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DETERMINATION OF SELECT POLYBROMINATED
DIPHENYL ETHERS AND METHOXYLATED
POLYBROMINATED DIPHENYL ETHERS IN SEDIMENT
CORES FROM TWO INLAND LAKES IN MICHIGAN

presented by

Patrick William Bradley

has been accepted towards fulfillment
of the requirements for the

Master of degree in Crop and Soil Sciences
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DETERMINATION OF SELECT POLYBROMINATED DIPHENYL ETHERS AND
METHOXYLATED POLYBROMINATED DIPHENYL ETHERS IN SEDIMENT
CORES FROM TWO INLAND LAKES IN MICHIGAN
By

Patrick William Bradley

A THESIS

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

MASTER OF SCIENCE
Crop and Soil Sciences

2009

ABSTRACT
DETERMINATION OF SELECT POLYBROMINATED DIPHENYL ETHERS AND
METHOXYLATED POLYBROMINATED DIPHENYL ETHERS IN SEDIMENT
CORES FROM TWO INLAND LAKES IN MICHIGAN
By
Patrick William Bradley
This study was conducted to determine if select polybrominated diphenyl ether
(PBDE) and methoxylated polybrominated diphenyl ether (MeO-PBDE) congeners
existed in two inland lakes in Michigan, and if so, to evaluate the patterns of relative
concentrations of congeners in the mixture. During 2006, sediment cores were collected
from the deepest portions of White and Muskegon Lakes. The cores were divided into
sections and subjected to analysis for carbon and organic matter content, PBDE and
MeO-PBDE concentrations, and strata aging by lead-210 dating. PBDEs were detected
in all strata in both lakes, while only Muskegon Lake sediments contained appreciable
amounts of MeO-PBDEs. Total PBDE concentrations in both lakes were comparable,
but patterns of relative concentrations of congeners were somewhat different. This was
likely due to different input sources and remediation histories. The overall trend in both
lakes is one of declining PBDE input. Organic matter and carbon content was correlated
with PBDE concentration. It is not known why methoxylated PBDE concentrations are

dissimilar between lakes, but it may be due to differences in the aquatic community

present in each lake.

DEDICATION

For my wife, Christina, who offered unconditional support and encouragement during the
course of this thesis, and for my children, Natalie, Gabrielle, Carter, and Isabelle, who

were patient and understanding with me as I completed my work. I am forever grateful.

iii

ACKNOWLEDGEMENTS

I would like to acknowledge the help and cooperation given to me by Dr. David
Long and the Aqueous & Environmental Geochemical Laboratories, Michigan State
University Department of Geological Sciences for their guidance during sample
collection and for their willingness to provide sedimentation rate and aging data in
support of this research. In addition, I would like to thank Nozomi Ikeda of the Wildlife
Toxicology Laboratory at Michigan State University for her help during the extraction
and clean-up phase of this project.

Also instrumental to the success of this research was the cooperation of the
Environmental Toxicology Laboratory at the University of Saskatchewan, Saskatoon,
Canada. The assistance of Dr. Yi Wan was invaluable during sample analysis, and the
guidance provided by Dr. Paul Jones during results quantitation was integral to my
continuing education.

I would also like to thank Professor Stephen Boyd and Professor Brian Teppen for
their continuing patience and support as members of my advisory committee. In
addition, Dr. John Newsted deserves my gratitude for the critical guidance he provided as
I approached the task of authoring my thesis. The direction and guidance he provided
during this time proved invaluable.

Finally, I would like to express my sincere appreciation to Professor John Giesy
for his friendship, for allowing me the opportunity to continue my education through this

research, and for gently guiding me along the way.

iv

TABLE OF CONTENTS

LIST OF TABLESVII
LIST OF FIGURES ................................................................................ viii
Chapter I
INTRODUCTION .................................................................................... 1
Chapter 11
MATERIALS AND METHODS .................................................................. 7
Sample Collection ........................................................................... 7
Sample Analysis .............................................................................. 7
Sediment Core Aging and Sedimentation Rate Determination ............... 7
Organic Matter and Carbon Determination ..................................... 8
Sample Extraction and Extract Clean-up ........................................ 9
HRGC/HRMS analysis ........................................................... 11
Quality Assurance .......................................................................... 12
Chapter III
RESULTS ............................................................................................ 14
Aging and Sedimentation Rates .......................................................... 14
Organic Matter and Carbon Percentage Determination ............................... 15
Percent Moisture ........................................................................... 15
Polybrominated Diphenyl Ethers ......................................................... 15
Methoxylated Polybrominated Diphenyl Ethers ....................................... 16
Analytical Considerations ................................................................. 16
Chapter IV
DISCUSSION ....................................................................................... 19
Aging and Sedimentation Rates .......................................................... 20
Organic Matter and Carbon Percentage Determination ............................... 21
Polybrominated Diphenyl Ethers ......................................................... 23
Total Polybrominated Diphenyl Ethers ........................................ 23
Comparison of Congener Profiles — All Congeners -— Upper Layer ........ 24
Select Congeners .................................................................. 25
Methoxylated Polybrominated Diphenyl Ethers ....................................... 28
APPENDICES ....................................................................................... 56
Appendix A. Sediment strata aging data for White and Muskegon
Lakes ......................................................................................... 57
Appendix B. Analytical instrument parameters for PBDE and MeO-PBDE
analysis ...................................................................................... 58
Appendix C. Analyte IUPAC names, CAS numbers, and calibration standard
concentrations .............................................................................. 59

Appendix D. 13C Labeled analog recovery (%) in White and Muskegon Lake

samples ...................................................................................... 61
Appendix E. PBDE and MeO-PBDE analysis: Calibration verification standard
recoveries (%) ............................................................................... 65
Appendix F. White and Muskegon Lake sample percent moisture ................ 67
Appendix G. PBDE congener concentration data for Muskegon Lake (pg/ g dry
wt) ............................................................................................ 68
Appendix H. PBDE congener concentration data for White Lake @g/ g dry
wt) ............................................................................................ 71
Appendix I. PBDE metabolite congener concentration data for Muskegon Lake
(pg/g dry wt) ................................................................................ 74
Appendix J. PBDE metabolite congener concentration data for White Lake (pg/g
dry wt) ....................................................................................... 77
LITERATURE CITED ............................................................................. 80

vi

Table 1.

Table 2.

Table 3.

Table 4.

Table 5.

Table 6.

LIST OF TABLES

Carbon/OM content as compared to analyte concentration .................. 33
Quality control sample spiking levels and recovery data (%) ............... 35
Total PBDE (233) concentration by sample (pg/g dry wt) ................... 36

Select PBDE congener contributions in White and Muskegon lakes. .....37
Parent : Metabolite ratios in Muskegon Lake ................................ I .38

Method blank congener concentrations ........................................ 39

vii

Figure 1.
Figure 2.
Figure 3.
Figure 4.
Figure 5.
Figure 6.
Figure 7.
Figure 8.
Figure 9.
Figure 10.

Figure 1 1.

LIST OF FIGURES

Generalized structure of PBDE molecule ...................................... 41
Comparison of select PBDE congeners in White and Muskegon Lakes...42
White Lake total PBDE and carbon comparison .............................. 47
Muskegon Lake total PBDE and carbon comparison ........................ 48

Muskegon Lake total Methoxylated PBDE and carbon comparison. . . .....49

Carbon normalized total PBDEs in White and Muskegon Lakes ........... 50
White and Muskegon Lake total PBDEs ....................................... 51
Upperrnost sediment layer congener comparison ............................. 52
Select White Lake PBDEs ....................................................... 53
Select Muskegon Lake PBDEs .................................................. 54
Methoxylated PBDEs in Muskegon Lake ...................................... 55

viii

CHAPTER I
INTRODUCTION

Polybrominated diphenyl ethers (PBDEs) are a group of compounds that contain
209 possible different compounds and isomers (congeners) that vary in the percentage as
well as the location of bromination, with the number of bromine atoms bonded to the
base structure ranging from one to ten (Figure 1). PBDEs were produced mainly in the
form of three commercial mixture types; Pentabromodiphenyl Ether (PeBDE, DE—7l,
Bromkal 70), Octabromodiphenyl Ether (OBDE, Saytex 111), and Decabromodiphenyl
Ether (DBDE). Each mixture contains a unique combination of congeners (CEPA,
2004). Pentabromodiphenyl ether, in particular, has been viewed as the commercial
mixture of greatest concern. This mixture is composed of approximately 30%
tetrabromodiphenyl ethers, 60% pentabromodiphenyl ethers, and 10%
hexabromodiphenyl ethers. Specific congeners within a homolog group have been
referred to either by the CAS number or according to the scheme proposed by
Ballschmiter and Zell for PCBs, which was later revised by Schulte and Malisch to
conform to IUPAC rules. Congeners of greatest abundance in the PeBDE mixture
Bromkal 70 are PBDE47, PBDE99, PBDEIOO, PBDE85, PBDE153, PBDE154, and
PBDE138 (Sjodin, 1998).

