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THESis '

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This is to certify that the
thesis entitled

MULTIPLE LINES OF EVIDENCE RISK ASSESSMENT OF
AMERICAN ROBINS EXPOSED TO POLYCHLORINATED
DIBENZOFURANS (PCDFS) AND POLYCHLORINATED
DIBENZO-P-DIOXINS (PCDDS) IN THE TITTABAWASSEE
RIVER FLOODPLAIN, MIDLAND, MICHIGAN, USA

presented by

DUSTIN L TAZELAAR

has been accepted towards fulfillment
of the requirements for the

MS. degree in Animal Science

 

 

 

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MSU is an Affirmative Action/Equal Opportunity Employer

PLACE IN RETURN BOX to remove this checkout from your record.
TO AVOID FINES return on or before date due.
MAY BE RECALLED with earlier due date if requested.

 

DATE DUE DATE DUE DATE DUE

 

 

 

 

 

 

 

 

 

 

 

 

 

 

5/08 KIProj/AafiPresIClRCIDateDue.indd

MULTIPLE LINES OF EVIDENCE RISK ASSESSMENT OF AMERICAN ROBINS
EXPOSED TO POLYCHLORINATED DIBENZOFURANS (PCDFS) AND
POLYCHLORINATED DIBENZO-P-DIOXINS (PCDDS) IN THE TITTABAWASSEE
RIVER F LOODPLAIN , MIDLAND, MICHIGAN, USA

By

Dustin L Tazelaar

A THESIS

Submitted to
Michigan State University
in partial fitlfillment of the requirements
for the degree of

MASTER OF SCIENCE
Animal Science

2010

ABSTRACT
MULTIPLE LINES OF EVIDENCE RISK ASSESSMENT OF AMERICAN ROBINS
EXPOSED TO POLYCHLORINATED DIBENZOFURANS (PCDFS) AND
POLYCHLORINATED DIBENZO-P-DIOXINS (PCDDS) IN THE TITTABAWASSEE
RIVER FLOODPLAIN, MIDLAND, MICHIGAN, USA
By
Dustin L Tazelaar
Polychlorinated dibenzofuran (PCDF) and polychlorinated dibenzo-p-dioxin

(PCDD) concentrations in floodplain soils and biota downstream of Midland, MI, USA
are greater than regional background concentrations. A multiple lines of evidence
approach was utilized to evaluate the potential for effects of PCDD/DFS to American
robins (Turdus migratorius; AR) breeding in the floodplains from 2005-2008. A dietary-
based hazard assessment indicated there was potential for adverse effects for ARs that
were predicted to have the greatest exposures; conversely, a tissue-based exposure
assessment based on on-site eggs indicated minimal potential. A reproductive endpoints
assessment indicated measures of hatch success for the study areas (SA) were
significantly less than those of reference areas (RA), however there was no contaminant
dose-response relationship. Given the dietary-based exposure and reproductive endpoint
assessments were in accordance, the present study suggests potential for adverse effects
to resident ARs exists and effects were observed. However, the tissue-based assessment
suggests no potential for adverse effects and is reinforced by the fact the response was
not does-related. It is likely the dietary assessment is overly conservative based on the
inherent uncertainties of estimating dietary exposure relative to the direct measure of the

tissue-based assessment. As such, ARs are not expected to be at risk to potential adverse

effects of exposure to PCDD/DFs.

This thesis is dedicated to my loved ones, who have shown their support throughout my

life, giving me the opportunity for education from the finest institutions.

 

 

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ACKNOWLEDGMENTS

I first would like to acknowledge the countless efforts of my colleagues Timothy
B. F redricks, Rita M. Seston, Sarah J. Coefield, Patrick W. Bradley, Shaun A Roark,
Denise P. Kay, John L. Newsted, John P. Giesy, Steven J. Bursian and Matthew J.
Zwiemik. Their guidance and assistance throughout this study were invaluable. I would
like to thank all staff and students of the Michigan State University — Wildlife
Toxicology Laboratory field crew, particularly M. Nadeau, S. Plautz and J. Moore.
Additionally, I would like to recognize M. Kramer and N. Ikeda for their assistance in the
laboratory, James Dastyck and Steven Kahl of the United States Fish and Wildlife
Service — Shiawassee National Wildlife Refuge, for their assistance and access to the
refuge, the Saginaw County Parks and Recreation Commission for access to Imerman
Park, the Tittabawassee Township Park Rangers for access to Tittabawassee Township
Park and Freeland Festival Park as well as Tom Lenon of the Chippewa Nature Center
for his assistance and access to the nature center. I would also like to acknowledge the
greater than 50 cooperating landowners throughout the study area who have granted
access to their property, making this research possible. I would also like to thank Wei
Wang of the Michigan State University Statistical Consulting Center for his statistical
analysis assistance. Funding was provided through an unrestricted grant from The Dow
Chemical Company, Midland, Michigan to J. Giesy and M. Zwiemik of Michigan State
University. Prof. Giesy was supported by the Canada Research Chair program and an at
large Chair Professorship at the Department of Biology and Chemistry and State Key

Laboratory in Marine Pollution, City University of Hong Kong.

TABLE OF CONTENTS

LIST OF TABLES .............................................................................................................. vi
LIST OF FIGURES .......................................................................................................... viii
LIST OF ABBREVIATIONS ........................................................................................... xii
INTRODUCTION ............................................................................................................... 1
MATERIALS AND METHODS ......................................................................................... 4
Site description ......................................................................................................... 4
Nest monitoring ....................................................................................................... 5
Food web sampling .................................................................................................. 7
Chemical analyses .................................................................................................... 9
Calculation of average daily potential dose ........................................................ 11
Toxicity reference values ....................................................................................... 12
Assessment of hazard and risk ............................................................................... 15
Statistical analyses ................................................................................................. 16
RESULTS .......................................................................................................................... 18
Site-specific endpoints ........................................................................................... 18
Tissue residues ....................................................................................................... 18
Dietary exposure .................................................................................................... 20
Potential average daily dose ................................................................................... 22
Reproductive success ............................................................................................. 22
Effects assessment ................................................................................................. 24
DISCUSSION .................................................................................................................... 25
Species selection .................................................................................................... 25
Multiple lines of evidence ...................................................................................... 26
Dietary-based exposure and assessment ................................................................ 27
Tissue-based exposure and assessment .................................................................. 29
Measures of individual and population condition .................................................. 31
Uncertainty assessment .......................................................................................... 33
CONCLUSION .................................................................................................................. 35
ANIMAL USE ................................................................................................................... 36
BIBLIOGRAPHY ............................................................................................................ 105

 

 

 

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LIST OF TABLES

Table 1. Toxicity reference values (TRVs) for total TEQSWHO-Avian concentrations

selected for comparison to American robins exposed to PCDD/DFs in the river systems
downstream of Midland, Michigan, USA during 2005—2008 ........................................... 38

Table 2. Potential average TEQWHO- Avian daily dose (ADDpot; ng/kg body weight/d)
calculated from site-specific food web-based dietary exposure for adult American robins

breeding during 2003-2006 within the river floodplains near Midland, Michigan,
USA ................................................................................................................................... 39

Table 3.Nest outcomes for American robins breeding in the floodplains near Midland, MI
during 2005-2008 ............................................................................................................... 40

Table 4. Productivity measurements for American robins breeding in the floodplains near
Midland, MI during 2005-2008 ......................................................................................... 42

Table 5. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin congeners in
eggs of American robins collected during 2005-2008 within the Chippewa,
Tittabawassee and Saginaw river floodplains, Midland, MI, USA. Values (ng/kg wet
weight) are given as the arithmetic mean :i: 1 SD over the range ...................................... 43

Table 6. Concentrations of selected co-contaminants in eggs of American robins
collected during 2005-2008 within the Chippewa, Tittabawassee and Saginaw river
floodplains, Midland, MI, USA. Values (ng/kg wet weight) are given as the arithmetic
mean i 1 SD over the range ............................................................................................... 45

Table 7. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin congeners in
nestlings of American robins collected during 2005-2008 within the Chippewa,
Tittabawassee and Saginaw river floodplains, Midland, MI, USA. Values (ng/kg wet
weight) are given as the arithmetic mean i 1 SD over the range ...................................... 47

Table 8. Concentrations of selected co-contaminants in American robin nestlings
collected during 2005-2008 within the Chippewa, Tittabawassee and Saginaw river
floodplains, Midland, MI, USA. Values (ng/kg wet weight) are given as the arithmetic
mean i: 1 SD over the range ............................................................................................... 49

Table 9. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin congeners in
American robin adults collected during 2005-2008 within the Chippewa, Tittabawassee
and Saginaw river floodplains, Midland, MI, USA. Values (ng/kg wet weight) are given
as the arithmetic mean i 1 SD over the range ................................................................... 51

Table 10. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin congeners in
Oligochaeta collected during 2005-2008 within the Chippewa, Tittabawassee and

vi

 

 

 

 

 

 

 

 

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Saginaw river floodplains, Midland, MI, USA. Values (ng/kg wet weight) are given as
the arithmetic mean :t 1 SD over the range ........................................................................ 54

Table 11. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin congeners in
Coleoptera collected during 2005-2008 within the Chippewa, Tittabawassee and Saginaw
river floodplains, Midland, MI, USA. Values (ng/kg wet weight) are given as the
arithmetic mean i 1 SD over the range ............................................................................. 57

Table 12. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin congeners in
Lepidoptera collected during 2005-2008 within the Chippewa, Tittabawassee and
Saginaw river floodplains, Midland, MI, USA. Values (ng/kg wet weight) are given as
the arithmetic mean i 1 SD over the range ........................................................................ 60

Table 13. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin congeners in
terrestrial plants collected during 2005-2008 within the Chippewa, Tittabawassee and
Saginaw river floodplains, Midland, MI, USA. Values (ng/kg wet weight) are given as
the arithmetic mean :t 1 SD over the range ........................................................................ 63

Table 14. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin congeners in
other dietary components collected during 2005-2008 within the Chippewa,
Tittabawassee and Saginaw river floodplains, Midland, MI, USA. Values (ng/kg wet
weight) are given as the arithmetic mean i 1 SD over the range ...................................... 66

Table 15. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin congeners in
soils collected during 2003-2006 within the Chippewa, Tittabawassee and Saginaw river
floodplains, Midland, MI, USA. Values (ng/kg wet weight) are given as the arithmetic
mean d: 1 SD over the range ............................................................................................... 69

Table 16. Raw productivity measurements for all nesting attempts for American robins in
the river floodplains near Midland, Michigan during 2005 ............................................... 72

Table 17. Raw productivity measurements for all nesting attempts for American robins in
the river floodplains near Midland, Michigan during 2006 ............................................... 74

Table 18. Raw productivity measurements for all nesting attempts for American robins in
the river floodplains near Midland, Michigan during 2007 ............................................... 77

Table 19. Raw productivity measurements for all nesting attempts for American robins in
the river floodplains near Midland, Michigan during 2008 ............................................... 82

vii

LIST OF FIGURES

Figure 1. Study site locations within the Chippewa River, Pine River, Tittabawassee
River and Saginaw River floodplains, Michigan, USA. Reference Areas (R-1 and R-2),
Tittabawassee River Study Areas (T-3 to T-6), and Saginaw River Study Areas (S-7 and
8-9) were monitored from 2005—2008. Only sediments and aquatic food web item
collection took place at 8-8, with the exception of a limited number of dietary item
samples. Direction of river flow is indicated with arrows; suspected source of
contamination is enclosed in a dotted oval ........................................................................ 87

Figure 2. Mean concentrations of XPCDD/DF TEQSWHO-Avian in American robin eggs
collected during 2005-2008 from the river floodplains near Midland, Michigan, USA.
Error bars indicate the 95% upper confidence level; Reference areas (R-1 and R-2);
Tittabawassee River study areas (T-3 to T-6); and Saginaw River study areas (S-7 and S-
9). Samples sizes are indicated in parentheses below the sample sites ............................ 89

Figure 3. Mean congener percent contributions in American robin eggs collected during
2005-2008 from the Chippewa, Tittabawassee and Saginaw river floodplains, Midland,
Michigan, USA. R-l to R-2 includes reference areas, T-2 to T-6 includes Tittabawassee
River study areas and S-7 and 8-9 includes Saginaw River study areas. Congeners
include octachlorodibenzo—p-dioxin (OCDD), heptachlorodibenzo-p-dioxin (HpCDD),
hexachlorodibenzo-p—dioxin (HxCDD), pentachlorodibenzo-p-dioxin (PeCDD),
tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofitran (OCDF),
heptachlorodibenzofuran (HpCDF), hexachlorodibenzofuran (HxCDF),
pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF) ........................ 90

Figure 4. Mean concentrations of XPCDD/DF TEQSWHO-Avian in American robin
nestlings collected during 2005-2008 from the river floodplains near Midland, Michigan,
USA. Error bars indicate the 95% upper confidence level; Reference areas (R-1 and R-
2); Tittabawassee River study areas (T-3 to T-6); and Saginaw River study areas (S-7 and
8-9). Samples sizes are indicated in parentheses below the sample sites ......................... 91

Figure 5. Mean congener percent contributions in nestling American robins collected
during 2005-2008 from the Chippewa, Tittabawassee and Saginaw river floodplains,
Midland, Michigan, USA. R-l to R-2 includes reference areas, T-2 to T-6 includes
Tittabawassee River study areas and 8-7 and S-9 includes Saginaw River study areas.
Congeners include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-dioxin
(HpCDD), hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-dioxin
(PeCDD), tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),
heptachlorodibenzofuran (HpCDF), hexachlorodibenzofuran (HxCDF),
pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF) ........................ 92

Figure 6. Mean concentrations of XPCDD/DF TEQSWHQ-AVian in American robin adults
collected during 2005-2008 from the river floodplains near Midland, Michigan, USA.
Error bars indicate the 95% upper confidence level; Reference areas (R-1 and R-2); and

viii

 

 

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below the sample sites ....................................................................................................... 93

Figure 7. Mean congener percent contributions in adult American robins collected during
2007 from the Chippewa and Tittabawassee river floodplains, Midland, Michigan, USA.
R-l to R-2 includes reference areas and T-3 to T-6 includes Tittabawassee River study
areas. Congeners include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-
dioxin (HpCDD), hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-dioxin
(PeCDD), tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),
heptachlorodibenzofuran (HpCDF), hexachlorodibenzofuran (HxCDF),
pentachlorodibenzofiiran (PeCDF) and tetrachlorodibenzofuran (TCDF) ........................ 94

Figure 8. Arithmetic mean concentrations of ZPCDD/DF TEQSW}10- Avian in key dietary
components collected during 2004-2006 from the river floodplains near Midland,
Michigan, USA. Error bars indicate the standard deviation; Reference areas (R-1 and R-
2); Tittabawassee River study areas (T-3 to T-6); and Saginaw River study areas (S-7 and
8-9). Samples sizes are indicated in parentheses within the bars ..................................... 95

Figure 9. Mean congener percent contributions in terrestrial plants collected during 2003-
2006 from the Chippewa, Tittabawassee and Saginaw river floodplains, Midland,
Michigan, USA. R-l to R-2 includes reference areas, T-3 to T-6 includes Tittabawassee
River study areas and 8-7 and 8-9 includes Saginaw River study areas. Congeners
include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-dioxin (HpCDD),
hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-dioxin (PeCDD),
tetrachlorodibenzo-p—dioxin (TCDD), octachlorodibenzofuran (OCDF),
heptachlorodibenzofuran (HpCDF), hexachlorodibenzofirran (HxCDF),
pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF) ........................ 96

Figure 10. Mean congener percent contributions in terrestrial Coleoptera collected during
2003-2006 from the Chippewa, Tittabawassee and Saginaw river floodplains, Midland,
Michigan, USA. R-l to R-2 includes reference areas, T-3 to T-6 includes Tittabawassee
River study areas and S-7 and 8-9 includes Saginaw River study areas. Congeners
include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-dioxin (HpCDD),
hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-dioxin (PeCDD),
tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),
heptachlorodibenzofuran (HpCDF), hexachlorodibenzofuran (HxCDF),
pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF) ........................ 97

Figure 11. Mean congener percent contributions in terrestrial Lepidoptera collected
during 2003-2006 from the Chippewa, Tittabawassee and Saginaw river floodplains,
Midland, Michigan, USA. R-l to R-2 includes reference areas, T-3 to T-6 includes
Tittabawassee River study areas and 8-7 and 8-9 includes Saginaw River study areas.
Congeners include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-dioxin
(HpCDD), hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-di0xin
(PeCDD), tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),

heptachlorodibenzofirran (HpCDF), hexachlorodibenzofuran (HxCDF),
pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF) ........................ 98

