DISTRIBUTION OF PHTHALATE ESTERS IN A MARINE AQUATIC...
Transcript of DISTRIBUTION OF PHTHALATE ESTERS IN A MARINE AQUATIC...
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.
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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
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
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
1. INTRODUCTION ..................................................................................................................................1 2. METHODS.............................................................................................................................................8
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
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 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
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. ..............................................................................................................................................140
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
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. ..............................................................................................................................................144
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
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. ..............................................................................................................................................148
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
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. ..............................................................................................................................................153
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
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. ..............................................................................................................................................154
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
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. ..............................................................................................................................................155
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
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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
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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
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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
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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(%)
No. Samples Detected
Samples > MDL(%)
No. Samples Detected
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
TP Prey Species and their Dietary Proportions
Predators Comments/ References
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
Pauly and Christensen
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
Pauly and Christensen
1996
55
Species Latin Name
Species Common
Name
TP Prey Species and their Dietary Proportions
Predators Comments/ References
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
DMPDEPDIBPDBPBBPDEHP
DOPDNP C6 C7 C8 C9C10
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
DMPDEPDIBPDBPBBPDEHP
DOPDNP C6 C7 C8 C9C10
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
DMPDEPDIBPDBPBBPDEHP
DOPDNP C6 C7 C8 C9C10
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).
3.2.2. Spatial Variability
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
0 2 4 6 8 10 12Log Kow (Seawater)
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
0 2 4 6 8 10 12Log Kow (Seawater)
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
3.4.2. Spatial Variability
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
)
North Central Marina East Basin
*
*
**
*
**
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
)
North Central Marina East Basin
**
*
*
**
*
*
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
)
North Central Marina East Basin
* *
**
*
*
*
*
*
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
)
North Central Marina East Basin
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
Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek Harbour.
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
0 1 2 3 4 5Trophic Position
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
Harbour Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid wt.)
(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
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.)
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
Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek Harbour.
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
Creek Harbour Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid
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
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
)
DiBP
-1
0
1
2
3
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
)DBP
0
1
2
3
4
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
)
C6
-3
-2
-1
0
1
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
)
C7
-3
-2
-1
0
1
0 1 2 3 4 5Trophic Position
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
Harbour Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid wt.)
(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
Harbour Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid wt.)
(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
Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek Harbour.
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
Harbour Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid 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.)
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
(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
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
Harbour Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid wt.)
(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
Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek Harbour.
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
Creek Harbour Expressed in Wet Weight (ng/g wet wt.) (top) and Lipid Weight (ng/g lipid
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
(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)
C9
118
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).
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
(ν), and Total (▬), C18 ( ), and Freely Dissolved ( ) Water from False Creek Harbour.
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
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
)DnOP
-5
-4
-3
-2
-1
0
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
)
DnNP
-5
-4
-3
-2
-1
0
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
)
C8
-3
-2
-1
0
1
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
)
C9
-3
-2
-1
0
1
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
)
C10
-6
-5
-4
-3
-2
-1
0 1 2 3 4 5Trophic Position
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
0 1 2 3 4 5Trophic Position
Log
Fuga
city
(nPa
) DMPDEPDiBPDBPDMP LinearDEP LinearDiBP LinearDBP Linear
-5
-4
-3
-2
-1
0
1
2
0 1 2 3 4 5Trophic Position
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
0 1 2 3 4 5Trophic Position
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
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.
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
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.
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
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.
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
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 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.
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
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.
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
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 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.
C7 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
C7 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) 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
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
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.
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
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.
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
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.
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
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
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.
C8 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
C8 BAFs - Lipid Normalized
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
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
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.
C9 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
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
C9 BAFs - Lipid Normalized
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
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
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.
C10 BAFs - Wet Weight
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
C10 BAFs - Lipid Normalized
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
0 1 2 3 4 5Trophic Position
Log
BAF
(L/k
g lip
id)
DMPDEPDiBPDBPLinear (DMP)Linear (DEP)Linear (DiBP)Linear (DBP)
1
2
3
4
5
6
0 1 2 3 4 5Trophic Position
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
0 1 2 3 4 5Trophic Position
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
Harbour. Error bars represent one standard deviation.
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
Harbour. Error bars represent one standard deviation.
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
Harbour. Error bars represent one standard deviation.
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
REFERENCES
Adams, W.J., G.R. Biddinger, K.A. Robillard, J.W. Gorsuch. 1995. A Summary of The Aquatic Toxicity of 14 Phthalate Esters to Representative Aquatic Organisms. Environmental Toxicology and Chemistry 14(9):1569-1574.
Albro, P.W., J.T. Corbett, J.L. Schroeder. 1993. The Metabolism of Di(2-Ethylhexyl)
Phthalate in the Earthworm Lumbriculus terrestris. Comparative Biochemistry and Physiology C. Pharmacology, Toxicology and Endocrinology 104(2): 335-344.
Barron, M.G., I.R. Schultz, W.L. Hayton. 1989. Presystemic Branchial Metabolism
Limits DEHP Accumulation in Fish. Toxicology and Applied Pharmacology 98(1):49-57.
Barron, M.G., P.W. Albro, W.L. Hayton. 1995. Biotransformation of Di(2-
Ethylhexyl)Phthalate by Rainbow Trout. Environmental Toxicology and Chemistry 14(5):873-876.
Barrows, M.E., S.R. Petrocelli, K.J. Macek, J.J. Carroll. 1980. Bioconcentration and
Elimination of Selected Water Pollutants by the Bluegill Sunfish (Lepomis macrochirus). In: R. Haque (Ed.). Dynamic Exposure Hazard Assessments of Toxic Chemicals. Ann Arbor Sci. Publ. Inc., Ann Arbor, MI. p 379-392.
Belise, A.A., W.L. Reichel, J.W. Spann. 1975. Analysis of Tissues of Mallard Ducks Fed
Two Phthalate Esters. Bulletin of Environmental Contamination and Toxicology 13:129-132
Berkley Electronic Library Website (see Wang, J.C.S. 1986.) Black, M.C., J.F. McCarthy. 1988. Dissolved Organic Molecules Reduce the Uptake of
Hydrophobic Organic Contaminants by the Gills of Rainbow Trout (Salmo gairdneri). Environmental Toxicology and Chemistry 7:593-600.