This class of compound has been used extensively as a flame retardant additive in
plastics (particularly in polyurethane foam) and since the PBDE structure is resistant to
microbial and chemical breakdown. PBDE can also be found in treated municipal
sewage sludge (biosolids) (Ciparis and Hale, 2005). Bioavailability, as well as

environmental fate and transport, can be directly related to the physical and chemical

properties of each specific level of bromination, as well as the compound’s lipophilicity
and tendency to sorb to organic carbon associated with sediment (Ter Laak et al., 2009).
Other studies, however, have demonstrated poor correlation between total organic carbon
and PBDE concentrations. These poor correlations have been attributed to the combined
effect of transport, mixing, and depositional mechanisms with uncontaminated sediments,
or possibly due to the continuous input of fresh PBDEs (Chen et al., 2009).

Concerns about the possible deleterious effects of PBDEs on human health and
the environment have led to restrictions on the use and production of these compounds in
the United States and especially in Europe. California, Hawaii, New York, Maine, and
other States have passed bills to reduce or eliminate PBDE usage, while states such as
Michigan are currently considering similar legislation (MDEQ, 2008). In Europe, many
countries have banned outright the production and import of brominated flame retardants
(BFRs). The Stockholm Convention recognizes PeBDE as meeting the criteria of Annex
D, indicating that this mixture may have the potential to cause harm to humans and the
environment. Similarly, the Convention for the Protection of the Marine Environment of
the North-East Atlantic (OSPAR Convention) has placed PBDEs on its List of Chemicals
for Priority Action.

PBDES have been shown to be ubiquitous in the environment. These compounds
have been detected in sediments from Switzerland, China, and the United Kingdom
(Kohler et al., 2008; Chen et al., 2009; Vane et al., 2009), in Canadian air, surface water,
and precipitation samples (Ueno et al., 2008), and in biota from remote or isolated

locations (Kelly et al., 2008; Haglund et al., 1997). Some congeners have been shown to

bioaccumulate in mussels (> log BCF of 6) (de Witt, 2002) and in fish and rays
(Christensen et al., 2002).

Previous sediment core studies have determined that tri- to hexa-BDE congeners
deposited in the 19703 are still present at significant concentrations (Covaci et al., 2005;
Nylund, et al. 1992; Li et al., 2006). Some evidence suggests that the persistent, lesser
brominated congeners. primarily nona-hexaBDEs, may be a byproduct of deca-BDE
photolytic debromination in the environment (deerstrom et al., 2004). Some of the most
commonly found PBDE congeners in environmental samples (BDE47, BDE99, BDE100)
have been shown to be only minor breakdown components of photolyzed BDE209.

PBDEs are suspected biaccumulative toxic compounds. Some studies suggest
that by initiating the AhR-mediated pathway, PBDEs and can hinder neurodevelopment,
cause liver damage and disrupt thyroid hormone levels (Zhou et al., 2002; Eriksson et al.,
2001). Another study has shown that the distribution of PBDEs within the tissues of a
study organism is different depending upon congener. BDE47, BDE99, BDEIOO, and
BDE153 have been shown to be preferentially deposited in the adipose tissues of mice,
but levels of BDE153 were 10-fold greater than BDE47 in brain. In addition, BDE153
and BDEIOO were preferentially absorbed over BDE47 and BDE99 (Staskal et al., 2006).

Environmental transport of PBDEs can occur through several mechanisms.
Regional and global distribution via the atmosphere has been demonstrated for both
PBDEs and their hydroxylated and methoxylated derivatives (Kelly et al., 2008; Wang et
al., 2009). PBDE distribution in the Great Lakes region is widespread. Concentrations
range from relatively small in more remote sections of Michigan’s Upper Peninsula to

relatively high concentrations in the metro Chicago area (Strandberg et al., 2001).

Prevalent congeners distributed by atmospheric deposition include PBDE47, PBDE99,
PBDEIOO, PBDE 153, and PBDE 154.

Another mechanism of transport is dissolution in the aqueous phase. Both PBDES
and hydroxylated PBDEs (OH-PBDEs) have been detected and quantified in rain, snow,
and surface water, although no regional depositional trend could be discerned in snow

samples (Ueno et al., 2008). Particulate organic carbon, present in the matrix and the
relative insolubility of the more highly brominated PBDEs in water (Log K0w 8.55 to

10.33) likely affects PBDE transport in watershed runoff (Palm et al., 2002).
Environmentally relevant humic acid concentrations have also been shown to directly
facilitate the transport of PBDES (Ter Laak et al., 2009).

Some PBDE congeners have been shown to be abundant in lake and river
sediments (Zhu et al., 2005; Eljarrat et al., 2004). Sources can be either local or regional
in nature based upon the congener profiles present. For example, Wang et a1. (2009)
have demonstrated that BDE47 is the predominant congener in remote Tibetan soils,
followed by BDE28 and BDE99. No BDE209 was detected, suggesting that atmospheric
deposition selectively transports lesser brominated, lighter congeners.

Recent studies have found a correlation between methoxylated and hydroxylated
PBDEs. A laboratory feeding study demonstrated that methoxylated forms of the parent
PBDE congener can be detected as metabolites in the feces of dosed mice (Staskal et al.,
2006). Methoxylated PBDEs (MeO-PBDEs) have been found in both freshwater
(Kierkegaard et al., 2004) and marine fish (Haglund et al., 1997). Other studies have
postulated that, at least in the marine environment, MeO-PBDEs are a natural product of

sponges and filamentous green algae (Cameron et al., 2000; Kuniyoshi et al., 1985).

Thus, in freshwater systems, it may be possible to use metabolite concentrations in
sediment as an indicator of PBDE exposure in aquatic organisms.

Hydroxylated and methoxylated PBDE isomers may be more toxic to organisms
than exposure to the parent compound. Hydroxylated adducts have been shown to
promote a variety of adverse effects (Hallgren et al., 2002; Canton et al., 2006; Harju et
al., 2007). Some studies suggest that MeO-BDEs and OH-BDES are generated as part of
the same metabolic pathway, such as hydroxylation of the parent PBDE in the liver
followed by methoxylation by microorganisms in the intestine (Haglund et al., 1997).
Other more recent studies, however, have shed doubt on this theory. This research
suggests that that the primary source of OH-PBDEs in the marine environment result
form the demethylation of naturally produced MeO-PBDEs (Yi et al., 2009), These

compounds are lipophilic as well. The octanol-water partitioning coefficient of MeO-
BDE47 and MeO-BDE68 approach log K0W z 6.85, indicating the likelihood that these

metabolites are bioaccumulative (Teuten et al., 2005).

PBDEs and the methoxylated adducts of these compounds have been the subject
of recent studies exploring the possible deleterious effects these persistent pollutants may
have on both aquatic and terrestrial organisms, and these compounds have been shown to
accumulate in the Great Lakes (Zhu and Hites, 2005). Samples for this study were
collected in conjunction with the Michigan Inland Lakes Sediment Trend Monitoring
Program which is made possible through a grant from the Michigan Department of
Environmental Quality. The purpose of this program is to inventory toxic pollutants in
the state’s inland lakes in order to assess the current status of the region’s surface waters,

and to identify possible issues for future scrutiny. While an in-depth inventory has been

established for several other species of halogenated organic contaminants in Michigan
inland lakes through this program, data gaps for the brominated flame retardants exist.
The purpose of this study is to elucidate whether or not:

- Concentrations of total PBDEs and MeO-PBDEs vary among sections
within a specific sediment core.

' PBDE congener and MeO-PBDE congener profiles vary among sections
within a specific sediment core.

- Concentrations of total PBDEs and MeO-PBDEs vary among sediment
cores of different lakes.

- PBDE congener profiles and MeO-PBDE congener profiles vary among
sediment cores of different lakes.

- The total organic carbon content of specific sediment cores is correlated
to PBDE and MeO-PBDE concentrations.

CHAPTER 11
MATERIALS AND METHODS
Sample Collection

Samples were collected using the Monitoring Vessel Nibi, which was specially
designed for taking core samples without disturbing the lake bottom in the process (MC-
400 Lake/ Shelf Multi-corer). Coring was done in quadruplicate in a single sampling
episode. One core each was designated for use in metals determination (Mg, Al, K, Ca,
Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Mo, Cd, Ba, Pb, and U), organic contaminant
determination (polybrominated diphenyl ethers and methoxylated metabolites, polycyclic
aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides),
porewater collection, and aging. Cores collected in this study were collected from the
deepest portion of the lake basin. The White Lake sampling site is located at 43° 22949
N & 86° 22.902' W and at a depth of 21.6 meters. The Muskegon Lake sampling site is
located at 43° 14.060' N & 86° 16.996' W and at a depth of 14.9 meters. Both cores were
taken during the 2006 sampling year.

Once collected, cores were transported to a temporary on-shore processing station
for sectioning. All cores were sectioned at 0.5 cm intervals for the top eight centimeters
and at 1.0 cm intervals thereafter. Sections were then individually stored in glass jars and
cooled in preparation for shipping to MSU. Once at the laboratory, organics samples

were stored at -20°C until analysis.

Sample Analysis

Sediment C are Aging and Sedimentation Rate Determination

Cores chosen for aging were sent to the Freshwater Institute (Winnipeg,
Manitoba, CA) for 210Pb aging by use of methods described previously (MDEQ, 2002).

Briefly, sedimentation rates for each core sample were determined using the four
different models; constant flux constant sedimentation (CFzCS), segmented CF :CS

(SCFzCF), rapid steady state mixing (RSSM), and constant rate of supply (CRS). The

validity of each model was verified using stable isotope abundance in the sample (ZIOPb

and I37Cs).

