BIOACCUMULATION POTENTIAL OF ORGANIC CONTAMINANTS IN AN ARCTIC

439 Pages·2006·5.22 MB·English

BIOACCUMULATION POTENTIAL OF ORGANIC
CONTAMINANTS IN AN ARCTIC MARINE FOOD WEB
Barry C. Kelly
MRM. Simon Fraser University, 1999
BSc. Trent University, 1993
THESIS SUBMITTED IN PARTIAL FULFILLMENT OF
THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
In the School of
Resource and Environmental Management
O Barry C. Kelly 2006
SIMON FRASER UNIVERSITY
Spring 2006
All rights reserved. This work may not be
reproduced in whole or in part, by photocopy
or other means, without permission of the author.
APPROVAL
Name: Barry C. Kelly
Degree: Doctor of Philosophy
Title of Thesis: Bioaccumulation Potential of Organic Contaminants in an
Arctic Marine Food Web
Examining Committee:
Chair: Dr. Kristina Rothley, Assistant Professor,
School of Resource and Environmental Management
Dr. Frank A.P.C. Gobas, Senior Supervisor,
Professor, School of Resource and Environmental Management
Dr. Michael G. Ikonomou, Supervisor, Adjunct Professor,
School of Resource and Environmental Management
Dr. Margo Moore, Supervisor, Associate Professor,
Department of Biology
Dr. Peter S. Ross, Supervisor, Ad-junct Professor,
School of Resource and ~nvironm&talM anagement
--
Dr. Leah Bendell-Young, Public Examiner,
Associate Professor, Department of Biology
Dr. Derek Muir, External Examiner,
Senior Research Scientist,
National Water Research Institute (NWRI), Environment Canada
Date Approved : September 26', 2005
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ABSTRACT
A chemical's octanol-water partition coefficient (Kow) and octanol-air partition coefficient (KOA)
are important factors affecting environmental fate and bioaccumulation of persistent organic
pollutants (POPs). This thesis involved an investigation of various organic chemicals (ranging in
Kow and KOA) in a Canadian Arctic marine food web (53" 59' N, 76" 32' W) aimed to (i)
determine levels of PCBs, organochlorine pesticides (OCPs), dialkyl phthalate esters (DPEs) and
polybrominated diphenyl ethers (PBDEs) in organisms by high resolution gas-
chromatography/high resolution mass-spectrometry (HRGCIHRMS), (ii) evaluate the extent of
chemical biomagnification and (iii) identify relationships between biomagnification and
influential physical-chemical properties such as Kow and KOA. The results show that recalcitrant
C15-C1, PCBs (e.g., PCB 153 and 180) typically exhibited the greatest biomagnification potential
and continue to be present at parts per million levels in Arctic biota, some 30 years post-
regulatory action. Predator-prey biomagnification factors (BMFs) of PCB 180 ranged from
approximately 11.5 in male ringed seals, 45.7 in male beluga whales and 106.3 in common eider
ducks. Relatively polar chemicals such as P-HCH (log Kow =3.8) tetrachlorobenzenes (log Kow
= 4.5) and P-endosulfan (log Kow = 3.4) in some cases exhibited substantial biomagnification in
seaducks and marine mammals. BMFs of P-HCH ranged from 5.2 in common eider ducks, 26.2
in male ringed seals and 50.5 in male beluga whales. No significant biomagnification of P-HCH
was observed in invertebrates and fish, likely due to efficient respiratory elimination via gills to
water. Extensive biornagnification of P-HCH in air-breathing animals (birds and marine
mammals) is likely due the chemical's high resistance to metabolic transformation and slow
respiratory elimination through air-exhalation because of its high KOA(, i.e.,log KOA= 8.9). While
DPEs and PBDEs were detected at appreciable levels, they appeared to be biotransformed by
organisms, demonstrated by very low BMFs and FWMFs compared to recalcitrant PCBs. Further
evidence of biotransformation was supported by the detection of primary metabolites, monoalkyl
phthalate esters (MPEs) and hydroxylated and methoxylated brominated, diphenyl ethers (OH-
BDEs / MeO-BDEs). Future regulatory initiatives should include chemical KOAa nd the
formation of potentially toxic metabolites as criteria for assessing the bioaccumulation potential
of POPs.