Figure 12. Mean congener percent contributions in depurated terrestrial Oligochaeta
collected during 2003-2006 from the Chippewa, Tittabawassee and Saginaw river
floodplains, Midland, Michigan, USA. R-l to R-2 includes reference areas, T-3 to T-6
includes Tittabawassee River study areas and 8-7 and 8-9 includes Saginaw River study
areas. Congeners include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-
dioxin (HpCDD), hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-dioxin
(PeCDD), tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),
heptachlorodibenzofuran (HpCDF), hexachlorodibenzofirran (HxCDF),
pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofirran (TCDF) ........................ 99

Figure 13. Hazard quotients (HQs) for the effects of potential XPCDD/DF TEQSWHQ-

Avian daily dietary dose from site-specific food web-based dietary exposure for adult
American robins during 2003-2006 from the river floodplains near Midland, Michigan
based on the no observable effect concentration (N OAEC) and the lowest observable
adverse effect concentration (LOAEC). HQs based on measured concentration ranges are
presented; left y-axis for reference areas (R-1 and R-2); right y-axis for Tittabawassee
River study areas (T-3 to T-6) and Saginaw River study areas (S-7 and 8-9); lower end of
bars bound by 50th centile HQ value and upper end bound by 95th centile HQ value;
dashed horizontal reference line of right y-axis indicates HQ value of 1 ........................ 100

Figure 14. Modeled probabilistic distribution of expected cumulative percent frequencies

for potential average TEQWHO_Avian daily dose (ADDpot; ng/kg body weight/d) calculated
from site-specific food web-based dietary exposure for adult American robins breeding
during 2003-2006 within the floodplains near Midland, Michigan, USA. 10,000
replications per site; R-1 and R-2 indicated by a dotted line; T-3 to T-6 indicated by a
solid line; 8-7 and 8-9 indicated by a dotted-dashed line; Y-axis offset to show R-1 and
R-2; NOAEC indicated by a vertical solid bar; LOAEC indicated by a vertical dashed
bar; TRVs derived from Nosek et a1. 1992 ...................................................................... 101

Figure 15. Hazard quotients (HQs) for the effects of XPCDD/DF TEQSWHO-Avian for
American robin eggs collected during 2005-2008 from the river floodplains near
Midland, Michigan based on the no observable effect concentration (NOAEC) and the
lowest observable adverse effect concentration (LOAEC). HQs based on 95%
confidence intervals (LCL/U CL) derived from arithmetic mean concentrations are
presented; left y-axis for reference areas (R-1 and R-2); right y-axis for Tittabawassee
River study areas (T-3 to T-6) and Saginaw River study areas (S-7 and 8-9); lower end of
bars bound by 95% LCL HQ value and upper end bound by 95% UCL HQ value ........ 102

Figure 16. Modeled probabilistic distribution of expected cumulative percent frequencies

for American robin egg TEQWHOAvian concentrations ng/kg wet weight in site-specific
eggs collected from the river floodplains near Midland, Michigan in 2005-2008. 10,000
replications per site; R-1 and R-2 indicated by a dotted line; T-3 to T—6 indicated by a

X

solid line; 8-7 and 8-9 indicated by a dotted-dashed line; Y-axis offset to show R-1 and
R-2; NOAEC indicated by a vertical solid bar; LOAEC (not indicated) is 10,000 ng
TEQs/kg wet weight; TRVs derived from Thiel et al. 1988 ............................................ 103

Figure 17. US EPA wildlife exposures handbook (USEPA WEH) equations utilized

during estimation of potential average daily dose (ADDpot) for American robins of the
Chippewa, Tittabawassee and Saginaw river floodplains during 2004:2006 ................. 104

xi

LIST OF ABBREVIATIONS
ADDpot - potential average daily dose

AhR - aryl hydrocarbon receptor

AR - American robin

BSA - biological sampling area

COC - contaminant of concern

DL - dioxin-like

DDT - dichloro-diphenyl-trichloroethane

DDX - dichloro-diphenyl-trichloroethane related metabolites
ED- effective dose

ERA - ecological risk assessment

HpCDD - heptachlorodibenzo-p-dioxin

HpCDF - heptachlorodibenzofuran

HRGC/HRMS - high-resolution gas chromatography/high-resolution mass spectroscopy
HxCDD - hexachlorodibenzo-p-dioxin

HxCDF - hexachlorodibenzofuran

HQ - hazard quotient

IP - intraperitoneal

LBD - ligand binding domain

LCE50 - lethal concentration for 50%

LOAEC - lowest observed adverse effect concentrations
LOQ - limit of quantification

NOAEC - no observed adverse effect concentrations

xii

OCDD — octachlorodibenzo-p-dioxin

OCDF - octachlorodibenzofiiran

PCB - polychlorinated biphenyl

PCDD - polychlorinated dibenzo-p-dioxin

PCDF - polychlorinated dibenzofiiran

PeCDD - pentachlorodibenzo-p-dioxin

PeCDF - pentachlorodibenzofuran

RA - reference area

SA - study area

SIM - single ion monitoring

SR - Saginaw River

TCDD - tetrachlorodibenzo-p-dioxin

TCDF - tetrachlorodibenzofuran

TEF - toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalency factor
TEQ - 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents
TR - Tittabawassee River

TRV - toxicity reference value

UCL - upper 95% confidence level

USEPA - US. Environmental Protection Agency
WEF H - Wildlife Exposure Factors Handbook

WHO - World Health Organization

xiii

Introduction

Soils and sediments of the Tittabawassee and Saginaw river floodplains
downstream of Midland, Michigan, USA are contaminated with polychlorinated
dibenzofurans (PCDFS) and polychlorinated dibenzo-p-dioxins (PCDDS) (Hilscherova et

al. 2003). Concentrations of PCDDs and PCDFs in sediments and soils collected from
the Tittabawassee River floodplain ranged from 1.0x102 to 5.4x104 ng/kg dry weight

(dw) while mean PCDD/DF concentrations in upstream reference areas (RAs) were 10-
to 20-fold less (Hilscherova et al. 2003). The spatial distribution and congener profile of
the contaminants suggest the sources of PCDD/DFs to the Tittabawassee River floodplain
were byproducts of historical production of industrial organic chemicals as well as on-site
storage, treatment and disposal during the early- to mid-19003 prior to modern regulation
and waste management practices (Amendola and Barna 1986). A primary level
ecological risk assessment (ERA) based on limited biological data noted the potential for
adverse impacts on resident wildlife (Galbraith 2003). In the study described herein, the
American robin (Turdus migratorius; AR) was studied as a terrestrial based receptor
species with a direct relationship to floodplain soils in a site-specific, multi-year, multiple
lines of evidence approach to further refine measures of exposure. Finally, direct
measures of reproductive performance were measured to test the hypothesis that the
potential for effects could be predicted based on predicted exposures and estimates of
toxicity reference values (TRVs) developed for other species or under laboratory
conditions.

The site-specific hydrology of the Tittabawassee River, the unique nature of the

graphite carbon source for PCDD/DF congeners (ATS 2009), the lipophilic properties

and slow rate of degradation rates of dioxin-like compounds when buried and out of
direct sunlight (Mandal 2005) have resulted in a unique mixture of contaminants
dominated by PCDF downstream of Midland, Michigan some 100 years after they were

released. The Tittabawassee River system receives drainage inputs from approximately
5,426 km2 of land surface, composed primarily of woodlands, agricultural lands, and

urban areas. River depth and width vary greatly with seasonal episodic rain events with
lesser, consistent variation resulting from upstream hydroelectricity generation, daily.
Sediments are mobilized and deposited in the floodplain as a result of extreme flood
events and ice sheet bank scouring associated with the spring thaw. The Tittabawassee
River flows southeast into the Saginaw River, which in turn flows northeast to the
Saginaw Bay of Lake Huron. The Saginaw River downstream of the Tittabawassee River
is wider with a lower flow rate. The Saginaw River is confined by engineered banks that
support shipping lanes within and onshore urban development. As a result, the Saginaw
River is less susceptible to deposition dynamics within the floodplain and as such, surface
sediment PCDD/DF concentrations of the Saginaw and Tittabawassee rivers were
similar, whereas floodplain surface soil concentrations of the Tittabawassee River were
greater than those of the Saginaw River (Kannan et al. 2008).

Selection of representative ecological receptor species is a critical component of
risk assessment. Guidance from the US Environmental Protection Agency (USEPA)
suggests, in order to apply comparisons across regions, selecting species based upon
geographic distribution, intensity and duration of exposure, appropriateness as a surrogate
species, sensitivity to some of the primary contaminants of concern (COCs) across sites,

ecological function, and relative ease of conducting studies with that organism as well as

other criteria (USEPA 1994). The species selected should ideally provide an accurate
indication of the magnitude and extent of contamination. As such, a variety of
appropriate receptor species were selected to represent the variable nature of
contamination about the Tittabawassee and Saginaw river floodplains (Zwiemik et‘ al.
2008; Seston et al. 2009; Coefield et al. 2010; Fredricks er al. 2010). For exposure and
effects assessments of terrestrial food-web based passerines researchers have utilized a
variety of species (Ankley et al. 1993; Bishop et al. 1995; Custer et al. 2005; Arena] et
al. 2004). In this study, the AR was selected as an appropriate receptor species based on
its direct relationship to soil and its exceptional study suitability (Henning et al. 2003;
Bennett et al. 2007).

The AR is the largest, most abundant and most widespread North American
thrush. It is easily recognizable with its very audible and unique song and defensive
vocalizations. The AR constructs an open cup nest from grass, soil and earthworm
castings to begin the breeding season (Sallabanks and James 1999), typically near short
grass habitats, at heights manageable for observation by researchers. As such, the
presence of the AR is relatively easy to predict, affording researchers an on-site species
presence and often sufficient nest density to quantify exposure and assess population
condition. Further, the AR has a limited home range during the breeding season (Knupp
et al. 1977) and has a diet rich with terrestrial plants and invertebrates including
earthworms (Howell 1942; Wheelwright 1986), which ensures concentrations of residues
of interest will be indicative of local exposure from soils.

A multiple lines of evidence approach was employed to evaluate contaminant

exposure and the associated potential for adverse effects. The approach minimizes

uncertainties associated with uncontrollable variables associated with single field-based
measurement endpoints (F airbrother 2003). The lines of evidence included here include
site-specific assessments of American robin exposure to PCDD/DFs were conducted for
both predicted dietary exposure and measured concentrations in tissues of American
robins. These exposures were compared to selected toxicity reference values (TRVs) to
estimate the risk of adverse effects present to American robin along the TR. This was

done in conjunction with site-specific individual and population health measures.

Materials and Methods
Site description

This study was conducted on the Tittabawassee, Chippewa, Pine and Saginaw
rivers in and near Midland, Michigan, USA (Figure 1). Nests were located and all
samples and reproductive data were collected from within the 100-year floodplain of the
individual rivers. Two reference areas (RAs) were located upstream of the suspected
sources of PCDD/DPS (Hilscherova et al. 2003) on the Tittabawassee River (R-1) and
Chippewa and Pine (R-2) rivers (Figure 1). Study areas (SAs) downstream of the
apparent sources of PCDDfDFs include approximately 72 km of free flowing river from
the upstream boundary, defined as the low-head dam within the city limits of Midland,
Michigan, through the confluence of the Tittabawassee and Saginaw rivers to where the
Saginaw River enters Saginaw Bay in Lake Huron. The SAs along the Tittabawassee
River downstream of Midland included four sites (T-3 to T-6) approximately equidistant,
and three sites (8—7 to 8-9) located at the initiation, median, and terminus of the Saginaw

River. The seven SAs (T-3 to 8-9) were selected from the Tittabawassee and Saginaw

rivers, respectively, based on the necessity to discern spatial trends, accessibility
privileges, and maximal receptor exposure potential based on floodplain width and
measured soil and sediment concentrations (Hilscherova et al. 2003). Reference areas
and SAs included intermittent agricultural, forested and short grass habitat areas and
spanned contiguous foraging areas of between one and three km of river. Only sediments
and aquatic food web item collection took place at 8-8, with the exception of a limited

number of dietary item samples, and as such will not be relevant to this study.

Nest monitoring

Nests were monitored in order to obtain eggs and nestlings for measurement of
concentrations of PCDD/DF as well as to collect information of reproductive
performance. Nest searching took place throughout the breeding seasons from 2005-
2008 and involved investigating suitable nest locations and defensive behavior of adult
AR. Robins construct an open cup nest from grass, soil and earthworm castings
(Sallabanks and James 1999). Nests are constructed by females at the beginning and
during the breeding season, typically on supporting branches of various tree and shrub
species, including, but not limited to, box elder (Acer negundo), silver maple (A cer
saccharinum), white pine (Pinus strobes), red pine (Pinus resinosa), and autumn olive
(Elaeagnus umbellate), as well as atop wild grape vines (Vitis sylvestris) and man-made
structures, such as comer posts of pavilions and supporting beams beneath bridges. Nests
located during this study were constructed at heights ranging from less than one meter
(m) to greater than 17 m, but typically were located at heights observable from the

ground with a bicycle mirror attached to a 1.5-3.0 m telescoping pole. For nests located

at heights greater than the reach of the telescoping pole, either a 1.8 m step ladder, a 4.7-
9.0 m extension ladder or tree climbing gear, including a saddle harness, cable harnesses
and tree climbing spikes, was utilized for access.

Nests were visited every third day following nest location (Martin and Guepel
1993) to monitor egg laying, incubation, hatching, fledging, predation and any other
event that may have affected nest outcome. The number of successful nests was
calculated by summing the number of nests that fledged at least one juvenile. Mayfield
nest success index was calculated based upon the duration of observations and daily
predation and survival rates (Mayfield 1975). Addled eggs were collected
opportunistically while a single viable egg was randomly collected from some clutches,
until a sample size of 6 was obtained from each study area, for use in residue
quantification. Hatching success was calculated in two ways for nests uninterrupted by
nest failure. First, the total number of nestlings following hatch completion was divided
by the total number of eggs present prior to hatch initiation. This approach ignored the
fertility and hatchability of any egg collected and was referred to as the range-low
hatching success. The second approach, range-high hatching success, was adjusted for
any viable egg collected and assumed that any such egg would have hatched. Together,
these two variables define the range of hatching success, as the range-low hatching
success alone may bias hatching success too low or vice versa for the range-high hatching
success alone (Henning et al. 2003). A maximum of one nestling per nesting attempt was
also randomly collected at about twelve days of age, until a sample size of 6 was obtained
for each study area, for use in residue quantification. Fledging success was calculated in

a similar manner for successful nests, or nests that fledged at least one nestling. The

range-low fledging success is equal to the total number of juveniles fledged divided by
the number of nestlings present following hatch completion while the range-high fledging
success was adjusted for any nestling collected and assumed that any such nestling would
have fledged. Productivity, defined as the number of juveniles fledged following the
nestling period divided by the number of eggs present prior to hatching, was calculated in
a similar manner as hatching and fledging success and was presented to reflect a range,
range-low productivity and range-high productivity, for nests observed during the egg-
laying or incubation period through the nestling period. Adjusting reproductive
endpoints was a necessary compromise of experimental design to obtain the most
accurate, nest-specific estimates of concentrations of PCDD/DFs. Clutch size was
monitored; however, adjustment for collected eggs was unnecessary. In order to avoid
affecting nest outcome, adult AR were collected from known nesting areas, following the
breeding season, but prior to migration. Nestlings and adults were monitored for gross

external morphological abnormalities during routine handling.

Food web sampling

Collection of AR food items, including invertebrates, plant matter and soil,
occurred at nine preselected biological sampling areas (BSAs), seven were located within
the SAs and two were located in the RAs. Each BSA included one 30 m x 30 m grid,
proximal to the river bank. Site-specific sampling of food items took place at RAs, R-
land R-2, and SAs, T-4 and T-6 in 2003. These, as well as T-3 to T-6, were sampled in
2004 and Saginaw River SAs, S-7 and 8-9 were added in 2006. Sampling events

occurred in mid-May, June and September to assess potential temporal variation in

dietary contaminant exposure.