210 . 222 .
Pb IS formed by decay of Rn from atmospherlc and water column sources.

The presence of this isotope in lake sediments is usually observed as increasing in
concentration as sediment age decreases. In addition, leaded gasoline use peaked in the
early to mid 1970’s, allowing for the use of excess elemental lead as another

confirmatory tool in the sedimentation rate model selection.
137CS was produced during thermonuclear weapons testing throughout the 1950’s

and 1960’s, peaking in 1963. Detection of this peak in sediment cores provides another
means of confirming proper sedimentation rate estimation. To aid in comparison with
other analyte profiles, the dates associated with both White Lake and Muskegon Lake
sediment strata are taken directly from the Inland Lakes Sediment Trends Monitoring

2005-2007 Final Report. Sample strata aging data are presented in Appendix A.

Organic Matter and Carbon Determination
Carbon and organic matter content of strata were determined by the Soil and Plant
Nutrient Laboratory, Michigan State University. The laboratory first determined carbon

content using the chromic acid oxidation (external heat applied) method (Missouri

Agricultural Experiment Station, 1998). Organic matter content was determined via
calculation assuming that 58% of the organic matter is composed of carbon. Organic

matter and carbon percentages are presented (Table 1).

Sample Extraction and Extract Clean-up

Sample extraction and cleanup procedures followed the protocol outlined in EPA
Method 1614 (USEPA, 2003). In order to achieve sufficient mass for analysis, sediment
strata were combined prior to extraction. For example, equal masses of the first two one-
centimeter aliquots from the Muskegon Lake sediment core generated during field
processing, samples MU 1 and MU 2, were decanted if necessary and combined to create
a pooled sample, MU 1+2. This procedure was continued for all sample strata generated
from the sediment core, reducing the total number of core subsamples by a factor of 2X.

After compositing, twenty grams of sample was weighed, mixed with granular

sodium sulfate, and put into a soxhlet extraction apparatus containing 3:1
dichloromethane in acetone. Each sample received 1.0 ml of '3C labeled internal

standard (MBDE-MXF S) while the laboratory control spike, matrix spike, and matrix
spike duplicate also received 1.0 ml of native polybrominated diphenyl ether stock
solution (BDE-MXF), (Wellington Laboratories, Guelph, Ontario, Canada). Samples
were permitted to reflux overnight (18 i 2 h). No methoxylated PBDE standards were
available at the time of extraction.

After extraction, extracts were allowed to cool and then transferred to Turbovap
concentration tubes (Caliper Life Sciences, Hopkinton, MA), and concentrated to

approximately 1.0 ml in preparation for sample splitting. Since multiple analyses were

required for each extract, extracts received a 1:1 split, with half of the volume reserved
for PAH and PBDE analysis, and the other reserved for PCB and pesticide analysis.
After PAH analysis, extracts were prepared for HRGC/HRMS PBDE analysis by again
performing a 1:1 split, reserving one 250 pl aliquot for possible future total bromine
analysis.

PBDE extracts received silica gel column clean up to improve detection limits.
Each extract received 10 pl of 13C labeled clean up standard (MBDE139),(Wellington

Laboratories, Guelph, Canada) and was then loaded onto the top of a liquid
chromatography column which was pre-eluted with 50 ml of hexane. Each column
contained, from bottom to top, a glass wool plug, 1 g granular sodium sulfate, 1 g silica
gel, 4 g basic silica gel, 1 g neutral silica gel, 8 g acidic silica gel, 2 g neutral silica gel,
and 4 g granular sodium sulfate. Specific procedures for acidic and basic silica gel
preparation can be found in the EPA method (USEPA, 2003). Extracts were first eluted
from the column with 200 ml hexane. This first fraction contained all the PBDEs as
determined during initial method evaluation, and was set aside for later concentration.
The second fraction containing the methoxylated PBDEs was eluted with 1 :1
dichloromethane in hexane. Both fractions were then concentrated to approximately 1 ml
using the Turbovap and transferred to 1 ml amber chromatography vials. Formation of
precipitates was observed during concentration, so copper granules were added to the
extracts to remove sulfur. The extract/copper slurry was stored overnight.

Determination of a final concentration was achieved by adding the extract to 10 pl

of nonane in a wide mouth low volume vial insert, and evaporating the mixture to 10 pl

10

using nitrogen evaporation. The extracts were capped and packaged for shipment to the

University of Saskatchewan for analytical determination.

HRGC/HRMS Analysis

In an effort to prevent contamination of the high resolution mass spectral system,
attempts were made to screen sample extracts for high levels of PBDEs using
HRGC/LRMS techniques (EPA Method 1614 modified), but poor instrument sensitivity
and relatively low analyte concentration prevented sample screening by these
methodologies. Extracts were shipped to the University of Saskatchewan without
screening results.

High resolution analytical determination was achieved after sample receipt at the
analytical facility. Samples were sorted into fraction one extracts for PBDE analysis and

fraction two extracts for methoxylated PBDE analysis, and all extracts received 10 pl of
13C labeled injection standard prior to analysis (MBDE-138), (Wellington Laboratories,

Guelph, Canada). Identification and quantification of all target compounds was
performed using a Hewlett-Packard 5890 series 11 high-resolution gas chromatograph
interfaced to a Micromass Autospec high-resolution mass spectrometer (HRGC-HRMS)
(Micromass, Beverly, MD). Chromatographic separation was achieved on a DB-5MS
fused silica capillary column for all target compounds (30 m length, 0.25 mm ID, 0.1 pm
film thickness, Agilent, Carlsbad, CA), with helium used as carrier gas. The mass
spectrometer was operated in a selected ion-monitoring (SIM) mode. The resolution for
all reference gas peaks in all time windows was more than 7,000. The injector

temperature was held at 285 °C and the ion source was kept at 285 °C. The electron

11

ionization energy was 37 eV and the ion current was 750 pA. The GC temperature
programs used for both the PBDEs and the Methoxylated PBDE are available in
Appendix B. PBDE calibration standards were purchased from Wellington Laboratories
as a complete set (BFR-CVS), and calibration levels one through four were used to
construct the PBDE calibration curve. Methoxylated PBDE calibration standards (levels
one through five) were not commercially available at this time and were obtained from
the Environmental Toxicology Laboratory at the University of Saskatchewan (Appendix
C).

Data generated during the course of analysis (OPUS data, Micromass, Beverly,
MD) was converted using Databridge for the MassLynx V4.1 platform
(Micromass/Waters Corporation, Milford, MA). PBDE sample concentrations were
determined by using a four point calibration curve and referencing labeled analog in each
homolog group. Methoxylated PBDE quantitation was achieved using a five point
calibration curve and by referencing the injection standard, as no labeled methoxylated

compounds were available at the time of analysis.

Quality Assurance

Standard laboratory quality assurance protocols were observed during the
extraction of sediment samples. An unspiked laboratory blank was prepared during each
extraction episode, and a matrix spike / matrix spike duplicate spike set and laboratory
control spike set was prepared for the PBDE analysis set for each lake. Recoveries for
the Muskegon Lake MS/MSD/LCS set are 77-100%, 72-98%, and 89-119% respectively,

while White Lake sample recoveries ranged from 82-101%, 82-313%, and 78-149%

12

respectively. The higher recoveries in the White Lake QC data set are observed in two
congeners, BDE47 and BDE99, and may be attributed to chromatographic interference
observed during sample integration. QC sample data is available in Table 2.

Labeled compound recovery was highly variable from lake to lake and from

sample to sample within a lake and ranged from not recovered (White Lake only,
congener l3C BDEIOO) to 111% in experimental samples (Appendix D). Detection limits

were sample specific, and equal to 3x the signal to noise (S/N) value for each native
congener. Clean up standard recovery ranged from 14% to 46% in experimental samples
and roughly paralleled labeled compound recovery, indicating that some percentage of
the target compounds may be lost during the clean-up procedure, however S/N values for
detected compounds were always greater than 3: 1 , and for PBDEs, any losses during
sample preparation are accounted for using the isotope dilution quantification method.
Possible losses of methoxylated PBDEs can not be quantified since labeled compounds
were not available during sample extraction.

Instrument performance was monitored using a series of initial calibration
verification injections. Each sequence contained at least one verification injection, and
recoveries of native and labeled compounds ranged from 68-126% in all but one
verification injection (-CS3 of the PATRICK-5B sequence). This injection appears to

have been poor due to low solvent/standard levels within the GC vial (Appendix E).

13

CHAPTER III
RESULTS
Aging and Sedimentation Rates
Age was determined for a total of 52 sediment samples from White Lake and 51
sediment samples from Muskegon Lake. White Lake sediments were assigned deposition
years from 2006 to older than 1901 (<1901) based upon averaged data and using the

SCFzCS sedimentation model. 2lOPb confirmation was not applicable in this case as it

has been postulated that sediment resuspension confounded the typical excess lead curve,
as it is usually observed as a linear decrease in abundance from the upper sediment layers
to the lower layers. No such pattern was observed here. A I37Cs peak was not detected,
as would be expected with sediments of this age, and so could not be used as a means of
confirmation. The disappearance of excess 210Pb tends to support this choice, as excess
lead begins to appear at approximately 1900 using this model.

