996

55

Species Latin Name

Species Common

Name



Mysids (Pelagic Inverts) ~ 0.60 Dogfish Amphipods (Benthic Inverts) ~ 0.20 Cod Other Crustaceans (Pelagic ~ 0.10 Turbot

Pandalus borealis

Pink Shrimp

3.16

Polychaetes (Benthic Inverts) ~ 0.10 Hake

Butler 1980

Amphipods (Benthic Inverts) ~ 0.10 Larger fish Shrimps (& Euphausiids) ~ 0.10

Algae ~ 0.15 Worms (Benthic Inverts)

Mussels ~ 0.05 Herring eggs (Larval Fish) ~ 0.02

Embiotoca lateralis

Striped Seaperch

3.05

Pelagic Invertebrates ~ 0.58

Hart 1973

Phytoplankton ~ 0.60 Sea stars Zooplankton ~ 0.15 Crabs

- suspension feeder

Panope abrupta

Geoduck Clams

2.53

Detritus ~ 0.25 Fish, Birds Pauly ...1996 Phytoplankton ~ 0.60 Diving ducks Zooplankton ~ 0.25 Sea stars

Bacteria Crabs

Mytilus edulis

Blue Mussels

2.48

Detritus ~ 0.15 Snails Urchins

- filter-feeder

Jamieson & Francis 1986

Diatoms (Phytoplankton) ~ 0.60 Sea stars Detritus ~ 0.15 Oyster drills

- suspension feeder

Crassostrea gigas

Pacific Oyster

2.48

Zooplankton ~ 0.25 Ctenophores Pauly…1996 Phytoplankton ~ 0.70 Water birds Zooplankton ~ 0.10

Tapes philippin-

arum

Manila Clams

2.40

Detritus ~ 0.20

- suspension feeder

Pauly…1996 2.33 Small crustaceans (Pelagic ~ 0.25 Fish

Copepods (Zooplankton) Amphipods (Benthic Inverts) ~ 0.05 Algae ~ 0.10

Cymato-gaster

aggregeta

Shiner Surfperch

(Minnows) Phytoplankton ~ 0.60

Wang 1986; Pauly &

Christensen 1996

56

Table 2.13. Summary of Trophic Positions for Species Collected from False Creek

Species Trophic Position Spiny Dogfish 4.07

Whitespotted Greenling 3.81 English Sole 3.74

Starry Flounder 3.54 “Sole” (Starry Flounder + English Sole) 3.64

Dungeness Crab 3.55 Staghorn Sculpin 3.51

Surf Scoter 3.49 Starfish 3.47

Pacific Herring 3.32 Surf Smelt 3.18

“Forage Fish” (Surf Smelt + Pacific Herring) 3.25 Striped Seaperch 3.05

Pile Perch 3.05 Geoduck Clams 2.53 Blue Mussels 2.48 Pacific Oyster 2.48 Manila Clams 2.40

Minnows 2.33 “Plankton” (Phytoplankton + Zooplankton) 1.00

Algae 1.00

57

3. RESULTS & DISCUSSION

Overview: The results section is divided into six parts describing (i) the concentrations

of phthalate esters and corresponding fugacities in the sediment (Section 3.1), (ii)

seawater (Section 3.2), and (iii) marine species (Section 3.4), and (iv) the distribution of

phthalate esters between the sediment and seawater (Section 3.3), (v) the biota and

seawater (i.e., bioaccumulation factors) (Section 3.5), and (vi) the biota and sediment

(i.e., biota-sediment accumulation factors) (Section 3.6). Data tables of mean phthalate

ester concentrations and fugacities in the various media, bioaccumulation and biota-

sediment accumulation factors, and summaries of reported phthalate ester concentrations

in various locations throughout the world are presented in Appendix F. The original

concentration data, including recoveries and supporting measurements (i.e., lipid and/or

organic carbon contents), are presented for each sample in Appendix G.

3.1. Sediment Concentrations of Phthalate Esters

3.1.1. Concentration Summary

All phthalate ester congeners and isomeric mixtures were detected in the ppb to

ppm range in False Creek Harbour sediments. The observed phthalate ester

concentrations in the sediments are presented in Table F.3.1 (Appendix F), and Figures

3.0 and 3.1. The results are expressed in terms of dry weight concentrations, Cdry (ng/g

dry sediment), organic carbon normalized concentrations, COC (ng/g organic carbon)

(Equation 2.5), and corresponding fugacities (Pa) (Equation 2.13).

58

Average sediment concentrations of the individual phthalates ranged from 4.0

ng/g dry wt. for DiBP to 2,090 ng/g dry wt. for DEHP. For the isomeric mixtures,

average concentrations ranged from 6.7 to 2,100 ng/g dry sediment for C6 and C8,

respectively (Table F.3.1 and Figure 3.0). DEHP and C8 isomers (including DEHP) were

present in the highest concentrations (2,100 ng/g dry weight). Sediments also contained

significant levels of DBP (114 ng/g dry), C9 (483 ng/g dry) and C10 isomers (385 ng/g

dry). In terms of total phthalate esters, determined as the sum of concentrations of DMP,

DEP, DiBP, DBP, BBP, C6, C7, DEHP, DnOP, C9 and C10, levels in the sediments were

approximately 3,270 ng/g dry wt. In False Creek, the average organic carbon content of

the sediments was 2.80% (± 0.31%, n=12). Organic carbon normalized concentrations

ranged from 137 to 75,200 ng/g OC for DiBP and C8, respectively (Table F.3.1, Figure

3.0).

Fugacities in the sediments ranged from 0.10 nPa for DnNP to 3,120 nPa for

DMP, and from 0.07 to 15.5 nPa for C10 and C8 isomers, respectively (Table F.3.1,

Figure 3.1). Phthalate fugacities in the sediments were relatively low for the high

molecular weight compounds, and higher for the low molecular weight PEs (Figure 3.1).

Figure 3.1B compares the concentration and fugacity profiles for phthalate esters in False

Creek Harbour sediments. It reveals that although the low molecular weight PEs (e.g.,

DMP, DEP, and DBP) are present at relatively low concentrations, they present the

highest fugacities in the sediments. This is in contrast to the high molecular weight PEs

(e.g., C8, C9, and C10), which are present at the highest concentrations but correspond to

the lowest fugacities in the sediment matrix.

Figure 3.1. Phthalate Ester Concentrations in False Creek Harbour Sediments, Expressed on a Dry Weight Basis (ng/g dry sediment)

(A), and on an Organic Carbon Normalized Basis (ng/g organic carbon) (B).

1

10

100

1000

10000

DMPDEPDIBPDBPBBPDEHP

DOPDNP C6 C7 C8 C9C10

Phthalate Ester

Con

cent

ratio

n (n

g/g

dry

wt.)

10

100

1000

10000

100000

1000000



Phthalate Ester

Con

cent

ratio

n (n

g/g

OC

)

A) B)

Figure 3.1. Phthalate Ester Fugacities (nPa) in False Creek Harbour Sediments (C), and Comparison of Phthalate Ester Concentration

(ng/n OC) and Fugacity (nPa) Profiles in False Creek Harbour Sediments (D).

1

10

100

1000

10000

100000

1000000



Phthalate Ester

Con

cent

ratio

n (n

g/g

OC

)

0.01

0.1

1

10

100

1000

10000

Fugacity (nPa)

Organic Carbon Fugacity

0.01

0.1

1

10

100

1000

10000



Phthalate Ester

Fuga

city

(nPa

)

C) D)

61

3.1.2. Spatial Variability

An Analysis of Variance (ANOVA) was used to determine whether there were

statistically significant differences in the concentrations of phthalate esters between the four

sediment stations within False Creek. The results indicate that the “North Central” sampling

station had statistically significantly lower levels of certain phthalate esters, particularly the

larger molecular weight PEs (i.e., BBP, DEHP, DnOP, C9, and C10), relative to the other

stations, particularly “East Basin” (Figure 3.2, Appendix E). This difference in

concentration is likely due to greater tidal flushing near the mouth of the embayment (North

Central), or reduced flushing in the more inland and protected sections of the harbour (e.g.,

East Basin). These high molecular weight substances have relatively long half-lives in

sediments, and are likely to persist with reduced mechanisms of removal. Also, there may

be additional sources of these high molecular weight phthalates in the eastern section of

False Creek, from, for example, municipal and industrial outflows.

Overall, however, the sediment concentrations within False Creek were sufficiently

homogenous to support combining all the data. Specifically, there were no statistically

significant differences between the sediment sampling stations for eight of the thirteen

phthalate esters, and for the substances that did exhibit statistically significant spatial

differences, concentrations between the low and high stations differed by only a factor of 2

to 3. Additionally, pooling the sediment data enables an assessment of the overall chemical

distribution in the environment and movement through the food web.

Figure 3.2. Concentrations (ng/g OC) of Phthalate Esters in Four Sediment Stations in False Creek Harbour. Starred bars indicate

statistically significant differences in concentration between 1 station and the other 3 (single star), or between 2 stations (double star).

63

3.2. Seawater Concentrations of Phthalate Esters

3.2.1. “Total” Seawater Concentration Summary

Total water concentrations of phthalates in seawater were determined as the sum of

the PE concentrations on the glass fibre filter and the C18 disks. These concentrations and

their standard deviations are presented in Table F.3.3 (Appendix F) and Figure 3.3 and

ranged from 3.5 ng/L for DMP and BBP to 275 ng/L for DEHP and C8 isomers. The

concentrations were determined as the geometric mean of the observations exceeding the

MDL. While other methods exist to account for observations below the MDL, this method

was selected because the main cause of samples not exceeding the MDL was background

contamination, rather than variability in phthalate ester concentrations between the replicate

water samples. A minimum of 4 observations above the MDL was considered to constitute

a large enough sample size to determine the average water concentration. Hence, the water

concentrations of C8 and C9 are only considered estimates. The total phthalate ester water

concentration, determined as the sum of concentrations of DMP, DEP, DiBP, DBP, BBP,

C6, C7, DEHP, DnOP, C9, and C10 was 735 ng/L. Significant losses due to biodegradation

have previously been reported to occur within a period of 3 to 17 days at 20ºC (Schouten et

al. 1979, Walker et al. 1984, and Russell et al. 1985) but were reported to be negligible at

4ºC (Ritsema et al. 1989). Biodegradation losses were not expected to be a factor in this

study because of the short pre-extraction period at 4ºC.

The concentration of DEHP in False Creek seawater (275 ng/L) was lower than the

USEPA adopted Maximum Acceptable Concentration of 6000 ng/L (USEPA 1991), and the

Canadian interim water quality guideline for freshwater of 16,000 ng/L (CCME 1999). The

64

concentration of DBP in False Creek seawater (110 ng/L) was also less than the Canadian

interim water quality guideline for freshwater of 19,000 ng/L (CCME 1999).

Figure 3.3. Total Concentrations (Mean ± Standard Deviations, ng/L) of Phthalate Esters in

Seawater Samples from False Creek Harbour. (Number of samples for which water

concentration exceeded the MDL, in brackets).


For those congeners with sufficient data above the MDL, there were no statistically

significant differences (ANOVA, p>0.05) between the geometric means of the water

concentrations from the four sampling stations, indicating that the distribution of phthalate

esters in the water was relatively homogeneous throughout the tested inlet.

1

10

100

1000

DMPDEP

DiBPDBP

BBPDEHP

DnOP

DnNP C6 C7 C8 C9

C10

Phthalate Ester

Tota

l Con

cent

ratio

n (n

g/L)

(12)

(11)

(8)

(7)

(11)

(4)

(5)

(4)

(5)

(5)

(2)

(3) (9)

65

3.2.3. Ratio of Seawater Concentrations to Aqueous Solubilities

A comparison of the observed total seawater concentrations to the aqueous

solubilities of phthalates (as reviewed by Cousins and Mackay 2000) indicates that while

DMP concentrations in seawater were only a minute fraction of DMPs solubility in water,

the ratio of the water concentration (Cw) and the solubility (Sw), i.e. Cw/Sw, appears to

increase with increasing log Kow to a maximum value of 60% for C10 (Figure 3.4). This

suggests that the C10 concentration in seawater is approaching the maximum amount of C10

that can actually be dissolved in water. The notion of C10 phthalate esters approaching their

“saturation level” in water is highly unlikely but indicates that small amounts of suspended

matter in the water column may play an overwhelming role in controlling the total water

concentration. Thus, a second series of data is presented in Figure 3.4, showing ratios based

on model-fitted freely dissolved water concentrations (see section 1.1.2.2), which illustrates

that the ratio between the freely dissolved water concentration and the aqueous solubility for

the high KOW phthalates is approximately 0.001%.

66

Figure 3.4. Ratio of the Seawater Concentrations (CW, ng/L) to the Aqueous Solubilities

(SW, ng/L) of Phthalate Esters, for the Total Seawater Concentration and the Freely

Dissolved Seawater Concentration, as a Function of the Octanol - Seawater Partition

Coefficient.

3.2.4. Distribution of Phthalate Ester Internal Standards between the

Glass Fibre Filter and C18 Extraction Disks

Table 3.5 and Figure 3.5 illustrate the distribution of the spiked internal standards

between the glass fiber filter (representing particle-sorbed phthalates) and the C18 extraction

disks (representing dissolved phthalates). It shows that the fraction of chemical on the C18

extraction disks falls with increasing Kow from 99% for DMP to 14% for DOP. This

relationship is in general agreement with the two-phase sorption model for organic

chemicals to suspended particulate matter, where the freely dissolved fraction (FDW,

unitless) of the total water concentration can be expressed as:

1E-10

1E-08

1E-06

0.0001

0.01

1

0 2 4 6 8 10Log Kow (Seawater)

Con

cent

ratio

n / S

olub

ility

Total Freely Dissolved

67

FDW = 1/[1 + (α · KOW)] (3.3)

Where α is the product of the concentration of suspended matter (ϕSM, kg/L), the organic

carbon content of the suspended matter (ϕOC, kg/kg), and a constant (ω, L/kg), which

represents (i) the ratio between the organic carbon-water partition coefficient of suspended

matter (KOC) and the octanol-water partition coefficient (KOW) (i.e., Koc/Kow), and (ii) the

degree of chemical disequilibrium between the suspended organic matter and the seawater

(i.e., Observed KOC / Predicted KOC), i.e., α = ϕSM · ϕOC · ω. Fitting equation 3.3 to the

observed data results in a value of 4.8 · 10-6 for α. The suspended matter concentration in the

seawater at our test site, as determined by the mass of suspended matter measured on the

glass fiber filters after filtration, was 1.47 (± 1.05) mg/L (n=12), and the organic carbon

content was 40%, indicating that ω was approximately 8.1 (L/kg).

Table 3.5. Mean Fractions of Internal Standards on the Glass Fibre Filter (GF) and C18

Extraction Disks (C18) in Well Water Blanks and False Creek Seawater Samples (%).

Well Water Blanks False Creek Seawater Internal Standard

Log KOW (Seawater) GF C18 GF C18

DMP-d4 1.80 0.14 (± 0.18) 99.86 (± 0.18) 0.05 (± 0.05) 99.95 (± 0.05)DBP-d4 4.58 13 (± 13) 87 (± 13) 15 (± 14) 85 (± 14)

DnOP-d4 8.20 85 (± 13) 15 (± 13) 94 (± 4) 6 (± 4)

68

Figure 3.5. Mean observed fractions (± standard deviation) of spiked phthalate ester internal

standards on the Glass Fibre Filter and C18 Extraction Disks in False Creek Harbour

seawater samples, and the model-fitted Freely Dissolved (FDW Model) and Particulate-

Bound (PB Model) Fractions, determined from Equation 3.3.