Boese, B.L. 1984. Uptake Efficiency of the Gills of English sole (Parophrys vetulus) for
Four Phthalate Esters. Canadian Journal of Fisheries and Aquatic Sciences 41:1713-1717.
Brown, D., R.S. Thompson. 1982a. Phthalates and the Aquatic Environment: Part I. The
Effect of Di-2-Ethylhexyl Phthalate (DEHP) and Di-Isodecyl Phthalate (DIDP) on the Reproduction of Daphnia magna and Observations on their Bioconcentration. Chemosphere 11(4):417-426.
Brown, D., R.S. Thompson. 1982b. Phthalates and the Aquatic Environment: Part II. The
Bioconcentration and Depuration of Di-2-Ethylhexyl Phthalate (DEHP) and Di-
179
Isodecyl Phthalate (DIDP) in Mussels (Mytilus edulis). Chemosphere 11(4):427-435.
Brown, D., R.S. Thompson, K.M. Stewart, C.P. Croudace, and E. Gillings. 1996. The
Effect of Phthalate Plasticizers on the Emergence of the Midge (Chironomus riparius) from Treated Sediments. Chemosphere 32(11):2177-2187.
Bunce, Nigel J. 1994. Sewage and Waste Disposal, In: Environmental Chemistry. 2nd ed.
Winnipeg, Manitoba: Wuerz Publishing Ltd. Chapter 8; 266-269.
Butler, T.H. 1964. Growth, Reproduction and Distribution of Pandalid Shrimps in British Columbia. Journal of the Fisheries Research Board of Canada. 21(6): 1403-1452.
Butler, T.H. 1980. Shrimps of the Pacific Coast of Canada. Canadian Bulletin of
Fisheries and Aquatic Sciences No. 202. Department of Fisheries and Oceans. [CCME] Canadian Council of Ministers of the Environment. 1999. Canadian
Environmental Quality Guidelines: Canadian Water Quality Guidelines for the Protection of Aquatic Life – Fact Sheet on Phthalate Esters. Winnipeg, MB, Canada: CCME Publications, c/o Manitoba Statutory Publications.
CITI. 1992. Biodegradation and Bioaccumulation Data of Existing Chemicals Based on
the CSCL Japan, Chemical Inspection & Testing Institute, Ministry of International Trade and Industry, Japan.
Call, D.J., L.T. Brooke, N. Abmad, J.E. Richter. 1983. Toxicity and Metabolism Studies
with Environmental Protection Agency [EPA] Priority Pollutants and Related Chemicals in Freshwater Organisms. U.S. Environmental Protection Agency. Report No. EPA/600/03. 120 p.
Call, D.J., T.P. Markee, D.L. Geiger, L.T. Brooke, F.A. VandeVenter, D.A. Cox, K.I.
Genisot, K.A. Robillard, J.W. Gorsuch, T.F. Parkerton and others. 2001a. An Assessment of the Toxicity of Phthalate Esters to Freshwater Benthos. 1. Aqueous Exposures. Environmental Toxicology and Chemistry 20(8):1798-1804.
Call, D.J., D.A. Cox, D.L. Geiger, K.I. Genisot, T.P. Markee, L.T. Brooke, C.N.
Polkinghorne, F.A. VandeVenter, J.W. Gorsuch, K.A. Robillard, and others. 2001b. An Assessment of the Toxicity of Phthalate Esters to Freshwater Benthos. 2. Sediment Exposures. Environmental Toxicology and Chemistry 20(8):1805-1815.
Canadian Environmental Protection Act, 1999. Canada Gazette Part III: Vol. 22 No.3
November 4, 1999. Statutes of Canada, 1999, Chapters 33 and 34, Acts assented to from 18 June to 14 September, 1999. Ottawa, Canada: the Minister of Public Works and Government Services, the Queen’s Printer for Canada.
180
Toxic Substances Management Policy: Persistence and Bioaccumulation Criteria under CEPA (1999) are Published in Canada Gazette Part 1: Vol. 133 No.50 December 11, 1999, and Canada Gazette Part 2: Vol. 134 No.07 March, 29, 2000. Ottawa, Canada: the Minister of Public Works and Government Services, the Queen’s Printer for Canada.
Carr, K.H., G.T. Coyle, R.A. Kimerle. 1997. Bioconcentration of [14C]Butyl Benzyl
Phthalate in Bluegill Sunfish (Lepomis macrochirus). Environmental Toxicology and Chemistry 16(10):2200-2203.
Cass, A.J., R.J. Beamish, G.A. McFarlane. Department of Fisheries and Oceans. 1990.
Lingcod (Ophiodon elongatus). Ottawa: Canadian Special Publication of Fisheries and Aquatic Sciences 109.
Casserly, D.M., E.M. Davis, T.D. Down, R.K. Guthrine. 1983. Sorption of Organics by
Selenastrum capricornutum. Water Research 17:1591-1594. Chan, P.K.L., M.E. Meek. 1994a. Di-n-Butyl Phthalate: Evaluation of Risks to Health from Environmental Exposure in Canada. Environmental Carcinogenesis & Ecotoxicological Reviews C12(2):257-268. Chan, P.K.L. and M.E. Meek. 1994b. Di-n-octyl Phthalate: Evaluation of Risks to Health
from Environmental Exposure in Canada. Environmental Carcinogenesis & Ecotoxicological Reviews. C12(2):319-326.
Clark, K.E., F.A.P.C. Gobas, D. Mackay. 1990. Model of Organic Chemical Uptake and
Clearance by Fish from Food and Water. Environmental Science and Technology 24(8):1203-1213.
Connell, D.W. 1990. Bioaccumulation of Xenobiotic Compounds. Boca Raton, Florida,
USA: CRC Press. Chapter 2, Evaluation of the Bioconcentration Factor, Biomagnification Factor, and Related Physiochemical Properties of Organic Compounds; p 9-42.
Connolly, J.P., C.J. Pedersen. 1988. A Thermodynamic-Based Evaluation of organic
Chemical Accumulation in Aquatic Organisms. Environmental Science and Technology 22(1):99-103.