Muskegon Lake sediments were pooled in the same manner as White Lake

sediments, and the CFzCS sedimentation rate model is the best fit for this data, since
neither a 2lon peak nor a 137Cs peak are observed in Muskegon Lake sediments.
Sediment strata year assignments range from 2006 to 1966.

In order to accurately reflect the ages represented in the pooled PBDE samples,
dating results for samples in the first eight centimeters were averaged determined as the
average of four 0.5cm sections. The remaining sections, sectioned in 1cm intervals, were

determined as the average of two. Data for both lakes is presented in Appendix A.

14

Organic Matter and Carbon Percentage Determination

Carbon and organic matter content was determined at 1 cm intervals for sediments
from both lakes. In order to accurately represent pooled experimental samples, results
from consecutive 1 cm layers were averaged.

Carbon content in sediments ranged from 13.6% in samples WH 3+4 and WH
7+8 to 1.73% in sample WH 39+40 and from 11.1% in sample MU 5+6 to 8.77% in
sample MU 39+40. Organic matter was derived from the carbon content results for each
sample assuming that the organic matter is equivalent to 58% carbon (MSU Soil and
Plant Nutrient Laboratory, personal communication). Organic matter content ranges
from 23.5% in samples WH 3+4 and WH 7+8 to 3.05% in sample WH 39+40 and from
19.1% in sample MU 5+6 to 15.2% in sample MU 39+40. Carbon and organic matter

data is presented in Table 1.

Percent Moisture

Percent moisture content of each composite sample was determined in order to
present concentrations based on dry weight. Moisture content ranged from 88.5% in
sample WH 25+26 to 59.7% in sample WH 41+42 and from 81.5% in sample MU 3+4 to

77.7% in sample MU 29+30. Percent moisture data is presented in Appendix F.

Polybrominated Diphenyl Ethers
A total of twenty two sediment samples from White Lake and twenty one
sediment samples from Muskegon Lake were analyzed for twenty three polybrominated

diphenyl ethers. All congeners were detected at least once in White Lake sediments, and

15

total PBDE concentrations ranged from 206 pg/ g dry weight (dw) (sample WH 39+40) to
2426 pg/g dw (sample WH 7+8). In contrast, BDE30, BDE77, and BDE126 were not
detected in any samples from Muskegon Lake. Total PBDE concentrations in Muskegon
Lake ranged from 983 pg/g dw (sample MU 33+34) to 3883 pg/g dw (sample MU

33+34). Data for PBDE concentrations (pg/g dw) are presented in Appendices G and H.

Methoxylated Polybrominated Diphenyl Ethers

A total of twenty two sediment samples from White Lake and twenty one
sediment samples from Muskegon Lake were analyzed for twelve species of
methoxylated polybrominated diphenyl ethers. The only MeO-BDES detected in White
Lake sediments were 6MBDE47 and 6MBDE85 where concentrations ranged from not
detected (< DL) to 9.90 pg/ g dw. In Muskegon Lake congeners 3PMBDE68, 6MBDE47,
5MBDE99, 4MBDE101, and 6MBDE85 were detected. Total MeO-BDE concentrations
ranged from ND in earlier sediment layers to 115 pg/ g dw in sample MU3+4. Data for
MeO-BDE concentrations (pg/ g dw) in Muskegon and White Lakes are presented in

Appendices I and J.

Analytical Considerations
The analytical techniques used closely paralleled the USEPA promulgated
method for PBDE extraction and analysis (Method 1614 — Draft, 2003). There were a

few instances, however, in which method guidelines could not be strictly adhered to in
this study. For example, 13C labeled analogs could not be acquired for the methoxylated

analytes prior to extraction of the sediment samples. This resulted in quantitation of

16

these compounds being based on an internal standard (13C BDE 138 injection standard)

rather than quantitation via isotope dilution. Consequently, a four-fold dilution factor
was applied to sample results to account for sample splitting prior to instrumental
injection. In addition, at the time that the high resolution mass spectrometer was
available for use the instrument was experiencing issues with sensitivity in the high mass
ranges greater than m/z 575. This prevented the analysis of the more highly brominated
congeners such as deca-BDE. Primary to secondary ion ratios were also difficult to
obtain in a consistent manner, as the software program used had difficulty identifying the
correct ions. Manual inspection of ion ratios was used to confirm proper target
compound identity, but some identification uncertainty exists for congeners present in the
downfield sections of the chromatogram, as baseline noise increased during later
retention times.

Several extraction related complications also arose during sample processing.
During initial concentration, the method blank associated with samples MU 1+2 thru MU
21+22 was lost due to glassware breakage. Another method blank was immediately
prepared and carried through the remainder of the preparative procedure in parallel with
the associated experimental samples. After analysis, however, the re-extracted method
blank was observed to have elevated levels of target analytes, while most samples
associated with the blank had no evidence of this suspected cross-contamination (see
Table 6), however laboratory contamination can not be conclusively ruled out for the
associated samples. All other method blanks prepared during the course of this study
showed little or no evidence of cross contamination. No MeO-PBDEs were detected in

and method blank. Several extracts were inadvertently concentrated to dryness during

17

clean-up, but no adverse effects were observed in sample internal standard recoveries,

and sample data quality is assumed to be unaffected.

18

CHAPTER IV
DISCUSSION
One goal of this study was to determine if PBDEs and/or methoxylated PBDEs

exist within the sediment core of a lake, and if present, to compare the congener profiles
within the sediment strata. Cores were taken from White Lake and Muskegon Lake, both
of which are inland lakes located in the western section of the lower peninsula of
Michigan, and both are proximal to Lake Michigan and to each other. A second goal of
this study was to evaluate the relationship of these brominated compounds to other
persistent anthropogenic compounds present in the sediments of these lakes.
Concentrations of PAHs, PCBs, and select chlorinated insecticides have previously been
measured in samples from these lakes as part of a sediment trends monitoring program.

Muskegon Lake is a mesotrophic lake situated within Muskegon County. It has a

surface area of 16.8 km2 and a maximum depth of approximately 15 meters. It is within

a watershed that measures approximately 53 km2 and ultimately drains into Lake

Michigan, which is approximately 1000 meters away. This lake is situated in an urban
area and receives heavy recreational use as well as input from upstream wastewater
treatment facilities and various industrial sites along its shore. These include the Sappi

Fine Paper plant and the Sealed Power manufacturing plant. The sedimentation rate for
this lake has been calculated to be 1607 g/mz/yr (Parsons etal., 2008). White Lake is
also a mesotrophic lake that is located within Muskegon County and has a surface area of

10.4 km2 and a maximum depth of approximately 22 meters. Its watershed area is

estimated at 1390 kmz, some of which is rural in nature. White Lake is classified as a

drowned river-mouth (freshwater estuary) and drains into Lake Michigan via a short

19

outflow to the west of the lake. It is also utilized recreationally, but has less recreational

usage that Muskegon Lake. The sedimentation rate in this lake has been calculated to be
977 g/mz/yr (Parsons et al., 2008).

White Lake has a legacy of pollution from human activities. Beginning in the late
1800’s, Whitehall Leather tannery operations on the shores of White Lake (Tannery Bay)
led to widespread contamination of the lake sediments with chromium, which continued
until the early 1970’s. In addition, discharges from Hooker /Occidental Chemical
Corporation, DuPont Chemical, and Koch Chemical likely added additional halogenated
organics, including PCBs, to the lake’s persistent organic pollutant burden (USEPA,
2004). In consideration of these issues the United States Army Corps of Engineers and
the Michigan Department of Environmental Quality developed a feasibility study and
remediation plan. Remediation via dredging of White Lake sediments was completed in
October of 2003 with particular focus on the Tannery Bay and the Dowies Point area

lakebed. Sediment cores used in the present study were collected in 2006.

Aging and Sedimentation Rates

Sediment core aging data obtained from the Freshwater Institute in Winnipeg
indicated that the sedimentation rate in Muskegon Lake was greater that the rate in White
Lake. Consequently, sediment core strata taken from White Lake represent a greater
temporal range, with the deepest strata ages estimated to be pre-1901. Muskegon Lake
core strata ages range from present to 1966 (Appendix A). This presents a challenge
when comparing the PBDE and MeO-BDE data from one lake to another. To clarify data

interpretation, some comparisons were made using only strata that matched in age

20

(Figure 2). Since the strata age estimation is achieved as a line-fitting exercise, sediment

disturbances may not be reflected in the aging results, as was the case in White Lake.