Keywords: biomagnification, contaminants, POPs, KOAp, olybrominated diphenyl ethers,
phthalate esters, metabolites, Arctic, marine, food web, beluga whales
DEDICATION
I dedicate this work to my wife, Laura and daughter, Erin, who help me keep
things in perspective and keep me smiling through it all and to my parents Ken
and Carol Kelly who have given great support along this long academic journey.
ACKNOWLEDGEMENTS
I wish to acknowledge the financial support of the Natural Sciences and Engineering Research
Council of Canada (NSERC), Environment Canada's Northern Ecosystems Initiative (NEI), the
Association of Canadian Universities for Northern Studies (ACUNS) and the Indian and Northern
Affairs Northern Science Training Program (NSTP). Also, I wish to thank Makivik
Coroporation, and Dr. Bill Doidge and Dr. Michael Kwan from the Nunavik Research Centre
(NvRC) in Kuujjuaq Quebec for coordinating field sampling in E. Hudson Bay. I would also
like to thank members of the REM Environmental Toxicology Research Group and staff at the
Institute of Ocean Sciences (10s) Regional Dioxin Laboratory (RDL). Special thanks in
particular go to Joel Blair, Michael Gibbs and Anne Morin for there extensive work on this
project. Lastly, I would like to thank Dr. Frank Gobas and members of my examining committee,
including Dr. Michael Ikonomou, Dr. Peter Ross, Dr. Margo Moore, Dr. Leah Bendell-Young
and Dr. Derek Muir for reviewing this thesis and their helpful comments and guidance to
strengthen my work.
TABLE OF CONTENTS
..
..........................................................................................................................................
Approval
11
...
.........................................................................................................................................
Abstract lu
......................................................................................................................................
Dedication iv
.........................................................................................................................
Acknowledgements v
..........................................................................................................................
Table of Contents vi
................................................................................................................................
List of Figures x
...............................................................................................................................
List of Tables xv
.......................................................................................................................
List of Appendices xvi
...
.....................................................................................................................................
Glossary xvm
..............................................................................................................
Chapter 1 Introduction 1
1.1 Background ..........................................................................................................................1. .
1.2 Different Classes of Environmental Contaminants ..............................................................2..
1.3 Temporal Trends of Persistent Organic Pollutants in the Canadian Arctic .........................1 3
1.4 Spatial Trends in Marine Mammals from Canadian coastal waters ....................................1 6
1.5 Rationale: Towards a science-based approach to toxic substance management ..................1 9
1.6 Hypothesis and Objectives .................................................................................................2..3
1.7 Short Term Objectives ........................................................................................................2. 3
1.8 Long Term Objectives .........................................................................................................2 4
1.9 Project Design and Methodologies .....................................................................................2. 4
1.9.1 Sample collections ...................................................................................................... 25
1.9.2 Food web characterization and designation of organism trophic levels .....................2 7
1.9.3 Ultra-Trace Chemical analyses ................................................................................... 30
1.9.4 Data analyses .............................................................................................................3. 0
1.9.5 Evaluative parameters for assessing chemical bioaccumulation potential .................3 1
1.10 Thesis Scope and Organization of Chapters .......................................................................3. 4
Chapter 2 Intestinal Absorption and Biomagnification of Organic Contaminants
.................................................................................
in Fish, Wildlife and Humans 36
2.1 Introduction ..........................................................................................................................3. 6
2.2 Theory ...................................................................................................................................3 9
2.2.1 Intestinal absorption of xenobiotic molecules . ...........................................................4 1
2.3 Mechanisms of Biomagnification ................................................... ...................................4. 2
.,
2.3.1 Biomass Conversion Model ........................................................................................ 42
2.3.2 Digestion Model ......................................................................................................... 43
2.3.3 Micelle Mediated Diffusion Model ...........................................................................4. 8
2.3.4 "Fat Flush" diffusion hypothesis ................................................................................5. 1
2.4 Discussion .........................................................................................................................5..4.