3.2.5. Distribution of Seawater Borne Phthalate Esters between the

Glass Fibre Filter and C18 Extraction Disks

Table 3.6 and Figure 3.6 illustrate the distribution of the seawater borne phthalates

between the glass fiber filter and the C18 extraction disks. They show that the fraction of

phthalates on the C18 extraction disks drops from 89 ± 4% (n=12) for DMP and 89 ± 10%

(n=12) for DEP to approximately 40% for DEHP and the other high KOW phthalate esters.

This relationship between the freely dissolved water fraction (FDW) and KOW, observed for

the seawater borne phthalates, is not consistent at high KOW with the inverse relationship

between FDW and Kow observed for the internal standards and expected from the two-

phase sorption model in equation 3.3. The main reason for this discrepancy is that the C18

extraction disks do not only capture freely dissolved phthalates but also phthalates sorbed to

0

0.2

0.4

0.6

0.8

1

1.2

0 2 4 6 8 10 12Log Kow (Seawater)

Frac

tion

of P

htha

late

Est

er o

n C

18 D

isk

C18 FDW Model

0

0.2

0.4

0.6

0.8

1

1.2


Frac

tion

of P

htha

late

Est

er o

n C

18 /

GF

C18 FDW ModelGF PB Model

69

small diameter (i.e. less than 0.45 μm) particulate matter. This small diameter suspended

matter (SDSM) was visible after extraction and was present at a concentration of 0.66 (±

0.28) mg/L (n=7). Phthalates captured on the C18 extraction disks, therefore, represent a

combination of phthalates in both the freely dissolved form and SDSM-sorbed form. A

three-phase sorption model describes this fraction (FC18) as:

FC18 = 1 + βSDSM·Kow / 1 + βSDSM·Kow + βLDSM·Kow (3.4)

Where βSDSM is the product of the concentration of small diameter suspended matter φSDSM

(kg/L), the organic carbon content φSDOC (kg/kg), and a constant ωSDSM (L/kg), which

represents the ratio of KOC to KOW, and the degree of chemical disequilibrium between the

small diameter suspended matter and the seawater, i.e., βSDSM = φSDSM · φSDOC · ωSDSM, and

βLDSM is the product of the concentration of large diameter suspended matter φLDSM (kg/L),

the organic carbon content φLDOC (kg/kg), and a constant ωLDSM (L/kg) representing

KOC/KOW and Observed KOC / Predicted KOC, i.e., βLDSM = φLDSM · φLDOC · ωLDSM. Fitting

this model to the data by minimizing the sum of squared deviations between observed and

predicted values resulted in a βLDSM of 2.0·10-5 and a βSDSM of 1.7·10-5, illustrating that, of

suspended-matter-bound phthalates, 55% was associated with large particles (>0.45 μm),

and 45% with small diameter suspended matter. These fractions are in approximate

agreement with the 69:31 ratio of the concentrations of LDSM, i.e. 1.47 (± 1.05) mg/L

(n=12), and SDSM, i.e. 0.66 (± 0.28) mg/L (n=7) suggesting that LDSM and SDSM exhibit

comparable sorption capacities. The latter suggests that, as long as organic matter contents

are equivalent, large and small diameter organic matter have a similar sorption affinity for

phthalate esters. This is in contrast with many other findings for organic chemicals that

suggest that “dissolved” organic matter exhibits only 10% of the sorption capacity of

70

particulate organic matter. The application of chemical spiking as a method for measuring

sorption capacity may explain some of the discrepancy between the sorption capacity

measured in this study to those in other studies. For example, fitting the measured C18-bound

fractions of the internal standards (which were applied by spiking) to equation 3.4, results in

a βLDSM of 4.9·10-6 and a βSDSM of 2.7·10-7, suggesting that SDSM has only 5% of the

sorptive capacity of LDSM. The difference in sorption between the spiked internal standards

and the seawater-borne phthalates is likely due to the difference in chemical sorption time,

i.e., 1 hr for the internal standards and much longer periods for the seawater borne

phthalates. Comparing the values for βLDSM and βSDSM between the spiked and water-borne

phthalates suggests that, after 1 hr, LDSM has reached only 29% of its sorption potential,

while SDSM has reached only 1.6% of its sorption potential. The slower sorption kinetics

onto SDSM compared to LDSM may explain the apparent lower sorption capacity of SDSM

in spiking studies.

Because of the inability of the C18 extraction disks to distinguish between freely

dissolved and SDSM-sorbed phthalates, freely dissolved seawater concentrations can only

be estimated by fitting the observed fractions of phthalate esters in the seawater to the 3-

phase sorption model:

FDW = 1 /( 1 + βSDSM·Kow + βLDSM·Kow) (3.5)

Where βLDSM is 2.0·10-5 and βSDSM is 1.7·10-5, resulting in estimates of the freely dissolved

fraction (FDW) ranging from virtually 100% for DMP to 8·10-5% for C10 (Table 3.7). A

breakdown of the composition of phthalate ester concentrations in seawater of False Creek is

illustrated in Figure 3.7 and suggests that, for example, of the total DEHP aqueous

concentration of 275 ng/L only 0.02% or 0.05 ng/L may be in the freely dissolved form.

71

Following the widely accepted hypothesis that only the freely dissolved chemical can be

absorbed via the respiratory surface of most aquatic organisms (Black and McCarthy 1988,

Landrum et al. 1985, McCarthy and Jimenez 1985, Gobas and Zhang 1994, Gobas and

Russell 1991), implies that, for the high molecular weight phthalates, the actual water

concentrations to which aquatic organisms are exposed via their respiratory surfaces, are

much lower than the observed total water concentrations.

Table 3.6. Mean Observed Fractions (%) (± Standard Deviations) of Seawater Borne

Phthalate Esters on the Glass Fibre Filter (GF) and C18 Extraction Disks (C18) in Well

Water Blanks and False Creek Seawater Samples.

Well Water Blanks False Creek Seawater Phthalate Ester

Log KOW (Seawater) GF C18 GF C18

DMP 1.80 17 (± 6) 83 (± 6) 11 (± 4) 89 (± 4) DEP 2.77 35 (± 10) 65 (± 10) 11 (± 10) 89 (± 10) DiBP 4.58 39 (± 8) 61 (± 8) 29 (± 6) 71 (± 6) DBP 4.58 36 (± 7) 64 (± 7) 32 (± 8) 68 (± 8) BBP 5.03 44 (± 7) 56 (± 7) 49 (± 10) 51 (± 10)

DEHP 8.20 61 (± 20) 39 (± 20) 55 (± 10) 45 (± 10) DOP 8.20 61 (± 28) 39 (± 28) 57 (± 19) 43 (± 19) DNP 9.11 61 (± 29) 39 (± 29) 60 (± 17) 40 (± 17) C6 6.69 54 (± 16) 46 (± 16) 47 (± 29) 53 (± 29) C7 7.44 53 (± 16) 47 (± 16) 55 (± 15) 45 (± 15) C8 8.20 58 (± 15) 42 (± 15) 53 (± 11) 47 (± 11) C9 9.11 53 (± 27) 47 (± 27) 53 (± 16) 47 (± 16) C10 10.6 57 (± 28) 43 (± 28) 66 (± 18) 33 (± 18)

72

Table 3.7. Mean Fractions (%) of Phthalate Esters Bound to Large and Small

Diameter Suspended Matter (LDSM, SDSM) and Freely Dissolved in False Creek

Harbour Seawater, Determined from the 3-Phase Sorption Model (Eqn 3.5).

Phthalate Ester

Log KOW (Seawater)

LDSM-Bound Fraction (%)

SDSM-Bound Fraction (%)

Freely Dissolved Fraction (%)

DMP 1.80 0.13 0.10 99.8 DEP 2.77 1.15 0.96 97.9 DiBP 4.58 31.8 26.4 41.8 DBP 4.58 31.8 26.4 41.8 BBP 5.03 43.6 36.1 20.3 C6 6.69 54.4 45.1 0.554 C7 7.44 54.6 45.3 0.098

DEHP 8.20 54.7 45.3 0.017 DnOP 8.20 54.7 45.3 0.017

C8 8.20 54.7 45.3 0.017 DnNP 9.11 54.7 45.3 0.002

C9 9.11 54.7 45.3 0.002 C10 10.6 54.7 45.3 8·10-5

73

Figure 3.6. Mean observed fractions (± standard deviations) of seawater-borne phthalate

esters on the C18 Extraction Disks in seawater samples from False Creek Harbour, the 2-phase

model-fitted Freely Dissolved Fraction (Eqn. 3.3) and the 3-phase model-fitted C18 Fraction

(SDSM-bound + FDW) (Eqn. 3.4) and Freely Dissolved Fraction (Eqn. 3.5).

0

0.2

0.4

0.6

0.8

1

1.2


Frac

tion

C18 FDW (2-phase model)C18 (3-phase model) FDW (3-phase model)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

DMPDEPDiBPDBPBBP C6 C7

DEHPDnO

P C8DnN

P C9C10

Phthalate Ester

Frac

tion

Freely Dissolved SDSM Bound LDSM Bound

0.0000001

0.000001

0.00001

0.0001

0.001

0.01

0.1

1

DMPDEPDiBPDBPBBP C6 C7

DEHPDnO

P C8DnN

P C9C10

Phthalate Ester

Frac

tion

Freely Dissolved SDSM Bound LDSM Bound

Figure 3.7. Fraction of Phthalate Esters Bound to Large Diameter Suspended Matter (LDSM) ( ), Bound to Small Diameter

Suspended Matter ( ), and Freely Dissolved ( ) in False Creek Harbour Seawater, Determined from the 3-Phase Sorption Model

(Eqn. 3.5). The y-axis on the right panel is expressed on a logarithmic scale.

75

3.2.6. Summary of the “Total”, “C18”, and “Freely Dissolved” Water

Concentrations

Three water concentrations were determined for phthalate esters in False Creek

Harbour seawater (Table F.3.8 in Appendix F, Figure 3.8). The “total” water concentration

includes all forms of chemical in the water phase, i.e., bound to large and small diameter

suspended matter, and freely dissolved. Total water concentrations ranged from 3.51 to 275

ng/L for DMP, and DEHP respectively. The “C18” water concentration includes chemical

associated with small diameter suspended matter, and freely dissolved chemical. Mean C18

concentrations ranged from 3.14 ng/L for DMP to 124 ng/L for DEHP and 130ng/L for C8

isomers. “Freely dissolved” water concentrations ranged from 5.9·10-5 ng/L for C10 isomers

to 123 ng/L for DEP.

Since the chemical substance must be in the freely dissolved form in order for it to

be taken up by organisms through their respiratory membranes, the freely dissolved water

concentration represents the actual phthalate ester levels in the water to which organisms are

effectively exposed. Filtering the water and determining the chemical concentration on the

C18 disks was conducted in an attempt to experimentally measure the freely dissolved

fraction of the substance in the water. However, the C18 disks captured both the freely

dissolved substance and chemical associated with small diameter suspended matter in the

water column. Measurements of suspended matter revealed significant amounts of small

diameter suspended material in the water samples. Model calculations indicate that this

SDSM played a major role in controlling the distribution of the chemicals in the water by

serving as sorptive material for the high KOW substances, in particular. The total water

concentration gives an indication of the overall mass of the chemical substance in both the

76

water and study system in general. Table 3.8 reveals that, although some of the high KOW

substances were present at relatively high concentration in the False Creek Harbour seawater

(e.g. DEHP, DnNP, C8, C9 and C10), the actual bioavailability of these substances,

indicated by the freely dissolved water concentration, was extremely low.

Figure 3.8. Mean Phthalate Ester Concentrations (± Standard Deviations, ng/L) in False

Creek Harbour Seawater. “Total” concentrations include chemical bound to large and small

diameter suspended matter (LDSM, SDSM) and freely dissolved chemical. “C18”

concentrations include SDSM-bound and freely dissolved chemical. The third bar represents

model estimates of the “Freely Dissolved” chemical concentration.

0.00001

0.0001

0.001

0.01

0.1

1

10

100

1000

DMPDEP

DiBPDBP

BBPDEHP

DnOP

DnNP C6 C7 C8 C9

C10

Phthalate Ester

Seaw

ater

Con

cent

ratio

n (n

g/L)

Total (LDSM+SDSM+FD) C18 (SDSM+FD) Freely Dissolved (FD)

77

3.2.7. Chemical Fugacities in the Water

Using the three concentrations of phthalate esters in False Creek Harbour seawater

(i.e., total, C18, and freely dissolved) (Figure 3.8), three fugacities were determined

following Equation 2.12, i.e., fW = CW / (1/H) (Table F.3.9 in Appendix F, Figure 3.9).

“Total” and ‘C18” fugacities of phthalates in the water ranged from 0.16 nPa for DMP to

4,630 nPa for C9 isomers. Fugacities based on the “freely dissolved” water fraction ranged

between 0.0034 for C10, and 220 nPa for DBP. As explained with the three water

concentrations, the “freely dissolved” fugacity is believed to be the best measure of the

actual chemical fugacity in the water to which the organisms are exposed, since only the

freely dissolved chemical is bioavailable to the organisms for uptake via their respiratory

surfaces. The difference between the three types of water is most significant for the high

molecular weight phthalates (e.g., phthalates with ≥ 6 carbon chains), whose effective or

freely dissolved fugacities in the water are relatively low (Figure 3.9).

78

Figure 3.9. Mean “Total”, “C18”, and “Freely Dissolved” Fugacities (± Standard Deviations,

Pa) in False Creek Harbour Seawater. “Total” fugacities include chemical bound to large

and small diameter suspended matter (LDSM, SDSM) and freely dissolved chemical. “C18”

fugacities include SDSM-bound and freely dissolved chemical. The third bar represents

estimates of the fugacity based on “Freely Dissolved” concentrations.

3.3. Sediment - Water Distribution of Phthalate Esters

Figure 3.10 illustrates organic carbon normalized sediment-water distribution

coefficients (KOC, L/kg OC) for phthalate esters as a function of KOW. The organic carbon

content of the False Creek bottom sediments was 2.8 (± 0.31)% (n=12). Linear regression

between log KOC (L/kg OC) (determined as the ratio of the sediment (Table 3.1) and “total”

water concentration (Table 3.8)), and log KOW resulted in:

1E-12

1E-11

1E-10

1E-9

1E-8

1E-7

1E-6

1E-5

DMPDEP

DiBPDBP

BBPDEHP

DnOP

DnNP C6 C7 C8 C9

C10

Phthalate Ester

Fuga

city

(Pa)

Total (LDSM+SDSM+FD) C18 (SDSM+FD) Freely Dissolved (FD)

79

Log KOC = 0.063 (± 0.060) · log KOW + 4.53 (± 0.45) r2 = 0.08, n = 12 (3.6)

Equation 3.6 illustrates a statistically insignificant relationship (p > 0.05) between sediment-

water partition coefficients and KOW, where standard deviations are reported for the y-

intercept and slope. The distribution of phthalates between sediment and water does not

appear to follow a Karickhoff style relationship where KOC is a linear function of KOW (Seth

et al. 1999). Relationships similar to equation 3.6 have been observed for PCBs and other

organochlorines and are not expected to be specific to phthalate esters (MacLean 1999). One

of the causes for the deviation between the observed distribution coefficients and the

reported equilibrium partition coefficients is expressing the sediment-water distribution

coefficients based on the “total”, rather than the “freely dissolved” water concentration, in

particular for the higher molecular weight phthalates. If the sediment-water distribution

coefficients (KOC, L/kg OC) are expressed based on the estimated “freely dissolved”

concentrations, the relationship improves substantially (p = 3.0·10-6, ± standard deviations

for y-intercept and slope), i.e.