Organic Matter and Carbon Percentage Determination

Percent carbon and organic matter (OM) data for both White and Muskegon Lake
follow a similar trend. In Muskegon Lake, total PBDE concentrations (ZPBDE23) tend to

track carbon percentages while the same is generally true for White Lake (Figure 3). As
can be seen in Figure 4, Muskegon Lake carbon percentages peak at 2002 when total
PBDE concentration maxima are also observed. Reductions in carbon percentages are
observed in Muskegon Lake in 1974 and 1968, with corresponding lesser total PBDE
concentrations in the corresponding strata. White Lake carbon concentration maxima
occur in years 2004, 1999, and 1973; minima occur in 2002, 1983, and < 1901 layers; and
consistent concentrations occur between 1983 and 1976. Total PBDE concentrations
generally follow this same trend. Correlations between organic matter concentration and
contaminant concentration have been observed in other studies. Strong relationships
between carbon content and total PBDE concentrations in Great Lakes sediments were
reported by Li et al. (2006), and it was postulated that the affinity of PBDEs for OM in
air and water may be greater than that of PCBs and PAHs due to higher K0w values. This
pattern was not observed for the methoxylated BDEs (Figure 5). While PBDES
associated with sediment are generally attributed to depositional processes outside of the

lentic system, it may be that methoxylated BDEs are synthesized within the aquatic

compartment as metabolites of parent PBDEs, or generated as natural products of certain

21

filamentous green algal communities, and therefore are not immediately associated with
atmospheric organic particulates or allocthanous carbon sources within the watershed.
Another means of evaluating the relationship between carbon and total PBDEs is

to normalize PBDE concentration to carbon values (Figure 6). Past studies have shown
that organic carbon partition coefficients (KOC) in sediments exhibit a high degree of

invariance over a broad range of sediment samples (Kile et al., 1995). In this study the
carbon normalized PBDE data present a similar trend in both lakes when compared to the
non-normalized data, especially in White Lake, indicating a relatively linear relationship
between the concentration of total PBDEs and carbon content. Compared to the Kile
study, however, the carbon-normalized concentration data exhibit somewhat increased
variability. This may be caused by several factors. First, since only a fraction of the total
commercially-produced PBDE congeners were quantatively determined in this study, it

may be possible that unquantified congeners are contributing to variations in sediment

K0c values. Second, tenacious sorption of neutral organic compounds has been shown to

affect K0C values in older soils (Steinberg et al., 1987). These soils exhibit hysteretic

sorption/desorption isotherms possibly due to retarded diffusion via microscale
partitioning. In addition, a previous study by Scribner et a1. (1992) observed that the
nonpolar herbicide simazine, after 20 years of continuous application to an agricultural
field, was present in an increasing portion of the in soil in a slowly reversible sorbed
state. The slowed desorption kinetics of aged anthropogenic organic compounds may
affect the ability of these compounds to reach equilibrium in both sediment stratum pore
water and within the sediment column itself, as well as result in reduced bioavailability

for microbial decomposition.

22

Polybrominated Diphenyl Ethers
Total Polybrominated Diphenyl Ethers

Total PBDE values for both lakes were calculated by summing all twenty three
congeners available in the analytical suite. Non-detected congeners were reported as zero
(Table 3). Total PBDE concentrations in Muskegon Lake begin to increase in 1974, and
peaked in 1991 at 3883 pg/g. Since then, concentrations gradually decreased to 2050
pg/ g in the 2006 layer (Figure 7). This trend is inconsistent with other anthropogenic
compounds measured in concurrent core samples for this lake. Examination of the
Sediment Monitoring project data reveals that total PAH concentrations peaked in 1977
while total PCB as well as total p,p’-DDE concentrations peaked in 1966. These trends
are most likely a result of differences in annual peak production for the various
compound classes. Total PBDE concentrations in White Lake exhibit a somewhat
different profile. Concentrations peaked in 1999 at 2426 pg/g with a second smaller peak
being observed in 1973 at 1369 pg/g. Both carbon and OM concentrations also exhibit an
uncharacteristic upswing at this point in time (Figure 7). This may be an artifact of
remediation activities (sediment resuspension) in the basin near where the sediment core
was sampled. Total PAH concentrations peak in 1990, p,p’-DDE in 1966 (consistent
with Muskegon Lake levels), and total PCBs in 1920. The total PCB maximum appears
to be incongruent with sediment strata age, and no reason for this is readily apparent.

Interestingly, total PBDE concentrations in Muskegon Lake decrease steadily
from 1968 to 1974, and 1968 concentrations roughly equal 1985 levels. White Lake

levels also increase steadily in the last three strata, but due to the limitations of the dating

23

methodology, accurate dates could not be assigned to these samples (older than 1901). It
is not likely that actual total PBDE concentrations are elevated in these older strata, and
may reflect some uncertainty in the analytical procedure. Congeners BDE171, BDE47,
and BDE183 represent the bulk of the total PBDE mass here. Examination of raw sample
data reveals that some chromatographic noise was present during quantitation of these
congeners, and may have contributed to elevated values in these samples.

Total PBDE concentrations in both White and Muskegon Lakes are similar to

those found in the literature for similar matrices. A recent study measured total PBDE
concentrations (29) from 0.019 to 0.91 ng/ g dw in sediments from the Beijiang River,
situated in an industrial region of China, and these levels compare similarly to levels
present in this study (223 White Lake = 0.002 to 2.43 ng/g dw; £23 Muskegon Lake =
0.983 to 3.88 ng/ g dw) (Chen et al., 2009). Another found much higher total PBDE
levels (215 not including BDE209) in UK sediment samples from Clyde Estuary ranging

from 1.00 to 307 ng/ g dw. Input to the estuary likely includes landfill runoff, sewage

plant discharge, and both heavy and light industrial discharges (Vane et al., 2009).

Comparison of C ongener Profiles — All C ongeners - Upper Layer

The percent contribution of each congener of the uppermost sediment layer from
each lake, dated to 2006, was compared to determine if differences existed between the
lakes (Figure 8). Present congener contributions to both lakes were similar, which
suggests that regional (atmospheric), as opposed to local (watershed) sources now
dominate input to the lakes. Congener BDE47 is the most prevalent congener in both

samples, followed by BDE183 in Muskegon Lake and BDE99 in White Lake. Both

24

BDE47 and BDE99 are congeners commonly found in abundance in sediment samples

(Kohler et al., 2008; Vane et al., 2009; Zhu and Hites, 2005; Li et al., 2006).

Comparison of Congener Profiles — Select Congeners

In order to more clearly compare the dominant congeners that exist in both lake
core samples, seven of the most frequently occurring congeners were selected (Table 4).
Selection of these congeners was achieved by identifying the five congeners that
contributed most to total PBDE concentration in each stratum for each lake. The
frequency of occurrence of each congener was determined for all samples in both lakes,
and the seven most frequent were selected for further evaluation. These include, in order
of greatest frequency, BDE47, BDE99, BDE183, BDE171, BDE49, BDE100, and
BDE180 (Figures 9 and 10). In addition, to enable a direct temporal comparison between
lakes, only sediment strata that were of equal ages were compared between the two sites.
This resulted in the selection of ten samples, dating from 2006 to 1966.

The most frequently occurring congeners in Muskegon and White Lake sediments
are similar to those found in other studies. Other than BDE209, which could not be
measured in this study due to instrument limitations, BDE47 was found to be the most
abundant congener both in Great Lakes sediments and sediments in this study (Li et al.,
2006). A recent study found BDE47 to be the most abundant congener in the Clyde
Estuary, UK, followed by BDE99, BDE183, and BDE153 (Vane et al., 2009). This also
corresponds to the major components of the commercial mixture BK-70, of which

BDE47, BDE100, and BDE99 are the three major components.

25

In Muskegon Lake, congeners BDE47, BDE99, BDE49, and BDE100 all follow a
similar trend, as does BDE49, BDE180, and BDE183 in White Lake (Figure 2).
Concentrations of each gradually increase from the mid to late 1970’s to a peak
concentration in the mid-1990’s, and then a gradual decrease in concentration up to the
present. In White Lake BDE47, BDE99, and BDE100 reveal a steady increase in
concentration beginning in 1983, and maximum concentrations are achieved in the
uppermost sediments. In addition, BDE47 and BDE99 appear at greater concentrations
in the 1966 stratum that in the 1983, 1985, and 1993 layers.

In Muskegon Lake (BDE47, BDE99, and BDE100) and in White Lake (BDE49,
BDE180, and BDE183) the trend of gradually decreasing concentrations from the mid
1990’s to present is consistent with previous studies, and may be attributed to decreasing
production and use of PeBDE mixtures and the increased use of OctaBDE and DecaBDE
mixtures due to legislative pressure (from approximately 3.6 million metric tons,
combined, worldwide in 1992 to 67,000 metric tons in 2003). Another factor
contributing to the decline in PBDE concentrations may be changes in urban wastewater
treatment processes. Combined sewer overflow (CSO) projects have been required by
the Michigan Department of Environment Quality since the late 1980’s. CSO projects
separate storm drain flow from sewer flow to prevent untreated sewage from accidental
discharge into rivers during high—flow storm events. It is possible that this reduction of
untreated sewage input from the watershed has contributed to the reduced levels of
PBDEs in the sediment record. Knoth et a1. (2007) found significant concentrations of

BDE99, BDE47, BDE100, BDE153, BDE154, and BDE183 in wastewater treatment

26

sludge, indicating that sorption onto wastewater sludge can result in reduced PBDE load
in treatment plant effluent.

Muskegon Lake sediment concentrations of BDE180 and BDE183 behaved
differently than the congeners mentioned previously. These compounds are observed at
relatively low concentrations in the uppermost strata, but BDE 180 concentrations tend to
diminish abruptly at the 1993 and 1985 strata before increasing again in the 1983 and
1966 strata. Literature values for this congener in sediment samples are limited, likely
due to the fact that BDE180 is not a substantial contributor to most commercial PBDE
mixtures. BDE183 maintains a relatively stable concentration from the surface stratum to
the 1995 stratum sample, at which point the concentration abruptly increases in the four
lowest strata (1993 to 1966). This congener is a principal component of the OctaBDE .
mixture (Geller et al., 2007). Others have demonstrated that BDE183 levels in some
aquatic organisms result from the debromination of higher brominated PBDEs (Yang et
al., 2009).