Cousins, I., D. Mackay. 2000. Correlating the Physical-Chemical Properties of Phthalate
Esters using the ‘Three Solubility’ Approach. Chemosphere 41:1389-1399. Cousins, I., D. Mackay. 2001. Strategies for Including Vegetation Compartments in
Multimedia Models. Chemosphere 44(4):643-654. [DFO] Department of Fisheries and Oceans see Pauly and Christensen, 1996.
181
Dalgaard, M., C. Nellman, H.R. Lam, I.K. Sorensen, O. Ladefoged. 2001. The Acute Effects of Mono(2-Ethylhexyl)Phthalate (MEHP) on Testes of Prepubertal Wistar Rats. Toxicology Letters 122(1):69-79.
Devault, D.S. 1985. Contaminants in Fish from the Great Lakes Harbours and Tributary
Mouths. Archives of Environmental Contamination and Toxicology 14:587-594. DiToro, D.M., C.S. Zarba, D.J. Hansen, W.J. Berry, R.C. Swartz, C.E. Cowan, S.P.
Pavlou, H.E. Allen, N.A. Thomas, P.R. Paquin. 1991. Technical Basis for Establishing Sediment Quality Criteria for Nonionic Organic Chemicals by Using Equilibrium Partitioning. Environmental Toxicology and Chemisty 10(12):1541-1586.
Dygert, P.H. 1990. Seasonal Changes in Energy Content and Proximate Composition
Associated with Somatic Growth and Reproduction in a Representative Age-Class of Female English Sole. Transactions of the American Fisheries Society 119(5):791-801.
Ema, M., R. Kurosaka., H. Amano, Y. Ogawa. 1995. Comparative Developmental
Toxicity of n- Butyl Benzyl Phthalate and Di-n-Butyl Phthalate in Rats. Archives of Environmental Contamination and Toxicology 28:223-228.
Ema, M., E. Miyawaki. 2001. Effects of Monobutyl Phthalate on Reproductive Function
in Pregnant and Pseudopregnant Rats. Reproductive Toxicology. 15(3):261-267. Environment Canada. 1997. Base-Neutral and Acid Extractables. A Fish Tissue Study.
Work Done Under Contract by Barringer Laboratories for Environment Canada, Atlantic Region.
Environmental Health Center (National Safety Council). 1996. Environmental Writer:
Di-(2-Ethylhexyl) Phthalate (C24H38O4) Chemical Backgrounder. Environmental Health Center, National Safety Council, Suite 1200, Washington DC, 200336. Available online at: www.nsc.org [Accessed 1999, June 15]
Fatoki, O.S., A.O. Ogunfowokan. 1993. Determination of Phthalate Ester Plasticizers in
the Aquatic Environment of Southwestern Nigeria. Environment International 19:619-623.
Fatoki, O.S., F. Vernon. 1990. Phthalate Esters in rivers of the Greater Manchester Area,
U.K. Science of the Total Environment 95:227-232. Forrester, C.R. 1969 (January). Life History Information on Some Groundfish Species.
Fisheries Research Board of Canada. Technical Report No. 105.
182
Foster, P.M.D., E. Mylchreest, K.W. Gaido, M. Sar. 2001. Effects of Phthalate Esters on the Developing Reproductive Tract of Male Rats. Human Reproduction Update 7(3):231-235.
Freitag, D., H. Geyer, A. Kraus, R. Viswanathan, D. Kotzias, A. Attar, W. Klein, F.
Korte. 1982. Ecotoxicological Profile Analysis VII. Screening Chemicals for Their Environmental Behavior by Comparative Evaluation. Ecotoxicology and Environmental Safety 6:60-81
Fukuoka, M., S. Niimi, T. Kibayashi, Y. Zhou, T Hayakawa. 1997. Possible Origin of
Testicular Damage by Phthalic Acid Esters. Japanese Journal of Toxicology and Environmental Health 43:21.
Furtmann, K. ([ECPI] European Council for Plasticizers and Intermediates). 1996.
Phthalates in the Aquatic Environment. Dusseldorf, Germany: Northrhine-Westfalia State Agency for Water and Waste. English Translation of Report No. 6/93 “Phthalate In Der Aquatischen Umwelt”. Contract No. D/1996/3158/4. 197 p and Appendices.
Garrett, C.L. (Environment Canada). 2002 (March). Phthalate Esters in Harbour Areas of
South Coastal British Columbia. Environment Canada, Environmental Protection Branch Pacific and Yukon Region. Regional Program Report in press. 100 p. Available from: Environment Canada, Environmental Protection Branch Pacific and Yukon Region.
Geyer, H. R., R. Viswanathan, D. Freitag, F. Korte. 1981. Relationship Between Water
Solubility of Organic Chemicals and their Bioaccumulation by the Alga Chlorella. Chemosphere 10:1307-1313.
Giam, C.S., H.S. Chan, G.S. Neff, E. Atlas. 1978. Phthalate ester plasticizers: A New
Class of Marine Pollutant. Science 27:419-421.
Giam, C.S., E. Atlas. 1980. Accumulation of Phthalate Ester Plasticizers in Lake Constance Sediments. Naturwissenschaften 67:508-510.
Gloss, S.P., G.R. Biddinger. 1985. Comparison of System Design and Reproducibility to
Estimate Bioaconcentration of Di-n-hexylphthalate by Daphnia magna. In: R.D. Cardwell, R. Purdy, R.C. Bahner (Eds.) Aquatic Toxicology and Hazard Assessment: Seventh Symposium, ASTM STP 854, American Society for Testing and Materials; 1985; Philidelphia. p 202-213.
Gobas, F. A.P.C. 1993. A Model for Predicting the Bioaccumulation of Organic
Chemicals in Aquatic Food Webs and Application to Lake Ontario. Ecological Modelling 69:1-17.
183
Gobas, F.A.P.C., D.C.G. Muir, D. Mackay. 1988. Dynamics of Dietary Bioaccumulation and Faecal Elimination of Hydrophobic Organic Chemicals in Fish. Chemosphere 17(5)943-962.
Gobas, F.A.P.C., E.J. McNeil, L. Lovett-Doust, G.D. Haffner. 1991. Bioconcentration of
Chlorinated Aromatic Hydrocarbons in Aquatic Macrophytes. Environmental Science and Technology 25(5):924-929.