Composite plant samples were collected by hand during each sampling from a 1
m x l m plot randomly selected from within each BSA. Chemically cleaned scissors
were used to sever the plants just above the root crown. Plants were separated by species
so sample size was based on the diversity of the plant community of the BSA. Once
plant material was removed soil was excavated by hand-digging with a chemically
cleaned shovel to a depth of 15 cm from which a composite soil and Oligochaeta
(earthworm) sample were collected. Forceps were employed to collect surface and
subsurface-dwelling terrestrial invertebrates prior to and during excavation of the 1 m x 1
m plot as well as from pitfall traps utilized for small mammal collection of food web
items of other receptors (Zwiemik et al. 2008). Finally, aerial and plant perching
invertebrates were collected from the entire 30 m x 30 m BSA grid utilizing sweep and/or
aerial invertebrate nets, as well as incidentally during the collection of aquatic emergent
insects attracted to a mercury halide lamp, white sheet, Insect Vac Collection Chambers
and Insect Vacs (Bioquip Products, Rancho Dominguez, CA). All collected food items
were transferred to a labeled, chemically cleaned glass jar (I-Chem brand, Rockwood,
TN). A minimum sample mass of 5 g was collected for each sample type in order to
satisfy detection limit standards for residue analysis. Samples were stored on wet ice
while in the field. Oligochaeta composite samples from each sampling event were split
into two samples with half being depurated of gut content for 24 h. Oligochaeta were
rinsed with distilled water prior to residue analysis. All other terrestrial invertebrates
were categorized to taxonomic order for each life stage collected during each sampling

period per site. Finally, samples were transferred to a -20°C freezer prior to

homogenization and extraction.

Chemical analyses

Concentrations of the seventeen 2,3,7,8-substituted PCDD/DP congeners were
quantified in all samples while concentrations of polychlorinated biphenyls (PCBs) and
dichloro-diphenyl-trichloroethane (DDT) and related metabolites (DDXS) were measured
in a subset of eggs and nestlings. Congeners were quantified in accordance with USEPA
Method 8290/ 1668A with minor modifications (USEPA 1998). Collected eggs were
opened around the girth with a chemically cleaned scalpel blade and assessed for stage of
development and the presence of any abnormalities. Contents were then lyophilized and
stored in clean jars until analysis (I-CHEM brand, Rockwood, TN). Concentrations of
PCDD/DF in eggs were reported on a fresh mass basis to account for any desiccation
during incubation and storage. Adjusted fresh mass was calculated based on egg volume
(Hoyt 1979). The mass of egg contents was determined by subtracting the eggshell mass
at the time of processing from adjusted fresh mass. Nestling‘and adult whole body
samples were homogenized following removal of beaks, stomach contents, feathers and
legs below the tibiotarsus. Nestling and adult whole body homogenates, egg contents and
dietary items were homogenized with anhydrous sodium sulfate, spiked with known
amounts of l3C-labeled analytes as internal standards to calculate extraction efficiency
and Soxhlet extracted in hexane: dichloromethane (1: 1) for 18 hours. The extract was
solvent exchanged to hexane and concentrated to 10 mL. Ten percent of each extract
was allocated to lipid content quantification. Extracts were then purified via concentrated

sulfuric acid treatment prior to passage through silica gel and sulfuric acid silica gel

columns and eluted with hexane. Additional column chromatography via elution through
acidic alumina produced two fractions for each extract. The first fraction contained the
majority of the PCB congeners and pesticide compounds while the second fraction
contained PCDD and PCDF congeners. The first fraction from the silica gel columns,
eluted with solvents, was combined with the first fraction of the acidic alumina columns
and was retained for possible co-contaminant analyses. The second fraction was then
passed through a carbon column packed with 1 g of activated carbon-impregnated silica
gel. The second fraction of the silica gel column, eluted with toluene, contained the
2,3,7,8-substituted PCDD/DFs and dioxin-like (DL) PCBs.

Individual congeners and compounds were identified and quantified by use of
high-resolution gas chromatography/high-resolution mass spectroscopy (HRGC/HRMS)
via a Hewlett-Packard 6890 GC (Agilent Technologies, Wilmington, DE) connected to a
MicroMass® high resolution mass spectrometer (Waters Corporation, Milford, MA).
PCDF and PCDD congeners were separated on a DB-5 capillary column (Agilent
Technologies, Wilmington, DE) coated at 0.25 pm (60 m x 0.25 mm id). The mass
spectrometer was operated at an El energy of 60 eV and an ion current of 600 uA.
Congeners were identified and quantified by use of single ion monitoring (SIM) at the
two most intensive ions of the molecular ion cluster. Concentrations of 2,3,7,8-
tetrachlorodibenzofirran (TCDF) were confirmed by using a DB-225 (60 m x 0.25 mm
id, 0.25 mm film thickness) column (Agilent Technologies, Wilmington, DE). Chemical
analyses included pertinent quality assurance practices, including matrix spikes, blanks,
and duplicates.

Concentrations of PCDD/DP were expressed as 2,3,7,8-tetrachlorodibenzo-p—

10

dioxin (2,3,7,8-TCDD) equivalents (TEQ). Concentration of TEQ were calculated as the
sum of the products of the concentration of each congener multiplied by it’s appropriate
toxic 2,3,7,8- tetrachlorodibenzo-p-dioxin equivalency factor (TEF) as specified by the

World Health Organization (WHO) (van den Berg et al. 1998) and concentrations

expressed as ng TEQWHO-Avian/ kg on a wet weight basis.

Calculation of average daily potential dose
The potential average daily dose (ADDpot) expressed as ng TEQWH0_Avian/l(g

body weight/day, was calculated utilizing the wildlife dose equations for dietary
exposures equation 4-8 of the US. Environmental Protection Agency (USEPA) Wildlife
Exposure Factors Handbook (WEFH) (USEPA 1993). Food intake rate was calculated
utilizing USEPA WEFH equation 3-4 with a body mass of 77 g. This approach assumed
that all foraging was done within the study area. A literature-derived dietary composition
(Howell 1942; Wheelwright 1986) was included: 25% Coleoptera (beetles), 25%
Lepidoptera (mostly moths), 18% Oligochaeta, 7% plant and 25% miscellaneous
Arthropoda including Orthoptera (mostly grasshoppers), Hemiptera (largely shield bugs
or stink bugs), Homoptera (particularly leaflroppers) and Arachnida (spiders). Site-
specific (R-1 and R-2; T-3 to T-6; S-7 and S-9) concentrations of TEQWl-lO-Avian were
calculated. For PCDD and PCDF, invertebrates have greater concentrations than do
plants, thus, the selected literature-derived dietary composition reflects a breeding season
dietary composition to calculate dietary exposure because a greater proportion of
invertebrates are consumed relative to plants at this time. The strategy applied assured a

daily dietary dose that was on the greater end of the exposure distribution that will result

11

in an effects assessment that is protective of the population.

Toxicity reference values

Potential for adverse effects was evaluated by comparing the concentrations of
TEQWHOAvian in the diet or eggs to available toxicity reference values. Toxicity

reference values are quantitative measures of toxicity used to estimate risk utilizing the
hazard quotient (HQ) method where the estimate of exposure is compared to a threshold
concentration for effect. Toxicity reference values represent concentrations in eggs or the
diet less than or at which adverse effects would be expected to occur. Several factors
were considered during selection of TRVs, including appropriateness of receptor species,
chemical compound, presence of a dose-response relationship, and quantification of

ecologically-relevant endpoints associated with sensitive life-stages. In an effort to
minimize additional uncertainties associated with the relationship between TEQWHO-Avian

values derived from PCB-based or PCDD/DF-based exposures (Custer et al. 2005),
consideration was only given to values derived from PCDD/DF-based exposures.
Literature-based no observed adverse effect concentrations (N OAECs) and lowest
observed adverse effect concentrations (LOAECs) were used in the determination of HQs
and subsequent assessment of potential risk. In the present study, TRVs based on
concentrations in the diet or in eggs were used to evaluate the potential adverse effects of
site-specific contamination.

No laboratory-based dietary dosing studies of the effects of PCDD/DF exist for
AR and are limited for Passeriformes in general. Therefore, a dosing study of adult hen

ring-necked pheasants (Phasianus colchicus) utilizing intraperitoneal (IP) injections of

12

 

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TCDD for a 10 wk exposure period was selected for the dietary exposure-based TRV for
this study (Nosek et al. 1992). While exposing hen pheasants to TCDD via IP injections
versus true dietary exposure may be considered grounds for uncertainty, dosing exposure
via injection should produce more direct and greater exposures than that of
gastrointestinal transfer resulting in any bias producing a lesser TRV or more
conservative effects assessment. Another source of uncertainty stems from the species
selection of this dosing study as ring-necked pheasant and American robins are not
members of the same taxonomic order. Galliformes species are traditionally considered
to exhibit greater sensitivity to dioxin-like compound exposures than passerine species
(Brunstrom and Reutergardh 1986; Brunstrom 1988; Powell et al. 1997a). However,
recent results suggest that specific differences in the ligand binding domain (LBD) of the
aryl hydrocarbon receptor (AhR) of birds are predictive differences in sensitivity to
dioxin-like compounds among species of birds (Karchner et al. 2006; Head et al. 2008).
Ring-necked pheasants and AR have the same amino acid sequence in the LBD of the
AhR and thus have similar sensitivities to the effects of AhR-active compounds such as
PCDD and PCDF (SW Kennedy personal communication).

Dietary-based TRVs were determined by converting the weekly exposure at
which adverse effects on fertility and hatching success were determined (1000 ng
TCDD/kg/wk) to a LOAEC for daily exposure of 140 ng TCDD/kg/d. The dosing
regime was based on orders of magnitude differences and adverse effects were not
present at the next lesser dose, 14 ng TCDD/kg/d, which was determined to be the

NOAEC for dietary exposure (Table 1). One uncertainty in applying dietary TRVs is that

correction by relative potencies among congeners by applying TEFSwHo-Avian does not

13

correct for differences in rates of assimilation or biotransformation and clearance that

would affect the internal dose resulting from a dietary dose. For these reasons, the
authors consider measurements of TEQWHO-Avian in eggs to be a more accurate estimate
of exposure.

The egg tissue-based TRV selected for comparison to concentrations of TEQWHQ-

Avian in AR eggs is based on an egg-injection study that involved dosing eastern bluebird

(Sialia sialis) eggs with 2,3,7,8-TCDD (Thiel et al. 1988). Field collected eastern
bluebird eggs were injected with concentrations of 2,3,7,8-TCDD in 10-fold increments
ranging from 1 to 100,000 ng/kg wet weight prior to replacement to their original
clutches and subsequently incubated by unexposed adults (Table l). Hatching success
was significantly adversely affected at doses greater than 10,000 ng/kg wet weight
(LOAEC), while endpoints associated with eggs exposed to less than 1,000 ng/kg wet
weight (N OAEC) were not significantly different than those of vehicle-injected controls.
Additionally, the key measurement endpoint of the study was hatching success, an
ecologically relevant endpoint, for which a dose-response relationship was observed.
The minimal taxonomic distance between the two species further strengthened the
applicability of the bluebird egg TRV to the eggs of the AR. Closely related species are
expected to exhibit similar sensitivity to dioxin-like compounds (Allard et al. 2010) and
both bluebirds and AR are of the family Turdidae. Not unexpectedly, both have the same
genetic code in the area of the genome that appears to dictate species sensitivity to
dioxin-like compounds further confirming their direct comparability (SW Kennedy
personal communication).

Several studies in which eggs were injected with 2,3,7,8-TCDD, were also

14

considered for the AR egg TRV, including ring-necked pheasant (Nosek 1993) and
double—crested cormorant (Phalacrocorax auritus) (Powell et al. 1998; Powell et

al. 1997b). However, based on the criteria we adopted for selection of a TRV, including
species relatedness, ecologically relevant endpoints, a clear dose-response relationship,
valid control groups and power to discern effects, none were as robust as the study of the

eastern bluebird.

Assessment of hazard and risk

Overall, the potential hazard of PCDD/DF to AR was assessed utilizing a multiple
lines of evidence approach incorporating both dietary- and egg-based exposure estimates
as well as quantification of site-specific productivity endpoints (Fairbrother 2003).

Potential effects of dietary- and egg-based exposures were assessed by calculating hazard

quotients. Concentrations of TEQSWHQ-AVian (ng/kg wet weight) in eggs and estimates of

dietary exposure ADDpot; expressed as ng TEQSWHO_AVian/kg/d, were divided by TRVs

based on either concentrations in eggs or diet and based on either the NOAEC or
LOAEC, respectively. Hazard quotients were determined based on the upper 95%
confidence level (UCL) for arithmetic means of concentrations in eggs at individual study
locations and based on 95th and 50th centile dietary exposures. Arithmetic means were
presented rather than geometric means as arithmetic means were greater and provided a
more conservative basis from which inferences could be drawn. Incorporation of both
dietary- and tissue-based assessment endpoints has been shown to reduce uncertainty in
risk assessments of persistent organic pollutants (POPS) (Leonards et al. 2008).

In addition to the point estimates of hazard, semi-probabilistic estimates of risk

15

were determined b y comparing the probability distributions of expected cumulative

percent frequencies of exposure based on concentrations of TEQSWHo-Avian in eggs of AR

and ADDpot based on TEQWHO-AVian to selected TRVs. Predicted probabilistic

distributions were generated utilizing a Monte Carlo approach in SAS® software
(Release 9.1; SAS Institute Inc., Cary, NC, USA) for the egg-based risk assessment and a
re-sampling approach in R software (Version 2.9.2, R Foundation for Statistical

Computing, Vienna, Austria) for the dietary-based risk assessment.

Statistical analyses

Total concentrations of the 17 individual 2,3,7,8-substituted PCDD/DP congeners
(ZPCDD/DF) are reported as the sum of all congeners expressed as ng/kg wet weight.
To be conservative, for individual congeners for which concentrations were less than the
limit of quantification (LOQ) a proxy value of half the LOQ was assigned. Total
concentrations of twelve non- and mono-ortho-substituted PCB congeners are reported as
the sum of these congeners (ZDL-PCBS) for a subset of egg samples that were screened
for co-contaminants. Additionally, dichloro-diphenyl-trichloroethane (2’,4’ and 4’,4’
isomers) and dichloro-diphenyl-dichloroethylene (4’,4’) are reported as the sum of the
o, p and p, p isomers (DDXs) for the same subset of samples as for PCBs.

Statistical analyses were performed using SAS® software (Release 9.1; SAS
Institute Inc., Cary, NC, USA) and R software (Version 2.9.2, R Foundation for
Statistical Computing, Vienna, Austria). The experimental unit for measurements
associated with eggs, nestlings and productivity was the nest, since individual

measurements within a clutch cannot be considered independent (Hurlbert 1984).

16

Similarly nest productivity measurements were reported on a per nes’t basis, thus making
each nesting attempt a separate experimental unit (Pinkowski 1979). Adults were
considered individual experimental units unassociated with nests. Prior to the use of non-
parametric statistical procedures with PROC NPARIWAY, normality was evaluated
using the Shapiro-Wilks test. To assess the influence of the random effect of year, PROC
GLIMMIX was then used for effect level comparisons following non-parametric
Kruskal-Wallis test comparisons. Least squares means tests were used to identify
significant differences among locations. Differences were considered to be statistically
significant at p < 0.05.

In order to avoid bias resulting from skewed data, a re-sarnpling approach with R

software (Version 2.9.2, R Foundation for Statistical Computing, Vienna, Austria) was
used to estimate 50th centile, 95th centile and maximum ADDpot. The dietary

concentrations component of USEPA WEFH equation 4-8 was repeatedly calculated,
each time using a randomly sampled dietary item concentration from the data set for each

dietary item category. This resulted in a distribution of 10,000 dietary concentrations of

which the median of the distribution represented the central tendency of ADDpot. The re-

sampling was performed on real measured data to estimate ADDpot rather than on a

continuous distribution inferred from the measured data or a range of data in order to
avoid assumptions about the distribution of the data. This method is similar to
assessments of American mink and great horned owl exposure to PCDD/DFs in the

Tittabawassee River floodplain (Zwiemik 2008; Coefield 2010).

17

Results
Site-specific endpoints

Among all study sites, 240 AR nests were initiated and monitored during the four
breeding seasons from 2005 through 2008. Measurement endpoints associated with
tissue concentrations of ZPCDD/DF were quantified in 84 eggs and 53 nestlings collected
from individual nesting attempts. Twelve adults were collected for quantification of
concentrations of EPCDD/DF following the breeding season and 158 composite samples
of individual dietary items were collected from the identified BSAs throughout the

nesting seasons from 2003-2006 and used to calculate dietary exposure to PCDD/DPS.