Log KOC = 0.823 (± 0.097) · log Kow + 2.07 (± 0.69) r2 = 0.87, n = 12 (3.7)

Comparing the observed sediment-water distribution coefficients (based on “freely

dissolved” water concentrations, i.e., equation 3.7), to the expected sediment-water

equilibrium partition coefficients (Seth et al. 1999), i.e., equation 3.8,

Log KOC = 1.0 · log Kow + log (0.35) (3.8)

= 1.0 · log Kow - 0.456

reveals that phthalate esters are at a chemical disequilibrium in False Creek Harbour

sediments and water (Figure 3.10). The sediment-water distribution coefficient (KOC) of

DMP was 17,700 fold greater than its equilibrium based sediment-water partition

80

coefficient. The observed degree of disequilibrium appeared to drop with increasing KOW to

a factor of 30 for DEP and to values ranging between 2.7 and 44 for all other phthalate esters

(Table 3.7). The surprisingly high degree of disequilibrium for DMP is unlikely to be due to

experimental error as extraction recoveries were high, pre-analysis losses are expected to be

low due to the short pre-extraction period, and evaporative losses were avoided (and DMP

has a low Henry Law constant of DMP, i.e., 9.78.10-3 Pa.m3.mol-1). Also, because of DMPs

low KOW, the total water concentration reflects virtually entirely freely dissolved chemical,

thus reducing potential error involved in the estimation of the freely dissolved fraction.

The importance of the observed sediment-water disequilibria is that it can affect the

exposure pathways of the organisms in the food web. High chemical concentrations in the

sediments relative to those in the water can elevate the transfer of phthalates from sediments

into organisms directly, through the ventilation of sediment pore-water, or indirectly,

through dietary transfer via the benthic food-chain. In other words, sediment-water

disequilibria increase the importance of the bottom sediments as a route of exposure.

81

Table 3.9. Observed and Predicted Sediment-Water Partition Coefficients (OBS KOC

and PRED KOC, L/kg OC) based on the Freely Dissolved Water Concentration, and the

Ratio between the Observed and Predicted Partition Coefficients.

PE OBS KOC PRED KOC Ratio OBS/PRED DMP 3.87 ·10+5 2.19 ·10+1 17,700 DEP 5.95 ·10+3 2.05 ·10+2 28.9 DiBP 6.35 ·10+4 1.33 ·10+4 4.79 DBP 7.99 ·10+4 1.33 ·10+4 6.03 BBP 1.64 ·10+6 3.74 ·10+4 43.9

DEHP 1.58 ·10+9 5.53 ·10+7 28.6 DnOP 8.20 ·10+8 5.53 ·10+7 14.8 DnNP 1.22 ·10+9 4.49 ·10+8 2.72

C6 4.66 ·10+6 1.71 ·10+6 2.73 C7 1.13 ·10+8 9.72 ·10+6 11.6 C8 1.78 ·10+9 5.53 ·10+7 32.3 C9 9.69 ·10+9 4.49 ·10+8 21.6 C10 2.45 ·10+11 1.24 ·10+10 19.8

Figure 3.10. Observed Sediment-Water Partition Coefficients (Log KOC, L/kg OC), based on

the Total Water Concentration “TOT”, and the Freely Dissolved Water Concentration “FD”,

and the Predicted Sediment-Water Equilibrium Coefficient (L/kg OC), based on Seth et al.

1999.

0

2

4

6

8

10

12

0 2 4 6 8 10 12Log Kow

Log

Koc

(L/k

g O

C)

Obs Koc (TOT) Obs Koc (FD) Pred Koc

82

3.4. Biota Concentrations of Phthalate Esters

3.4.1. Biota Concentration Overview

Concentrations of phthalate esters in False Creek biota samples are reported in terms

of (i) wet weight concentrations (Tables F.3.10 and F.3.11 in Appendix F), (ii) lipid

normalized concentrations (Tables F.3.12 and F.3.13 in Appendix F), and (iii) fugacities

(Tables F.3.14 and F.3.15 in Appendix F).

Average biota concentrations of the individual phthalates ranged from < 0.1 ng/g wet

wt. for DnOP in Whitespotted Greenling and DnNP in Forage Fish to 310 ng/g wet wt. for

DEHP in Green Algae. For the isomeric mixtures, average concentrations ranged from < 0.1

ng/g wet tissue for C6 in Striped Seaperch and Pile Perch to 200 ng/g wet wt. for C8 in

Spiny Dogfish liver samples. Significant levels of DEHP (up to 310 ng/g wet wt.), C8

isomers (up to 200 ng/g wet wt.), C10 isomers (up to 72 ng/g wet wt.), C9 isomers (up to 71

ng/g wet wt.), and DBP (up to 60 ng/g wet wt.) were detected in certain marine species

(Tables F.3.10 and F.3.11 in Appendix F). Mean lipid and organic carbon contents in the

biota species were presented in Table 2.11 (Section 2.5.3), and the lipid normalized

concentrations of phthalate esters in the species ranged from 2.2 ng/g lipid (DnOP in dogfish

liver) to 28,700 ng/g lipid (C8 in plankton) (Table F.3.12 and F.3.13 in Appendix F).

Fugacities ranged from 9.1 · 10-5 nPa for DnOP in Spiny Dogfish liver samples to

2,950 nPa for DBP in Plankton. Fugacities of the isomers ranged from 9.3 · 10-6 nPa for C10

in Spiny Dogfish embryo samples to 5.1 nPa for C6 in Surf Scoter liver samples. Phthalate

fugacities in the biota were relatively low for the high molecular weight phthalates (i.e.,

DEHP, DnOP, DnNP, C8, C9, and C10), and higher for the low and intermediate molecular

weight phthalates, particularly DBP and DEP (Tables 3.14 and 3.15).

83


Figure 3.11 illustrates the concentration of phthalate esters at three biota sampling

stations within False Creek. An Analysis of Variance (ANOVA) was used to determine

whether there were statistically significant differences in the concentrations of phthalate

esters in the biota between the three stations. The results indicate that, as in the sediment

matrix, some of the less mobile species (i.e., green algae, plankton, geoduck clams, and

pacific oysters) in the East Basin sampling station had higher levels of certain phthalate

esters, particularly the larger molecular weight PEs (i.e., BBP, DEHP, DnOP, DNP, C7, C8,

C9, C10), compared to the organisms in the North Central and Marina stations (Figure 3.11,

Appendix D). This difference in concentration is likely due to reduced tidal flushing in the

East Basin section of the harbour, which is the most inland station. Also, the elevated levels

of the high molecular weight phthalates in the sediment matrix of the East Basin station may

act as a source for the benthic or sedentary organisms, resulting in elevated concentrations in

these organisms. For the fish species (e.g., striped seaperch Figure 3.11), there was no

evidence of spatial differences in concentration. To assess the general trends in chemical

movement through the food web, the biota data from the three stations were pooled for

analysis. However to address the spatial variability, biota-sediment accumulation factors for

the benthic species have been calculated on a station-specific basis (see section 3.5 Biota-

Sediment Distribution).

84

A) Plankton

1

10

100

1000

10000

100000

1000000

DMPDEP

DiBPDnB

PBBP

DEHPDnO

PDNP C6 C7 C8 C9

C10

Phthalate Ester

Con

cent

ratio

n (n

g/g

lipid

)

North Central Marina East Basin

*

*

*

*

*

B) Green Algae

1

10

100

1000

10000

100000

DMPDEP

DiBPDnB

PBBP

DEHPDnO

PDNP C6 C7 C8 C9

C10

Phthalate Ester

Con

cent

ratio

n (n

g/g

lipid

)


*

*

**

*

**

85

C) Geoduck Clams

1

10

100

1000

10000

100000

DMPDEP

DiBPDnB

PBBP

DEHPDnO

PDNP C6 C7 C8 C9

Phthalate Ester

Con

cent

ratio

n (n

g/g

lipid

)


**

*

*

**

*

*

D) Pacific Oyster

1

10

100

1000

10000

100000

DMPDEP

DiBPDnB

PBBP

DEHPDnO

PDNP C6 C7 C8 C9

Phthalate Ester

Con

cent

ratio

n (n

g/g

lipid

)


* *

**

*

*

*

*

*

86

Figure 3.11. Mean Lipid Concentrations (± Standard Deviations, ng/g lipid wt.) of Phthalate

Esters in Marine Biota Samples from Three Sampling Stations (“NC” = North Central, “Ma”

= Marina, and “EB” = East Basin) in False Creek Harbour. Species presented are: A)

Plankton, B) Green Algae, C) Geoduck Clams, D) Pacific Oysters, and E) Striped Seaperch.

Starred bars (*) indicate statistically significant differences in concentration between 1

station and the other 2 (single star per chemical), or between 2 specific stations (two stars

per chemical).

3.4.3. Distribution of Phthalate Esters in Sediment, Seawater, and Biota

and Chemical Transfer through the Food Web

3.4.3.1. Low Molecular Weight Phthalates

For all biota samples, dimethyl phthalate concentrations were relatively low, ranging

from 4 to 192 ng/g lipid wt. (0.2 to 2.5 ng/g wet wt.) (Figure 3.12). Fugacities of DMP in the

organisms ranged between 3 and 104 nPa, and fell between those in the sediment (3,120

E) Striped Seaperch

1

10

100

1000

10000

100000

DMPDEP

DiBPDnB

PBBP

DEHPDnO

PDNP C6 C7 C8 C9

Phthalate Ester

Con

cent

ratio

n (n

g/g

lipid

)


87

nPa) and the water (0.2 nPa), for which a substantial sediment-water chemical

disequilibrium existed (i.e., 17,700 fold) (Figure 3.13). Diethyl phthalate concentrations in

the marine biota were higher than those observed for DMP and ranged between 32 and 968

ng/g lipid wt. (1 and 19 ng/g wet wt.) (Figure 3.14). Fugacities in the organisms ranged

between 6 and 181 nPa, and were also between those in the sediment (391 nPa) and water

(14 nPa) (Figure 3.15).

To assess whether there was significant evidence of either biomagnification or

trophic dilution in the food chain, linear regression analysis of fugacity (f) as a function of

trophic position (TP) was conducted. The results for all phthalate esters are summarized in

Table 3.17 (Section 3.4.5), where “p” values indicate whether the slope of the correlation is

statistically significantly different from zero. A positive slope indicates biomagnification is

occurring, and a negative slope provides evidence of trophic dilution. For the low molecular

weight phthalates, the fugacities did not show a statistically significant correlation with

trophic position (Table 3.17, Figure 3.16). Rather, the fugacities were relatively constant

throughout the food chain (i.e., fprey ≅ fpredator). In terms of the overall environmental

distribution of these low molecular weight phthalates, the fugacities of DMP in all the

species, and DEP in the majority of species (i.e., approximately 70%) were significantly

lower than the sediment fugacity (ANOVA, p<0.05) and significantly higher than the water

fugacity (ANOVA, p<0.05) (Tables E.3.1, and E.3.2, Appendix E). In summary, the

fugacities of these low molecular weight substances appear to decrease from the sediments,

to the biota, to the water (i.e., fsediment > fprey ≅ fpredator > fwater).

88

Figure 3.12. Concentrations of Dimethyl Phthalate in Marine Biota from False Creek

Harbour Expressed in Wet Weight (ng/g wet wt.) (top), Lipid Weight (ng/g lipid wt.)

(bottom).

0.1

1

10

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Con

cent

ratio

n (n

g/g

wet

wt.)

1

10

100

1000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

)

DMP

89

Figure 3.13. Fugacities (nPa) of Dimethyl Phthalate in Marine Biota (λ), Sediment (ν), and

Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek Harbour.

1

10

100

1000

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Fuga

city

(nP

a)

DMP

0.1

1

10

100

1000

10000

Wat

erSe

dim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

90

Figure 3.14. Concentrations of Diethyl Phthalate in Marine Biota from False Creek Harbour

Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid wt.) (bottom).

0.1

1

10

100

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Con

cent

ratio

n (n

g/g

wet

wt.)

DEP

1

10

100

1000

10000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

)

91

Figure 3.15. Fugacities (nPa) of Diethyl Phthalate in Marine Biota (λ), Sediment (ν), and


1

10

100

1000

Wat

erS

edim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (

4.07

)

Fuga

city

(nP

a)

1

10

100

1000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

DEP

92

Figure 3.16. Log Fugacity (nPa) Versus Trophic Position for Dimethyl Phthalate (left) and

Diethyl Phthalate (right).

3.4.3.2. Intermediate Molecular Weight Phthalates

Di-iso-butyl phthalate concentrations in the marine biota ranged from 7 to 229 ng/g

lipid wt. (0.2 and 4.1 ng/g wet wt.), or from 1 to 29 nPa on a fugacity basis (Figures 3.17

and 3.18). Di-n-butyl phthalate levels in the organisms were relatively high with lipid-based

concentrations ranging between 89 and 11,700 ng/g (3 and 60 ng/g wet wt.) and fugacities

ranging between 11 and 1,460 nPa (Figures 3.19 and 3.20). Concentrations of butylbenzyl

phthalate in the biota ranged between 15 and 1,400 ng/g lipid (0.7 and 30 ng/g wet wt.), or

between 0.09 and 8.6 nPa on a fugacity basis (Figures 3.21 and 3.22).

In terms of the overall environmental distribution of DiBP, DBP, and BBP, the

fugacities of these substances in the biota were approximately 1 – 2 orders of magnitude

lower than the sediment fugacity, and were less than or equal to the fugacity in the water.

Although the fugacities of DiBP and DBP in several species were up to an order of

magnitude lower than the water fugacity (freely dissolved), these differences were not

statistically significant (ANOVA, p > 0.05) (Table E.3.2, Appendix E). The fugacities of

DMP

0

1

2

3

0 1 2 3 4 5Trophic Position

Log

Fuga

city

(nPa

)DEP

0

1

2

3


Log

Fuga

city

(nPa

)

93

DiBP, DnBP, and BBP showed a slight decline with trophic position (Figure 3.18), yet

regression analysis indicated that this negative correlation was not statistically significant

(Table 3.17). However, ANOVA tests revealed that the fugacities of these substances in the

dogfish muscle and liver samples were statistically significantly lower than fugacities in

some of the lower trophic species such as plankton, green algae, geoduck clams, striped

seaperch, and staghorn sculpin (ANOVA, p < 0.05, see Tables E.3.3 and E.3.4, Appendix

E). In summary, the fugacities of these chemicals were found to be highest in the sediment

and lower in the water and biota. Additionally, fugacities in the higher trophic organisms

were lower than those in the water and the prey species (i.e., fsediment > fwater ≅ fprey ≥ fpredator)

(Figures 3.18, 3.20, 3.22, 3.24, and 3.26, and Table E.3.1, Appendix E).

For the isomers with intermediate molecular weights, concentrations in the marine

organisms ranged from 11 to 772 ng/g lipid wt. (0.09 to 17 ng/g wet wt.) for di-iso-hexyl

phthalate (C6), and from 28 to 2,060 ng/g lipid wt. (0.4 to 45 ng/g wet wt.) for di-iso-heptyl

phthalate (C7) (Figures 3.23 and 3.25). For both C6 and C7, fugacities in the sediment (2.0

and 2.8 nPa) and the in the water (freely dissolved fraction: 0.74 and 0.24 nPa) were

approximately equal to the highest fugacities in the biota, which ranged from 0.01 to 2.1 nPa

for both chemicals (Figures 3.24 and 3.26). ANOVA tests revealed that approximately half

of the marine species tested exhibited chemical fugacities that were significantly lower than

those in the sediments, while only a few of the species (i.e., Dungeness Crab for C6, and

minnows, Pile Perch, and Whitespotted Greenling for C6 and C7) exhibited fugacities that

were significantly lower than those in the water (Tables E.3.1 and E.3.2 Appendix E). In

terms of the chemical movement through the food chain, the fugacities of di-iso-hexyl

phthalate (C6), and di-iso-heptyl phthalate (C7) did not show a statistically significantly

94

increase or decrease with increasing trophic position in the food chain (Table 3.17, Figure

3.18). Overall for these substances, the fugacities appeared slightly higher in the sediments

relative to the water and biota, which exhibited comparable fugacities, with the exception of

a few higher trophic and pelagic fish species (i.e., fsediment ≥ fwater ≅ fprey ≥ fpredator).