Gobas, F.A.P.C., J. Maldonado, C.E. Mackintosh, N. Hoover, M.G. Ikonomou. In
preparation. Distribution of Polychlorinated Biphenyls in a Marine Aquatic Food Web.
Gobas, F.A.P.C., J.W.B. Wilcockson, R.W. Russell, G.D. Haffner. 1999. Mechanism of
Biomagnification in Fish under Laboratory and Field Conditions. Environmental Science and Technology 33(1):133-141.
Gobas, F.A.P.C., R.W. Russell. 1991. Bioavailability of Organochlorines in Fish.
Comparative Biochemistry and Physiology (Mini-Review) 100C(1/2):17-20. Gobas, F.A.P.C., X. Zhang. 1994. Chapter 2. Interactions of Organic Chemicals with
Particulate and Dissolved Organic Matter in the Aquatic Environment. In: J.L. Hamelink, P.F. Landrum, H.L. Bergman, W.H. Benson (Eds.). Bioavailability Physical Chemical and Biological Interactions. Proceedings of the 13th Pellston Workshop; Pellston, Michigan; August 17-22, 1992. Society of Environmental Toxicology and Chemistry [SETAC] Special Publication Series. Florida, USA; Lewis Publishers/ CRC Press Inc. p 83-91.
Gobas, F.A.P.C., X. Zhang, R. Wells. 1993. Gastrointestinal Magnification: The
Mechanism of Biomagnification and Food Chain Accumulation of Organic Chemicals. Environmental Science and Technology 27(13):2855-2863.
Gray, T.J.B., S.D. Gangolli. 1986. Aspects of the Testicular Toxicity of Phthalate Esters.
Environmental Health Perspectives 65:229-235. Harries, J.E., S. Jobling, P. Matthiessen, D.A. Sheahan, J.P. Sumpter (Ministry of
Agriculture, Fisheries and Food, UK; Department of Biology and Biochemistry, Brunel University, Uxbridge, Middlesex). 1995. Effects of Trace Organics on Fish - Phase 2. London, England: Published by the Foundation for Water Research [FWR] for the Department on the Environment, Water Directorate. Report No. FR/D 0022. Available from: the Foundation for Water Research [FWR], Marlow, England.
Hart, J.L. 1973. Pacific Fishes of Canada. Fisheries Research Board of Canada. Bulletin
180.
184
Heidolph, B.B., W.E. Gledhill (Monsanto Company). 1979. Bioconcentration, Distribution and Elimination of 14C-Labeled Saniticizer 160 by Bluegill (Lepomis macrochirus). St. Louis, MO: Monsanto Industrial Chemical Environmental Sciences. Report No. E5-79-SS-19.
Hiatt, M. H. 1999. Leaves as an Indicator of Exposure to Airborne Volatile Organic
Compounds. Environmental Science and Technology 33:4126-4133. Hites, R.A. 1973. Phthalates in the Charles and Merrimack Rivers. Environmental Health
Perspectives 3:17-21. Hites, R.A., W.L. Budde. 1991. EPA’s Analytical Methods for Water: The Next
Generation. Environmental Science and Technology 25:998-1006. Hobson, J.F., D.E. Carter, D.V. Lightner. 1984. Toxicity of Phthalate Ester in the Diet of
a Penaied Shrimp. Journal of Toxicology and Environmental Health 13:959-968. Hogan, J.W. 1977. Unpublished data. Cited in: Johnson, B.T., D.L. Stalling, J.W. Hogan,
R.A. Schoettger. Fate of Pollutants in the Air and Water Environments. New York: Wiley. P 292.
Holadova K, J Hajslova. 1995. A Comparison of Different Ways of Sample Preparation
for the Determination of Phthalic-Acid Esters in Water and Plant Matrices. International Journal Of Environmental Analytical Chemistry 59(1):43-57.
Ho, K.T., R.A. McKinney, A. Kuhn, M.C. Pelletier, R.B. Burgess. 1997. Identification of
Acute Toxicants in New Bedford Harbour Sediments. Environmental Toxicology and Chemistry 16(3):551-558.
Hudson, R.A., C.F. Austerberry, J.C. Bagshaw. 1981. Phthalate Ester Hydrolases and
Phthalate Ester Toxicity in Synchronously Developing Larvae of the Brine Shrimp (Atremia). Life Sciences 29:1865-1872.
Ikonomou, M.G., H. Jing, Z. Lin, N. Hoover, C.E. Mackintosh, A. Chong, F.A.P.C
Gobas. In preparation. Electron Spray Ionization Tandem Mass Spectrometry for Characterization of Phthalate Esters and Their Analysis in Marine Biological Samples.
Jamieson, G.S., and K. Francis. 1986. Invertebrate and Marine Plant Fishery Resources of British Columbia. Canadian Special Publication of Fisheries and Aquatic Sciences 91. Department of Fisheries and Oceans.
Jeng, W.L. 1986. Phthalate Esters in Marine Sediments Around Taiwan. Acta
Oceanographica Taiwanica 17:61-68.
185
Jobling, S., T. Reynolds, R. White, M. G. Parker, J. P. Sumter. 1995. A Variety of Environmentally Persistent Chemicals, Including Some Phthalate Plasticizers, Are Weakly Estrogenic. Environmental Health Perspectives 103(6):582-587.
Johnson, B.T., W. Lulves. 1975. Biodegradation of Di-n-Butyl Phthalate and Di-2-
Ethylhexyl Phthalate in Sheepshead Minnow Cyprinodon variegatus. Aquatic Toxicology 5:181-195.
Johnson, B.T., D.L. Stalling, J.W. Hogan, R.A. Schoettger. 1977. Dynamics of Phthalic
Acid Esters in Aquatic Organisms. Advances in Environmental Science and Technology 8:283-300.
Jones, B.C. 1976. Feeding, Growth and Reproduction of Spiny Dogfish in British Columbia Waters [Ph.D.] Burnaby, BC, CAN; Department of Biology, Simon Fraser University.
Jones, B.C., G.H. Geen. 1977. Food and Feeding of Spiny Dogfish (Squalus acanthias) in
British Columbia Waters. Journal of the Fisheries Research Board of Canada 34:2067-2078.