Tissue residues

Concentrations of PCDD/DPS and TEQWHO-Avian were quantified in AR eggs,

nestlings and adults collected at each site. Mean concentrations of TEQWHo-Avian in eggs

from the Tittabawassee River SAs were 8- to 71-fold greater than those from RAs (Figure
2), while concentrations in eggs collected from the Saginaw River SAs were 2- to 24-fold
greater than those of eggs collected from RAs. Profiles of relative concentrations of
PCDD/DF comprising TEQWHO-AVian in eggs were primarily PCDD congeners at RAs,
while downstream SAs were dominated by PCDF congeners, particularly 2,3,4,7,8-
pentachlorodibenzofuran (2,3,4,7,8-PeCDF), which accounted for approximately 35% of
all congeners in eggs at T-3 to T-6 and 25% at S-7 and S-9 (Figure 3). The maximum
egg concentration of EPCDD/DF TEQSWHO_,5Man was 1662 ng/kg from T-6. Co-

contaminants in eggs were not significantly different between RAs and SAs for ZDL-

PCBs concentrations, DL-PCB TEQs, or DDXs. However, mean DL-PCB TEQ

18

concentrations were 8- and 3-fold greater at Saginaw River SA than RAs and
Tittabawassee River SAS, respectively. Mean ZDL-PCB concentrations were 7— and 2-
fold greater at Saginaw River SA than RAs and Tittabawassee River SAS, respectively.
Mean ZDDX concentrations were 2-fold greater at Tittabawassee River SAS than RAs
and Saginaw River SAs (p = 0.0345). The greatest ZDL-PCB TEQ concentration was
from an egg collected from S-9 (11 ng/kg wet weight). The PCB congener PCB 118

contributed approximately 58% to the total ZDL-PCB concentration of that egg.

Concentrations of PCDD/DFs and TEQWHo-Avian in nestlings were greater at SAs

than at reference areas. The mean concentrations of TEQWHO-Avian in nestlings were 4-
to 116-fold greater in Tittabawassee River SAS than RAs, while mean concentrations of

TEQWH0_AVian in nestlings from the Saginaw River SA were 2- to 36-fold greater than

nestlings collected from RAs (Figure 4). The maximum concentration of TEQSWHo- Avian

was 709 ng/kg in nestlings from T-5.

Profiles of relative concentrations of congeners in nestlings resembled those in
eggs. Profiles in nestlings from RA were primarily comprised of PCDD while profiles in
nestlings from SA were dominated by PCDF, particularly 2,3,4,7,8-PeCDF, which
accounted for approximately 31% and 27% in T-3 to T-6 and S-7 and S-9, respectively
(Figure 5).

Concentrations of the other residues, monitored in this study, were not
significantly different between RAs and SAS. Mean DL-PCB TEQ concentrations were
15- and 5-fold greater at Saginaw River SA than RAs and Tittabawassee River SAS,
respectively. Mean ZDL-PCB concentrations were 22- and 6-fold greater at Saginaw

River SA than RAs and Tittabawassee River SAs , respectively. Mean ZDDX

19

concentrations were 9- to 4-fold greater at Tittabawassee River SAs than RAs and

Saginaw River SAS), respectively.
The mean concentrations of TEQWHOAVian in AR adults from the Tittabawassee

River SAS were 48-fold greater than those from RAs (Figure 6). The relative
contribution of the 17 individual congeners to the sum total for whole body adults was
consistent on a spatial basis with those of both eggs and nestlings. Congeners of PCDD
were prevalent in adult AR from RA while PCDF congeners were prevalent in adult AR
from SAs, particularly 2,3,4,7,8-pentachlorodibenzofuran (2,3,4,7,8-PeCDF), which

accounted for approximately 42% of all congeners (Figure 7). The maximum
concentration of TEst;.{0-A,..ian in adult AR was 268 ng/kg from T-6.

There were no observations of morphological deformities in the observed and/or

collected nestlings and adults.

Dietary exposure

Concentrations of ZPCDD/DFs and TEQWHO-Avian were quantified on a temporal
and spatial basis for co-located soils, terrestrial plants and a number of invertebrate
orders. In general, the mean concentrations of ZPCDD/DFS and TEstnOMm were
significantly greater in SA dietary items than in RAs. Arithmetic mean TEQWHQ- Avian

concentrations in dietary items were 11- to l77—fold greater in Tittabawassee River SAs

than in RAs in terrestrial plants and Oligochaeta, respectively, while Saginaw River SA
mean concentrations of TEst} 10- Avian in dietary items were as great as l44-fold greater

than that of RAs in Oligochaeta, while terrestrial plants were similar between areas

20

(Figure 8). The maximum concentration of TEQSWHO, Avian was 1900 ng/kg wet weight

and occurred in Coleoptera collected from T-4.

Profiles of relative concentrations of congeners in dietary items varied in
proportion of PCDD and PCDF (Figures 9, 10, 11 and 12). RA dietary items were
dominated by PCDD, particularly octachlorodibenzofuran (OCDD), which accounted for
approximately 57% to 73% of all congeners in RA dietary items. Plants of Tittabawassee
River SAs were dominated by PCDD, with OCDD contributing approximately 53% to
the congener composition while Saginaw River SA congeners were similar in the
percentage of dioxin and furan congener contribution. At S-7 and S-9 the congener
pattern in terrestrial plants was dominated by OCDD, which contributed approximately
25%, but also was comprised of approximately 17% 2,3,7,8-tetrachlorodibenzofuran
(2,3,7,8-TCDF). Congener profiles of Coleoptera, Lepidoptera and Oligochaeta collected
from Tittabawassee River SAS were characterized by slightly greater percentages of
PCDF than PCDD and were dominated by OCDD, which contributed 40% to Coleoptera,
35% to Lepidoptera and 41% to Oligochaeta congener profiles. 2,3,7,8-TCDF
contributed 27%, 27% and 17% to Tittabawassee River SA Coleoptera, Lepidoptera and
Oligochaeta, respectively, while octachlorodibenzofuran (OCDF) also contributed
approximately 13% to the congener profile of Tittabawassee River SA Oligochaeta.
Congener profiles of dietary invertebrates from the Saginaw River SA varied in congener
contribution, but were largely dominated by OCDD which contributed 48%, 50% and
39% to the relative congener contributions of Coleoptera, Lepidoptera and Oligochaeta,

respectively.

21

Potential average daily dose

Potential average TEQWHo-Avian daily doses (ADDpot ) expressed as ng/kg body
weight (bw)/d) for adult AR were greater at SAs relative to RAs. The 50th centile
ADme were 142- and 46-fold greater at Tittabawassee and Saginaw river SAs,
respectively, while 95th centile ADme were 116- to 39-fold greater at Tittabawassee and

Saginaw river SAs, respectively. The maximum ADDpot of 880 ng/kg bw/d was

observed at Tittabawassee River SAS (Table 2).

Reproductive success

Sixty-eight nests were identified in RAs, while 133 nests were located in
Tittabawassee River SAs and 39 in Saginaw River SAs. Nest location varied per site
with as few as 15 nests located at S-9 and as many as 64 nests located at T-6. Of the 215
nests for which the outcome was known, 46% fledged at least one nestling. Of the nests
of known outcome at least one nestling was fledged at 42%, 50% and 37% of nests in
RAs, Tittabawassee River SAs and Saginaw River SAS, respectively (Table 3). The
Mayfield daily mortality rate for all nest observations with known outcomes for RAs for
743.5 nest days with 36 nest losses was 0.048 per nest day. Mayfield daily mortality
. rates were 0.044 per nest day (1284 nest days and 57 nest losses) and 0.053 per nest day
(359 nest days and 19 nest losses) in Tittabawassee River and Saginaw River SAS,
respectively.

Nests that were preyed upon comprised the majority of nests that were not
successful. Criteria for depredation included the loss of all eggs or nestlings prior to a

date at which nestlings would have been old enough to fledge, the presence of damaged

22

eggs, such as that of an avian predator puncturing the shell, or evidence of preyed upon
nestlings or adults, such as lacerations on the carcass of deceased birds or piles of
feathers below the nest.

Mayfield daily mortality rates were significantly different among RAs (743.5
exposure days), Tittabawassee River SAS (1284 exposure days) and Saginaw River SAs
(359 exposure days) based on a chi-square test (p < 0.0001). Daily mortality rates were
0.048 nest losses/exposure day in RAs, 0.044 nest losses/exposure day in Tittabawassee
River SAs and 0.053 nest losses/exposure day in Saginaw River SAs. Daily mortality
rates were significantly different between RAs and Tittabawassee River SAS (p < 0.001),
between RAs and Saginaw River SAS (p = 0.0008) and between Tittabawassee River SAS
and Saginaw River SAs (p < 0.001).

In general, most reproductive endpoints were not significantly different between
RAs and SAs with the exception of hatch success (Table 4). Mean clutch size was 3.2,
3.2 and 3.5 for RAs, Tittabawassee River SAS and Saginaw River SAs, respectively.
Range-low hatch success was 87% in RAs, 74% for T-3 to T-6 and 65% in S-7 and S-9,
while range-high hatch success was 96%, 82% and 75% in RAs, Tittabawassee River
SAs and Saginaw River SAS, respectively. Range-low fledging success was 74%, 76%
and 80%, while range-high fledging success was 93%, 98% and 100% for R-1 and R-2,
T-3 to T-6 and S-7 to S-9, respectively. Range—low productivity was 72%, 59% and 49%
for RAs, Tittabawassee River SAs and Saginaw River SAs, respectively. Range-high

productivity was 84% in R-1 and R-2, 72% in T-3 to T-6 and 62% in S-7 and S9

23

Effects assessment

The 50th centile, 95‘h centile and maximum ADme for Tittabawassee River SAS
exceeded both the dietary-based LOAEC and NOAEC. The 50th centile ADme
exceeded only the NOAEC, while the 95th centile and maximum ADDpot exceeded both

the LOAEC and NOAEC for Saginaw River SAs. 95th centile HQs at Tittabawassee
River SAs were greater than 40 based on the NOAEC and greater than 4 based on the
LOAEC, while 95th centile HQs at Saginaw River SAs were greater than 10 based on the
NOAEC and greater than 1 based on the LOAEC. RA ADDpot did not exceed either

dietary-based TRV (Figure 13).

The predicted probabilistic distributions of expected cumulative percent
frequencies based on concentrations of potential average ADDpot calculated from site-
specific food web-based dietary exposure for adult ARs were compared to selected
TRVs. The probability of the ADme exceeding the NOAEC (14 ng/kg/d wet weight;
(Nosek et al. 1992)) at Tittabawassee and Saginaw River SAs, was approximately 99%
and approximately 92%, respectively, while that of the ADme for the RA was < 1%
(Figure 14). The probability of the ADme exceeding the LOAEC (140 ng/kg/d wet
weight; (Nosek et al. 1992)) at Tittabawassee and Saginaw River SAs, was
approximately 99% and 20%, respectively, while that of the ADme for the RA was <
1%.

The hazard quotients generated from TEQsmmAvian concentrations in eggs

compared to relevant TRVS were not indicative of hazard to American robins. The upper

24

95% confidence level (UCL: arithmetic mean) of TEQSWHO-Avian concentrations in eggs

were not greater than the TRVS based on either the LOAEC or NOAEC. Egg HQs based
on both LOAECS and NOAECS were less than 1 among all sites (Figure 15).

The predicted probabilistic distributions of expected cumulative percent

frequencies based on concentrations of ZPCDD/DF TEQSWHQ-AVian in eggs of ARs were

compared to selected TRVs. Predicted distributions of ZPCDD/DF TEstquvian in

eggs exceeded the NOAEC (1,000 ng/kg wet weight; (Thiel et al. 1988)) at
Tittabawassee and Saginaw River SAs, while that of the RAs did not (Figure 16).
Approximately 4% of the Tittabawassee River SA predicted distribution exceeded the
NOAEC, while < 1% of the predicted distribution of the Saginaw River SAs exceeded
the NOAEC. The Tittabawassee River SA predicted distribution exceeded the LOAEC

(10,000 ng/kg wet weight; Thiel et al. 1988) by < 1%.

Discussion
Species selection

American robins were a useful receptor species. The AR allowed evaluation of
accumulation of PCDD/DF from soil, plants and invertebrates by a species that was
probably maximally exposed. Widespread distribution and sufficient breeding and
foraging habitat on site also allowed for assessment of reproductive output of the
population. Both eggs and nestlings were of sufficient mass to meet analytical detection
limits and not as limited as other terrestrial passerine species, such as the house wren.
The size of the AR population was sufficient relative to other terrestrial passerine species,

such as the eastern bluebird, which were more limited in suitable habitat availability for

25

this study. The major limiting factor for gathering data for this AR study was person
hours available for locating active nests. Unlike the aforementioned cavity nesting
terrestrial species, the AR will not occupy a nest box of known location predetermined by
the researchers. Therefore, many hours of observation are necessary to search for nests.
Furthermore, mark and recapture data are more readily obtainable from species that
utilize nest boxes, whereas trapping species that utilize open cup nests presents additional
challenges to researchers. Trapping of adult ARs is difficult and very time consuming
with a greater potential to injure adults than for the cavity nesting birds that can easily be

trapped in the box.

Multiple lines of evidence

American robins residing within the Tittabawassee River floodplain were exposed
to elevated concentrations of dioxin-like compounds, however the comprehensive site-
specific data set described within, when employed in a multiple-line-of evidence
approach, was unable to identify with any certainty either the potential for, or site-
measured contaminant related individual- or population-level adverse effects.
Establishing whether or not a site-relevant contaminant exposure has the potential to
adversely impact individuals is a key component in ascertaining causation when
differences in individual or population health are noted in field-measured parameters.
Two different methods of exposure and effects assessments indicated contrasting

potential for hazard to ARs in the SA.

26

Dietary-based exposure and assessment

A hazard assessment based on estimated ADDspot and applicable TRVS indicated
there was potential for adverse effects for ARs in Tittabawassee River SAs and most
likely for ARs in Saginaw River SAs while no potential for adverse effects was indicated
in RAs. The expected threshold for effects should be observed at concentrations between

the LOAEC and NOAEC. Therefore, based on this line of evidence, there is some

ambiguity about the Saginaw River SA hazard assessment due to the 50th centile being <
1.0, however, adverse affects seem likely as the LOAEC-based HQ for the 95th centile

and both the 50th and 95th centile NOAEC-based HQs were > 1.0 for dietary items in

Saginaw River SAs (Figure 13).

In comparison, concentrations in pooled dietary samples from tree swallow
nestlings exposed to dioxin-like compounds ranged from 72 to 230 ng TEQ/kg from the
Woonasquatucket River in Rhode Island, USA (Custer et al. 2005). This corresponded to
reduced hatching success for exposed tree swallow populations. While this approach
suggests exposure for Woonasquatucket River study area tree swallows was 6 to 18 times

greater than concentrations that are considered safe, the dietary samples were pooled and
subsequently not directly comparable to the estimated ADDpot of the present study. Also,

the congener profiles in dietary item samples were dissimilar between the studies as
Woonasquatucket River study area dietary items were dominated by 2,3,7,8-TCDD,
1,2,3,4,6,7,8-HpCDD and OCDD while the SAs of the present study were dominated by

2,3,7,8-TCDF, OCDD and to a lesser extent OCDF, further making the studies less

comparable as the toxicokinetics may vary between congeners.

27

American robin ADDspot were equal to or less than those of house wrens of a

parallel assessment in the same SAs where no adverse effects were observed in house

wrens (Fredricks et al. 2010b). The 50th centile AR ADDspot were within the 95%

confidence interval estimated ADDspot of house wrens, however, no adverse effects were

indicated in individual and population condition measurements for house wrens. More
weight may be afforded to the house wren study relative to the Woonasquatucket River
tree swallow study for comparison purposes as the relative contributions of congeners to

the mixture of dioxin-like compounds should be more similar between parallel studies.

Assessing the exposure by use of the ADDpot approach is less certain than

measuring concentrations in adults, nestlings or eggs. Application of the ADDpot is
useful if it is not possible to make measurements of concentrations in eggs or nestlings
and information is available for the potential dietary items or these concentrations can be
predicted from measurements in soils. In applying the ADme approach it is assumed
that literature-based dietary composition is appropriate. Also, it might be more
conservative as the proportion of earthworms is greater than that suggested by the
literature from which the dietary composition was derived. It was felt that earthworms
were understated in those studies (Howell 1942; Wheelwright 1986) as the frequencies
were based on stomach content analysis which may misrepresent Oligocheata as they are

soft-bodied and more readily digestible relative to more chitinous invertebrates. The
ADDpot approach also assumes the normalized ingestion rate is appropriate and that the

ARs limit their foraging to the floodplain. Further, the estimated potential average daily

dose is what is potentially available, not necessarily what is bioavailable for uptake.

28

Another uncertainty in applying dietary TRVS is that correction by relative potencies
among congeners by applying TEFSWHQ does not correct for differences in rates of

assimilation or biotransformation and clearance that would affect the internal dose

resulting from a dietary close. For these reasons, the authors consider measurements of

TEQWHO-Avian in eggs to be a more accurate estimate of exposure.