95

Figure 3.17. Concentrations of Di-iso-butyl Phthalate in Marine Biota from False Creek

Harbour Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid wt.)

(bottom).

0.1

1

10

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Con

cent

ratio

n (n

g/g

wet

wt.)

DiBP

1

10

100

1000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

)

96

Figure 3.18. Fugacities (nPa) of Di-iso-butyl Phthalate in Marine Biota (λ), Sediment (ν),

and Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek Harbour.

0.1

1

10

100

Wat

erSe

dim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

0.1

1

10

100

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dog

fish

L. (4

.07)

Dog

fish

M. (

4.07

)D

ogfis

h E.

(4.0

7)

Fuga

city

(nP

a)

DiBP

97

Figure 3.19. Concentrations of Di-n-butyl Phthalate in Marine Biota from False Creek


(bottom).

1

10

100

1000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dog

fish

L. (4

.07)

Dog

fish

M. (

4.07

)D

ogfis

h E.

(4.0

7)

Con

cent

ratio

n (n

g/g

wet

wt.)

DBP

10

100

1000

10000

100000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

)

98

Figure 3.20. Fugacities (nPa) of Di-n-butyl Phthalate in Marine Biota (λ), Sediment (ν), and

Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek. Harbour.

1

10

100

1000

10000

Wat

erSe

dim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

1

10

100

1000

10000

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Fuga

city

(nP

a)

DBP

99

Figure 3.21. Concentrations of Butylbenzyl Phthalate in Marine Biota from False Creek


(bottom).

0.1

1

10

100

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Con

cent

ratio

n (n

g/g

wet

wt.)

BBP

1

10

100

1000

10000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

)

100

Figure 3.22. Fugacities (nPa) of Butylbenzyl Phthalate in Marine Biota (λ), Sediment (ν), and


0.01

0.1

1

10

100

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Fuga

city

(nP

a)

BBP

0.01

0.1

1

10

100

Wat

erSe

dim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

101

Figure 3.23. Concentrations of Di-iso-hexyl Phthalate (C6) in Marine Biota from False

Creek Harbour Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid

wt.) (bottom).

1

10

100

1000

10000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

wt.)

0.01

0.1

1

10

100

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

now

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lam

s (2

.53)

S. P

erch

(3.0

5)P

. Per

ch (3

.05)

Frge

Fis

h (3

.25)

Star

fish

(3.4

7)S

. Sco

ter (

3.49

)S

culp

in (3

.51)

D. C

rabs

(3.5

5)S

ole

(3.7

4)G

reen

ling

(3.8

1)Do

gfis

h L

(4.0

7)Do

gfis

h M

. (4.

07)

Dogf

ish

E. (

4.07

)

Con

cent

ratio

n (n

g/g

wet

wt.)

C6

102

Figure 3.24. Fugacities (nPa) of Di-iso-hexyl Phthalate (C6) in Marine Biota (λ), Sediment

(ν), and Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek. Harbour.

0.001

0.01

0.1

1

10

100

1000

Wat

erS

edim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (

4.07

)

Fuga

city

(nP

a)

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

C6

103

Figure 3.25. Concentrations of Di-iso-heptyl Phthalate (C7) in Marine Biota from False


wt.) (bottom).

1

10

100

1000

10000

100000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

wt.)

0.1

1

10

100

1000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

wet

wt.)

C7

104

Figure 3.26. Fugacities (nPa) of Di-iso-heptyl Phthalate (C7) in Marine Biota (λ), Sediment

(ν), and Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek. Harbour.

0.001

0.01

0.1

1

10

100

1000

10000

Wat

erSe

dim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dog

fish

L (4

.07)

Dog

fish

M. (

4.07

)D

ogfis

h E.

(4.0

7)

Fuga

city

(nP

a)

C7

105

Figure 3.27. Fugacity (nPa) Versus Trophic Position for Di-iso-butyl Phthalate (top left),

Di-n-butyl Phthalate (top right), Benzylbutyl Phthalate (middle), Di-iso-hexyl Phthalate (C6)

(bottom left), and Di-iso-heptyl Phthalate (C7) ( bottom right).

BBP

-1

0

1

2


Log

Fuga

city

(nPa

)

DiBP

-1

0

1

2

3


Log

Fuga

city

(nPa

)DBP

0

1

2

3

4


Log

Fuga

city

(nPa

)

C6

-3

-2

-1

0

1


Log

Fuga

city

(nPa

)

C7

-3

-2

-1

0

1


Log

Fuga

city

(nPa

)

106

3.4.3.3. High Molecular Weight Phthalates

Di-2-ethylhexyl and C8 (di-iso-octyl) phthalate were both present in relatively high

concentrations in the marine organisms, ranging between 79 and 16,700 ng/g lipid (1 and

305 ng/g wet weight) for DEHP, and between 17 to 13,900 ng/g lipid wt. (3 to 180 ng/g wet

wt.) for C8 (Figures 3.28, and 3.32). Fugacities of both DEHP and C8 in the biota ranged

from 0.001 to 1.8 nPa and appeared to decline with increasing trophic position (Figures

3.29, and 3.33). Both di-n-octyl, and di-n-nonyl phthalate were present in the marine

organisms at concentrations ranging from 2 to 2,120 ng/g lipid wt. (0.07 to 25 ng/g wet wt.)

(Figures 3.30, and 3.34). The fugacities of these substances in the organisms were relatively

low and ranged from 2.8·10-5 to 0.13 nPa (Figures 3.31, 3.35). C9 (di-iso-nonyl) and C10

(di-iso-decyl) phthalate isomers were detected in the organisms at relatively high levels

ranging between 260 and 11,000 ng/g lipid wt. (0.8 to 71 ng/g wet wt.) for C9, and between

6 and 13,900 ng/g lipid (0.6 and 72 ng/g wet wt.) for C10 (Figures 3.36, and 3.38).

Fugacities of both substances in the marine biota were low (1·10-3 to 2 nPa for C9 and 1·10-5

to 0.02 nPa for C10), and appeared to decline at higher levels in the food chain (Figures

3.37, and 3.39).

These high molecular weight phthalates exhibited similar environmental

distributions and fugacity patterns in the food chain (Figures 3.29, 3.31, 3.33, 3.35, 3.37, and

3.39). For these substances (i.e., DEHP, DnOP, DnNP, C8, C9, and C10 isomers), there is a

considerable difference between the fugacities determined from the three water

concentrations (i.e., total, C18, and freely dissolved). Specifically, “total” and “freely

dissolved” fugacities in the water differ by approximately 4 to 6 orders of magnitude for C8

and C10 phthalates, respectively. As discussed in section 3.2, the freely dissolved

107

concentration best represents the chemical concentration in the water that can be absorbed

via the respiratory surface area of the organism. Therefore, the fugacity determined from the

freely dissolved chemical concentration is believed to be the most appropriate for inter-

media comparison. This is particularly apparent for the high molecular weight phthalates

where the freely dissolved fraction appears to be close to an equilibrium with the sediment

fugacity, whereas the fugacities based on the “total” and “C18” concentrations are orders of

magnitude greater than the fugacities in the sediment and biota compartments. In terms of

the environmental distribution of these high molecular weight phthalates, the sediment

fugacities were typically up to an order of magnitude greater than the freely dissolved water

fugacities, which were approximately equal to the highest fugacities in the biota, usually

occurring in the algae and plankton species at the base of the food chain. The fugacities of

the high molecular weight phthalates significantly declined with trophic position in the food

chain (p < 0.05 for DEHP, DnOP, DnNP, C8, and C9, and p = 0.065 for C10, Table 3.17,

Figure 3.40). Fugacities of these substances in some of the fish and higher trophic species

(e.g., minnows, perch, Dungeness crab, Whitespotted Greenling and Spiny Dogfish), were

significantly lower than the freely dissolved water fugacity (ANOVA, p < 0.05, Table E.3.1

Appendix E). Thus, the fugacities in the various compartments appear to decrease from

sediment to water to biota (i.e., fsediment ≤ fwater(FD) ≅ fprey < fpredator) (Tables E.3.1, E.3.2, E.3.3

and 3.17).

108

Figure 3.28. Concentrations of Di(2-ethylhexyl) Phthalate in Marine Biota from False Creek


(bottom).

0.1

1

10

100

1000

10000

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Con

cent

ratio

n (n

g/g

wet

wt.)

10

100

1000

10000

100000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

)

DEHP

109

Figure 3.29. Fugacities (nPa) of Di(2-ethylhexyl) Phthalate in Marine Biota (λ), Sediment

(ν), and Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek Harbour.

0.0001

0.001

0.01

0.1

1

10

100

1000

10000

Wat

erS

edim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (

4.07

)

Fuga

city

(nP

a)

0.0001

0.001

0.01

0.1

1

10

100

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

now

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lam

s (2

.53)

S. P

erch

(3.0

5)P

. Per

ch (3

.05)

Frge

Fis

h (3

.25)

Star

fish

(3.4

7)S

. Sco

ter (

3.49

)S

culp

in (3

.51)

D. C

rabs

(3.5

5)S

ole

(3.7

4)G

reen

ling

(3.8

1)Do

gfis

h L.

(4.0

7)Do

gfis

h M

. (4.

07)

Dogf

ish

E. (

4.07

)

Fuga

city

(nP

a)

DEHP

110

Figure 3.30. Concentrations of Di-n-octyl Phthalate in Marine Biota from False Creek


(bottom).

0.01

0.1

1

10

100

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Con

cent

ratio

n (n

g/g

wet

wt.)

1

10

100

1000

10000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

)

DnOP

111

Figure 3.31. Fugacities (nPa) of Di-n-octyl Phthalate in Marine Biota (λ), Sediment (ν), and


0.0001

0.001

0.01

0.1

1

10

100

1000

Wat

erSe

dim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

0.0001

0.001

0.01

0.1

1

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Fuga

city

(nP

a)

DnOP

112

Figure 3.32. Concentrations of Di-iso-octyl Phthalate (C8) in Marine Biota from False Creek


(bottom).

1

10

100

1000

10000

100000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

wt.)

1

10

100

1000

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Con

cent

ratio

n (n

g/g

wet

wt.)

C8

113

Figure 3.33. Fugacities (nPa) of Di-iso-octyl Phthalate (C8) in Marine Biota (λ), Sediment


0.0001

0.001

0.01

0.1

1

10

100

1000

10000

Wat

erS

edim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (

4.07

)

Fuga

city

(nP

a)

0.0001

0.001

0.01

0.1

1

10

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

now

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lam

s (2

.53)

S. P

erch

(3.0

5)P

. Per

ch (3

.05)

Frge

Fis

h (3

.25)

Star

fish

(3.4

7)S

. Sco

ter (

3.49

)S

culp

in (3

.51)

D. C

rabs

(3.5

5)S

ole

(3.7

4)G

reen

ling

(3.8

1)Do

gfis

h L

(4.0

7)Do

gfis

h M

. (4.

07)

Dogf

ish

E. (

4.07

)

Fuga

city

(nP

a)

C8

114

Figure 3.34. Concentrations of Di-n-nonyl Phthalate in Marine Biota from False Creek


(bottom).

0.01

0.1

1

10

100

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

now

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lam

s (2

.53)

S. P

erch

(3.0

5)P

. Per

ch (3

.05)

Frge

Fis

h (3

.25)

Star

fish

(3.4

7)S

. Sco

ter (

3.49

)S

culp

in (3

.51)

D. C

rabs

(3.5

5)S

ole

(3.7

4)G

reen

ling

(3.8

1)Do

gfis

h L.

(4.0

7)Do

gfis

h M

. (4.

07)

Dogf

ish

E. (

4.07

)

Con

cent

ratio

n (n

g/g

wet

wt.)

1

10

100

1000

10000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

)

DnNP

115

Figure 3.35. Fugacities (nPa) of Di-n-nonyl Phthalate in Marine Biota (λ), Sediment (ν), and


0.00001

0.0001

0.001

0.01

0.1

1

10

100

1000

10000

Wat

erSe

dim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L.

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

0.00001

0.0001

0.001

0.01

0.1

1

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L. (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Fuga

city

(nP

a)

DnNP

116

Figure 3.36. Concentrations of Di-iso-nonyl Phthalate (C9) in Marine Biota from False


wt.) (bottom).

10

100

1000

10000

100000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

wt.)

0.1

1

10

100

1000

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Con

cent

ratio

n (n

g/g

wet

wt.)

C9

117

Figure 3.37. Fugacities (nPa) of Di-iso-nonyl Phthalate (C9) in Marine Biota (λ), Sediment


0.001

0.01

0.1

1

10

100

1000

10000

Wat

erSe

dim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dog

fish

L (4

.07)

Dog

fish

M. (

4.07

)D

ogfis

h E.

(4.0

7)

Fuga

city

(nP

a)

C9

118

Figure 3.38. Concentrations of Di-iso-decyl Phthalate (C10) in Marine Biota from False


wt.) (bottom).

1

10

100

1000

10000

100000

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Con

cent

ratio

n (n

g/g

lipid

wt.)

0.1

1

10

100

1000

Pla

nkto

n (1

.00)

B. A

lgae

(1.0

0)G

. Alg

ae (1

.00)

Min

nows

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S

. Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D

. Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L (4

.07)

Dogf

ish

M. (

4.07

)Do

gfis

h E

. (4.

07)

Con

cent

ratio

n (n

g/g

wet

wt.)

C10

119

Figure 3.39. Fugacities (nPa) of Di-iso-decyl Phthalate (C10) in Marine Biota (λ), Sediment


0.000001

0.00001

0.0001

0.001

0.01

0.1

1

10

100

1000

10000

Wat

erS

edim

ent

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scu

lpin

(3.5

1)D.

Cra

bs (3

.55)

Sol

e (3

.74)

Gre

enlin

g (3

.81)

Dog

fish

L (4

.07)

Dog

fish

M. (

4.07

)D

ogfis

h E

. (4.

07)

Fuga

city

(nP

a)

0.000001

0.00001

0.0001

0.001

0.01

0.1

1

Plan

kton

(1.0

0)B

. Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws

(2.3

3)M

. Cla

ms

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)S

tarfi

sh (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)D

ogfis

h L

(4.0

7)D

ogfis

h M

. (4.

07)

Dog

fish

E. (4

.07)

Fuga

city

(nP

a)

C10

120

Figure 3.40. Log Fugacity (nPa) Versus Trophic Position for Di(2-ethylhexyl) Phthalate

(top left), Di-n-octyl Phthalate (top right), Di-iso-octyl Phthalate (C8) (middle left) and Di-

n-nonyl Phthalate (middle right). and Di-iso-nonyl Phthalate (C9) (bottom left), and Di-iso-

decyl Phthalate (C10) (bottom right).

DEHP

-4

-3

-2

-1

0

1

2


Log

Fuga

city

(nPa

)DnOP

-5

-4

-3

-2

-1

0


Log

Fuga

city

(nPa

)

DnNP

-5

-4

-3

-2

-1

0


Log

Fuga

city

(nPa

)

C8

-3

-2

-1

0

1


Log

Fuga

city

(nPa

)

C9

-3

-2

-1

0

1


Log

Fuga

city

(nPa

)

C10

-6

-5

-4

-3

-2

-1


Log

Fuga

city

(nPa

)

121

3.4.4. Summary of Food Chain Bioaccumulation Results

Fugacity is plotted as a function of trophic position for all phthalate esters in Figures

3.41 (individual phthalate esters) and 3.42 (isomeric mixtures). Statistical results of the

regression between fugacity (f) and trophic position (TP) for all phthalate esters are

summarized in Table 3.17. For the low molecular weight phthalates (i.e., DMP and DEP),

the fugacity does not increase or decrease in a statistically significant manner with

increasing trophic position in the food-chain. For the mid-molecular weight individual

phthalates (i.e., DiBP, DBP, and BBP), a declining trend in fugacity, with increasing trophic

position, becomes apparent; however, the relationship is not statistically significant (Table

3.17). For C6 and C7 phthalate ester isomeric mixtures, there is no statistically significant

increase or decrease in fugacity with increasing trophic position. For the high Kow

substances (i.e., DEHP, DnOP, DnNP, C8, C9, and C10), a statistically significant negative

correlation between fugacity and trophic position exists.