Karara, A.H., W.L. Hayton. 1984. Pharmacokinetic Model for the Uptake and
Disposition of Di-2-Ethylhexyl Phthalate in Sheepshead Minnow Cyprinodon variegatus. Aquatic Toxicology 5(3):181-195
Karara, A.H., and W.L. Hayton. 1989. A Pharmacokinetic Analysis of the Effect of
Temperature on the Accumulation of di-2-Ethylhexyl Phthalate (DEHP) in Sheepshead Minnow. Aquatic Toxicology 15(1):27-36
Karara, A.H., and W.L. Hayton. 1988. Metabolic Inhibition and Di-2-Ethylhexyl
Phthalate Pharmacokinetics in Fish. Drug Metabolism and Disposition 16(1):146-150.
Kennicut, M.C., J.M. Brooks, E.L. Atlas, C.S. Giam. 1988. Organic Compounds of
Environmental Concern in the Gulf of Mexico – A Review. Aquatic Toxicology 11:191-212.
Ketchen, K.S. 1996. The Spiny Dogfish (Squalus acanthias) in the Northeast Pacific
and a History of Its Utilization. Department of Fisheries and Oceans, Ottawa, Canada.
Landrum, P.F., M.D. Reinhold, S.R. Nihart, B.J. Eadie. 1985. Predicting the
Bioavailability of Organic Xenobiotics to Pontoporeia hoyi in the Presence of Humic and Fulvic Materials and Natural Dissolved Organic Matter. Environmental Toxicology and Chemistry 4:459-467.
186
Larsson, P., A. Thuren. 1987. Di-2-Ethylhexyl Phthalate Inhibits the Hatching of Frog Eggs and is Bioaccumulated by Tadpoles. Environmental Toxicology and Chemistry 6(6):417-422.
Law, R.J., T.W. Fileman, P. Matthiessen. 1991. Phthalate Esters and Other Industrial
Organic Chemicals in the North and Irish Seas. Water Science and Technology 24(10):127-134.
Leah, T.D. 1977. Environmental Contaminants Inventory Study No. 4 - The Production, Use, and Distribution of Phthalic Acid Esters in Canada. Fisheries and Environment Canada, Report Series No. 47. Inland Waters Directorate, Ontario. Lech J., M. Melancon. 1980. Uptake and Metabolism Disposition of Xenobiotic
Chemicals in Fish. United States Environmental Protection Agency [US EPA]. Report No. EPA-600/13-80-082.
Levy, David A. 1985. Biology and Management of Surf Smelt in Burrard Inlet,
Vancouver BC. Technical Report No. 28. Westwater Research Center. University of British Columbia, Vancouver BC. ISBN 0-920146-30-9
Lin, Z.P., M.G. Ikonomou, C.E. Mackintosh, J. Hongwu, F.A.P.C. Gobas. In preparation. Determination of Phthalate Ester Congeners and Mixtures in Sediments and Biota of an Urbanized Coastal Marine Inlet.
Lopez-Avila, V., J. Milanes, F. Constantine, W.F. Beckert. 1990. Typical Phthalate Ester
Contamination Incurred Using EPA Method 8060. Journal of the Association of Analytical Chemistry 73(5):709-720.
Macek, K.J., S.R. Petrocelli, and B.H. Sleight. 1979. Considerations in Assessing the
Potential for and Significance of Biomagnification of Chemical Residues in Aquatic Food Chains. In: L.L. Marking and R.A. Kimerle, (Eds.). Aquatic Toxicology, ASTM STP 667, American Society for Testing and Materials; 1979. p 251-268.
Mackay, D. 1982. Correlation of Bioconcentration Factors. Environmental Science and
Technology 16(5):274-278. Mackay, D. 1991. Multimedia Environmental Models: The Fugacity Approach. Chelsea,
MI: Lewis Publishers. Chapter 5, Phase Equilibrium; p 67-113. MacLean, L.G. 1999. The Role of Sediment Diagenesis in Promoting Chemical
Disequilibria for Organic Contaminants in Aquatic Systems. [Master of Resource Management]. Burnaby, BC, CAN: School of Resource and Environmental Management Report No. 242, Simon Fraser University. 93p. Available from: Ottawa, National Library of Canada, Canadian Theses on Microfiche, AS 044 5736.
187
Mayer, F.L. 1976. Residue Dynamics of Di-2-Ethylhexyl Phthalate in Fathead Minnows
(Pimephales promelas). Journal of the Fisheries Research Board of Canada. 33:2610-2613
Mayer, F.L. Jr., D.L. Stalling, J.L. Johnson. 1972. Phthalate Esters as Environmental
Contaminants. Nature 238:411-413. Mayer, F.L. Jr., H.O. Sanders. 1973 (Jan). Toxicology of Phthalic Acid Esters in Aquatic
Organisms. Environmental Health Perspectives. 4: 153-157. McCarthy, J.F., B.D. Jimenez. 1985. Reduction in Bioavailability to Bluegills of
Polycyclic Aromatic Hydrocarbons Bound to Dissolved Humic Material. Environmental Toxicology and Chemistry 4:511-521.
Meek, M.E., P.K.L Chan. 1994. Bis(2-ethylhexyl)phthalate: Evaluation of Risks to
Health from Environmental Exposure in Canada. Environmental Carcinogenesis and Ecotoxicological Reviews C12(2):179-194.
Mehrle, P.M., F.L. Mayer. 1976. Di-2-Ethylhexyl Phthalate: Residue Dynamics and
Biological Effects in Rainbow Trout and Fathead Minnows. In: Trace Substances in Environmental Health. Proceedings of the University of Missouri’s Annual Conference on Trace Substances in Environmental Health 10:519-524.
Melancon, M.J., J. Saybolt, J.J. Lech. 1977. Effect of Piperonyl Butoxide on Disposition
of Di-2-Ethylhexyl Phthalate by Rainbow Trout. Xenobiotica 7:633-640. Melancon, M.J. 1979. Metabolism of Phthalate Esters in Aquatic Species. In: M.A.Q.
Khan, J.J. Lech, J.J. Menn (Eds.). Pesticide and Xenobiotic Metabolism in Aquatic Organisms, ACS Symposium Series 99. American Chemical Society. p 77-94.