BDE171 was selected for evaluation due to its concentration and frequency
characteristics in core samples from both lakes. A pattern is difficult to discern in either
lake, however, due to the random nature of its occurrence in sediment strata. Literature
values for this BDE171 in any matrix are limited, likely due to its small contribution to
commercial PBDE mixtures. Because of the randomness of BDEl 71 concentrations in
the data, the qualitative identification of this compound received additional scrutiny. In
all cases where it was detected, both the primary and secondary ion was present.
However, chromatograms reveal increased baseline noise at the retention time of

BDE171, which may contribute to increased uncertainty when evaluating this congener.

27

Methoxylated Polybrominated Diphenyl Ethers

Sediment samples from both lakes were analyzed for twelve methoxylated
polybrominated diphenyl ethers (MeO-BDES), (Appendix C). The analysis of White
Lake sediments detected only one compound in each of three samples, all at low levels
(<10 pg/ g dw). An examination of Muskegon Lake sediments identified at least one of
three primary MeO-BDE congeners in a majority of strata. Results for MeO-BDE
analysis of both lakes are presented in Appendices I and J. Levels of total MeO-BDEs
begin to appear in 1977, increase in concentration up to a peak in 2004 at a concentration
of 1 15 pg/ g, and drop to about half this level in the uppermost stratum (2006). A
congener-specific plot reveals that the primary contributor to Muskegon Lake MeO-
BDEs is 6MBDE47, which generally increased in concentration up to 2006, at which
point the concentration of this congener in the upper layer was less than half the peak
levels (Figure 1 l). The dominance of 6MBDE47 in the profile is not unexpected if one
assumes that it is a metabolite or decomposition product of the parent material, BDE47,
which appears as the most abundant congener in the total PBDE profile. The two other
MeO-BDE congeners, 6MBDE85 and 3PMBDE68, both follow a similar trajectory. One
anomaly in this trend is at the 2004 time point where only 6MBDE47 was detected at
lesser concentrations than in strata either before or after it. Examination of the labeled
injection standard recovery indicated reasonable instrument performance, however, since
no labeled analog standards were available at the time of extraction, loss of analyte
during preparation of this sample cannot be ruled out. The total MeO-BDE concentration

profile in Muskegon Lake is noteworthy in that it differs from the total PBDE profile.

28

While total PBDEs generally peak in the early 1990’s, the total MeO-BDEs appear in
greatest concentration in the 2004 stratum. A survey of the Canadian arctic marine food
web enumerated various MeO-PBDEs in marine biota, but detected none in marine
sediments (Kelley et al., 2008).

When comparing the Parent PBDE/MeO—BDE concentration ratios (Table 5),
only metabolites for which parent compounds existed in the analytical suite were
evaluated. Comparisons were made in three representative strata, years 2006, 2004, and
1995, as these represent the maxima for 6MBDE47, 6MBDE85, and 5MBDE99,
respectively. PBDE/MeO-BDE ratios in the upper sediments demonstrate a relatively
greater concentration of MeO-BDE as compared to parent PBDEs, while in the 1995
sediment layer MeO-BDE concentration are appreciably lower. This disparate temporal
trend in PBDE and MeO-BDE ratios was also observed in pike (Esox lucius) from
Swedish waters, suggesting different sources (Kierkegaard et al., 2004). In sediment
samples, the differing trends may be due to selective chemical or biological
decomposition of the MeO-BDEs in sediment due to the chemically active methoxyl
functional group present. Another possible reason for the lower ratio may be related to
the hypothesis that these compounds are not anthropogenic in nature, but rather the
natural byproducts of algal communities or other aquatic organisms (Teuten et al., 2005).

It is not clear why MeO-BDEs were consistently detected in Muskegon Lake but
not in White Lake. It is possible that these compounds are natural byproducts of the
pelagic or benthic fauna, and that the aquatic communities in the two lakes differ. Using
radiocarbon analysis, Teuten et al. (2005) determined that MeO-BDEs found in the

blubber of a beaked whale were not anthropogenic in nature, and were isotopically very

29

similar to a methoxybrominate found in the Pacific marine sponge Phyllospongia
foliascens. Approximately thirty species of freshwater sponge exist in North America.
Perhaps these methoxylated bromine compounds are metabolites of freshwater analogs of
the marine sponges.

The total PBDE concentration profile in Muskegon Lake differs from that found
in White Lake in the lower core strata, suggesting local sources influenced the total
PBDE load in each lake. Similar concentrations of total PBDEs in later sections of both
lakes (early 20005 to present) indicate that contributions from local sources have been
reduced in recent years and the PBDE load is now dominated by regional inputs (i.e.
atmospheric). In addition, when comparing select congeners, temporal shifts in congener
patterns exist in both lakes. This result is consistent with a flux of PBDE source material
and a likely flux in regional/local input influence. The concentration of both carbon and
organic matter in each sample appears to be correlated with total PBDE concentrations.
As strata analyte concentration increases, so does carbon and OM. One exception seems
to be in the older sediments. This may be due to greatly reduced PBDE concentrations.
Methoxylated PBDE concentration has little relationship to carbon and OM percentages.
MeO-BDEs were detected most consistently in Muskegon Lake sediments, while only a
few were observed in White Lake sediments. This has prevented a valid congener
comparison between lakes. The reason for this difference is not known, but may be
influenced by a biotic community unique to each lake.

Future work involving PBDEs and lake sediments may benefit from the inclusion
of additional methoxylated PBDEs and hydroxylated PBDEs in the analytical suite. Past

research has suggested that the MeO-BDEs may be natural products, while current

30

research has demonstrated that the hydroxylated species are likely derived via
demethylation of naturally occurring MeO-PBDES (Wan et al., 2009). Measurements of
total bromine in core samples would allow for the development of a mass budget for

bromine, clarifying the role of PBDEs and their metabolites in lentic and lotic systems.

31

TABLES

32

Table 1. Carbon/OM content as compared to analyte concentration.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

White Lake
Sample ID Total PBDE Conc Carbon % Organic Matter %
WH1+2 2091 13.430 23.15
WH3+4 2376 13.640 23.5
WH5+6 2205 13.085 22.55
WH7+8 2426 13.640 23.5
WH9+10 2252 12.435 21.45
WH11+12 1638 12.335 21.3
WH13+14 749 12.710 21.9
WH15+16 644 12.020 20.7
WH17+18 723 11.820 20.4
WH19+20 537 11.650 20.1
WH2 1 +22 454 10.995 18.95
WH23+24 764 11.180 19.3
WH25+26 734 10.830 18.65
WH27+28 1087 10.435 17.95
WH29+30 1369 13.280 22.9
WH31+32 1305 9.490 16.35
WH33+34 888 9.530 16.4
WH35+36 389 7.980 13.8
WH37+38 397 6.265 10.8
WH39+40 206 1.730 3 .05
WH41+42 520 1.760 3.1
WH43+44 781 3.935 6.8

 

 

 

 

33

 

Table 1 (cont’d).

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Muskegon Lake
Sample Total PBDE Total MeO-PBDE Carbon Organic
ID Conc Conc % Matter °/o

MU1+2 2050 53.02 10.460 18.05
MU3+4 2146 115.48 10.485 18.1
MU5+6 2676 73.74 11.060 19.05
MU7+8 2441 5.93 10.725 18.5
MU9+10 2896 38.58 10.265 17.7
MU11+12 2981 15.17 10.115 17.45
MU13+14 3414 33.14 10.055 17.35
MU15+16 3130 18.66 10.265 17.7
MU17+18 3883 11.01 10.660 18.35
MU19+20 2810 12.87 10.005 17.25
MU21+22 2739 10.85 10.005 17.25
MU23+24 2624 5.35 9.840 16.95
MU25+26 2338 7.58 9.765 16.85
MU27+28 2313 7.59 9.390 16.2
MU29+30 2029 3.57 9.485 16.35
MU31+32 2327 0.00 10.425 18
MU33+34 983 0.00 8.955 15.45
MU35+36 1348 0.00 9.265 15.95
MU37+38 1726 0.00 9.140 15.75
MU39+40 2585 0.00 8.770 15.15
MU41+42 2096 0.00 9.670 16.65

 

 

 

 

 

34

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

e: 3.8 3 3.3 8.8 3 3.3 3.8 83 35mm
8 3.8 3 3.8 8.8 8 3.8 3.8 33 3QO
3 3.8 3 8.8 8.8 3 3.8 3.8 8.3 82QO
3_ 3.3 3 8.8 8.8 2: 3.3 3.8 8.3 3QO
m: 3.3 3 8.3 8.8 3 3.8 3.8 3.2 3QO
3 3.8 3 3.8 8.8 8 3.8 3.8 3.8 8135
8 3.8 3 8.8 8.8 8 3.8 3.8 83 3QO
2 _ 3.8 3 3.8 8.8 8 3. s 3.8 8.3 8QO
3 2.8 3 3.8 8.8 2: 3.3 3.8 83 3QO
8m ewe 8m awe 333 8m 83 awe an 88:8
3 83 m3 3 83 mm: a888, 033m 3 m2 Enema. 8:3 83 m2:
3_ ow. _ m 3: 3.8 3.8 2: :3 3.8 83 33:5
3 3.8 2: 8.3 3.8 3 3.8 3.8 83 5QO
3 2.8 2: 3.3 3.8 3 3.8 3.8 83 82QO
3 3.8 3 8.8 3.8 3 3.8 3.8 83 3QO
2 a 8.8 32 3.2 _ 3.8 3 8.8 3.8 8.: 3QO
3 3.8 3: 3.3 3.8 3 3.8 3.8 33 3.QO
3 8.8 8 3.8 3.8 8 3.8 3.8 33 3QO
3: 3.3 m: 8.2: 3.8 3 3. K 3.8 3.3 8QO
3 3.8 NS :3 3.8 3 3.8 3.8 2: 3QO
8m 333 one @§ 933 8x 83m 3.3.5 333 5:880
3 883 m3 3 883 am: “582 8:3 3 m2 ascent 3am 83m 35

 

 

 

 

 

 

 

 

 

 

 

63v 3% >358»: use 295— wEo—Em 295m .8250 bmfizo .N 033.