Table 3.17. Statistical Results of Regression: Fugacity versus Trophic Position (TP)

PE Saltwater KOW

n “b” y-intercept

“m” Slope

p value for slope

R2

DMP 1.80 18 1.31 0.017 0.860 0.002 DEP 2.77 18 1.45 0.048 0.646 0.014 DiBP 4.58 18 1.04 -0.091 0.322 0.061 DBP 4.58 18 2.41 -0.154 0.199 0.101 BBP 5.03 18 0.45 -0.115 0.353 0.054

DEHP** 8.20 18 0.02 -0.419 0.012** 0.335 DnOP** 8.20 16 -1.13 -0.524 0.006** 0.434 DnNP** 9.11 15 -1.50 -0.490 0.030** 0.315

C6 6.69 16 -0.75 0.014 0.931 0.001 C7 7.44 15 -0.90 -0.038 0.831 0.004

C8** 8.20 18 -0.04 -0.298 0.030** 0.261 C9** 9.11 12 -0.59 -0.335 0.022** 0.422 C10* 10.5 15 -2.08 -0.336 0.065* 0.238

*p < 0.10, **p < 0.05

122

Figure 3.41. Fugacity Versus Trophic Position for Individual Phthalate Esters (DMP, DEP,

DiBP, and DBP (top), BBP, DEHP, DnOP, and DnNP (bottom)) in Marine Biota from False

Creek Harbour.

-2

-1

0

1

2

3

4

5


Log

Fuga

city

(nPa

) DMPDEPDiBPDBPDMP LinearDEP LinearDiBP LinearDBP Linear

-5

-4

-3

-2

-1

0

1

2


Log

Fuga

city

(nPa

) BBPDEHPDnOPDnNPBBP LinearDEHP LinearDnOP LinearDnNP Linear

123

Figure 3.42. Fugacity Versus Trophic Position for Phthalate Ester Isomeric Mixtures (C6,

C7, C8, C9, and C10) in Marine Biota from False Creek Harbour.

3.4.5. Discussion

The objective of the field study was to determine the extent of food-chain

bioaccumulation of phthalate esters in the marine system and to distinguish between the

occurrence of biomagnification, trophic dilution and lipid-water equilibrium partitioning.

Mechanistically, there are several chemical uptake and elimination processes that occur

within biological organisms, the relative rates of which determine the resulting levels in the

organisms, and the distributional patterns of the chemical in the food chain. For the marine

aquatic organisms in the field study, chemical uptake processes include (1) chemical uptake

from the water via the gill membrane, and adsorption via the skin, and (2) chemical uptake

-5

-4

-3

-2

-1

0

1


Log

Fuga

city

(nPa

)C6C7C8C9C10C6 LinearC7 LinearC8 LinearC9 LinearC10 Linear

124

from diet via the gastrointestinal tract membrane. Chemical elimination processes include

(1) gill elimination, (2) fecal egestion, (3) metabolism, (4) gut hydrolysis and (5) growth

dilution (Figure 3.43) (Gobas 1993, Gobas et al. 1999). The results of the field study

indicate that the pattern of chemical movement through the food chain is dependent on the

chemical’s octanol-seawater partition coefficient. Thus, different patterns of chemical

distribution in the food chain were observed for the low, intermediate, and high molecular

weight phthalate esters.

Figure 3.43. Chemical Uptake and Elimination Routes in Fish

For the low Kow phthalates (i.e., DMP and DEP), fugacities in the organisms remain

relatively constant throughout the food chain, providing no evidence of either

biomagnification or trophic dilution. For these more water-soluble chemicals, chemical

uptake from the water, through the gills and/or the skin, is likely the most dominant intake

process. For diethyl phthalate, fugacities in the marine biota were similar to, or greater than

those in the water, and lower than those in the sediment. Both the comparable fugacities in

the water and biota, and the lack of biomagnification indicate that equilibrium partitioning

Metabolism

DietaryUptake

Gill Uptake

Gill Elimination Growth Dilution

Fecal Egestion

Gut Hydrolysis

125

of the chemical between the water and the lipid tissue of the organisms is the dominant

process controlling the bioaccumulation of this substance. In the case of dimethyl phthalate,

the higher fugacities in the organisms relative to those in the water may reflect exposure of

the organisms to a higher chemical fugacity in the sediment matrix, resulting from

ventilation of higher fugacity sediment pore water, and/or the ingestion of sediments. The

organisms may achieve a steady state fugacity that is in between the higher chemical

fugacity in the sediment, and the lower chemical fugacity in the water, and reflects exposure

of the organisms to both media. Another possible explanation for the higher fugacities of

DMP in the biota, relative to the water, is that this substance may have an affinity for

binding to a non-lipid matrix within the biota (e.g. protein). In summary, lipid-water

partitioning mediated by gill uptake and elimination appear to dominate and control the

overall mass of the lower molecular weight phthalates in the organisms. Additionally, it

appears that exposure of the organisms to significantly higher fugacities in the sediments

results in the elevation of the biota fugacities to levels above those in the water.

As Kow increases, fugacities of some of the intermediate molecular weight phthalates

(i.e., DiBP, DBP, BBP) appear to decline slightly with increasing trophic level in the food

chain, although this decrease was not statistically significant. However, the fugacities of

DiBP, DBP, and BBP in the dogfish were significantly lower than those in the primary

producers and some of the smaller fish (e.g., perch and sculpin). For these phthalates with

intermediate molecular weights, the freely dissolved water fugacities were generally

comparable to those in the organisms, although the fugacities of DBP in the dogfish liver,

and fugacities of C6 and C7 in minnows, crabs, and greenlings, dropped below the levels in

the water. Comparable fugacities in the biota and water suggest that equilibrium partitioning

126

between the water and the organisms is occurring, and that the processes of gill uptake and

gill elimination drive the resulting chemical body burdens (Figure 3.43). The slight decline

in fugacity throughout the food chain that was observed for DiBP, DBP and BBP, suggests

that metabolic transformation may occur. However, the general agreement between

fugacities in the water and those in the organisms of the food chain, indicate that metabolism

is too minor to affect the observed lipid-water partition coefficients. Woffard et al. (1981)

and Carr et al. (1997) suggest that biotransformation of di-n-butyl phthalate and butylbenzyl

phthalate occurs, although metabolic transformation rates have not been quantified.

Substances with high KOW’s have a high potential to bioaccumulate in marine

organisms and biomagnify through the food chain. Significant evidence of food chain

bioaccumulation for non-metabolizable substances such as PCB’s in aquatic ecosystems,

such as the Great Lakes, has been reported in the literature (e.g., Oliver and Niimi, 1988,

Connolly and Pedersen, 1988, Morrison et al. 1997). However, in the current study, the

fugacities of the high KOW phthalates in the marine organisms decreased significantly with

increasing trophic position, providing evidence of trophic dilution. Additionally, the water

fugacities were generally equal to the levels in the plankton and algae, and greater than those

in the higher trophic organisms. This pattern indicates that chemical uptake decreases,

and/or elimination rates increase at each step in the food chain. Potential mechanisms and

factors that may contribute to the observed pattern of trophic dilution include: (1) a reduced

bioavailability of the high KOW substances in the water, and (2) the occurrence of gut

hydrolysis and/or (3) metabolism. The reduced bioavailability of these substances in the

water is likely to limit chemical uptake through the respiratory surface of the marine

organisms and may reduce the overall mass of chemical entering the organisms.

127

Additionally, chemical entering the organism through the dietary pathway may be subject to

hydrolysis in the gastrointestinal tract, reducing dietary assimilation and the overall

chemical uptake. Dietary assimilation efficiencies for bluegills (Macek et al. 1979), and

paneaid shrimp (Hobson et al. 1994) fed a C14 labeled DEHP contaminated diet were

estimated by Staples et al. (1997a) to range between 0.25 and 0.30. However, since

radiolabeled chemicals were used, they report that the assimilation of parent DEHP may be

lower than the estimated value due to metabolism in the gut. Parkerton et al. (2001)

determined a dietary assimilation efficiency of 0.20 for di-iso-heptyl phthalate (C7) in

rainbow trout based on laboratory dietary uptake experiments. These estimated values are

generally lower than dietary assimilation efficiencies reported for PCBs of similar KOW,

which range from approximately 0.25 up to >0.60 (Gobas et al. 1988, Gobas et al. 1993,

Morrison et al. 1997). Thus, biotransformation of phthalate esters in the gastrointestinal

tract may be the cause of this difference in dietary assimilation efficiencies between the two

classes of chemicals. Another possible explanation is that metabolic transformation of these

chemicals in the organisms may increase the overall elimination (or transformation) of these

substances, and may play a role in driving the fugacities in the organisms to levels below

that in their diet and the water. Evidence of metabolic transformation of DEHP has been

reported for several aquatic or marine organisms (Metcalf et al. 1973, Stalling et al. 1973,

and Wofford et al. 1981, Barron et al. 1995, Sabourault 1998, and Karara and Hayton 1988).

The metabolism of DnOP in aquatic organisms has been described by Sanborn et al., 1975.

However, metabolic rate constants have not been quantified.

Qualifiers: It is important to note that the fugacity versus trophic position

correlation is heavily dependent on the two extremes of the food web: the primary producers

128

(e.g., plankton and green algae: trophic position = 1.00) and the top predator (i.e., spiny

dogfish: trophic position = 4.07). For all of the phthalates, the fugacities in the algae and

plankton tended to be relatively high, while those in the dogfish tended to be relatively low.

However, at both extremes, there is uncertainty or confounding factors that influence the

resulting trends.

First, there is uncertainty in the determination of the fugacity capacity for green

algae and plankton. Direct measurements of the fugacity capacity of these organisms have

not been reported, and there is debate in the literature as to the best method of normalizing

concentrations (i.e., whether to base the normalization on organic carbon or lipid content).

Skoglund and Swackhamer (1999) suggest that organic carbon is the best matrix to use for

the normalization of PCB accumulation in plankton. Based on a review of available data,

Seth and others (1999) suggested that organic carbon has a sorbing capacity for organic

chemicals that ranges between 0.14 and 0.89 that of lipids, and suggest values of 0.35-0.41.

Hiatt (1999) and Tolls and McLachlan (1994), suggest that terrestrial plants behave as

though they have 0.1% - 10% octanol equivalence. Cousins and Mackay (2001) recommend

using a 1% lipid value for chemical partitioning into terrestrial plants based on a literature

assessment and model validations. Alternatively, plankton and algae data may be

normalized based strictly on the measured lipid contents, which were 0.1% and 0.2%

respectively in our study. Gobas et al. (1991) report that bioconcentration in aquatic

macrophytes is effectively a chemical partitioning process between the plant lipids (which

were approximately 0.2%) and water. Normalizing the concentrations based solely on the

lipid contents of the organisms results in a low fugacity capacity, and therefore a relatively

high fugacity. These three methods of calculating the fugacity capacity (i.e., using measured

129

organic carbon contents, a 1% lipid content, or measured lipid contents) yield resulting

fugacities that differ by up to two-orders of magnitude. This consequently affects the slope

of the regression between fugacity and trophic position. The purpose of lipid normalizing

the data or calculating fugacities, is to remove the effect of differences in lipid contents or

sorbing matrices between organisms, since these differences greatly affect the overall

chemical concentration. Algae and plankton contain low lipid contents (i.e., plankton ≅

0.1%, green algae ≅ 0.2% (wet wt.)), and high organic carbon contents (i.e., plankton ≅ 40%

dry wt. (or 0.6% wet wt.), green algae ≅ 34% dry wt. (or 6.1% wet wt.)). Organic carbon

serves as the organism’s energy and carbon source, and due to its relatively high content, it

is likely to serve as an important site for chemical accumulation. Thus, our normalization

(fugacity capacity calculation) incorporated lipid, organic carbon, and moisture contents of

the algae and plankton (Eqn. 2.10), since all are likely to contribute to the overall sorption of

the chemicals in these organisms.

The spiny dogfish (Squalas acanthias) was the top predator in the food chain, and

they generally exhibited lower fugacities for all of the phthalates, relative to the other

species (Tables E.3.3 and E.3.4 in Appendix E). The dogfish are larger and more mobile

than the other species in the study and, as a result, inhabit larger spatial ranges. Dogfish tend

to move into foraging areas accompanying an incoming tide; and it was during this period in

the tidal cycle that the organisms were collected from False Creek. Likely, the dogfish

moved into the harbour to forage just prior to collection, and the concentrations in these

organisms may be more reflective of their overall exposure to phthalate levels throughout

their geographical range (i.e., Georgia Basin), where phthalate levels tend to be lower than

in False Creek (Garrett 2002). Additionally, dogfish have a low metabolic rate, and digest

130

their food slowly (Ketchen 1996). Jones and Geen (1977) estimated that 16 days elapse

between feedings for dogfish in British Columbia. Given the slow digestion and metabolic

rate of the dogfish, as well as the relatively long half-lives of some of these chemicals, it is

possible that the dogfish were not exposed to the phthalate levels in False Creek long

enough to achieve a steady state with the ambient environment. The concentrations of the

higher molecular weight phthalates in the dogfish may therefore be lower than their steady-

state levels in False Creek. This factor could be a significant contributor to the lower

phthalate ester levels in this species, relative to the levels in other biota.

Additionally, the correlation between fugacity and trophic position is naturally

dependent on the determination of trophic position. In this study, trophic position was

calculated based on quantitative dietary information from the literature (i.e., dietary

proportions of each prey species). This approach has two major advantages: (i) it provides a

more complete picture of the dietary preferences of each species, rather than a “snap-shot”

representation would have been obtained from a gut-content analysis of the samples, and (ii)

it enables us to determine direct trophic linkages, such that food-chain bioaccumulation

models for phthalate esters can be constructed. However, because dietary preferences vary

with changes in prey abundance, season, and age or life-stage of the predator, there is some

natural variability in trophic level that may not be taken into account. Thus, in order to

assess some of the potential variability, and as an additional method for the determination of

trophic positions, stable nitrogen and carbon isotope ratio analysis will be conducted on the

samples (i.e., δN15 and δC13). Stable isotope analysis is becoming increasingly common as a

means to assess community structure and ecological function. Nitrogen and carbon isotope

ratios in animal tissues are related to those found in their diet, and can be used as tracers to

131

assess trophic position and initial carbon sources. The results of this analysis will be

reported in a later publication.

3.5. Biota - Water Distribution Of Phthalate Esters

3.5.1. Overview

Bioaccumulation Factors (BAFs), relating the chemical concentrations in the marine

biota to those in the water, are reported in Tables F.3.18 to F.3.30 of Appendix F for all

phthalate esters. For each chemical, the BAFs are determined on both a wet weight

(Equation 3.9), and lipid weight (Equation 3.10) basis.

BAFwet = Cbiota / Cwater (3.9)

BAFlipid = Clipid / Cwater (3.10)

Where the BAFwet is the wet weight bioaccumulation factor (L/kg wet weight); Cbiota is the

wet weight chemical concentration in the organism (ng/kg wet weight); and Cwater is the

chemical concentration in the water (ng/L). In the lipid BAF (L/kg lipid) calculation

(Equation 3.10), the lipid normalized chemical concentration in the organism (Clipid, ng/kg

lipid) is utilized. Since the concentration data were lognormally distributed (Appendix D),

the mean BAFs (ΧBAF) were calculated from the mean logarithmic concentration values in

the organism (Χ(C bio)) and water (Χ(C wat)) (Equation 3.11a), and then converted back to the

original units. Standard deviations (SDBAF) were determined accordingly on a logarithmic

basis (Equation 3.11b).