Metcalf, R.L., G.M. Booth, C.K. Schuth, D.J. Hansen, P.Y. Lu. 1973 (June). Uptake and
Fate of Di-2-ethylhexyl Phthalate in Aquatic Organisms and in a Model Ecosystem. Environmental Health Perspectives. June:27-34
Miller, Bruce Stuart. 1967. Stomach Contents of Adult Starry Flounder and Sand Sole in East Sound, Orcas Island, Washington. Journal of the Fisheries Research Board of Canada 24(12):2515-2526.
Environment Canada and Health Canada. 1994. Canadian Environmental Protection Act.
Bis(2-ethylhexyl) Phthalate, Priority Substances List Assessment Report. Ottawa: Minister of Supply and Services, Beauregard Printers Ltd. Cat. No. En 40-215/37E. ISBN 0-662-22031-5. 44 p. Available from: Commercial Chemicals Branch, Environmental Canada, 14th Floor, Place Vincent Massey, 351 St. Joseph Boulevard, Hull, Quebec, K1A 0H3.
188
Morita, M., H. Nakamura, S. Mimura. 1974. Phthalic Acid Esters in Water. Water
Research 8:781-788. Morrison, H.A., F.A.P.C. Gobas, R. Lazar, G.D. Haffner. 1996. Development and
Verification of a Bioaccumulation Model for Organic Contaminants in Benthic Invertebrates. Environmental Science and Technology 30(11):3377-3384.
Morrison, H.A., F.A.P.C. Gobas, R. Lazar, G.D. Haffner. 1997. Development and
Verification of a Benthic/Pelagic Food Web Bioaccumulation Model for PCB Congeners in Western Lake Erie. Environmental Science and Technology 31(11):3267-3273.
Murie, D.J. 1995. Comparitive feeding ecology of two sympatric rockfish congeners,
Sebastes caurinus (Copper rockfish) and S. maliger (Quillback rockfish). Marine Biology 124: 341-353.
Nikonorow, M., H. Mazur, H. Peikacz. 1973. Effect of Orally Administered Plasticizers
and Polyvinyl Chloride in the Rat. Toxicology and Applied Pharmacology 54:141-147.
Nybakken, James W. 1997. Marine Biology an Ecological Approach 4th edition.
Addison-Wesley Educational Publishers Inc. Reading, Massachusetts. Oliver, B.G., A.J. Niimi. 1988. Trophodynamic Analysis of Polychlorinated Biphenyl
Congeners and Other Chlorinated Hydrocarbons in the Lake Ontario Ecosystem. Environmental Science and Technology 22:388-397.
Onate, F. Corcobado. 1991. Food and daily ration of the rock sole Lepidopsetta bilineata
(Pleuronectidae) in the Bering Sea. Marine Biology. 108:185-191. Park, C.W., H. Imamura, T. Yoshida. 1990. Uptake, Excretion, and Metabolism of 14C-
Labelled Di-2-ethylhexyl Phthalate by Mullet, Mugil cephalus. Bulletin. Korean Fisheries Society 22(6):424-428
Parkerton, T.F. 1993. Estimating Toxicokinetic Parameters for Modeling the
Bioaccumulation of Non-Ionic Chemicals in Aquatic Organisms [Ph.D.]. New Jersey, USA; Rutgers University. 336 p. Available from U.M.I. Dissertation Services, Order No. 9333437.
Parkerton, T.F., W.J. Konkel (Exxon Mobil Biomedical Services, Inc.). November 2000
(Draft Report). Evaluation of the Production, Consumption, End Use and Potential Emissions of Phthalate Esters. Prepared for the American Chemistry Council [ACC], 1300 Wilson Ave., Arlington, VA.
189
Parkerton, T.F., D. Letinski, E. Febbo, R. Davi, C. Dzamba, M. Connelly, K. Christensen, D. Peterson. 2001. A Practical Testing Approach for Assessing the Bioaccumulation Potential of Poorly Water Soluble Organic Chemicals. 11th Annual Meeting of the Society of Environmental Toxicology and Chemistry [SETAC] Europe; 2001 May 6-10; Madrid, Spain. p 56. Abstract No. 251.
Parkman, H., M. Remberger (Swedish Environmental Research Institute[IVL]). 1995.
Phthalates in Swedish Sediments. Stockholm: Swedish Environmental Research Institute [IVL]. Report No. 1167. Contract No. 95MR R 230. 23p. Available from: IVL, Publikationsservice, Box 21060, S-100 31 Stockholm, Sweden.
Pauly, D., V. Christensen (Eds.). 1996. Mass-balance Models of Northeastern Pacific
Ecosystems. Proceedings of a Workshop held at the Fisheries Centre, University of British Columbia, Vancouver B.C. Canada; November 6-10, 1995. Vancouver, BC: Fisheries Centre, UBC, Research Reports 1996, 4(1), 131 p.
Penalver, A., E. Pocurull, F. Borrull, R.M. Marcee. 2001. Comparison of Different Fibers for the Solid Phased Microextraction of Phthalate Esters from Water. Journal of Chromatography A (Short Communication) 922:377-384.
Perez, K.T., E.W. Davey, N.F. Lackie, G.E. Morrison, P.G. Murphy, A.E. Soper, D.L.
Winslow. 1983. Environmental Assessment of a Phthalate Ester, Di(2-Ethylhexyl) Phthalate (DEHP), Derived From a Marine Microcosm. In: W.E.Bishop, R.D.Cardwell, B.B.Heidolph (Eds.). Aquatic Toxicology and Hazard Assessment, 6th Symposium, ASTM STP 802; 1983; Philadelphia. p 180-191
Persson, P.E., H. Penttinen, P. Nuorteva. 1978. DEHP in the Vicinity of an Industrial
Area in Finland. Environmental Pollution 16:163-166. Peterson, J.C., D.H. Freeman. 1982. Phthalate Ester Concentration Variations in Dated
Sediment Cores from the Chesapeake Bay. Environmental Science and Technology 16(8):464-469.
Pierce, R.C., S.P. Mathur, D.T. Williams, M.J. Boddington. 1980. Phthalate Esters in the
Aquatic Environment. Ottawa, Ontario: National Research Council of Canada [NRCC] Associate Committee on Environmental Quality NRCC No. 17583.