Tissue-based exposure and assessment

PCDD/DPS in AR egg, nestlings and adults were greater in SA tissues than in the
RA AR tissues, as was the case in downstream dietary items. The generally dominant
furan congener, however, differed between dietary item and receptor tissue congener
contributions. Dietary item congener profiles were dominated by 2,3,7,8-TCDF while
robin tissue profiles were dominated by 2,3,7,8-PeCDF. This may be the result of TCDF
metabolism as avian (Elliott et al. 1996; Kubota et al. 2005) and mammalian research
suggests the rate of metabolism of 2,3,7,8-TCDF with increased concentrations of dioxin-
like compounds and induction of cytochrome P450 while 2,3,4,7,8-PeCDF is sequestered
in the liver (van den Berg et al. 1994; Zwiemik et al. 2008). This is a potential result of
the differing number of carbon hydrogen bonds, however, caution must be observed
when extrapolating this to avian species as laboratory toxicokinetics studies of dioxin-
like compounds are limited for birds.

In contrast to the dietary-based hazard assessment, a hazard assessment based on
measured egg TEQSWH()_AVian concentrations indicated there was minimal potential for

adverse effects for ARs upstream and downstream of Midland as LOAEC- and NOAEC-

based HQs were < 1 (Figure 15). The predicted frequency distributions of concentrations

29

of TEQWHO-AVian in eggs suggest 4% of the eggs in Tittabawassee River SAs exceed the

NOAEC, while less than 1% of Saginaw River SAs exceed the same threshold value
(Figure 16). The same distributions indicate that less than 1% of Tittabawassee River SA
eggs exceed the LOAEC, while Saginaw River SA eggs do not exceed the LOAEC.
Assuming the actual threshold for effects occurs between the NOAEC and the LOAEC,
based on relevant egg-based TRVs and 95% UCL exposures in eggs, adverse effects are
not expected for ARs.

The aforementioned Woonasquatucket River tree swallow study indicated that an
estimated lethal concentration for 50% (LCE50) of the tree swallow eggs exposed to
dioxin-like compounds was 1,700 ng/kg TEQs, which corresponded to reduced hatch
success (Custer 2005). This LCE50 value is greater than 6-fold the mean TEQ
concentrations of AR eggs in the most exposed study areas of the Tittabawassee River
floodplain. As such, we expect that being 6-fold lesser than the LCE50 suggests little to
no potential for adverse effects. However, this does not suggest TEQ concentrations
similar to those in eggs of the Tittabawassee River would not occur at an ecologically
relevant point on the lethal concentration estimate curve below the 50% effective dose for
the Woonasquatucket River study. Also, mean study area TEQ concentrations in AR
eggs were less than those in study area house wren eggs in a parallel study (Fredricks et
al. 2010) where house wren individual and population condition adverse effects were not
indicated, which further enforces the expectation for a lack of potential for adverse

effects to ARs downstream of Midland.

30

Measures of individual and population condition

Of the individual and population health parameters quantified for the field
measure of effects, hatching success was deemed to be the most sensitive and robust.
Other ecologically relevant endpoints were measured, such as fledging success, nest
success and productivity to understand the overall population health, however, there are
uncertainties associated with these endpoints as populations experiencing reduced
hatching success could experience compensatory mechanisms in post hatch survival due
to less within nest competition for resources. Additionally, the TRVS selected are based
on hatching success, thus allowing for a direct comparison of the same measurement
endpoint between the field and controlled laboratory studies. While each quantified
endpoint is relevant to the overall individual and population condition assessment,
hatching success should be considered of significant importance due to the
aforementioned criteria.

There were significant differences about range-low hatch success and range-high
hatch success, however, these differences did not appear to be related to PCDD/DF
exposure, but rather as a random effect of year. Kruskal-Wallis comparisons indicated
significant differences between areas for range-low hatch success (p = 0.0297) and range-
high hatch success (p = 0.0145). Comparisons utilizing generalized linear mixed models
in PROC GLIMMIX suggest the random effect of year accounts for some or all of the
variability as the differences of range-low hatch success (p = 0.0838) are no longer
significant while the significance of the differences among range-high hatch success is

reduced (p = 0.0570). This suggests the random effect of year on the data may contribute

31

to the significant differences rather than site-specific exposure. Additionally, a key factor
for establishing causation is the presence of a dose-response effect. For this study the

range-low and range-high hatch success for the Tittabawassee River SAs were
intermediate while the AR tissue ZPCDD/DF TEQWl-lO-Avian concentrations were
greatest. Conversely the range-low success and range-high hatch success were least in
Saginaw River SAs where ZPCDD/DF TEanOmm concentrations were intermediate.

This suggests these significant differences in hatch success are not dose-dependent
relative to PCDD/DF exposure.

Mayfield daily mortality rates were significantly different between RAs and SAs.
The difference among daily mortality rates was also not dose-dependent as the greatest
daily mortality rate was observed where PCDD/DF concentrations in tissues were
intermediate and least where concentrations in tissues were greatest. Interestingly, where
daily mortality rate was greatest (Saginaw River SAS), no nests were abandoned.
Depredation accounted for the loss of each failed nest. While depredation accounted for
the majority of nest failure in RAs and Tittabawassee River SAS, each area experienced
nest failure due to abandonment (two nests per area).

Rates of hatching success observed for American robins nestling within the
Tittabawassee River floodplain were comparable to values reported as species norms.
Range-high hatch success and range-low hatch success were greater than or similar to
that of ARs from a DDE study in which hatching success (60-69%) was unaffected by
contaminant burden (Elliott et al. 1994). Range-high hatch success and range-low hatch
success were also within the range of measured hatching success (45-100%) of 99 avian

species from a genetic similarity and hatching success study (Spottiswoode and Moller

32

2004). Further, range-high hatch success and range-low hatch success of the present
study were all greater than the hatching success reported by Young (1955) in the
reference areas of a breeding behavior and nesting study. The proportions of successful
nests of RAS and all SAS in this study were also greater than those (25 and 21-24%) of

RAS of other studies of AR (Henning et al. 2003; Ortega et al. 1997).

Uncertainty assessment

The greatest uncertainty regarding the present study, like many other hazard
assessments, was rooted about the selection of TRVS, as the chosen TRVS may have a
significant influence on the subsequent assessment of risk. Applicable TRVS should
reflect endpoints relevant to survival or fitness and limit extrapolations across species and
taxonomic class while considering the context of variability in chemical-Specific
toxicological data set and species-specific response. Recent research (Allard et al. 2010)
suggests methods for deriving TRVS through the compilation of data from multiple
studies for a single species, or multiple species where applicable, in order to generate
dose-response curves in order to isolate appropriate effective doses (EDS) to use as TRVS
rather than the more conventional NOAEC and LOAEC approach of HQ quantification.
While we recognize the validity of the ED approach, sufficient data were not available to
generate EDS for this study.

The greatest proportion of research investigating the effects dioxin-like
compounds on avian species has been conducted on the white domestic chicken (Gallus
domesticus) and has overwhelmingly acknowledged the chicken as the most sensitive

species to these POPS (Brunstrom and Reutergardh 1986; Brunstrom 1988; Powell et al.

33

1996; Henshel et al. 1997; Brunstrom and Halldin 1998; Blankenship et al. 2003). While
this research has revealed reliable ED data relative to applicable endpoints, there is now a
strong enough data set to conclude that the selection of chicken derived EDS as TRVS
will most likely result in overly conservative hazard assessments. Moreover, recent
research further supports this conclusion, suggesting there is a molecular basis for
variation in avian Species-specific sensitivities to dioxin-like compounds and that the
chicken is unique (Karchner et al. 2006; Head et al. 2008). AS such, TRVS were selected
from studies based on species relatedness, including genetic congruence of the ligand
binding domain of the aryl hydrocarbon receptor (AhR) construct to that of the AR. The
egg tissue-based exposure TRVS selected, while displaying limitations inherent in field
studies, was based on a study of the eastern bluebird which like the AR is a member of
the family Turdidae (Thiel et al. 1988). The dietary-based exposure TRVS selected were
derived from intraperitoneal injections of TCDD in hen ring-necked pheasants (N osek et
al. 1992a). The major limitation of this study stems from the differences in absorption,
distribution, metabolism and excretion from intraperitoneal injections rather than a true
dietary dosing study.

Additional confidence in the appropriate selection TRVS is granted from recent
research investigating the differences between Species-specific sensitivities to dioxin-like '
compounds which suggest sensitivities are potentially tied to amino acid substitution
differences in the AhR LBD between species (Kennedy in preparation). Based on these
AhR LBD results, the AR was classified as a species with moderate sensitivity to dioxin-
like compounds. The eastern bluebird has an AhR LBD that is identical to the AR while

the ring-necked pheasant is only one substitution different but responds similarly to

34

exposure to dioxin-like compounds. Thus, based on numerous criteria we concluded that
the most scientifically defensible TRVS for this AR hazard assessment were the

individual studies selected.

Conclusion

Hazard assessments of dietary-based exposures of AR populations downstream of
Midland predicted there was potential for adverse effects; however, tissue-based
exposures based on PCDD/DPS residue concentrations in eggs were not indicative of the
potential for adverse effects. Subsequent assessment of reproductive endpoints revealed
significant differences between reference and study areas hatching success in AR
populations of the floodplains near Midland. Interestingly, the significant differences
between reference areas and study areas were least where exposure was greatest and
greatest where exposure was intermediate, and the effect did not appear to be dose-
related. Moreover, all measures of individual and population health for ARs exposed to
dioxin-like compounds in this study were similar to or greater than those reported in the
literature for un-exposed AR population. Further, a parallel study of house wrens with
Similarly greater exposure to PCDD/DFS in SAS revealed no observable effects. Possible
explanations for the disagreement between the tissue- and dietary-based exposure
assessments included the possibility that the tissue-based TRVS were too liberal as the
doses utilized, which established the NOAEC and LOAEC, may not have characterized
well the true threshold values for potential effects or the dietary-based TRVS may have

been overly conservative based on intraperitoneal injections in the ring-necked pheasant

35

instead of true dietary adsorption. Uncertainties about the estimate of ADDpot values
including dietary composition and time spent on-site may also explain this disparity.
Based on the weight-of—evidence we were not able to conclude that ARS foraging
and breeding within the Tittabawassee River floodplain are at risk to experience adverse
population-level effects as a result of their exposure to PCDD/DFS. While the dietary-
based hazard assessment as well as noted differences in hatching success suggested both
the potential for and presence of adverse effects, the remaining lines of evidence either
conflicted or weakened this interpretation. The more directly measured tissue based
exposure assessment did not identify the potential for adverse effects. Furthermore,
individual and population health measures including clutch Size, fledging success and
productivity were not different between exposed and reference areas and similar to
hatching success, were not different than values reported as normal in the literature.
Mayfield survival estimates noted that reproductive survival rates were greatest in the TR
SAS, which consistently had the greatest exposure. Moreover, hatching success, which
was generally lesser in the exposed areas could not be directly linked to contaminant
exposure as a key criteria for establishing stressor causation is the identification of a dose
response. When measured egg contaminant burdens were compared to hatching success

by the eight individual study Sites the response did not appear to be dose related.

Animal Use
All aspects of the study that involved the use of animals were conducted in the
most humane way possible. To achieve that objective, all aspects of the study design

were performed following standard operating procedures (Protocol for Monitoring and

36

Collection of Box-Nesting Passerine Birds 03/04-045-00; Field studies in support of
Tittabawassee River Ecological Risk Assessment 03/04-042-00) approved by Michigan
State University’s Institutional Animal Care and Use Committee (IACUC). All of the
necessary state and federal approvals and permits (Michigan Department of Natural
Resources Scientific Collection Permit SC1252, US Fish and Wildlife Migratory Bird
Scientific Collection Permit MB102552-1, and sub-permitted under US Department of

the Interior Federal Banding Permit 22926) are on file at MSU-WTL.

37

Table 1. Toxicity reference values (TRVS) for total TEQSWHQ-Avian
concentrations selected for comparison to American robins exposed to
PCDD/DF S in the river systems downstream of Midland, Michigan, USA
during 2005—2008.

 

 

 

Exposure type NOAEC LOAEC Reference
Dietary exposure-baseda 14 140 Nosek et al. 1992
Egg exposure-basedb 1,000 10,000 Thiel et al. 1998

a ng/kg/d wet weight

b ng/kg wet weight

38

Table 2. Potential average TEQWH0_Aviana daily. dose (ADDpot; ng/kg body weight/d)

calculated from site-specific food web-based dietaryb exposure for adult American robins
breeding during 2003-2006 within the river floodplains near Midland, Michigan, USA.

 

 

R-1 and 114C T-3 to T-6 S-7 and S9
50th Centile 1.9‘Le 270 89
95th Centile 5.1 590 200
Maximum 6.3 880 290

 

a TEQWH0-Avian were calculated based on the 1998 avian WHO TEF values
b Literature based dietary composition (Howell 1942; Wheelwright 1986)

c R-l to R-2 = Tittabawassee and Chippewa rivers reference area; T-3 to T-6 =
Tittabawassee River study area; S-7 to S-9 = Saginaw River study area

d Values were rounded and represent only two significant figures

6 Food ingestion rate was calculated from equations in The Wildlife Exposure Factors
Handbook (US EPA 1993)

39

 

Table 3. Nest outcomes for American robins breeding in the floodplains near Midland,

MI during 2005-2008.

 

All nesting attempts

 

 

 

 

 

 

 

 

 

R-1 and R-2 T-3 to T-6 S7 and 89‘11
n Total (%)b n Total (%) n Total (%)
2005
Hatchedc 8 5 (63%) 12 9 (75%) - -
Fledgedd 9 5 (56%) 12 7 (58%) - -
Predated 9 4 (44%) 12 3 (25%) - -
Abandoned 9 0 (0%) 12 1 (8%) - -
Other 9 0 (0%) 12 l (8%)f - -
Unknown 9 0 (0%) 12 0 (0%) - -
Failede 9 0 (0%) 12 0 (0%) - -
2006
Hatched 2 2 (100%) 12 7 (58%) 10 8 (80%)
Fledged 1 0 (0%) 17 5 (29%) 10 4 (40%)
Predated l 1 (100%) 16 10 (59%) 10 6 (60%)
Abandoned l 0 (0%) 16 1 (6%) 10 0 (0%)
Other 1 0 (0%) 16 0 (0%) 10 0 (0%)
Unknown 1 0 (0%) 16 0 (0%) 10 O (0%)
Failed 1 0 (0%) 16 0 (0%) 10 0 (0%)
2007
Hatched 32 14 (44%) 43 27 (63%) 9 4 (44%)
Fledged 31 11 (35%) 43 19 (44%) 9 3 (33%)
Predated 31 18 (58%) 43 24 (56%) 9 6 (66%)
Abandoned 31 2 (6%) 43 0 (0%) 9 0 (0%)
Other 31 0 (0%) 43 0 (0%) 9 0 (0%)
Unknown 31 0 (0%) 43 0 (0%) 9 0 (0%)
Failed 31 0 (0%) 43 0 (0%) 9 0 (0%)

4O

Table 3. con't

 

 

 

2008
Hatched 22 14 (64%) 51 34 (67%)
F ledged 22 10 (45%) 50 30 (60%)
Predated 22 11 (50%) 50 19 (38%)
Abandoned 22 0 (0%) 50 0 (0%)
Other 22 1 (5%)g 50 1 (2%)f
Unknown 22 0 (0%) 50 0 (0%)
Failed 22 0 (0%) 50 0 (0%)
Overall
Hatched 64 35 (54%) 118 77 (65%)
Fledged 63 26 (42%) 122 61 (50%)
Predated 63 34 (53%) 121 56 (46%)
Abandoned 64 2 (3%) 121 2 (2%)
Other 64 1 (2%) g 121 2 (3%)f
Unknown 64 0 (0%) 121 0 (0%)
Failed 64 0 (0%) 121 O (0%)

11
11
11
ll

11
11
11

30
30
30
30
30
30
3O

7 (64%)
4 (36%)
7 (64%)
0 (0%)
0 (0%)
0 (0%)
0 (0%)

19 (62%)

11 (37%)

19 (63%)
0 (0%)
0 (0%)
0 (0%)
0 (0%)

 

a S-7 and S-9 were monitored 2006-2008
b Percent of n

c At least one egg in clutch hatched

d At least one nestling from brood fledged
6 Each egg failed to hatch

f Weather related failure

g Human disturbance related failure

41

 

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42

Table 5. Concentrations of seventeen 2,3,7,8-Substituted furan and dioxin
congeners in eggs of American robins collected during 2005-2008 within the
Chippewa, Tittabawassee and Saginaw river floodplains, Midland, MI, USA.