Log ΧBAF = Log Χ(C bio) - Log Χ(C wat) (3.11a)

Log SDBAF = Log SD(C bio) + Log SD(C wat) (3.11b)

As explained previously, three different water concentrations were measured or

estimated in this study: “Total water”, “C18 water”, and “Freely Dissolved water”. As a

132

result, one can express the BAF values for each congener in three ways, depending on the

type of water concentration. These three wet weight and lipid weight BAFs are compared to

the appropriate Canadian Environmental Protection Act (CEPA, 1999) bioaccumulation

criteria (i.e., 5000 L/kg wet wt. or 100,000 L/kg lipid wt.) for each phthalate ester in Figures

3.44 to 3.56. Since, through their respiratory surfaces, organisms are only effectively

exposed to freely dissolved chemical in the water phase, the BAF based on this fraction (i.e.,

BAFFD) most accurately represents the actual degree of bioaccumulation of a substance, and

is thus, the most appropriate value for comparison with the CEPA BAF criterion.

Additionally, the lipid normalized BAF can be directly compared to the octanol – seawater

partition coefficient of a substance to assess whether equilibrium partitioning of the

chemical between the water and lipids is occurring. Specifically, the lipid normalized BAF

will equal the KOW under equilibrium conditions.

3.5.2. Bioaccumulation Factors (BAFs)

3.5.2.1. Low Molecular Weight Phthalate Esters

For the lower molecular weight phthalate esters, i.e., dimethyl phthalate and diethyl

phthalate, the majority of the chemical in the water phase is in the freely dissolved form.

Hence, there are no differences in the bioaccumulation factors based on the “total”, “C18”,

and “freely dissolved” water concentrations. For DMP, there was significant variability in

the BAFs between the different species. The mean wet weight BAFs ranged between 53 (23

- 107) and 790 (380 - 3,100) L/kg wet weight, with most falling below 180 L/kg, while the

lipid-based values ranged between 1,090 (386 - 3,050) and 61,500 (14,000 - 269,000) L/kg

lipid (Table F.3.18, Figure 3.44). For DEP, the mean wet weight BAFs ranged between 9 (3

- 27) and 169 (41 - 693) L/kg wet wt., while the lipid-based BAFs varied between 254 (54 -

133

1,200) and 8,620 (1,550 - 48,000) L/kg lipid wt. (Table F.3.19, Figure 3.45). Since the

observed water concentrations (i.e., total, C18, and freely dissolved) for both DMP and DEP

were relatively consistent, the intra-species variability in the BAFs can be mainly attributed

to variability in the biota concentrations. Both chemicals exhibited BAFs that were higher

than expected based on equilibrium partitioning of the substances between the organisms

and the water. The lipid based BAFs of DMP were approximately 100 - 300 fold greater

than the chemical’s Kow of 62, while those for DEP were approximately 2 - 10 times greater

than expected from DEP’s KOW of 587 (Figures 3.44, and 3.45). For both DMP and DEP, all

of the mean BAFs were lower than the CEPA bioaccumulation criteria, both on a wet weight

and lipid weight basis (i.e., 5000 L/kg wet wt., and 100,000 L/kg lipid wt., respectively).

134

Figure 3.44. Bioaccumulation factors expressed on a wet weight (L/kg wet wt.) (top), and lipid

weight (L/kg lipid wt.) (bottom) basis for dimethyl phthalate in False Creek marine biota. The

BAFs are calculated from “total” (▬), “C18” (σ), and “freely dissolved” (○) water

concentrations. The CEPA bioaccumulation criterion ( — ― ), and octanol-seawater

partition coefficient (⎯) are presented. Error bars represent one standard deviation.

DMP BAFs - Wet Weight

1 E+1

1 E+2

1 E+3

1 E+4

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g w

et w

t.)

TOTC18FDCEPA

DMP BAFs - Lipid Normalized

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id)

TOTC18FDCEPAKow

135


weight (L/kg lipid wt.) (bottom) basis for diethyl phthalate in False Creek marine biota. The




DEP BAFs - Wet Weight

1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g w

et w

t.)

TOTC18FDCEPA

DEP BAFs - Lipid Normalized

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id) TOT

C18FDCEPAKow

136

3.5.2.2. Intermediate Molecular Weight Phthalate Esters

For the mid molecular weight phthalate esters (i.e., di-iso-butyl, di-n-butyl, and

butylbenzyl phthalate), the fraction of chemical in the water that was estimated to be freely

dissolved was comparable to the C18-bound fraction (which includes both freely dissolved

and dissolved organic carbon bound chemical), and ranged from approximately 0.50 for

BBP to 0.75 for DiBP, and DBP. Thus, the observed BAFs differed for the three water

concentrations. Specifically, the BAFs based on the “C18” and “freely dissolved” water

concentrations were approximately 40 to 50% greater than those based on the “total” water

concentration (Figures 3.46, 3.47, and 3.48).

For DiBP and DBP, the mean wet weight BAFs ranged from approximately 29 to

1,100 L/kg, and for BBP they ranged from 187 up to 8,700 (“total”), 17,000 (“C18”), and

43,000 (“freely dissolved”) L/kg wet wt. The lipid normalized BAFs ranged from 1,330 to

107,000 L/kg lipid for DiBP, from 807 to 64,500 L/kg lipid for DBP (excluding the BAFFD

for plankton, which was 254,000 L/kg lipid), and from 4,370 up to 1.99 million L/kg lipid

for BBP (Tables F.3.20, F.3.21, and F.3.22, Figures 3.46, 3.47, and 3.48).

For both DiBP and DBP, the highest lipid BAFs in the marine species were

approximately equal the chemicals’ octanol-seawater partition coefficients (i.e., 37,900).

The majority of BAFs for other species were within an order of magnitude below the KOW,

indicating lower than expected concentrations in the organisms, relative to the water. For

BBP, the lipid based BAFs were comparable to the chemical’s KOW (i.e., 106,740), and fell

within an order of magnitude above and below the KOW.

The mean wet weight and lipid weight BAFs of DiBP and DBP in the marine

organisms fell below the CEPA bioaccumulation criteria, with the exception of plankton in

137

DBP on a lipid weight basis (which was 106,000 and 157,000 L/kg lipid for “total” and

“C18” water concentrations, respectively). However, the upper standard deviations of the

lipid BAFs of DiBP and DBP in plankton, brown algae, green algae, geoduck clams, striped

seaperch, surf scoters, staghorn sculpin, english sole, and whitespotted greenling exceeded

the criteria, indicating that a certain proportion of the individuals in these distributions (i.e.,

at least 16%) exhibited BAFs that exceeded the guideline (Figures 3.46, and 3.47).

For BBP, there were several species with BAFs that exceeded the CEPA

bioaccumulation criteria. On a wet weight basis, the mean BAFs for brown and green algae,

spiny dogfish (liver and embryo), dungeness crabs, and surf scoters exceeded the criterion,

based on one or more of the water concentrations. As well, the upper standard deviations of

the BAFs for all the species except whitespotted greenling exceeded the guideline, again

demonstrating that a certain fraction of the individuals in these populations had BAFs

greater than 5,000 L/kg wet wt (Figure 3.48). On a lipid basis, BAFs for BBP in plankton,

green algae, geoduck clams, striped seaperch, pile perch, pacific staghorn sculpin, and surf

scoter exceeded the CEPA criterion based on all three water concentrations (i.e., “total”,

“C18” and “freely dissolved”). The mean BAFs for the all of the other marine species,

except forage fish, starfish, and dogfish (liver, muscle, embryo), were greater than 100,000

L/kg lipid, based on at least the “freely dissolved” water concentration (Figure 3.48).

138


weight (L/kg lipid wt.) (bottom) basis for di-iso-butyl phthalate in False Creek Marine Biota.

The BAFs are calculated from “total” (▬), “C18” (σ), and “freely dissolved” (○) water



DiBP BAFs - Wet Weight

1 E+1

1 E+2

1 E+3

1 E+4

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA

DiBP BAFs - Lipid Normalized

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id)

TOTC18FDCEPAKow

139


weight (L/kg lipid wt.) (bottom) basis for di-n-butyl phthalate in False Creek marine biota. The




DBP BAFs - Wet Weight

1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA

DBP BAFs - Lipid Normalized

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id)

TOTC18FDCEPAKow

140


weight (L/kg lipid wt.) (bottom) basis for butylbenzyl phthalate in False Creek Marine Biota.




BBP BAFs - Wet Weight

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g w

et w

t.)

TOTC18FDCEPA

BBP BAFs - Lipid Normalized

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id) TOT

C18FDCEPAKow

141

3.5.2.3. Intermediate Molecular Weight Phthalate Ester Isomeric

Mixtures

For di-iso-hexyl (C6) and di-iso-heptyl (C7) phthalate, the BAFs based on the “total”

and “freely dissolved” water concentrations varied by approximately 2 orders of magnitude

for C6, and 3 orders of magnitude for C7. Additionally, there was approximately 2 orders of

magnitude difference in the BAFs that were calculated from the same water concentration,

due to interspecies differences in phthalate ester concentrations.

Wet weight BAFs based on “total” and “C18” water concentrations ranged from 9 to

1,270 L/kg for C6, and from 12 to 7,130 L/kg for C7. Those based on the “freely dissolved”

water fraction ranged from 1,560 to 301,000 and from 12,600 to 3.28 million L/kg wet wt.

for C6 and C7, respectively (Tables F.3.26, and F.3.27, and Figures 3.49, and 3.50).

The lipid weight BAFs based on the “total” and “C18” water concentrations ranged

from 1,080 L/kg up to 161,000 L/kg for C6, and from 1,350 to 287,000 L/kg for C7. The

“freely dissolved” lipid BAFs ranged from 194,000 to 14.0 million for C6, and from 1.38

million to 132 million L/kg for C7. Figures 3.49 and 3.50 reveal that the “freely dissolved”

lipid based BAFs are, on the whole, slightly lower than expected based on equilibrium

partitioning of the chemical between the organisms and water. Specifically, they range from

approximately ½ an order of magnitude above the chemicals’ octanol - seawater partition

coefficients to 1 ½ orders of magnitude below KOW, where KOW is ca. 4.88 million (C6) and

27.8 million (C7).

With the exception of the lipid based BAFs in geoduck clams, and surf scoter birds,

all of the “total” and “C18” BAFs for C6 were below the CEPA bioaccumulation criteria

both on a wet weight and lipid weight basis. Similarly for C7, only the lipid based BAFs for

142

plankton, surf scoters, and staghorn sculpin, and the wet weight BAF for dogfish (liver)

exceeded the CEPA bioaccumulation criteria, using the “total” and “C18” water

concentrations. However, based on the “freely dissolved” water concentrations, the majority

of species exhibit BAFs that exceed the CEPA criteria. The only species with BAFs that did

not exceed CEPA criteria were striped seaperch and pile perch for C6 phthalate, determined

on a wet weight basis (Figures 3.49, and 3.50).

143


weight (L/kg lipid wt.) (bottom) basis for di-iso-hexyl phthalate in False Creek marine biota.




C6 BAFs - Wet Weight

1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA

C6 BAFs - Lipid Normalized

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id) TOT

C18FDCEPAKow

144


weight (L/kg lipid wt.) (bottom) basis for di-iso-heptyl phthalate in False Creek marine biota.





1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA


1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

1 E+9

1 E+10

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id) TOT

C18FDCEPAKow

145

3.5.2.4. High Molecular Weight Phthalate Esters

Due to the high octanol-water partition coefficients of these substances (i.e., di-2-

ethylhexyl, di-n-octyl, and di-n-nonyl phthalate), the majority of the chemical in the water

phase are associated with particulate matter and dissolved organic carbon, which greatly

reduces their bioavailability for uptake via the respiratory surface area. While the observed

fractions on the C18 extraction disks (which include freely dissolved and dissolved organic

carbon-bound chemical) ranged from 40% for DnNP to 45% for DEHP, the model estimated

freely dissolved fractions were only 0.017% for DEHP and DnOP, and 0.002% for DnNP,

suggesting that a substantial amount of these chemicals was bound to small diameter

particulate matter. As a result, there are large differences between the BAFs based on the

“total”, “C18” and “freely dissolved” water concentrations. Specifically, the BAFs for

DEHP and DnOP varied by 3 orders of magnitude, while those for DnNP varied by 3.5

orders of magnitude.

In addition to the variability in BAFs due to the different water concentrations, there

was also substantial interspecies variability in the BAFs. On a lipid weight basis, this

resulted in approximately 3 orders of magnitude variability in BAFs that were based on the

same water concentration. For both DEHP and DnOP, the wet weight BAFs based on the

“total” and “C18” water concentrations ranged between 5 and 2,560 L/kg wet weight, while

those based on the “freely dissolved” fraction ranged from 26,900 to 6.41 million L/kg wet

weight. For DNP, the “total” and “C18” BAFs ranged from 1 to 762 L/kg wet weight, and the

“freely dissolved” BAFs ranged from 43,800 to 14.5 million L/kg wet weight (Tables

F.3.23, F.3.24, F.3.25 and Figures 3.51, 3.52, and 3.53).

146

Mean lipid-based BAFs for DEHP were between 202 to 135,000 L/kg (“total” and

“C18”), and 1.17 million to 353 million L/kg based on the “freely dissolved” water

concentrations. For DnOP, the lipid based BAFs ranged from 154 to 368,000, L/kg lipid,

based on the “total”, “C18”, water concentrations and from 894,000 and 912 million based on

the “freely dissolved” water concentration. For DNP, lipid-based BAFs ranged from 21 to

67,700 L/kg lipid for “total” and “C18” water concentrations, and from 993,000 to 1.29

billion L/kg lipid for the “freely dissolved” water concentration (Tables F.3.23, F.3.24, and

F.3.25 and Figures 3.51, 3.52, and 3.53).

For these high molecular weight phthalate esters, the “freely dissolved” lipid-based

BAFs were generally lower than expected based on equilibrium partitioning, indicating

lower than expected concentrations in the biota, relative to those in the water. For DEHP

and DnOP, the “freely dissolved” lipid-based BAFs range from approximately the

chemicals’ octanol-seawater partition coefficients (i.e., ~158 million) for plankton and algae,

to 2 orders of magnitude below that, for the higher trophic species. The BAFs based on

“total” and “C-18” water concentrations were 3 to 6 orders of magnitude below the octanol -

seawater partition coefficients’ of DEHP and DnOP (Figures 3.51, and 3.52). The pattern

was similar for DnNP, where the “freely dissolved” lipid based BAFs range from the

BAF=KOW equilibrium line (i.e., 1.28 billion) to 3 orders of magnitude below that, and the

“total” and “C18” BAFs are 4 to 7 orders of magnitude lower than expected based on

equilibrium partitioning (Figure 3.53).

With the exception of the lipid-based BAFs for DEHP in green algae and DEHP and

DnOP in plankton, all of the lipid and wet weight BAFs based on the “total” and “C18” water

concentrations fell below the CEPA bioaccumulation criteria for all three chemicals.

147

However, all of the BAFs of these substances based on the “freely dissolved” water

concentration exceeded the guidelines, both on a wet weight and lipid weight basis (Figures

3.51, 3.52, and 3.53).

148


weight (L/kg lipid wt.) (bottom) basis for di-2-ethylhexyl phthalate in False Creek marine

biota. The BAFs are calculated from “total” (▬), “C18” (σ), and “freely dissolved” (○) water



DEHP BAFs - Wet Weight

1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA

DEHP BAFs - Lipid Normalized

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

1 E+9

1 E+10

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id)

TOTC18FDCEPAKow

149


weight (L/kg lipid wt.) (bottom) basis for di-n-octyl phthalate in False Creek marine biota. The




DnOP BAFs - Wet Weight

1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA

DnOP BAFs - Lipid Normalized

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

1 E+9

1 E+10

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id)

TOTC18FDCEPAKow

150


weight (L/kg lipid wt.) (bottom) basis for di-n-nonyl phthalate in False Creek marine biota.