Pratasik, S. B. 1993. Habitat use and seasonal changes in the relative abundance of the
red rock crab, Cancer productus, in Indian Arm. MSc. Thesis, Department of Biology, Simon Fraser University.
Richards, L. J. 1987. Copper rockfish (Sebastes caurinus) and quillback rockfish
(Sebastes maliger) habitat in the Strait of Georgia, British Columbia. Canadian Journal of Zoology. 65: 3188-3191.
190
Ricketts, E.F., J. Calvin, J.W. Hedgpeth, D.W. Phillips. 1985. Between Pacific Tides 5th edition. Stanford University Press. Stanford, California.
Ritsema, R. W.P. Cofino, P.C.M. Fintrop, U.A.Th Brinkman. 1989. Trace Level Analysis
of Phthalate Esters in Surface Water and Suspended Particulate Matter by Means of Capillary Gas Chromatography with Electron-Capture and Mass-Selective Detection. Chemosphere 18(11/12):2161-2175.
Robles, C. 1987. Predator Foraging Characteristics and Prey Population Structure on a Sheltered Shore. Ecology. 68(5):1502-1514.
Russell D.J., B. McDuffie, S. Fineberg. 1985. The Effect of Biodegradation on the
Determination of Some Chemodynamic Properties of Phthalate Esters. Journal of Environmental Science and Health A20:927-941.
Rhodes, J.E., W.J. Adams, G.R. Biddinger, K.A. Robillard, J.W. Gorsuch. 1995. Chronic
Toxicity of 14 Phthalate Esters to Daphnia magna and Rainbow Trout (Oncorhynchus mykiss). Environmental Toxicology and Chemistry 14(11):1967-1976.
Sabourault, C. J.B. Berge, M. Lafaurie, J.P. Girard, M. Amichot. 1998. Molecular
Cloning of a Phthalate-Inducible CYP4 Gene (CYP4T2) in Kidney from the Sea Bass, Dicentrarchus labrax. Biochemical and Biophysical Research Communications 251(Sept):213-219.
Sanborn, J.R., R.L. Metcalf, C.C. Yu, P.Y. Lu. 1975. Plasticizers in the Environment:
The Fate of Di-n-octyl Phthalate (DOP) in Two Model Ecosystems and Uptake and Metabolism of DOP by Aquatic Organisms. Archives of Environmental Contamination 3(2):244-255.
Sanders, H.O., F.L. Mayer Jr., D.F. Walsh. 1973. Toxicity, Residue Dynamics, and
Reproductive Effects of Phthalate Esters in Aquatic Invertebrates. Environmental Research 6(3):84-90.
Scholz, N., R. Diefenbach. 1996. Biodegradation and Bioaccumulation of Phthalates.
17th Annual Society of Environmental Toxicology and Chemistry Meeting; November 1996; Washington, D.C.
Schouten, M.J., J.W. Copius Peereboom. U.A.Th. Brinkman. 1979. Liquid
Chromatography Analysis of Phthalate Esters in Dutch River Water. International Journal of Environmental Analytical Chemistry 7:13-23.
Schults, D.W., S.P. Ferraro, G.R. Ditsworth, K.A. Sercu. 1987. Selected Chemical
Contaminants in Surface Sediments of Commencement Bay and the Tacoma Waterways, Washington, USA. Marine Environmental Research 22:271-295.
191
Schwartz, H.E., C.J.M. Anzion, H.P.M. Van Vliet, J.W. Copius Peereboom. U.A.Th. Brinkman. 1979. Analysis of Phthalate Esters in Sediments from Dutch Rivers by means of High Performance Liquid Chromatography. International Journal of Environmental Analytical Chemistry 6:133-144.
Seth, R., D. Mackay, J. Muncke. 1999. Estimating the Organic Carbon Partition
Coefficient and its Variability for Hydrophobic Chemicals. Environmental Science and Technology 33:2390-2394.
Sharpe, R.M., J.S. Fisher, M.M. Millar, S. Jobling, J.P. Sumpter. 1995. Gestational and
Lactational Exposure of Rats to Xenoestrogens Results in Reduced Testicular Size and Sperm Production. Environmental Health Perspectives 103(12):1136-1143.
Skoglund, R.S, D.L. Swackhamer. 1999. Evidence for the Use of Organic Carbon as the
Sorbing Matrix in the Modeling of PCB Accumulation in Phytoplankton. Environmental Science and Technology 33:1516-1519.
Solbakken, J.E., A.H. Knapp, P.L. Orr. 1985. Uptake and Elimination of Lindane and a
Phthalate Ester in Tropical Corals and Mussels. Marine Environmental Research 16:103-113
Stalling, D.L., J.W. Hogan, and J.L. Johnson. 1973. Phthalate Ester Residues - Their
Metabolism and Analysis in Fish. Environmental Health Perspectives 3:159-173 Stalschmidt-Allner, P., B. Allner, J. Rombke, T. Knacker. 1997. Endocrine Disrupters in
the Aquatic Environment. Environmental Science and Pollution Research 4(3)155-162.
Staples, C.A., D.R. Peterson, T.F. Parkerton, W.J. Adams. 1997a. The Environmental
Fate of Phthalate Esters: A Literature Review. Chemosphere 35(4):667-749. Staples, C.A., W.J. Adams, T.F. Parkerton, J.W. Gorsuch, G.R. Biddinger, K.H. Reinert.
1997b. Aquatic Toxicity of Eighteen Phthalate Esters. Environmental Toxicology and Chemistry. 16(5): 875-891.
Starr, M., J.H. Himmelman, Jean-Claude Therriault. 1990. Direct Coupling of Marine
Invertebrate Spawning with Phytoplankton Blooms. Science (Reports) 247:1071-1074.
Streufert, J.M., J.R. Jones, and H.O. Sanders. 1980. Toxicity and Biological Effects of Phthalate Esters on Midges (Chironomus plumosus). Transactions. Missouri Academy of Science 14:33-40
192
Suzuki, T., K. Yagushi, S. Suzuki, T. Suga. 2001. Monitoring of Phthalic Acid Monoesters in River Water by Solid Phase Extraction and GC-MS Determination. Environmental Science and Technology 35(18):3757-3763.