35

Table 3. Total PBDE (223) concentration by sample (pg/g dry wt).

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sample Year Conc Sample Year Conc
WH1+2 2006 2091 MU1+2 2006 2050
WH3+4 2004 2376 MU3+4 2004 2146
WH5+6 2002 2205 MU5+6 2002 2676
WH7+8 1999 2426 MU7+8 2001 2441

WH9+10 1997 225 2 MU9+10 1999 2896

WH11+12 1995 1638 MU11+12 1997 2981

WH13+14 1993 749 MU13+14 1995 3414

WH15+16 1990 644 MU15+16 1993 3130

WH17+18 1988 723 MU17+18 1991 3883

WH19+20 1985 537 MU19+20 1989 2810

WH2 1 +22 1983 454 MU21+22 1987 2739

WH23+24 1980 764 MU23+24 1985 2624

WH25+26 1978 734 MU25+26 1983 2338

WH27+28 1976 1087 MU27+28 1981 2313

WH29+30 1973 1369 MU29+30 1979 2029

WH31+32 1971 1305 MU3 1 +32 1977 2327

WH33+34 1966 888 MU33+34 1974 983

WH35+36 1949 389 MU35+36 1972 1348

WH37+38 1920 397 MU37+38 1970 1726

WH39+40 <1901 206 MU39+40 1968 2585

WH4 1 +42 <1901 520 MU41+42 1966 2096

WH43+44 <1901 781

 

 

 

 

 

 

36

 

Table 4. Select PBDE congener contributions in White and Muskegon lakes.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

White Lake
Congener Number Percent Contribution to total
BDE47 28.5
BDE183 17.6
BDE99 16
BDE171 7.49
BDE49 4.62
BDE100 4.58
BDE180 2.37
Muskegon Lake
Congener Number Percent Contribution to total
BDE47 23.6
BDE99 15
BDE171 9.48
BDE180 9.37
BDE49 8.39
BDE183 7.91
BDE100 5.2

 

 

 

 

37

Table 5. Parent : Metabolite ratios in Muskegon Lake.

 

Muskegon Lake Parent:Metabolite Ratios

 

 

 

 

 

 

 

 

PBDEzMetabolite 2006 2004 1995
BDE47:6MBDE47 16.4 7.1 64.7
BDE9925MBDE99 N/A N/A 82.0
BDE85z6MBDE85 1.3 1.0 2.3

 

Compared all parent/metabolite sets available. Only maximum values used.

38

 

Table 6. Method blank congener concentrations.

 

 

 

BLANK BLANK MU23-42 MU1-22
Congener 52407 WH13-34 BLK 5807 BLK BLK“
BDE28 < DL 2.63 < DL 3.16 29.49
BDE17 < DL < DL < DL < DL 11.06
BDE30 < DL < DL < DL < DL < DL
BDE71 < DL < DL < DL < DL < DL
BDE49 5.27 3.16 < DL 2.63 46.87
BDE47 91.10 87.41 < DL 81.10 1332.81
BDE66 < DL < DL < DL 2.63 24.75
BDE77 < DL < DL < DL < DL < DL
BDEIOO 13.69 14.22 9.48 11.06 148.50
BDE119 2.11 1.05 <DL <DL <DL
BDE99 54.77 68.98 31.07 48.97 737.23
BDE85 2.11 4.74 2.63 2.11 28.44
BDE126 2.11 1.58 < DL < DL < DL
BDE154 10.53 10.53 6.32 7.90 63.19
BDE153 15.27 15.80 15.80 14.22 104.27
BDE139 < DL 1.58 1.58 0.53 5.79
BDE140 0.53 1.05 1.05 1.05 3.16
BDE138 2.63 2.63 < DL 1.05 10.01
BDE183 16.85 18.96 < DL 17.38 261.19
BDE184 < DL < DL < DL < DL 7.90
BDE180 < DL < DL < DL 4.21 20.01
BDE191 1.05 1.05 < DL < DL 25.80
BDE171 <DL '<DL <DL <DL <DL

 

 

 

 

 

 

 

5-8 QC set also applies to samples WH 1+2 thru WH 11+12
5-24 QC set also applies to WH-35 to WH-44

* this blank lost during extraction and re-created during sample clean up

39

FIGURES

40

IO
"3

 

 

Brm

Figure 1. Generalized Structure of PBDEs (where (m+n) = 2 to 10 bromines)

41

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43

(Mp fi/Bd) 'ouog

BDE 183

     
 

 

I

 

 

 

[IjMuskean gage;

 

 

1! White. Lake _

 

1999 1997 1995

2002

2004

 

 

 

 

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44

Strata Age

Figure 2 (cont’d).

BDE 171

 

 

hite Lake

W W-WWWW__‘

Muskegon Lake 1

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45

100 ~

  
    
   
  
   

  

1993 1985 1983 1966

1995

Strata Age

Figure 2 (cont’d).

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48

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49

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52

Select White Lake PBDEs

 

     

§3 IN

y..._._.._.__- -;

03%

E BDE100
§ BDE49

a; BDE 1 8

I 31313171 1 5
C1 BDE183 Pfifi...‘
a BDE99 g ‘
_E18_9§41J———-- -

 

 

 

 

    
 

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--
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_-

 

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35%

 

 

 

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523’ -\:;:;_,, 32222;: 0

 

 

 

 

 
 

 
 

A

 
 

 

 

 

 

2000 A

‘ ‘ 00
O O O O O O O O O O C“
O O O O O O O O 0
co (0 V N O m (D V N
r- 1— 1— t- ‘—

(Mp fi/fid) "auog

53

Strata Age
Figure 9. Select White Lake PBDEs.

 

_

7-?QO m:
_ 8QO s

% ,‘ -E i“.mMZmOmU
1, :Lmn—ml

w
1 1 ‘1 Sigma
a» mam myW

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54

Methoxylated PBDEs in Muskegon Lake

 

El 3PMBDE68 ;

I

i
I

 

E..~W__.<_~ ._ _. V_4 WW __Q

B 6MBDE47
E 6MBDE85

i
i
I
4 “.44”! ”v

w
l
1
i

 

 

 

 

 

 

 

120

(Mp S/Sd) 'ouog)

55

 

’\‘3‘b\9’\h'b0‘b‘b
\°?\9%>9P\9%é\é\\é\\é\\é\é°\°?

Strata Age

Figure 11. Methoxylated PBDEsvin Muskegon Lake

APPENDICES

56

Appendix A. Sediment strata aging data for White and Muskegon Lakes.

 

 

 

 

 

 

 

White Lake Year Muskegon Lake Year
WH 1+2 2006 MU 1+2 2006
WH 3+4 2004 MU 3+4 2004
WH 5+6 2002 MU 5+6 2002
WH 7+8 1999 MU 7+8 2001
WH 9+10 1997 MU 9+10 1999

WH11+12 1995 MU 11+12 1997

WH13+14 1993 MU 13+14 1995

WH15+16 1990 MU 15+16 1993

WH17+18 1988 MU 17+18 1991

WH l9+20 1985 MU l9+20 1989

WH 21+22 1983 MU 21+22 1987

WH 23+24 1980 MU 23+24 1985

WH 25+26 1978 MU 25+26 1983

WH 27+28 1976 MU 27+28 1981

WH 29+30 1973 MU 29+30 1979

WH 31+32 1971 MU 31+32 1977

WH 33+34 1966 MU 33+34 1974

WH 35+36 1949 MU 35+36 1972

WH 37+38 1920 MU 37+38 1970

WH 39+40 <1901 MU 39+40 1968

WH41+42 <1901 MU 41+42 1966

WH 43+44 <1901

 

57

 

Appendix B. Analytical instrument parameters for PBDE and MeO-PBDE analysis.