DnNP BAFs - Wet Weight

1 E-1

1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

1 E+9

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA

DNP BAFs - Lipid Normalized

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

1 E+9

1 E+10

1 E+11

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id) TOT

C18FDCEPAKow

151

3.5.2.5. High Molecular Weight Phthalate Ester Isomeric Mixtures

For di-iso-octyl (C8), di-iso-nonyl (C9), and di-iso-decyl (C10) phthalate, the BAF

results are similar to those for the high molecular weight individual phthalates. Specifically,

due to their high octanol-seawater partition coefficients (i.e. log KOW’s of 8.20 for C8, 9.11

for C9, and 10.6 for C10), these substances are mainly associated with large and small

diameter particulate matter in the water phase. The observed fractions on the C18 extraction

disks (which include freely dissolved and small diameter particulate bound chemical) ranged

from 47% for C8 and C9 to 33% for C10, while the model estimated freely dissolved

fractions were only 0.017% for C8, 0.002% for C9, and 7.7 · 10-5 % for C10. As a result,

there is a large difference between the “total” and “freely dissolved” water concentrations

for these substances. Consequently, the corresponding “total” and “freely dissolved” BAFs

differed by approximately 3.8, 4.7, and 6.1 orders of magnitude for C8, C9, and C10,

respectively. In addition to variability due to the water concentration, differences in

concentrations between the marine species resulted in approximately 2.0 (C8), 1.1 (C9), and

3.5 (C10) orders of magnitude variability in the BAFs that were based on the same water

concentration.

For C8 to C10 inclusive, the wet weight BAFs based on the “total” and “C18” water

concentrations ranged between 9 and 2,740 L/kg wet weight. “Freely dissolved” wet weight

BAFs ranged from 66,700 to 4.13 million L/kg for C8; 353,000 to 36.5 million L/kg for C9;

and 13.9 million to 1.20 billion L/kg for C10 (Tables F.3.28, F.3.29, and F.3.30).

The “total” and “C18” lipid-based BAFs for C8, C9, and C10 varied from 59 to

536,000 L/kg. The “freely dissolved” lipid based BAFs were between 344,000 and 605

152

million L/kg for C8; 135 million and 5.71 billion L/kg for C9; and 97.1 million and 236

billion L/kg for C10 (Tables F.3.28, F.3.29, and F.3.30).

For these high molecular weight isomeric mixtures, the “freely dissolved” lipid-

based BAFs were slightly lower than expected from equilibrium partitioning; generally

falling one order of magnitude below the chemicals’ octanol - seawater partition

coefficients. Figures 3.54, 3.55, and 3.56 also indicate an apparent decline in the BAFs with

increasing trophic position in the food chain.

A comparison of the wet weight bioaccumulation factors to the CEPA guideline of

5000 L/kg wet wt. reveals that, for C8, C9, and C10, all of the “total” and “C18” based BAFs

are lower than the criteria, while all of the BAFs based on the “freely dissolved” water

concentration exceed the criteria (Figures 3.54, 3.55, and 3.56). This is generally true for

the lipid based BAFs, where all of the “freely dissolved” BAFs exceeded the 100,000 L/kg

lipid wt. CEPA guideline. However, a few of the “total” and/or “C18” lipid based BAFs also

exceeded the criteria (i.e., C8 in plankton, C9 in plankton, green algae, blue mussels and

geoduck clams, and C10 in plankton, green algae, and striped seaperch) (Figures 3.54, 3.55,

and 3.56).

153


weight (L/kg lipid wt.) (bottom) basis for di-iso-octyl (C8) phthalate in False Creek marine





1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA


1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

1 E+9

1 E+10

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id)

TOTC18FDCEPAKow

154


weight (L/kg lipid wt.) (bottom) basis for di-iso-nonyl (C9) phthalate in False Creek marine





1 E+0

1 E+1

1 E+2

1 E+3

1 E+4

1 E+5

1 E+6

1 E+7

1 E+8

1 E+9

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA


1 E+03

1 E+04

1 E+05

1 E+06

1 E+07

1 E+08

1 E+09

1 E+10

1 E+11

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id)

TOTC18FDCEPAKow

155


weight (L/kg lipid wt.) (bottom) basis for di-iso-decyl (C10) phthalate in False Creek marine





1 E+0

1 E+11 E+2

1 E+3

1 E+41 E+5

1 E+6

1 E+7

1 E+81 E+9

1 E+10

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

s (L

/kg

wet

wt.)

TOTC18FDCEPA


1 E+011 E+021 E+031 E+041 E+051 E+061 E+071 E+081 E+091 E+101 E+111 E+12

Plan

kton (

1.00

)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2.

33)

M. C

lams (

2.40

)M

usse

ls (2

.48)

Oyste

rs (2

.48)

G. C

lams (

2.53

)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)

Frge

Fish

(3.2

5)St

arfis

h (3.

47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish E

. (4.

07)

BAF

(L/k

g lip

id) TOT

C18FDCEPAKow

156

3.5.3. Chemical Distribution in the Food Chain

The lipid based BAFs determined from the “total” water concentration are plotted as a

function of trophic position for all phthalate esters in Figures 3.57 (individual phthalate

esters), and 3.58 (isomeric mixtures). Results of the linear regression between the lipid –

based BAFs and trophic position for each phthalate ester are presented in Table 3.31, where

“p” values indicate whether the slope of the regression is statistically significantly different

from zero.

Figures 3.57 and 3.58 and Table 3.31 reveal that the lipid-based BAFs exhibit the

same patterns as those in the fugacity plots. Specifically, the BAFs do not increase or

decrease in a statistically significant manner throughout the food chain for the low and mid

molecular weight phthalates (i.e., DMP, DEP, DiBP, DBP, BBP, C6, and C7). However, for

phthalates with carbon chains greater than or equal to eight (i.e., DEHP, DnOP, DnNP, C8,

C9, and C10), there was a statistically significant decline in the lipid normalized BAF with

increasing trophic position.

Table 3.31. Statistical Results of Regression: Log BAF (L/kg lipid wt.) versus Trophic

Position

PE Kow n “b” y-intercept

“m” Slope

p value for slope

R2

DMP 1.80 18 4.30 -0.12 0.26 0.077 DEP 2.77 18 3.14 0.04 0.74 0.007 DiBP 4.58 18 4.23 -0.09 0.32 0.062 DBP 4.58 18 4.25 -0.15 0.22 0.093 BBP 5.03 18 5.10 -0.11 0.38 0.049

DEHP* 8.20 18 4.93 -0.46 2.27E-03* 0.451 DnOP* 8.20 16 5.02 -0.56 3.72E-03* 0.463 DnNP* 9.11 14 4.27 -0.45 4.15E-02* 0.303

C6 6.69 17 3.87 -0.01 0.96 1.60E-04 C7 7.44 15 4.17 -0.04 0.82 0.004 C8* 8.20 18 4.71 -0.30 3.08E-02* 0.260 C9* 9.11 13 5.25 -0.34 1.69E-02* 0.418 C10* 10.5 16 4.86 -0.35 3.98E-02* 0.268

* p < 0.05

157

Figure 3.57. Lipid based Bioaccumulation Factors (L/kg lipid wt.) plotted as logarithms

versus trophic position for individual phthalate esters (DMP, DEP, DiBP, and DBP (top),

BBP, DEHP, DnOP, and DnNP (bottom)) in marine biota from False Creek Harbour.

1

2

3

4

5

6


Log

BAF

(L/k

g lip

id)

DMPDEPDiBPDBPLinear (DMP)Linear (DEP)Linear (DiBP)Linear (DBP)

1

2

3

4

5

6


Log

BAF

(L/k

g lip

id)

BBPDEHPDnOPDnNPLinear (BBP)Linear (DEHP)Linear (DnOP)Linear (DnNP)

158

Figure 3.58. Lipid Based Bioaccumulation Factors (L/kg lipid wt.) plotted as logarithms

Versus Trophic Position for Phthalate Ester Isomeric Mixtures (C6, C7, C8, C9, and C10) in

Marine Biota from False Creek Harbour.

3.5.4. Relationship between the Lipid BAFs, based on the “Total” water

concentration, and the Octanol – Seawater Partition Coefficient

The lipid-based BAFs, based on the “Total” water concentration, are plotted as a

function of KOW in Figures 3.59a and 3.59b for all of the marine species included in the

study. Figure 3.59 (“total water”) reveals that there is substantial variability in the BAFs

between the various marine species. This variability may in part be due to the observed

trophic dilution in the food chain, where the fugacities, or lipid normalized chemical

concentrations, of the high KOW phthalates were highest for the plankton and algae species,

and lowest in the large predatory fish species (e.g., spiny dogfish).

1

2

3

4

5

6


Log

BAF

(L/k

g lip

id) C6

C7C8C9C10Linear (C6)Linear (C7)Linear (C8)Linear (C9)Linear (C10)

159

Figure 3.59 also reveals that the BAFs of the low molecular weight phthalate esters

(DMP, and DEP) are greater than expected from equilibrium partitioning of the chemical

between the organisms and the water (i.e., the BAFLipid = KOW line). This result may be due

to the sediment - water disequilibrium that was present in the system, where the organisms

are being exposed to high chemical fugacities in the sediments, and relatively low fugacities

in the water. Thus, the organisms achieve steady state concentrations in between those in

the two surrounding media. The lipid normalized BAFs of the mid molecular weight

phthalates (i.e., dibutyl and butylbenzyl) are approximately equal to the values expected

from equilibrium partitioning of the chemical between the organisms and water, while those

for the higher molecular weight phthalates fall below the equilibrium line.

With the exception of DMP, the BAFs tend to increase with increasing KOW up to

BBP, and then either decline, or remain relatively constant for the higher KOW substances

(i.e., exhibiting either parabolic or logarithmic curve patterns). The magnitude of this

relationship varies for the different organisms. For example, plankton exhibits the highest

BAFs, which increase with increasing KOW initially, up to a value of 200,000 L/kg lipid or

for BBP; the levels then remain around 100,000 L/kg lipid for the higher KOW phthalates.

Similarly, for green algae, the BAF increases up to a maximum value of approximately

100,000 L/kg lipid for BBP; the BAFs then remain relatively constant (above 10,000 L/kg)

for the higher molecular weight phthalates. For geoduck clams, a similar relationship is

observed, but the BAFs are approximately 10 fold lower than those in green algae. The

maximum BAF value reaches approximately 100,000 L/kg lipid for BBP; levels then

slightly decline in the higher KOW substances (i.e., ca. 30,000 - 40,000 L/kg lipid). The lipid-

based BAFs for the dungeness crabs increase with increasing KOW to approximately 30,000

160

L/kg lipid for BBP; BAFs then significantly drop off to approximately 1,000 L/kg lipid for

the high molecular weight phthalates. For the fish species, the initial increase in the BAF

values with increasing Kow is followed by a subsequent decline for the higher molecular

weight phthalates. In the fish, the lipid BAFs are highest for the smaller forage fish species

(e.g., striped seaperch maximum BAF was 230,000 L/kg lipid), followed by the larger fish

species (e.g., whitespotted greenling maximum BAF was 40,000 L/kg Lipid), and lowest for

the top-predator (i.e., spiny dogfish maximum BAF was 15,000 L/kg lipid). In the surf

scoter marine bird species, the lipid BAFs increase up to a value of 400,000 L/kg lipid for

BBP. The BAFs then drop off for the higher molecular weight phthalates, particularly for

the C8, and C9 substances.

Figure 3.59b illustrates that the lipid normalized BAFs determined from the “total”

water concentration, generally, do not exceed the CEPA bioaccumulation criteria, although

the BAFs of several of the high KOW phthalates in plankton exceed the criteria. The other

exception is butylbenzyl phthalate, where the BAFs for approximately one-third of the

species exceed the criteria.

Figure 3.59a. Lipid Normalized Bioaccumulation Factors, Based on “Total” Water Concentrations, of Phthalate Esters in Marine Biota

from False Creek Harbour Versus the Octanol - Seawater Partition Coefficient. The CEPA Criteria (⎯) and BAFLipid = KOW line (▬)

are presented.

1 E+01

1 E+02

1 E+03

1 E+04

1 E+05

1 E+06

1 E+07

1 E+08

1 E+09

1 E+10

1 E+11

1E+01 1E+03 1E+05 1E+07 1E+09 1E+11Kow

BAF

(L/k

g lip

id)

PlanktonAlgaeBenthosBirdSmall FishLarge FishKowCEPA

1 E+01

1 E+02

1 E+03

1 E+04

1 E+05

1 E+06

1E+01 1E+03 1E+05 1E+07 1E+09 1E+11

Kow

BAF

(L/k

g lip

id) Plankton

AlgaeBenthosBirdSmall FishLarge FishCEPA

Figure 3.59b. Lipid Normalized Bioaccumulation Factors, Based on “Total” Water Concentrations, of Phthalate Esters in Marine

Biota from False Creek Harbour Versus the Octanol - Seawater Partition Coefficient. The CEPA Criteria (⎯) is presented.

163

3.5.5. Relationship between the Lipid BAFs, based on the “Freely

Dissolved” water concentration, and the Octanol – Seawater

Partition Coefficient

Figure 3.60 illustrates the lipid BAFs, determined from the freely dissolved water

concentration, as a function of the octanol-seawater partition coefficient, and indicates that

the lipid BAFs generally follow the “BAFLipid = KOW” line. Comparing Figures 3.59 and

3.60 reveals that the BAFs of DMP and DEP remain unchanged by the water concentration,

since most of the chemical is in the freely dissolved form. The BAFs for the mid molecular

weight phthalates increase slightly (i.e., by a factor of two), since approximately 50% of the

chemical is in the freely dissolved form. The water concentration used in the BAF

calculation has the greatest effect on the BAF values of the high molecular weight

phthalates, indicated by the contrast between the “total water” BAFs and the “freely

dissolved water” BAFs, since only a minute fraction of the chemical is estimated to be in the

freely dissolved phase (i.e., ≤ 0.017%).

Similar to Figure 3.59 (total water concentrations), the lipid normalized BAF values

for DMP and DEP were generally greater than their octanol - seawater partition coefficients,

those for DiBP, DBP, BBP, C6, and C7 were approximately equal to KOW, while those for

the C8 to C10 phthalates were generally lower than expected from equilibrium partitioning.

However, in contrast to the Figure 3.59 (BAFs determined from “total” water

concentrations), the maximum “freely dissolved” BAFs of the high molecular weight

phthalates approximately equal or exceed equilibrium levels. Again, for these high KOW

substances, the highest BAFs occurred in plankton and algae, and the lowest occurred in the

higher trophic organisms, and these differences are likely due to the occurrence of trophic

dilution in food chain for these substances. The observation that the “freely dissolved” lipid

164

BAFs of these high molecular weight phthalates generally did not exceed the equilibrium

partitioning line (i.e., BAFLipid = KOW) except in plankton and algae, gives evidence that

these chemicals are not biomagnifying in the food chain. Therefore, although the lipid

normalized BAFs of some of the intermediate and, in particular, the high molecular weight

phthalates exceed the CEPA bioaccumulation criteria (Figure 3.60), this is really only due to

the low bioavailability of the substances, and not due to biomagnification in the food chain.

1E+01

1E+02

1E+03

1E+04

1E+05

1E+06

1E+07

1E+08

1E+09

1E+10

1E+11

1E+12

1E+01 1E+03 1E+05 1E+07 1E+09 1E+11Kow

BAF

(L/k

g lip

id)

PlanktonAlgaeBenthosBirdSmall FishLarge FishKowCEPA

Figure 3.60. Lipid normalized Bioaccumulation Factors, based on “Freely Dissolved” water concentrations, of phthalate esters in

marine biota from False Creek Harbour versus the octanol - seawater partition coefficient. The CEPA criteria (⎯) and BAFLipid = KOW

line (▬) are presented.