Swain, L.G. and D.G. Walton. 1990a. Report on the 1989 Boundary Bay monitoring
program. Fraser River Estuary Monitoring Program (FREMP). Vancouver, BC: Fraser River Harbour Commission and British Columbia Ministry of Environment. ISBN 0772612617. 172 p.
Swain, L.G. and D.G. Walton. 1990b. Report on the 1989 Fraser River Sediment Monitoring Program (FREMP). Vancouver, BC: Fraser River Harbour Commission and British Columbia Ministry of Environment. ISBN 0772612757. 47 p.
Tan, G.H. 1995. Residue Levels of Phthalate Esters in Water and Sediment Samples from
the Klang River Basin. Bulletin of Environmental Contamination and Toxicology 54:171-176.
Tarr, B.D., M.G. Barron, W.L. Hayton. 1990. Effect of Body Size on the Uptake and
Bioconcentration of Di-2-Ethylhexyl Phthalate in Rainbow Trout. Environmental Toxicology and Chemistry. 9(8):989-995
Taylor, F.H.C. 1964. Life history and present status of British Columbia herring stocks.
Fisheries Research Board of Canada. Bulletin No. 143.
Thuren, A. 1986. Determination of Phthalates in Aquatic Environments. Bulletin of Environmental Contamination and Toxicology 36:33-40.
Thuren, A. and P. Woin. 1991. Effects of Phthalate Esters on the Locomotor Activity of
the Freshwater Amphipod, Gammarus pulex. Bulletin of Environmental Contamination and Toxicology 46:159-166.
Tolls, J. and M.S. MacLachlan. 1994. Partitioning of Semivolatile Organic Compounds
Between Air and Lolium multiflorum (Welsh Ray Grass). Environmental Science and Technology 28:159-166.
Toxic Substances Control Act, 1976, 15 United States Code [U.S.C.] s/s 2601 et seq. [UNECE] United Nations Economic Council of Europe 1979 Convention on Long Range
Transboundary Air Pollution and its 1998 Protocols on Persistent Organic Pollutants. New York, USA and Geneva, Switzerland: United Nations. Report No. ECE/EB.AIR/66. ISBN: 9211167248. 91 p. Avaialble from: United Nations publication sales no. E.99.II.E.21.
[US EPA] United States Environmental Protection Agency. 1998. Proposed Category for Persistent, Bioaccumulative, and Toxic Chemicals. Washington, DC, USA:
193
Federal Registry. FR63(192):53417-53423: October 5,1998. Available from Office of Pollution Prevention and Toxics, Washington, DC.
[US EPA] United States Environmental Protection Agency. 1991. Drinking Water
Criteria Document for Phthalic Acid Esters (PAES), Final Report. Cincinnati, Ohio: Office of Health and Environmental Assessment, Environmental Criteria and Assessment Office. 321 p.
[US EPA] United States Environmental Protection Agency. 1980 (October). Ambient
Water Quality Criteria for Phthalate Esters. Washington, DC: United Stated Environmental Protection Agency, Office of Water Regulations and Standards Criteria and Standards Division. Report No. EPA 440/5-80-067. Available from National Technical Information Service, Springfield, VA.
Van Iperen, J., W. Helder. 1985. A Method for the Determination of Organic Carbon in
Calcareous Marine Sediments. Marine Geology (Letter Section) 64:179-187. Van Wezel, A.P., P. Van Vlaardingen, D.T.H.M. Sijm. 2000. Environmental Risk Limits
for Two Phthalates, with Special Emphasis on Endocrine Disruptive Properties. Ecotoxicology and Environmental Safety 46(3):305.
Vander Zanden, M.J., J.B. Rasmussen. 1996. A Trophic Position Model For Pelagic Food
Webs; Implications For Contaminant Bioaccumulation By Lake Trout. Ecological Monographs 66(4):451-477.
Vermeer, K., R.C. Ydenburg. 1989. Feeding Ecology of Marine Birds in the Strait of
Georgia. In K. Vermeer, R.W. Butler (Eds.). The Ecology and Status of Marine and Shoreline Birds in the Strait of Georgia, British Columbia. Ottawa, CAN: Special Publication of the Canadian Wildlife Service. 1989. p 62-73.
Walker, W.W., C.R. Cripe, P.H. Pritchard, A.W. Bourquin. 1984. Dibutylphthalate
Degradation in Estuarine and Freshwater Sites. Chemosphere 13(12):1283-1294. Wang, X., C.P.L. Gradie Jr. 1994. Comparison of Biosorption Isotherms for Di-n-Butyl
Phthalate in Estuarine and Freshwater Sites. Chemosphere 13:1283-1294. Wang, J.C.S. (California Department of Fish and Game). 1986 (January). Fishes of the
Sacramento – San Joaquin Estuary and Adjacent Waters, California: A Guide to the Early Life Histories. Prepared for the Interagency Ecological Study Program for the Sacramento - San Joaquin Estuary. Berkley, CA: California Department of Water Resources, California Department of Fish and Game, US Bureau of Reclamation, US Fish and Wildlife Service. Technical Report 9. FS/BIO-4 ATR 86-9. Contact No. DWR-B54336 and DWR B-54463 (Cal. Dept. Wat. Res.) and 4-PG-20-06480. 806 p.
194
Williams, D.T. 1973. Dibutyl- and Di-(2-ethylhexyl)phthalate in Fish. Journal of Agriculture and Food Chemistry (Communications) 21(6)1128-1129.
Wofford, H.W., C.D. Wilsey, G.S. Neff, C.S. Giam, and J.M. Neff. 1981.
Bioaccumulation and Metabolism of Phthalate Esters by Oysters, Brown Shrimp and Sheepshead Minnows. Ecotoxicology and Environmental Safety 5:202-210.
Woin, P., P. Larsson. 1987. Phthalate Esters Reduce Predation Efficiency of Dragonfly
Larvae, Odonate aeshna. Bulletin of Environmental Contamination and Toxicology 38:220-225.
Xie, W.H., W.Y. Shiu, D. Mackay. 1997. A Review of the Effect of Salts on the
Solubility of Organic Compounds in Seawater. Marine Environmental Research 44(4):429-444.
Zitko, V. 1972. Determination of Phthalates in Biological Samples. International Journal of Environmental Analytical Chemistry 2:241-252.
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