2.5 Acknowledgements .............................................................................................................5. 7
2.6 Tables ..................................................................................................................................5. 8
2.7 Figures ................................................................................................................................. 59
Chapter 3 Bioaccumulation of POPs in a Canadian Arctic Marine Food Web and
..............
Related Human Dietary Exposure of an Aboriginal. Inuit Population 69
3.1 Introduction. .........................................................................................................................6 9
3.2 Materials and Methods ........................................................................................................7. 1
3.2.1 Sample collections ......................................................................................................7 1
3.2.2 Food web characterization and designation of organism trophic positions. ............... 72
3.2.3 Extraction, cleanup and analysis of PCBs and OC Pesticides. ..................................7. 3
3.2.4 Data analysis. .............................................................................................................7. 4
3.2.5 Calculation of Biomagnification Factors (BMFs) and Elimination Index (EI) ..........7 5
3.3 Results and Discussion ......................................................................................................7..5
3.3.1 PCB levels in E . Hudson Bay marine sediments and biota ........................................7 6
3.3.2 Organochlorine pesticide (OCP) levels in E . Hudson Bay marine sediments
and biota ................................................................................................................7 6
3.3.3 Comparison to other Arctic POPS bioaccumulation studies ......................................7. 8
3.3.4 Contaminant accumulation patterns of PCBs and organochlorine pesticides. ............ 79
3.3.5 Age and Sex related Trends and Maternal Transfer ...................................................8 2
3.3.6 BMF and Elimination Index estimations. ...................................................................8 2
3.3.7 Compound and Species-specific Biotransfonnation Capacity. .................................. 86
3.3.8 Biomagnification and dietary exposure of POPs in the Aboriginal Inuit
population. ............................................................................................................. 87
3.4 Acknowledgements. ............................................................................................................. 89
3.5 Figures ................................................................................................................................. 90
Chapter 4 Physical-Chemical and Biological Determinants of Biomagnification
................
Potential of Organic Contaminants in an Arctic Marine Food Web 108
4.1 Introduction. .................................................................................................................... 108
4.2 Materials and Methods. ......................................................................................................1 10
4.2.1 Sample collections. ...................................................................................................1 10
4.2.2 Food web characterization and designation of organism trophic levels. ..................1 10
4.2.3 Extraction, cleanup and analysis of POPS in tissue samples. ...................................1 11
4.2.4 Data compilation/treatment and statistics. ................................................................ 112
4.2.5 Evaluative parameters for assessing chemical bioaccumulation potential ............... 114
4.3 Results and Discussion ...................................................................................................... 114
4.3.1 Chemical concentration relationships with trophic level and FWMFs ..................... 114
4.3.2 POPS biornagnification potential ...............................................................................1 15
4.3.3 Effect of Kow and KO, on chemical bioaccumulation potential ................................1 17
4.3.4 Regulatory implications of bioaccumulative "low" Kow - "high" KOA
chemicals ............................................................................................................1..2 1
4.4 Acknowledgements. ........................................................................................................... 125
4.5 Figures ........................................................................................................................... 126
Chapter 5 Biotransformation and Trophic Dilution of Dialkyl Phthalate Esters in
.................................................................
a Canadian Arctic Marine Food Web 133
5.1 Introduction. ....................................................................................................................... 133
5.2 Materials and Methods .......................................................................................................1 36
5.2.1 Sample collections. ...................................................................................................1 36
5.2.2 Food web characterization and designation of organism trophic positions. ............. 136
5.2.3 Extraction, cleanup and analysis of DPEs ................................................................1 37
5.2.4 Extraction, cleanup and analysis of MPEs ................................................................1 38
5.2.5 Data treatment/compilation and statistics. ................................................................ 139
5.2.6 Evaluative parameters for assessing chemical bioaccumulation potential ............... 140
vii
5.3 Results and Discussion ......................................................................................................1 40
5.3.1 Data qualification. ....................................................................................................1. 40
5.3.2 Levels and congener profiles of dialkyl phthalate esters in E . Hudson Bay
food web .............................................................................................................. 141
5.3.3 Levels of monoalkyl phthalate esters (MPEs). .........................................................1 42
5.3.4 Spatial Trends of DPE levels in biota ......................................................................1. 43
5.3.5 Concentration relationships with trophic level and FWMFs ....................................1 43
5.3.6 Estimated Air (CAGa) nd Seawater (CwD)C oncentrations and BAFs .......................1 44
5.3.7 Biomagnification Potential of Dialkyl Phthalate Esters ...........................................1 46
5.4 Acknowledgements. ..........................................................................................................1. 47
5.5 Tables ................................................................................................................................1. 48
5.6 Figures ............................................................................................................................... 153
Chapter 6 Bioaccumulation Potential of Polybrominated Diphenyl Ethers in a
....................................................................