Valuesa (ng/kg wet weight) are given as the arithmetic meanb 1 1 SD over the

 

 

 

range.
R-1 and R-2 T-3 to T-6 S-7 and S-9
Contaminantc n=2 1 n=49 n= 1 4
2378-TCDF 02710.13 11115 211.4
0.11-0.53 0.27-72 0.3-4.4
ND=18 ND=3 ND=1
23478-PeCDF 1.510.56 2401280 87170
0.4-2.6 16-1600 2.7-190
12378-PeCDF 0.2110073 7.6199 1.311
0.085-0.36 0.12-50 0.2-3.2
ND=16 ND=4 ND=4
234678-HxCDF 05310.3 7,417.1 312.1
0.18-1.4 066-37 065-61
ND=4 ND=2 ND=O
123789-HxCDF 0.361011 1.211 08410.35
0.14-0.59 0.21-7.4 0.4-1.6
123678-HxCDF 0.921051 31132 1219.4
0.31-2.2 1.1-160 1.2-26
123478-HxCDF 1210.58 9710.99 47138
0.36-2.5 4.4-490 1.5-100
1234789-HpCDF 05810.30 2.511.5 1.210.69
014-15 052-66 036-26
ND=19 ND=9 ND=6
1234678-HpCDF 2.712.] 50134 38127
0.6-8.1 3.7-130 4.3-78

43

Table 5. con't
12346789-OCDF

23 78-TCDD

123 78-PeCDD

123789-HxCDD

123678-HxCDD

123478-HxCDD

1234678-HpCDD

12346789-OCDD

1.311.2
0.26-4.4
ND=7

2.8115
0.73-6

2611.3
0.97-6.4

0.741036
0.31-1.8
ND=5

5.1139
1.7-20

1.710.86

O.62-4.1

8.5111

1.8-52

13113
2.6-66

21123
1.2-130
ND=4

3911.9
1.1-8.5

3311.8
0.96-11

1.110.48
0.4-2.5
ND=12

1317.7
3.8-32

2.110.93
0.57-5.8
ND=2

28121
5.7-130

81174
11-400

11110
1.3-31
ND=O

2.411
0.91-4.3

3.312
1.2-8.6

0.811024
O.27-1.2
ND=3

1215.4
3.4-21

2611.4

0.65-6.1

1818.3

4.8-35

41125
9-91

 

a Values have been rounded and represent only two Significant figures

b Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below
detection limit indicated below range

0 TCDF = tetrachlorodibenzofuran; PeCDF = pentachlorodibenzofilran;
HxCDF= hexachlorodibenzofuran; HpCDF = heptachlorodibenzofuran; OCDF
= octachlorodibenzofuran; TCDD = tetrachlorodibenzo-p-dioxin; PeCDD =
pentachlorodibenzo-p-dioxin; HxCDD = hexachlorodibenzo-p-dioxin; HpCDD
= heptachlorodibenzo-p-dioxin; OCDD = octachlorodibenzo-p-dioxin

44

Table 6. Concentrations of selected co-contaminants in eggs of American
robins collected during 2005-2008 within the Chippewa, Tittabawassee and

Saginaw river floodplains, Midland, MI, USA. Valuesa (ng/kg wet weight) are
given as the arithmetic meanb 1 1 SD over the range.

 

Contaminant

PCB 77

PCB 81

PCB 126

PCB 169

PCB 105

PCB 114

PCB118

PCB 123

 

 

 

 

R-1 and R-2 T-3 to T-6 S-7 and S-9
n=5 n=28 n=l2
1.911 4.816.] 16125
0.75-3.2 1.1-33 1.7-88
ND=4 ND=26 ND=9
211.1 4916.7 12114
0.81-3.5 1.2-37 1.9-40
ND=4 ND=27 ND=11
2811.6 5314.4 11110
0.82-4.8 1-24 2.1-38
ND=5 ND=26 ND=8
4.5122 1018.6 1115.1
l.1-6.8 3.5-43 4.6-23
ND=4 ND=13 ND=7
67142 1401220 65011300
14-120 16-850 35-4400
1318.2 61153 1101140
4.5-26 5.7-260 14-400
ND=1
4101240 120011800 350015300
160-760 1 10-8500 270-18000
7.4153 10113 741150
3.3-17 1.1-51 2.3-500
ND=1 ND=17 ND=8

45

Table 6. con't

 

PCB 156

PCB 157

PCB 167

PCB 189

2,4'-DDTC

2',4'-DDE d

4,4'-DDT

170164
84-260

54121
26-83

51122
32-87

30116
13-54

0.1 110.085
0.029-0.24
ND=1

78161
37-180

12122
0.47-52

52011 100
99-5900

1401270
30-1500

911130
13-640
ND=2

1 10183
35-400

009610.098
0.02-0.54
ND=13

1601110
25-550

12112
0.034-43
ND=1

7601640
1 30-2000

2501260
32-890

2101270
23-940

2601240
49-920

002710.01
0.012-0.048
ND=1 1

61149
20-190

2112.4
0.029-6.1
ND=1

 

a Values have been rounded and represent only two Significant figures

b Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below

detection limit indicated below range

C DDT = dichloro-diphenyl-trichloroethane
d DDE = dichloro-diphenyl-dichloroethylene

46

Table 7. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin
congeners in nestlings of American robins collected during 2005-2008 within
the Chippewa, Tittabawassee and Saginaw river floodplains, Midland, MI,

USA. Valuesa (ng/kg wet weight) are given as the arithmetic meanb 1 1 SD

over the range.

 

. C
Contammant

2378-TCDF

23478-PeCDF

12378-PeCDF

234678-HxCDF

123789-HxCDF

123678-HxCDF

123478—HxCDF

1234789-HpCDF

 

 

 

 

 

 

R-1 and R-2 T-3 to T-6 S-7 and S-9
n=12 n=25 n=8
1.5148 15125 4.1158
0.046-17 0.3-120 0.47-18
ND=8
0.871047 1601150 54153
0.27-1.8 4.1-630 3.8-140
01610.14 11118 314
0041-055 0.089-94 0.12-12
ND=10 ND=3
0.351023 5.6149 2,111.7
0.1-0.75 0.28-20 O.97-5.6
ND=4
02510.20 05210.54 02910.18
0.054-0.57 016-24 013-06
ND=1 1 ND=20 ND=7
0.431025 16114 6116.2
0.13-0.83 0.54-51 1.3-19
0.711044 76165 2813]
018-16 1.3-250 2.3-90
03210.19 2.812.] 1.111.4
0.11-0.64 019-86 031-38
ND=10 ND=4 ND=2

47

Table 7. con't
1234678-HpCDF

12346789-OCDF

23 78-TCDD

12378-PeCDD

123789-HxCDD

123678-HxCDD

l23478-HxCDD

1234678-HpCDD

12346789-OCDD

1.51098
0.4-3.7

110.67
0.2421

1.511
0.27-3.6

1.21077
037-3.1

0.391021
013-081
ND=4

1.9116
0.5-6

07210.49
0.24-1.9
ND=1

4513.8
1.1-12

9817.0
3-23

41131
1.6-110

24120
0.6-79

2.711.4
0.82-6.3

2.611.2
0.83-6

08610.47
0.22-1.9
ND=2,

6.9142
1.5-19

1.710.84
0.58-4.1
25118

3.5-69

76158
7.4-210

22124
7.5-78

11115
2.6-45

1.210.66
0.56-2.4

2212.5
0.79-8.2

0.591032
0.25-1.2
ND=2

6417.4
1.5-20

1.612.1

045-67

15115

3.5-41

36135
8.1-100

 

a Values have been rounded and represent only two significant figures

b Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below
detection limit indicated below range

0 TCDF = tetrachlorodibenzofuran; PeCDF = pentachlorodibenzofuran;
HxCDF= hexachlorodibenzofilran; HpCDF = heptachlorodibenzofuran; OCDF
= octachlorodibenzofuran; TCDD = tetrachlorodibenzo-p-dioxin; PeCDD =
pentachlorodibenzo-p-dioxin; HxCDD = hexachlorodibenzo-p-dioxin; HpCDD
= heptachlorodibenzo-p—dioxin; OCDD = octachlorodibenzo-p-dioxin

Table 8. Concentrations of selected co-contaminants in American robin
nestlings collected during 2005-2008 within the Chippewa, Tittabawassee

and Saginaw river floodplains, Midland, MI, USA. Valuesa (ng/kg wet
weight) are given as the arithmetic meanb 1 1 SD over the range.

 

Contaminant

PCB 77

PCB 81

PCB 126

PCB 169

PCB 105

PCB 114

PCB 118

PCB 123

PCB 156

PCB 157

PCB 167

 

 

R-1 and R-2 T-3 to T-6 S-7 and S-9
n=5 n=5

0.46 1.711.4 5.115.9

- 0.8-4.2 056-12

0.35 2512.5 7219.8

- 0.48-6.5 061-23

0.59 1.51058 4.5147

- 0.8-2.4 0.82-11
ND=1 ND=1

1.1 3811.9 3913.2

- 1.8-6.3 1-9.2

1.7 51119 4701660

- 20-66 15-1500

4.2 861110 911140

- 15-280 12-340

126 6601680 280014200

- 124-1850 117-9800

3.7 1711 1 901110

- 5.2-32 5.6-220

50 2701330 5301700

- 41-850 60-1700

13 55154 1501190

- 11-150 15-400

16 36135 1501190

- 6-97 9-430

49

Table 8. con't
PCB 189

2,4’-DDT C

2',4'-DDE d

4,4'-DDT

10

0.008

9.2

0.37

69155
18-140

0.02110015
00095-0047

90150
36-170

4.7121
1269

1301150
16-380

0012100013
0011-0014

20116
7.3-48

0.510.48
0.19-l.3

 

a Values have been rounded and represent only two significant figures

b Concentrations below limit of detection assigned a concentration of 1/2
the detection limit in the calculation of arithmetic means; total number
below detection limit indicated below range

C DDT = dichloro-diphenyl-trichloroethane
d DDE = dichloro-diphenyl-dichloroethylene

50

Table 9. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin
congeners in American robin adults collected during 2005-2008 within the
Chippewa, Tittabawassee and Saginaw river floodplains, Midland, MI, USA.

Valuesa (ng/kg wet weight) are given as the arithmetic meanb 1 1 SD over the

 

 

 

 

 

range.
R-1 and R-2 T-3 to T-6

Contaminantc n=6 n=6

2378-TCDF 006910034 8.8166
0034-013 1.6-19
ND=2

23478-PeCDF 0721021 140185
0.43-0.93 22-240

12378-PeCDF 01110065 57138
0025-02 1.4-10
ND=6

234678-HxCDF 0.1810088 2511.2
0099-032 0.67-4
ND=3

123789-HxCDF 0.221014 0.371018
0.1-0.49 0.19-0.61
ND=6 ND=6

123678-HxCDF 02510.1 1 914.5
0.16-0.45 1.9-14
ND=1

l23478-HxCDF 036102 55131
0.17-0.74 8.1-81
ND=1

l234789-HpCDF 0.321016 1.21065
0.14-0.54 026-18
ND=6 ‘

51

Table 9. con't
123467 8-HpCDF

12346789-OCDF

2378-TCDD

l2378-PeCDD

123789-HxCDD

123678-HxCDD

123478-HXCDD

1234678-HpCDD

12346789-OCDD

0.471029
0.29-0.18
ND=2

0.271015
0081-046
ND=5

110.72
0.35-2

1.111
0.56-3.2

0.411038
011-1.]
ND=3

1.912
0.75-5.9

0871095
028-28
ND=1

1.911 .9
049-58

3.7128
1-7.8

18112
3.8-35

12116
0.86-44

1.31052
0.64-1.8

1.51073
055-25

0.421018
0.21-0.65
ND=2

3.512.5
1.3-8.2

0.941076

023-24

9.917.]

1.7-21

53171
4.6-190

 

a Values have been rounded
and represent only two
significant figures

Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below
detection limit indicated below range

52

 

Table 9. con't

c TCDF = tetrachlorodibenzofuran; PeCDF = pentachlorodibenzofuran;
HxCDF= hexachlorodibenzofuran; HpCDF = heptachlorodibenzofuran; OCDF
= octachlorodibenzofuran; TCDD = tetrachlorodibenzo-p-dioxin; PeCDD =
pentachlorodibenzo-p-dioxin; HxCDD = hexachlorodibenzo-p-dioxin; HpCDD
= heptachlorodibenzo-p-dioxin; OCDD = octachlorodibenzo-p-dioxin

 

53

 

Table 10. Concentrations of seventeen 2,3,7,8—substituted furan and dioxin
congeners in Oligochaeta collected during 2005-2008 within the Chippewa,

Tittabawassee and Saginaw river floodplains, Midland, MI, USA. Valuesa
(ng/kg wet weight) are given as the arithmetic meanb 1 1 SD over the range.

 

- C
Contamlnant

2378-TCDF

23478-PeCDF

12378-PeCDF

234678-HxCDF

123789-HxCDF

l23678-HxCDF

l23478-HxCDF

1234789-HpCDF

 

 

 

 

 

 

R-1 and R-2 T-3 to T-6 S-7 and S-9
n=6 n=12 n=4
0391041 170194 1301160
0.078-1.1 53-390 6.7-360
ND=3
0.231019 42127 40148
0037-054 12-100 2.5-110
ND=2
009610066 60139 49159
0034-018 16-150 2.9-130
ND=5
0.1210068 311.9 1,511.7
0041-022 09-78 0.22-4
ND=4 ND=1 ND=2
00911005 0.751055 0.821064
005-016 0.19-2 027-1.5
ND=6 ND=5 ND=4
0.191013 9.717 5.315
0039-039 2.9-28 1-12
ND=2
0.311018 42132 3113]
0096-053 13-120 4.5-72
ND=1
01910.12 3.5128 2.111.]
0.08-0.41 1-11 1.2—3.5
ND=5 ND=1

54

Table 10 con't
1234678-HpCDF

 

12346789-OCDF

23 78-TCDD

12378-PeCDD

123789-HxCDD

123678-HxCDD

l23478-HXCDD

1234678-HpCDD

12346789-OCDD

171152
046-36

2.511.6
0.41—4.5

03210.41
0.021 -1 . l
ND=2

02110.17
0039-051
ND=2

0221014
0073-046
ND=2

0310.23
0.075-072
ND=2

01110067
0041-021
ND=5

3.6124
1.1-7.5

30119
8.5-59

76160
21-200

1401110
34-3 80

(19118
034-63

12111
0.25-4
ND=1

110.74
0.29-2.7
ND=4

3.613
0.7-9.8
ND=1

0.721072
016-2.8
ND=8

43126
10-96

4301290
1 10-1 100

76126
41-100

82136
42-110

1.211 .5
0.2-3.5

1.411 .3
079-82

05810.42
0.2-1 .2
ND=3

2.9122
078-56

0.511043
0.21-1 .1
ND=4

24116
11-45

2501160
111-420

 

a Values have been rounded and represent only two significant figures

b Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below
detection limit indicated below range

Table 10. con't

 

C TCDF = tetrachlorodibenzofilran; PeCDF = pentachlorodibenzofuran;
HxCDF= hexachlorodibenzofuran; HpCDF = heptachlorodibenzofuran; OCDF
= octachlorodibenzofuran; TCDD = tetrachlorodibenzo-p—dioxin; PeCDD =
pentachlorodibenzo-p-dioxin; HxCDD = hexachlorodibenzo-p-dioxin; HpCDD
= heptachlorodibenzo-p—dioxin; OCDD = octachlorodibenzo-p-dioxin

56

Table 1]. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin
congeners in Coleoptera collected during 2005-2008 within the Chippewa,

Tittabawassee and Saginaw river floodplains, Midland, MI, USA. Valuesa
(ng/kg wet weight) are given as the arithmetic meanb 1 1 SD over the range.