Primary Column

Injection Port Type
Injection Liner Type
Injection Volume
Injection Port Temperature
Purge Flow

Purge On Time

Carrier Gas

Initial pressure

Mode

Detector Temperature

Initial Temperature
Initial Hold

Ramp 1 Rate

Final Temperature 1
Hold Time 1

Ramp 2 Rate

Final Temperature 2
Hold Time 2

Ramp 3 Rate

Final Temperature 3

Hold Time 3

Agilent DB—SMS (30m x 0.25mm ID x 0.1 mm)

Split/splitless-in splitless mode

Focus liner split/splitless

1 ul
285°C

5 ml/min
2 min
Helium
200 kpa

Constant pressure

 

285°C

PBDE Analysis MeO-PBDE Anagsis
110°C 150°C
10.00 min 2.00 min
25°C/min 2°C/min
250°C 245°C
N/A 2.00 min
1.5°C/min 30°C/min
260°C 320°C
N/A 2 min
25°C/min N/A
323°C N/A

15 min N/A

58

Appendix C. Analyte IUPAC names, CAS numbers, and calibration standard

 

 

 

concentrations.
B/Z CAS Cal Conc

Number IUPAC Name Number (ng/ml)

0.25, 1, 5,
BDE] 7 2,2',4-Tribromodiphenyl ether 147217-75-2 20

0.25, 1, 5,
BDE28 2,4,4'-Tribromodiphenyl ether 41 3 18-75-6 20

0.25, 1, 5,
BDE30 2,4,6-Tribromodiphenyl ether 155999-95-4 20

0.5, 2, 10,
BDE47 2,2',4,4'-Tetrabromodiphenyl ether 5436-43-1 40

0.5, 2, 10,
BDE49 2,2',4,5 ’-Tetrabromodiphenyl ether 243 982-82-3 40

0.5, 2, 10,
BDE66 2,3 ',4,4'-Tetrabromodiphenyl ether 189084-61-5 40

0.5, 2, 10,
BDE71 2,3',4',6-Tetrabromodiphenyl ether 189084-62-6 40

0.5, 2, 10,
BDE77 3,3',4,4’-Tetrabromodiphenyl ether 93 703-48-1 40

0.5, 2, 10,
BDE85 2,2',3 ,4,4'-Pentabromodiphenyl ether 1 82346-21-0 40

0.5, 2, 10,
BDE99 2,2',4,4',5-Pentabromodiphenyl ether 60348-60-9 40

0.5, 2, 10,
BDE 1 00 2,2',4,4',6-Pentabromodiphenyl ether 1 89084-64-8 40

0.5, 2, 10,
BDE] 19 2,3',4,4',6-Pentabromodiphenyl ether 189084-66-0 40

0.5, 2, 10,
BDE126 3 ,3',4,4',S-Pentabromodiphenyl ether 366791 -32-4 40

0.5, 2, 10,
BDE13 8 2,2',3 ,4,4',5'-Hexabromodiphenyl ether 182677-30-1 40

0.5, 2, 10,
BDE139 2,2',3 ,4,4',6-Hexabromodiphenyl ether N/A 40

0.5, 2, 10,
BDE140 2,2',3,4,4',6'-Hexabromodiphenyl ether 243982-83-4 40

0 5, 2, 10,
BDE153 2,2',4,4',5,5'-Hexabromodiphenyl ether 68631-49-2 40

0 5, 2, 10,
BDE154 2,2',4,4',5,6'-Hexabromodiphenyl ether 207122-15-4 40
BDE171 2,2',3,3',4,4',6-Heptabromodiphenyl ether N/A 1, 4, 20, 80
BDE180 2,2',3,4,4',5,5'-Heptabromodiphenyl ether N/A 1, 4, 20, 80
BDE183 2,2',3,4,4',5',6-Heptabromodiphenyl ether 207122-16-5 1, 4, 20, 80
BDE184 2,2',3,4,4',6,6'rHeptabromodiphenyl ether N/A 1, 4, 20, 80
BDE191 2,3,3',4,4’,5',6-Heptabromodiphenyl ether N/A 1, 4, 20, 80

 

 

 

 

59

 

Appendix C (cont’d).

 

 

 

B/Z CAS Cal Conc
Number IUPAC Name Number (ng/ml)

1, 4, 20, 80,

4MBDE] 7 4'-Methoxy-2,2‘,4-Tribromodiphenyl ether N/A 400
1, 4, 20, 80,

6MBDE1 7 6'-Methoxy-2,2',4-Tribromodiphenyl ether N/A 400
5-Methoxy-2,2’,4,4'-Tetrabromodiphenyl l, 4, 20, 80,

5MBDE47 ether N/A 400
6-Methoxy-2,2',4,4'-Tetrabromodipheny1 1, 4, 20, 80,

6MBDE47 ether N/A 400
4‘-Methoxy-2,2',4,5’-Tetrabromodiphenyl 1, 4, 20, 80,

4PMBDE49 ether N/A 400
3'-Methoxy-2,3',4,5'-Tetrabromodiphenyl l, 4, 20, 80,

3PMBDE68 ether N/A 400
6-Methoxy-2,2',3,4,4'-Pentabromodiphenyl l, 4, 20, 80,

6MBDE85 ether N/A 400
6-Methoxy-2,2‘,3,4',5-Pentabromodiphenyl 1, 4, 20, 80,

6MBDE90 ether N/A 400
5-Methoxy-2,2',4,4',5-Pentabromodiphenyl l, 4, 20, 80,

5MBDE99 ether N/A 400
5-Methoxy-2,2',4,4',6-Pentabromodiphenyl 1, 4, 20, 80,

5MBDE100 ether N/A 400
4-Methoxy-2,2',4,5,5'-Pentabromodiphenyl l, 4, 20, 80,

4MBDE101 ether N/A 400
4-Methoxy-2,2',4,5',6-Pentabromodiphenyl 1, 4, 20, 80,

4MBDE103 ether N/ A 400

 

 

 

 

60

 

 

 

 

 

 

 

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cm mm mm mm mm mm mm mDU Jam—mam

mm mm mm mm wm mm mm flux—mam

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.8253 a 5283

62

 

 

 

 

 

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Om mm mm mm Nm mm m ADO 402QO

cm om e_ 3 mm M: R AmeDm

mm am _N om ow mm mm 1:2QO

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mm NN mm aw mm Nm Nm m2— 4&2QO
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63

353833 82 u m2

552% .5535 5253 n 9:
55555 a: 530 8533 n So

 

 

 

 

 

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Om: mZD

 

 

5.253 a 58.5?

64

Appendix E. PBDE and MeO-PBDE analysis: Calibration verification standard
recoveries (%).

 

 

 

 

 

PBDE Analysis
CONGENER SEQUENCE ID
PATR- PATR- PATR- PATR-

5 5A SB 5C
BDE138L TNJ 143 160 250 517
BDE28 104 86 4 84
BDE28L 126 126 256 73
BDE17 94 74 4 78
BDE30 112 102 0 102
BDE47L 116 114 13 68
BDE71 95 98 1 90
BDE49 94 92 15 82
BDE47 93 93 .111 81
BDE66 85 85 4 75
BDE77 94 88 0 79
BDE100L 118 111 15 84
BDE100 89 89 27 81
BDE119 85 85 O 73
BDE99L 112 105 15 79
BDE99 86 89 89 79
BDE85 82 86 0 78
BDE126 86 92 0 88
BDE154L 108 107 14 101
BDE154 95 97 17 88
BDE153L 103 100 13 98
BDE153 92 94 26 86
BDE139 992 93 1 87
BDE140 86 90 1 86
BDE138 94 94 6 89
BDE183L 110 107 4 108
BDE183 98 101 36 96
BDE184 89 94 3 84
BDE180 84 89 9 81
BDE191 69 79 3 71
BDE171 69 82 19 75
BDE139L CUP 100 98 36 97

 

 

 

65

Appendix E (cont’d).

 

MeO-PBDE Analysis

 

 

 

 

 

POSITION IN SEQUENCE

Congener 1 ST 2ND 3RD 4TH

BDE138L IN] 105 0 249 364
6MBDE17 85 0 55 52
4MBDE17 90 0 60 60
3PMBDE68 87 0 69 29
6MBDE47 90 0 72 35
5MBDE47 99 0 76 34
4PMBDE49 91 0 71 33
6MBDE90 90 0 69 74
5MBDE100 90 0 84 73
4MBDE103 101 0 84 77
5MBDE99 93 0 84 80
4MBDE101 85 0 84 81
6MBDE85 80 O 76 73

 

CUP = Labeled Clean Up standard
IN] = Labeled Injection standard

66

 

Appendix F.

White and Muskegon Lake sample percent moisture.

 

Sample

%

Sample

%

 

 

MU1+2
MU3+4
MU5+6
MU7+8
MU9+10
MUl 1+12
MU13+14
MU15+16
MU17+18
MU19+20
MU21+22
MU23+24
MU25+26
MU27+28
MU29+3O
MU31+32
MU33+34
MU35+36
MU37+38
MU39+4O
MU41+42

81.17
81.49
81.12
79.83
78.48
79.12
78.45
78.96
78.71
78.28
78.01
77.83
79.08
79.28
77.68
79.31
79.91
81.13
80.09
78.28
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WH3+4
WH5+6
WH7+8
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WH11+12
WH13+14
WH15+16
WH17+18
WH19+20
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WH23+24
WH25+26
WH27+28
WH29+3O
WH31+32
WH33+34
WH35+36
WH37+38
WH39+4O
WH41+42
WH43+44

87.96
84.79
83.61
84.66
85.25
86.09
86.02
85.19
85.65
86.33
87.05
86.72
88.47
88.33
87.97
86.30
87.05
85.32
79.53
60.60
59.73
72.26

 

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8O

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