Canadian Arctic Marine Food Web 161
6.1 Introduction .......................................................................................................................1. 61
6.2 Materials and Methods ......................................................................................................1. 63
6.2.1 Sample collections. ..................................................................................................1. 63
6.2.2 Food web characterization and designation of organism trophic levels. .................. 163
6.2.3 Extraction, cleanup and analysis of BDEs ..............................................................1..6 4
6.2.4 Data treatmentkompilation and statistics. ...............................................................1. 66
6.3 Results and Discussion ...................................................................................................... 167
6.3.1 Levels and congener profiles of BDEs in marine sediments and biota .................... 167
6.3.2 Chemical concentration relationships with trophic level and FWMFs ..................... 170
6.3.3 Chemical BAFs and Concentration Estimates in Air (CAGa) nd Seawater
(CwD.). .................................................................................................................1 71
6.3.4 Biomagnification potential of BDEs .........................................................................1 72
6.4 Acknowledgements ...........................................................................................................1. 76
6.5 Tables ...............................................................................................................................1..7 7
6.6 Figures ..............................................................................................................................1..7 9
Chapter 7 Hydroxylated and Methoxylated Polybrominated Diphenyl Ethers in a
Canadian Arctic Marine Food Web: PBDE Metabolites or Natural
...................................................................................
Biogenic Organohalogens? 190
7.1 Introduction .......................................................................................................................1..9 0
7.2 Materials and Methods ..................................................................................................1 92
7.2.1 Sample collections. ....................................................................................................1 92
7.2.2 Food web characterization and designation of organism trophic levels. .................. 192
7.2.3 Chemicals and reagents ............................................................................................1 93
7.2.4 Extraction and cleanup of BDEs ............................................................................... 193
7.2.5 Extraction and cleanup of OH-BDEs and MeO-BDEs. ............................................1 94
7.2.6 Instrumental Analysis ...............................................................................................1 96
7.2.7 Quality control ..........................................................................................................1 98
. .
7.2.8 Data treatmentkompilation and statistics. ................................................................1 98
7.2.9 Biomagnification Factors (BMF) and Food Web Magnification Factors
(FWMF). ..............................................................................................................1 99
7.3 Results and Discussion ......................................................................................................1 99
7.3.1 Identification of OH- and MeO-BDEs in environmental and biological
samples. ...............................................................................................................1 99
7.3.2 Levels and congener profiles of BDEs, OH-BDEs and MeO-BDEs ........................ 199
7.3.3 Trophic Transfer and Food Web Magnification. ......................................................2 01
...
Vlll
7.3.4 Potential Sources of OH- and MeO-BDEs in Arctic Biota .......................................2 01
7.4 Acknowledgements. ........................................................................................................ 203
7.5 Tables ..........................................................................................................................2 0 4
7.6 Figures ........................................................................................................................... 209
................................................................................................................
Chapter 8 Summary 218
8.1 ThesisSumrnary ................................................................................................................2 18
8.2 Determinants of chemical bioaccumulation potential in marine food webs ...................... 219
8.2.1 Kinetics of chemical bioconcentration and biomagnification ..................................2 20
8.2.2 Non-metabolizable compounds. ............................................................................. 223
8.2.3 Biotransformation ................................................................................................. 224
8.3 Conclusion ........................................................................................................................ 225
...............................................................................................................................
Bibliography 226
Literature Cited ........................................................................................................................2..2. 6
Internet Refernces ......................................................................................................................2. 48
..................................................................................................................................
Appendices 249