 

- C
Contamlnant

23 78-TCDF

23478-PeCDF

12378-PeCDF

234678-HxCDF

123 789-HxCDF

l23678-HxCDF

123478-HxCDF

1234789-HpCDF

 

 

R-1 and R-2 T—3 to T-6 S-7 and S-9
n=9 n=12 n=9
2 .2128 4701410 68166
035-88 100-1600 18-210
ND=2
0.910.97 1201100 15114
023-3.] 11-350 3.5-45
ND=1
05910.81 120191 18119
0079-26 9.8-370 2.2-62
ND=4
0510.4 6314.4 1.5112
0.19-l.3 0.88-16 055-42
ND=3 ND=1
02210.09 09110.97 04410.29
0.11-0.39 014-4.] 0.083-098
ND=9 ND=10 ND=9
0661064 14111 2.9123
0.21-2 2.6-41 0.61-7.l
ND=3 ND=1
1.21l.6 58145 1018.2
021-49 7.6-160 2.1-27
ND=6
0381027 3.3125 1.5132
0.15-0.91 0.89-11 0.11-10
ND=8 ND=2 ND=7

57

 

Table 1 1. con't
1234678-HpCDF

12346789-OCDF

23 78-TCDD

12378-PeCDD

123789-HxCDD

123 678-HxCDD

123478-HxCDD

1234678-HpCDD

12346789-OCDD

6.418
041-25

6.2111
039-36

1.1107
023-2.l

0.910.51
022-1.7
ND=2

110.7
023-22
ND=2

2311.8
029-59
ND=1

0691036
0.24-1.1
ND=2

21124
1.4-83

1301170
5.5-560

79148
14-160

69172
12-320

3511.6
146.4

2911.3
1.2-6.4

3913.9
092-17

916.3
2.1-29

2211.2
089-49

9316]
21-230

7101520
86-2000

561110
6.2-340

47189
2-260

1.11055
033-2.]

1.21057
033-21

1.511.7
023-5.8
ND=1

12126
0.98-82

06910.38
024-1 .3
ND=4

1201270
12-830

3601560
69-1800

 

a Values have been rounded and represent only two significant figures

b Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below
detection limit indicated below range

58

Table] 1. con't

c TCDF = tetrachlorodibenzofuran; PeCDF = pentachlorodibenzofuran;
HxCDF= hexachlorodibenzofuran; HpCDF = heptachlorodibenzofuran; OCDF
= octachlorodibenzofilran; TCDD = tetrachlorodibenzo-p-dioxin; PeCDD =
pentachlorodibenzo-p-dioxin; HxCDD = hexachlorodibenzo-p-dioxin; HpCDD
= heptachlorodibenzo-p-dioxin; OCDD = octachlorodibenzo—p-dioxin

59

 

Table 12. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin
congeners in Lepidoptera collected during 2005-2008 within the Chippewa,

Tittabawassee and Saginaw river floodplains, Midland, MI, USA. Valuesa
(ng/kg wet weight) are given as the arithmetic meanb 1 1 SD over the range.

 

- C
Contamlnant

23 78-TCDF

23478-PeCDF

l2378-PeCDF

234678-HXCDF

123789-HxCDF

123678-HxCDF

123478-HxCDF

1234789-HpCDF

 

 

 

 

R-1 and R-2 T-3 to T-6 S-7 and S-9
n=7 n=6 n=8
0371025 42130 9.7185
0.1-0.7 6.7-73 2-27
ND=4
01810081 1118.5 2.6124
0.057-029 1.4-21 053-7.]
ND=3
01410.066 1319.3 312.7
0.059-024 2.1-23 0.63-7
ND=3
009710.049 0851069 09311.7
0.063-017 0.1-2 0079-5.l
ND=6 ND=2 ND=3
0110033 02110078 0271012
0077-017 0.11-0.31 001-045
ND=7 ND=6 ND=8
0.1110057 1.7112 1.4124
0061-021 0.24-29 021-72
ND=5 ND=1 ND=2
0.231013 7.515.] 2.6122
0.067-04 091-14 0.41-61
ND=3
0.1910057 0.411022 03410.2
0.11-0.27 02-073 0092-066
ND=7 ND=4 ND+6

60

Table 12. con't

1234678-HpCDF

12346789-OCDF

23 78-TCDD

12378-PeCDD

l23789-HxCDD

l23678-HxCDD

l23478-HxCDD

1234678-HpCDD

1 2346789-OC DD

0.7103
037-13

04810.25
0.19-93
ND=4

01510056
0.067-02
ND=4

01910.057
0.1-0.26
ND=4

0.2410096
0.14-0.37
ND=3

02810.12
0.16-0.44
ND=3

01710044
0.099-022
ND=4

2.510.81
l.2-3.4

1114.9
5-17

5814.3
1.4-11

4.815.9
1.1-l6

04110.14
0.25-0.62

0.410085
0.27-0.52
ND=1

051021
0.17-0.74
ND=1

0.681034
0.25-1.2
ND=1

02610.13
016-05
ND=4

7.314
3.3-14

44128
19-86

4.513.3
089-105

414.8
0.17-15
ND=3

0261016
0075-045
ND=3

0610.88
014-28
ND=4

1.8143
0.11-12
ND=5

2415.2
0.25-15
ND=1

07211.4
012-4.3
ND=6

38190
2.6-260

1601370
8.2-1100

 

a Values have been rounded and represent only two significant figures

b Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below
detection limit indicated below range

Table12. con't

 

C TCDF = tetrachlorodibenzofuran; PeCDF = pentachlorodibenzofuran;
HxCDF= hexachlorodibenzofuran; HpCDF = heptachlorodibenzofuran; OCDF
= octachlorodibenzofuran; TCDD = tetrachlorodibenzo-p-dioxin; PeCDD =
pentachlorodibenzo-p-dioxin; HxCDD = hexachlorodibenzo-p-dioxin; HpCDD
= heptachlorodibenzo-p-dioxin; OCDD = octachlorodibenzo-p-dioxin

62

Table 13. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin
congeners in terrestrial plants collected during 2005-2008 within the
Chippewa, Tittabawassee and Saginaw river floodplains, Midland, MI, USA.

Valuesa (ng/kg wet weight) are given as the arithmetic meanb 1 1 SD over the

 

 

 

 

 

 

range.
R-1 and R-2 T3 to T-6 s7 and S9
Contaminantc n=9 n=1 8 n=1 2
2378-TCDF 1.110.98 35130 312.4
0.44-28 1.5-91 086-9.3
ND=6 ND=1
23478-PeCDF 0.84106 9.9183 0.9109
0.3122 0.64-25 0.15-2.9
ND=6 ND=2 ND=5
12378-PeCDF 08210.85 12110 0.9311
027.29 0.63-27 0.14-3.5
ND=7 ND=2 ND=5
234678-HxCDF 07410.51 1,410.9 0.310.18
0.3-1.9 0.34 0.11-0.66
ND=9 ND=9 ND=12
123789-HxCDF 110.64 110.65 0.411024
0.3525 0.4133 0.1509
ND=8 ND=18 ND=12
123 678-HxCDF 08610.54 2.5121 0.36102
028-19 0.2772 0.11072
ND=7 ND=7 ND=10
123478-HxCDF 09510.66 1018.6 0.611055
0.3122 0.81-27 0.11-1.9
ND=7 ND=1 ND=7

63

Table 13. con't
1234789-HpCDF

1234678-HpCDF

12346789-OCDF

2378-TCDD

12378-PeCDD

123789-HxCDD

123678-HxCDD

l23478-HxCDD

1234678-HpCDD

12346789-OCDD

0.910.34
049-1.5
ND=9

1 .611 .1
0.46-4
ND=4

3.713.]
0.65-10
ND=4

09810.73
0.35-26
ND=8

0881034
049-1.4
ND=6

0.910.42
032-1.5
ND=6

0751043
0.3-1.7
ND=9

07410.41
037-1.6
ND=9

4611.7
1.9-7

33126
12-92

211.2 '
046-53
ND=1]

, 24123

1.8-85
ND=1

45147
2.3-190
ND=1

0941053
026-22
ND=14

0971041
038-1.8
ND=15

1.31076
031-3.4
ND=14

1.81l.2
035-5
ND=12

1.11068
033-3.]
ND=18

22118
2.1-71

1901150
18-600

0.67105
0091-15
ND=12

111.]
0072-34
ND=9

1.311.]
015-3.3
ND=10

02710.16
0093-057
ND=12

03910.26
014-1.1
ND=1]

04210.19
0.17-0.69
ND=12

0.481022
0.19-0.81
ND=12

0.421019
017-07
ND=12

1.11067
0.3-2.4
ND=5

514.6
0.75-13
ND=4

Table 13. con't

 

a Values have been rounded and represent only two Significant figures

b Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below
detection limit indicated below range

c TCDF = tetrachlorodibenzofuran; PeCDF = pentachlorodibenzofilran;
HxCDF= hexachlorodibenzofuran; HpCDF = heptachlorodibenzofuran; OCDF
= octachlorodibenzofuran; TCDD = tetrachlorodibenzo-p-dioxin; PeCDD =
pentachlorodibenzo-p-dioxin; HxCDD = hexachlorodibenzo-p—dioxin; HpCDD
= heptachlorodibenzo-p-dioxin; OCDD = octachlorodibenzo-p-dioxin

65

 

Table 14. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin
congeners in other dietary components collected during 2005-2008 within the
Chippewa, Tittabawassee and Saginaw river floodplains, Midland, MI, USA.

Valuesa (ng/kg wet weight) are given as the arithmetic meanb 1 1 SD over the

range.

 

. C
Contamlnant

23 78-TC DF

23478-PeCDF

12378-PeCDF

234678-HxCDF

123789-HXCDF

l23678-HxCDF

123478-HxCDF

1234789-HpCDF

 

 

 

 

R-1 and R-2 T-3 to T-6 S-7 and S-9
n=13 n=15 n=8
0.510.27 50179 7.7111
0054-046 3.5-290 0.043-063
ND=2
0221012 13120 1.9124
0054-046 1-75 0.16-68
ND=1
01310.066 14122 2.1129
0.048-0.26 1.2-79 016-8.]
ND=4 ND=1
01610.12 1311.5 02410.22
0062-042 0.21-5.4 0063-067
ND=8 ND=2 ND=6
01210036 0.251014 01810.11
0058-02 0046-054 0082-042
ND=] 3 ND=13 ND=8
0.181015 2.2128 0.431047
0.06-0.55 0.31-10 0.065-1.1
ND=7 ND=1 ND=5
0281034 8.8110 1.311.5
0063-13 0.76-35 0062-36
ND=5 ND=1
01910.12 0.711076 0.3103
0069-05 0.14-3 0088-094
ND=13 ND=8 ND=7

66

Table 14. con't
1234678-HpCDF

12346789-OCDF

23 78-TCDD

12378-PeCDD

l23789-HxCDD

l23678-HxCDD

123478-HxCDD

1234678-HpCDD

12346789-OCDD

1.212
0.1-7.5
ND=3

07310.98
0.14-3.8
ND=4

0291037
0.048—1.4
ND=7

0341032
0092-1.3
ND=5

0371046
0077-1.4
ND=7

06710.99
008-3.7
ND=5

0361051
0079-19
ND=7

7.6114
097-52

48178
3.8-280

15118
2.1-59

15113
2.5-45

0631075
0086-24
ND=5

0631063
0.1-1.9
ND=6

07810.77
0.11-28
ND=4

1.611.7
029-4.9
ND=2

0.541046
0.049-1 .5
ND=7

19119
2.8-58

1601160
17-550

6111]
0.26-33

1301320
1.4-930
ND=1

0191019
0.043-063
ND=5

03710.38
011-1.2
ND=6

0.381055
0061-1.7
ND=7

112.1
0071-61
ND=6

031034
0.062-1
ND=7

13132
021-93

8.9119
0.12-56

 

a Values have been rounded and represent only two significant figures

b Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below
detection limit indicated below range

 

Table 14. con't

c TCDF = tetrachlorodibenzofuran; PeCDF = pentachlorodibenzofuran;
HxCDF= hexachlorodibenzofuran; HpCDF = heptachlorodibenzofuran; OCDF
= octachlorodibenzofuran; TCDD = tetrachlorodibenzo-p-dioxin; PeCDD =
pentachlorodibenzo-p-dioxin; HxCDD = hexachlorodibenzo-p-dioxin; HpCDD
= heptachlorodibenzo-p-dioxin; OCDD = octachlorodibenzo-p-dioxin

68

Table 15. Concentrations of seventeen 2,3,7,8-substituted furan and dioxin
congeners in soils collected during 2003-2006 within the Chippewa,

Tittabawassee and Saginaw river floodplains, Midland, MI, USA. Valuesa
(ng/kg wet weight) are given as the arithmetic meanb 1 1 SD over the range.

 

. C
Contamlnant

23 78-TCDF

23478-PeCDF

12378-PeCDF

234678-HxCDF

123789-HxCDF

123678-HxCDF

123478-HXCDF

l234789-HpCDF

 

 

R-1 and R-2 T-3 to T-6 S-7 and S-9
n=1] n=23 n=8
3.7128 380013100 190012300
1.1-9 260- 1 3000 3 .6-6700
1.811.6 150011200 6001620
057-55 1 10-4600 098-1900
1.411.] 200011600 7501760
0.4-3.6 130-6000 1-2300
ND=4
1.11071 140198 63138
0.47-21 13-360 0.31-130
ND=2
0281028 2712] 1319.4
0.081-1 1.6-72 0.19-31
ND=1 l ND=10 ND=1
1.41] 3201230 1601110
0.53-3.3 30-840 038-350
ND=2
3.813 160011100 7101500
1.4-9.7 130-4200 1.3-1700
1.11074 2101130 120161
0.19-22 29-560 027-210

ND=3

Table 15. con't
1234678-HpCDF

12346789-OCDF

23 78-TCDD

12378-PeCDD

123789-HxCDD

123678-HxCDD

123478-HxCDD

1234678-HpCDD

12346789-OCDD

14111
4.5-35

22115
7.2-48

2413.3
013-91
ND=1

1.711.7
037-52

2211.7
075-62

2712.]
098-7.4

09310.73
0.19-22
ND=2

35123
13-77

3001190
108-590

320012200
450-8400

510013500
1200-13000

41146
7.7-180

36126
6.2-110

53140
13-200

1 10170
29-310

22116
4.9-83

200011 100
700-4400

20000112000

6000-47000

280011800
5.8-5500

350011800
8.5-5900

1418.4
0.1-28
ND=1

1919
0.22-3 1

28112
0.79-40

66130
0.62-100

1 116
0.22-21
ND=1

9001410
7.9-1400

960014400
58-14000

 

a Values have been rounded and represent only two Significant figures

b Concentrations below limit of detection assigned a concentration of 1/2 the
detection limit in the calculation of arithmetic means; total number below

detection limit indicated below range

Table 15. con't

c TCDF = tetrachlorodibenzofuran; PeCDF = pentachlorodibenzofuran;
HxCDF= hexachlorodibenzofuran; HpCDF = heptachlorodibenzofuran; OCDF
= octachlorodibenzofuran; TCDD = tetrachlorodibenzo-p-dioxin; PeCDD =
pentachlorodibenzo-p-dioxin; HxCDD = hexachlorodibenzo-p-dioxin; HpCDD
= heptachlorodibenzo-p-dioxin; OCDD = octachlorodibenzo-p-dioxin

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86

Figure 1. Study site locations within the Chippewa River, Pine River, Tittabawassee
River and Saginaw River floodplains, Michigan, USA. Reference Areas (R-1 and R-2),
Tittabawassee River Study Areas (T-3 to T-6), and Saginaw River Study Areas (S-7 and

S-9) were monitored from 2005—2008. Only sediments and aquatic food web item
collection took place at S-8, with the exception of a limited number of dietary item
samples. Direction of river flow is indicated with arrows; source of contamination is
enclosed in a dotted oval.

87

Q :93: 9.3

 

 

 

88

Arithmetic mean concentration (95 % UCL) of

ZPCDD/DF TEQs woman in eggs (mg /kg WW)

l000 -

800 -

600 '

400 '

200 *

 

R-l
(l2)

 

 

R-Z T-3 T—4 T-5 T-6 S-7 S-9

(9) (7) (10) (10) (22) (10) (4)
Sample site

Figure 2. Mean concentrations of ZPCDD/DF TEQSWHO-Avian in American robin eggs
collected during 2005-2008 from the river floodplains near Midland, Michigan, USA.
Error bars indicate the 95% upper confidence level; Reference areas (R-1 and R—2);
Tittabawassee River study areas (T-3 to T-6); and Saginaw River study areas (S-7 and S-
9). Samples sizes are indicated in parentheses below the sample sites.

89

 

//

 

 

0
100%) I 12346789-OCDD

 

 

 

90% I 1234678-HpCDD
I 123478-HxCDD
80% 1 i m 123678-HxCDD
1.... ‘ l123789-HxCDD
o 1. ,"n":»‘ r»: '
7M 4 , Illllllllll .137811111
10".: \\ \\\\\
60% ., vigil: W ElZ378-TCDD
. 12346789-OCDF
50% "ii ‘ DIZ34678-HpCDF
40% a 1234789-HpCDF
V . m 123478-HxCDF
&\ :zzz: Ill/Illlll
30% - 52: _ El 123678-HxCDF
”1’1 555555 I 123789-HxCDF
20% 555555
10% I 12378-PeCDF
212347801:an
0% I2378-TCDF

R-1 and R—2 T—3 to T-6 S-7 and S-9

 

 

 

Figure 3. Mean congener percent contributions in American robin eggs collected during
2005-2008 from the Chippewa, Tittabawassee and Saginaw river floodplains, Midland,
Michigan, USA. R-l to R—2 includes reference areas, T-2 to T-6 includes Tittabawassee
River study areas and S-7 and S-9 includes Saginaw River study areas. Congeners
include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-dioxin (HpCDD),
hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo—p-dioxin (PeCDD),
tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),
heptachlorodibenzofuran (HpCDF), hexachlorodibenzofuran (HxCDF),

pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF).