166

3.6. Biota - Sediment Distribution Of Phthalate Esters

3.6.1. Overview

Biota - sediment accumulation factors are reported for all thirteen phthalate esters in

Tables F.3.32 to F.3.34 of Appendix F. The BSAF (kg OC/kg lipid) is the ratio between the

chemical concentration in an organism to that in the sediments (Equation 3.12).

BSAF = Clipid / Csediment (3.12)

Where “Clipid” (μg PE/kg lipid) is the lipid normalized phthalate ester concentration in the

organism, and “Csediment” (μg PE/kg OC) is the organic carbon normalized concentration in

the sediments. Similar to the BAFs, the BSAFs were calculated from the mean logarithmic

concentration values in the organism and sediments, and then converted back to the original

units (see Equation 3.11). For species which exhibited spatial differences phthalate ester

concentrations (e.g., plankton, green algae, geoduck clams, and pacific oysters), station –

specific BSAFs were derived and are presented.

3.6.2. Biota - Sediment Accumulation Factors (BSAFs)

The BSAFs are presented in Figures 3.61 to 3.67 for all phthalate esters. A BSAF

value of unity suggests that equilibrium partitioning of the chemical between the sediments

and the organism is occurring, assuming that organic carbon and lipid have equal sorbing

capacities for the substance. The BSAFs of all of the phthalate esters were generally less

than unity, which indicates that the chemical concentrations in the organic carbon

compartment of the sediments were greater than those in the lipid tissue of the organisms.

For DMP, the BSAFs were relatively low and ranged from 0.003 to 0.1 kg OC/kg lipid

(Figure 3.61, Table F.3.32). The BSAFs for DEP, DiBP, DBP, BBP, C6, and C7 were

167

similar and ranged from 0.01 to over 1 kg OC/ kg lipid (Figures 3.61, 3.62, 3.63, and 3.65,

and Tables F.3.32, F.3.33, and F.3.34). The absolute values of the BSAFs for the higher

molecular weight phthalates (i.e., DEHP, DnOP, DnNP, C8, C9, and C10), were relatively

low and ranged from 0.0008 to just less than 1 kg OC/ kg lipid (Figures 3.63, 3.64, 3.66, and

3.67, and Tables F.3.33, and F.3.34).

In terms of patterns of the BSAFs throughout the food chain, the BSAF values

appeared relatively constant throughout the food chain for the low and mid molecular weight

phthalates (i.e., DMP, DEP, DiBP, DBP, BBP, C6, and C7). However, a declining pattern

in the BSAFs with increasing trophic level is apparent for the higher molecular weight

phthalates (i.e., DEHP, DnOP, DnNP, C8, C9, and C10), which is consistent with the trends

in fugacity throughout the food chain.

168

Figure 3.61. Biota - Sediment Accumulation Factors (kg OC / kg lipid) of dimethyl

phthalate (top), and diethyl phthalate (bottom) in marine biota from False Creek Harbour.

Error bars represent one standard deviation.

DMP BSAFs

0.0001

0.001

0.01

0.1

1

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lams

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scul

pin (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)Do

gfish

L (4

.07)

Dogfi

sh M

. (4.

07)

Dogf

ish

E. (4

.07)

BSA

F (k

g O

C/k

g lip

id)

DEP BSAFs

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B.

Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lams

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Sculp

in (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gre

enlin

g (3

.81)

Dogf

ish

L (4

.07)

Dogfi

sh M

. (4.

07)

Dogf

ish E

. (4.

07)

BSA

F (k

g O

C/k

g lip

id)

169

Figure 3.62. Biota - Sediment Accumulation Factors (kg OC / kg lipid) of di-iso-butyl

phthalate (top), and di-n-butyl phthalate (bottom) in marine biota from False Creek

Harbour. Error bars represent one standard deviation.

DIBP BSAFs

0.01

0.1

1

10

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)Oy

ster

s (2

.48)

G. C

lams

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish (3

.25)

Star

fish

(3.4

7)S.

Sco

ter (

3.49

)Sc

ulpin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)Gr

eenli

ng (3

.81)

Dogf

ish L

(4.0

7)

Dogf

ish M

. (4.

07)

Dogf

ish

E. (4

.07)

BSA

F (k

g O

C/k

g lip

id)

DBP BSAFs

0.001

0.01

0.1

1

10

100

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lams

(2.4

0)M

usse

ls (2

.48)

Oyst

ers

(2.4

8)G.

Clam

s (2

.53)

S. P

erch

(3.0

5)P.

Per

ch (3

.05)

Frge

Fish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scul

pin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)Gr

eenl

ing (3

.81)

Dogfi

sh L

(4.0

7)

Dogf

ish

M. (

4.07

)

Dogfi

sh E

. (4.

07)

BSA

F (k

g O

C/k

g lip

id)

170

Figure 3.63. Biota - Sediment Accumulation Factors (kg OC / kg lipid) of butylbenzyl

phthalate (top), and di(2-ethylhexyl) phthalate (bottom) in marine biota from False Creek


BBP BSAFs

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lams

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scul

pin (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)Do

gfish

L (4

.07)

Dogfi

sh M

. (4.

07)

Dogf

ish

E. (4

.07)

BSA

F (k

g O

C/k

g lip

id)

DEHP BSAFs

0.00001

0.0001

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B.

Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lam

s (2

.53)

S. P

erch

(3.0

5)P.

Per

ch (3

.05)

Frge

Fis

h (3

.25)

Star

fish

(3.4

7)S.

Sco

ter (

3.49

)Sc

ulpin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)Gr

eenli

ng (3

.81)

Dogfi

sh L

(4.0

7)

Dogfi

sh M

. (4.

07)

Dogf

ish E

. (4.

07)

BSA

F (k

g O

C/k

g lip

id)

171

Figure 3.64. Biota - Sediment Accumulation Factors (kg OC / kg lipid) of di-n-octyl

phthalate (top), and di-n-nonyl phthalate (bottom) in marine biota from False Creek


DnOP BSAFs

0.0001

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lams

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G.

Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish (3

.25)

Star

fish

(3.4

7)S.

Sco

ter (

3.49

)Sc

ulpin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)Gr

eenl

ing (3

.81)

Dogf

ish L

(4.0

7)

Dogfi

sh M

. (4.

07)

Dogfi

sh E

. (4.

07)

BSA

F (k

g O

C/k

g lip

id)

DNP BSAFs

0.0001

0.001

0.01

0.1

1

10

100

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lams

(2.4

0)M

usse

ls (2

.48)

Oyst

ers

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish (3

.25)

Star

fish

(3.4

7)S.

Sco

ter (

3.49

)Sc

ulpin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)Do

gfish

L (4

.07)

Dogf

ish M

. (4.

07)

Dogfi

sh E

. (4.

07)

BSA

F (k

g O

C/k

g lip

id)

172

Figure 3.65. Biota - Sediment Accumulation Factors (kg OC / kg lipid) of di-iso-hexyl

(C6) phthalate (top), and di-iso-heptyl (C7) phthalate (bottom) in Marine Biota from False

Creek Harbour. Error bars represent one standard deviation.

C6 BSAFs

0.001

0.01

0.1

1

10

100

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lams

(2.4

0)M

usse

ls (2

.48)

Oys

ters

(2.4

8)G.

Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish (3

.25)

Star

fish

(3.4

7)S.

Sco

ter (

3.49

)Sc

ulpin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)Gr

eenl

ing (3

.81)

Dogf

ish L

(4.0

7)

Dogfi

sh M

. (4.

07)

Dogfi

sh E

. (4.

07)

BSA

F (k

g O

C/k

g lip

id)

C7 BSAFs

0.001

0.01

0.1

1

10

100

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lams

(2.4

0)M

usse

ls (2

.48)

Oyst

ers

(2.4

8)G

. Cla

ms

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish (3

.25)

Star

fish

(3.4

7)S.

Sco

ter (

3.49

)Sc

ulpin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)G

reen

ling

(3.8

1)Do

gfish

L (4

.07)

Dogf

ish M

. (4.

07)

Dogfi

sh E

. (4.

07)

BSA

F (k

g O

C/k

g lip

id)

173

Figure 3.66. Biota - Sediment Accumulation Factors (kg OC / kg lipid) of di-iso-octyl (C8)

phthalate (top), and di-iso-nonyl (C9) phthalate (bottom) in marine biota from False Creek


C8 BSAFs

0.00001

0.0001

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lams

(2.5

3)S.

Per

ch (3

.05)

P. P

erch

(3.0

5)Fr

ge F

ish

(3.2

5)St

arfis

h (3

.47)

S. S

cote

r (3.

49)

Scul

pin (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nling

(3.8

1)Do

gfish

L (4

.07)

Dogfi

sh M

. (4.

07)

Dogf

ish

E. (4

.07)

BSA

F (k

g O

C/k

g lip

id)

C9 BSAFs

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B.

Alga

e (1

.00)

G. A

lgae

(1.0

0)M

innow

s (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lam

s (2

.53)

S. P

erch

(3.0

5)P.

Per

ch (3

.05)

Frge

Fis

h (3

.25)

Star

fish

(3.4

7)S.

Sco

ter (

3.49

)Sc

ulpin

(3.5

1)D.

Cra

bs (3

.55)

Sole

(3.7

4)Gr

eenli

ng (3

.81)

Dogfi

sh L

(4.0

7)

Dogfi

sh M

. (4.

07)

Dogf

ish E

. (4.

07)

BSA

F (k

g O

C/k

g lip

id)

174

Figure 3.67. Biota - Sediment Accumulation Factors (kg OC / kg lipid) of di-iso-decyl (C10)

phthalate in marine biota from False Creek Harbour. Error bars represent one standard

deviation.

3.6.3. Relationship Between the BSAF in Benthic Species and the

Octanol-Seawater Partition Coefficient

Biota - sediment accumulation factors in the benthic marine species from False

Creek Harbour are plotted as a function of the octanol - seawater partition coefficient for all

phthalates esters in Figure 3.68. The figure demonstrates that, even for these benthic

species, there is significant variability in the BSAFs between the various species. In general,

the BSAFs are highest for the burrowing geoduck clams, followed by the other bivalves

(i.e., blue mussels and pacific oysters); values are lowest for the dungeness crab and

common seastar, an epibenthic species. Differences in the BSAFs between species may, to

some degree, reflect differences in habitat usage between the species. As presented in

C10 BSAFs

0.0001

0.001

0.01

0.1

1

10

Plan

kton

(1.0

0)B.

Alg

ae (1

.00)

G. A

lgae

(1.0

0)M

inno

ws (2

.33)

M. C

lam

s (2

.40)

Mus

sels

(2.4

8)O

yste

rs (2

.48)

G. C

lam

s (2

.53)

S. P

erch

(3.0

5)P.

Per

ch (3

.05)

Frge

Fis

h (3

.25)

Star

fish

(3.4

7)S.

Sco

ter (

3.49

)Sc

ulpi

n (3

.51)

D. C

rabs

(3.5

5)So

le (3

.74)

Gree

nlin

g (3

.81)

Dogf

ish L

(4.0

7)

Dogf

ish

M. (

4.07

)

Dogf

ish

E. (4

.07)

BSA

F (k

g O

C/k

g lip

id)

175

Section 3.3, we observed a sediment-water disequilibrium in the system, particularly for the

low KOW substances, where chemical fugacities in the sediments were greater than those in

the water. Thus, benthic organisms, such as the geoduck clam, that are closely tied to the

sediments and it’s associated pore water, are likely being exposed to higher chemical levels

in the sediments (relative to those in the water), resulting in greater internal body residues.

For the higher molecular weight phthalate esters, there were greater differences in the

BSAFs between species. These differences may be partly due to the observed trophic

dilution, where the fugacities, or lipid-normalized concentrations, decrease at higher levels

in the food chain (i.e., dungeness crab, and seastar). Higher order species such as the crabs,

may have a more developed enzymatic system relative to the clams, and thus may be better

able to metabolize these chemicals. It is also possible that the diet is a relatively more

important exposure route in the crab and seastar than in the filter feeding bivalves.

Therefore, if these chemicals are being metabolized in the gastrointestinal tract of the

organisms prior to assimilation, then the crab / seastar would uptake lower levels of the

chemical.

Additionally, the BSAFs tend to exhibit a parabolic trend with KOW. In general, the

BSAFs are lowest for DMP, they increase for the mid molecular weight phthalates, and then

tend to drop off for the high molecular weight phthalates. The BSAFs in the geoduck clams

are greatest for C6 phthalate and then appear to decrease slightly for the larger molecular

weight substances (i.e., BSAFs are lowest for the C8 and C10 phthalates, although those for

C9 approach unity). This pattern is the same for the BSAFs in mussels and oysters,

although the absolute values are about 3 times lower (or 0.5 orders of magnitude lower).

176

Again, the same pattern is observed in the crabs and starfish; however, the C8 and C10

BSAFs drop off more significantly in these organisms.

With the exception of C6 phthalate in geoduck clams and blue mussels, all BSAFs

are less than unity. Thus, while the BSAFs approach this line of equilibrium, they tend not

to exceed it, indicating that biomagnification is not occurring.

Figure 3.68 Biota - Sediment Accumulation Factors (kg OC / kg lipid) on a Logarithmic Scale versus Log Octanol - Seawater

Partition Coefficients for Phthalate Esters in Benthic Marine Biota from False Creek Harbour.

-3.5

-2.5

-1.5

-0.5

0.5

1 3 5 7 9 11Log Kow

Log

BSA

F (k

g O

C /

kg li

pid)

G. ClamsMusselsOysters StarfishD. CrabsBSAF=1

178

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195

APPENDIX A

BACKGROUND INFORMATION ON PHTHALATE ESTERS

210

APPENDIX B

TROPHODYNAMIC INTERACTIONS AND LIFE HISTORY

INFORMATION ON SELECTED RESIDENT MARINE SPECIES IN

SOUTHWESTERN BRITISH COLUMBIA

267

APPENDIX C

DIETARY MATRIX FOR CALCULATION OF TROPHIC POSITIONS

270

APPENDIX D

QUALITY ASSURANCE AND CONTROL OF DATA (QA/QC)

TABLES AND FIGURES FROM SECTION 2.4

287

APPENDIX E

STATISTICAL ANALYSES ON PHTHALATE ESTER

CONCENTRATION DATA

I) NORMALITY TESTS ON DISTRIBUTIONS OF PHTHALATE

ESTER CONCENTRATION DATA II) STATISTICAL TESTS ON THE SPATIAL DISTRIBUTION OF

PHTHALATE ESTERS IN FALSE CREEK HARBOUR III) STATISTICAL TESTS ON THE DISTRIBUTION OF

PHTHALATE ESTERS IN THE ENVIRONMENTAL MEDIA AND SPECIES OF FALSE CREEK HARBOUR

310

APPENDIX F

DATA TABLES FROM SECTION 3 (RESULTS & DISCUSSION)

I) MEAN PHTHALATE ESTER CONCENTRATIONS AND FUGACITIES IN SEDIMENT, SEAWATER AND BIOTA FROM FALSE CREEK HARBOUR

II) COMPARISON OF REPORTED PHTHALATE ESTER

CONCENTRATIONS IN VARIOUS LOCATIONS THROUGHOUT THE WORLD TO OBSERVED CONCENTRATIONS IN FALSE CREEK HARBOUR

III) MEAN BIOACCUMULATION FACTORS IV) MEAN BIOTA-SEDIMENT ACCUMULATION FACTORS

349

APPENDIX G

ORIGINAL RAW DATA OF PHTHALATE ESTER

CONCENTRATIONS IN SEDIMENT, SEAWATER AND MARINE

BIOTA SAMPLES FROM FALSE CREEK HARBOUR

Documents

DISTRIBUTION OF PHTHALATE ESTERS IN A MARINE AQUATIC …rem-main.rem.sfu.ca/theses/MackintoshCheryl_2002_MRM295.pdf · benefited. Many thanks to my second supervisor, Dr. Margo Moore,