90

 

 

  

 

 

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a 0 #_“ 7 . -. .
R-l R-2 T-3 T-4 T-S T-6 s-7 s-9
(6) (6) (6) (6) (6) (7) (6) (2)
Sample site

Figure 4. Mean concentrations of ZPCDD/DF TEQSWHO-Avian in American robin
nestlings collected during 2005—2008 from the river floodplains near Midland, Michigan,
USA. Error bars indicate the 95% upper confidence level; Reference areas (R-1 and R-
2); Tittabawassee River study areas (T-3 to T-6); and Saginaw River study areas (S-7 and

S-9). Samples sizes are indicated in parentheses below the sample sites.

91

 

 

 

 

0
10% I 12346789-OCDD
I 123478-HxCDD
80% m 123678-HxCDD
' I 123789-HxCDD
70% W ""1“""12278 26cm)
% ;\\\\\\\\‘ \\ -
60% ////////% u 2378-TCDD
. 12346789-OCDF
50% ‘il U l234678-HpCDF
. [1 -
40% |||||l||||| iiijzngHgf
\ Ill/Illlll m _
30% .. “555,: I: 123678-HxCDF
W . 553': 52:55:55} I 123789-HxCDF
20% - :55 555555;
a 234678-HxCDF
10% . I 12378-PeCDF
5:53:55? ’3: “1 23478-PeCDF
0% I 2378-TCDF
R—1 and R-2 T-3 to T-6 s7 and 3.9

 

 

 

Figure 5. Mean congener percent contributions in nestling American robins collected
during 2005-2008 from the Chippewa, Tittabawassee and Saginaw river floodplains,
Midland, Michigan, USA. R-l to R-2 includes reference areas, T-2 to T-6 includes
Tittabawassee River study areas and S-7 and S-9 includes Saginaw River study areas.
Congeners include octachlorodibenzo-p—dioxin (OCDD), heptachlorodibenzo-p-dioxin
(HpCDD), hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-dioxin
(PeCDD), tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),
heptachlorodibenzofuran (HpCDF), hexachlorodibenzofuran (HxCDF),

pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF).

92

 

 

 

 

 

 

 

 

 

 

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“a E
as
o _ __
D 2:,” 500 i
°\° e
m I—
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.9 E
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a I
8 a
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E m
o r—
.5 at
°’ 9
100 .
52
u:
< 8
N 0 fi—
R-l T-3 T-6
(6) (3) (3)

Sample site
Figure 6. Mean concentrations of ZPCDD/DF TEQSWHQ- Avian in American robin adults
collected during 2005-2008 from the river floodplains near Midland, Michigan, USA.
Error bars indicate the 95% upper confidence level; Reference areas (R-1 and R-2); and
Tittabawassee River study areas (T-3 to T-6). Samples sizes are indicated in parentheses

below the sample sites.

93

 

 

100% I 12346789-OCDD
90% I 1234678-HpCDD
I 123478-HxCDD
80% m 123678-HxCDD
70% I 123789—HxCDD
12378-PeCDD
60% l2378-TCDD
12346789-OCDF
50% a 1234678-HpCDF
40% c3 1234789-HpCDF
r5 123478-HxCDF
30% a 123678-HxCDF
I 123789-HxCDF
20% 8234678-HxCDF
10% I 12378-PeCDF
so 23478-PeCDF
0% I 2378-TCDF
R-1 and R—2 T-3 to T-6

 

 

 

Figure 7. Mean congener percent contributions in adult American robins collected during
2007 from the Chippewa and Tittabawassee river floodplains, Midland, Michigan, USA.
R-l to R-2 includes reference areas and T-3 to T-6 includes Tittabawassee River study
areas. Congeners include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-
dioxin (HpCDD), hexachlorodibenzo-p—dioxin (HxCDD), pentachlorodibenzo-p-dioxin
(PeCDD), tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),
heptachlorodibenzofilran (HpCDF), hexachlorodibenzofuran (HxCDF),

. pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF).

94

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O
u:
|

_.

O
N
I

Y

._.
o.—
I
Q
3'.

 

O
:1

_.
O
539
1% QB!
‘1,"
'C
I

'r.“
Other 1X13}:

Log (exp) arithmetic mean concentration (SD) of ZPCDD/DF
TEQs “mam.“ 1n key dietary components (ng lkg ww)
3 x‘
3.
Other

Plants C16 W J

Plants
Other
Plants

Oligocaeta m

Coleoptera ’
Coleoptera
Oligocaeta ‘g
Coleoptera ; .. 9'
Lepidoptera
Oligocaeta 'e

a Lepidoptera Q4
Lepidoptera

7.“
FU
N
75
w
8
’73
ex
7’
\x
g
o.
‘.’J
\0

Figure 8. Arithmetic mean concentrations of ZPCDD/DF TEQSWHo-Avian in key dietary
components collected during 2004-2006 from the river floodplains near Midland,
Michigan, USA. Error bars indicate the standard deviation; Reference areas (R—1 and R-
2); Tittabawassee River study areas (T-3 to T-6); and Saginaw River study areas (S-7 and

S-9). Samples sizes are indicated in parentheses within the bars.

95

 

100%

90%

80%

70%

60%

50%

40%

30%

20%

10%

0%

 

 

Ill/III!!!

mac

F‘V.V.V.V.V"

R—1 and R-2

|||||l||lll
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{0202020203

 

T—3 to T—6 S-7 and S-9

 

I 12346789-OCDD
I 1234678-HpCDD
I 123478-HXCDD
[I] 123678-HXCDD
I 123789-HxCDD
12378-PeCDD

t3 2378-TCDD
12346789-OCDF
C! 1234678-HpCDF
E1 1234789-HpCDF
[:1 123478-HxCDF
El 123678-HXCDF
I 123789-HXCDF
a 234678-HxCDF
I 12378-PeCDF

El 23478-PeCDF

I 2378-TCDF

 

Figure 9. Mean congener percent contributions in terrestrial plants collected during 2003-

2006 from the Chippewa, Tittabawassee and Saginaw river floodplains, Midland,

Michigan, USA. R—l to R-2 includes reference areas, T-3 to T-6 includes Tittabawassee

River study areas and S—7 and S-9 includes Saginaw River study areas. Congeners

include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-dioxin (HpCDD),

hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-dioxin (PeCDD),

tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),

heptachlorodibenzofuran (HpCDF), hexachlorodibenzofuran (HxCDF),

pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF).

96

 

\‘u

L

 

100%

90%

80%

70%

60%

50%

40%

30%

20%

10%

0%

 

 

-

m

v'o'o'o'o'o'
fo’o’o’o’o‘.

 

R-1 and R-2 T-3 to T-6 S-7 and S-9

 

I 12346789-OCDD
I 1234678-HpCDD
I 123478-HXCDD
[I] 123678-HxCDD
I 123789-HXCDD
12378-PeCDD

E] 23 78-TCDD
12346789-OCDF
[31234678-HpCDF
Cl 1234789-HpCDF
m 123478-HXCDF
El 123678—HxCDF
I 123789-HXCDF
E 234678-HxCDF
I 12378-PeCDF

El 23478-PeCDF

I 2378-TCDF

 

Figure 10. Mean congener percent contributions in terrestrial Coleoptera collected during

2003-2006 from the Chippewa, Tittabawassee and Saginaw river floodplains, Midland,

Michigan, USA. R-l to R-2 includes reference areas, T-3 to T-6 includes Tittabawassee

River study areas and S-7 and S-9 includes Saginaw River study areas. Congeners

include octachlorodibenzo—p-dioxin (OCDD), heptachlorodibenzo-p-dioxin (HpCDD),

hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-dioxin (PeCDD),

tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),

heptachlorodibenzofuran (HpCDF), hexachlorodibenzofuran (HxCDF),

pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF).

97

 

 

 

 

 

100% I 12346789-OCDD
90% I 1234678-HpCDD
I 123478-HxCDD
80% m 123678—HxCDD
I 123789-HxCDD
70%
12378-PeCDD
60% m 2378-TCDD
12346789-OCDF
50% u 1234678-HpCDF
40% ‘ i. u 1234789—HpCDF
r5 123478-HxCDF
30% g. %//% n 123678-HxCDF
— I 123789-HxCDF
20% . a 234678-HxCDF
10% I 12378-PeCDF
z: 23478-PeCDF
0% I 2378-TCDF
R-1 and R-2 T—3 to T—6 s-7 to s-9

 

 

 

Figure l 1. Mean congener percent contributions in terrestrial Lepidoptera collected
during 2003-2006 from the Chippewa, Tittabawassee and Saginaw river floodplains,
Midland, Michigan, USA. R-l to R-2 includes reference areas, T-3 to T-6 includes
Tittabawassee River study areas and S-7 and S-9 includes Saginaw River study areas.
Congeners include octachlorodibenzo-p-dioxin (OCDD), heptachlorodibenzo-p-dioxin
(HpCDD), hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo-p-dioxin
(PeCDD), tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),
heptachlorodibenzofuran (HpCDF), hexachlorodibenzofman (HxCDF),

pentachlorodibenzofirran (PeCDF) and tetrachlorodibenzofuran (TCDF).

98

 

100%

90%

80%

70%

60%

50%

40%

30%

20%

10%

0%

 

 

R-1 and R-2

D'O'O'O'Q’OV'
40202029202

 

T-3 to T-6

S-7 to S-9

 

I 12346789-OCDD
I 1234678-HpCDD
I 123478-HXCDD
[l] 123678-HxCDD
I 123789-HxCDD
12378-PeCDD

E] 2378-TCDD
l2346789-OCDF
El l234678-HpCDF
El 1234789-HpCDF
L’J 123478-HXCDF
E] 123678-HxCDF
I 123789-HxCDF
E 234678—HxCDF
I 12378-PeCDF

El 23478-PeCDF

I 2378-TCDF

 

Figure 12. Mean congener percent contributions in depurated terrestrial Oligochaeta

collected during 2003-2006 from the Chippewa, Tittabawassee and Saginaw river

floodplains, Midland, Michigan, USA. R-l to R-2 includes reference areas, T-3 to T-6

includes Tittabawassee River study areas and S-7 and S-9 includes Saginaw River study

areas. Congeners include octachlorodibenzo-p—dioxin (OCDD), heptachlorodibenzo-p-

dioxin (HpCDD), hexachlorodibenzo-p-dioxin (HxCDD), pentachlorodibenzo—p-dioxin

(PeCDD), tetrachlorodibenzo-p-dioxin (TCDD), octachlorodibenzofuran (OCDF),

heptachlorodibenzofuran (HpCDF), hexachlorodibenzofuran (HxCDF),

pentachlorodibenzofuran (PeCDF) and tetrachlorodibenzofuran (TCDF).

99

 

 

 

 

 

 

 

 

 

 

 

5 50
I NOAEC
4 _ 1:1 LOAEC 40
A 7:?
<1) an
on s:
:2.
CD .5
.5 o
o :2
:s c"
C" “o
g 2 e 20 §
2’:
:I: I
l - 10
0
R-1 and R-2 T-3 to T-6 S-7 and S-9

Study site
Figure 13. Hazard quotients (HQs) for the effects of potential ZPCDD/DF TEQSWHQ-
Avian daily dietary dose from site-specific food web-based dietary exposure for adult

American robins during 2003-2006 from the river floodplains near Midland, Michigan
based on the no observable effect concentration (N OAEC) and the lowest observable
adverse effect concentration (LOAEC). HQs based on measured concentration ranges are
presented; left y-axis for reference areas (R-1 and R-2); right y-axis for Tittabawassee
River study areas (T-3 to T-6) and Saginaw River study areas (S-7 and S-9); lower end of

bars bound by 50th centile HQ value and upper end bound by 95th centile HQ value;

dashed horizontal reference line of right y-axis indicates HQ value of 1.

100

100— 5

 

     

 

 

 

 

 

 

 

 

i ,/
l /
E/
y
g 75 ‘ ---------------- R-1 and R-2
5. i T-3 to T-6
«2 i _ ..... S-7 and 8.9
8‘ i
a: 50 ‘ :
a) l
.2 :
‘5 :
“:5 :
E :
a 25 -— / a
I :
f i
.’ :
/ :
0 _ ' l l I l J
200 400 600 800

Concentration of ZPCDD/DF TEQs WHO_Avian(ng/kg ww)

Figure 14. Modeled probabilistic distribution of expected cumulative percent frequencies
for potential average TEQWHO-Avian daily dose (ADme; ng/kg body weight/d) calculated
from site-specific food web-based dietary exposure for adult American robins breeding
during 2003-2006 within the floodplains near Midland, Michigan, USA. 10,000
replications per site; R-1 and R-2 indicated by a dotted line; T-3 to T-6 indicated by a ,
solid line; S-7 and S-9 indicated by a dotted-dashed line; Y-axis offset to show R-1 and
R-2; NOAEC indicated by a vertical solid bar; LOAEC indicated by a vertical dashed

bar; TRVS derived from Nosek et al. 1992.

101

 

 

 

 

 

       

 

 

 

 

0.10 0.6
I NOAEC
5 1:1 LOAEC ‘ 0-5 9
o _ u
a 0.08 °\o
e — 0.4 3
*a T:
a) I:
.g .g
‘6’- 0.05 — 0.3 8
.0 U‘
‘5 2
$4 S
I - 0.2 I
0.03 - I
— 0.1
- f "
— - 1:. I:
0.00 =— [ 3 '2' -— 0.0
R-l R-2 T-3 T-4 T-5 T-6 s-7 S-9
Study site

Figure 15. Hazard quotients (HQs) for the effects of ZPCDD/DF TEQSWHQ_AVian for

American robin eggs collected during 2005-2008 from the river floodplains near
Midland, Michigan based on the no observable effect concentration (N OAEC) and the
lowest observable adverse effect concentration (LOAEC). HQs based on 95%
confidence intervals (LCL/U CL) derived from arithmwc mean concentrations are
presented; lefi y-axis for reference areas (R-1 and R—2); right y-axis for Tittabawassee
River study areas (T-3 to T-6) and Saginaw River study areas (S-7 and S-9); lower end of

bars bound by 95% LCL HQ value and upper end bound by 95% UCL HQ value.

102

 

 

 

 

 

 

 

 

 

 

100— _______________________________________
5 . ,,..—— f
G 75 _ """"""""" R-1 and R-2
a, T-3 to T-6
>s
3 - ------ S-7 and S-9
8
O"
.23 50 g
a)
.2
*a’
'5
E
c.) 25 -
O — 5 I l l
0 500 1000 1500 2000

Concentration of ZPCDD/DF TEQs WHO_AVian(ng/kg ww)

Figure 16. Modeled probabilistic distribution of expected cumulative percent frequencies
for American robin egg TEQWHO_Avian concentrations ng/kg wet weight in site-specific
eggs collected from the river floodplains near Midland, Michigan in 2005-2008. 10,000
replications per site; R-1 and R-2 indicated by a dotted line; T-3 to T-6 indicated by a
solid line; S-7 and S-9 indicated by a dotted-dashed line; Y-axis offset to show R-1 and
R-2; NOAEC indicated by a vertical solid bar; LOAEC (not indicated) is 10,000 ng

TEQs/kg wet weight; TRVS derived from Thiel et al. 1988.

103

Equation 3-4. Derived by Nagy (1987) - Food ingestion (FI) rate from metabolizable
energy and free-living metabolic rate:

Fl(g/day) = 0.398Wt0'850

where Wt = average mass of passerine receptor
Equation 4-8. Generic equation for estimating oral doses of contaminants in wildlife:

m
ADDpm (ng/kg bw/day)= z (Ck x FRk x NIRk)
k=1

where ADme = potential average daily does (ng/kg-day), Ck = Average contaminant
concentration in k”1 type of food (ng/kg), F Rk = fraction of intake of the kth food type that

is contaminated, NIRk = normalized ingestion rate of ktln food type on a wet weight basis
(ng/kg-day) and m = number of contaminated food types

Figure 17. US EPA wildlife exposures handbook (USEPA WEH) equations utilized

during estimation of potential average daily dose (ADDpot) for American robins of the
Chippewa, Tittabawassee and Saginaw river floodplains during 2004:2006.

104

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109

  
    

     

 

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