Sponsored Projects

Below is a list of projects sponsored by the GLAD Program from 2004 through 2010:

2004

Dioxin Monitoring in Air Collected near the Great Lakes
Principal Investigator: Ronald A. Hites, Ph.D.
Institution: Indiana University
Project start date: April, 2004
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Project Title: Dioxin Monitoring in Air Collected Near the Great Lakes

Chemicals Studied: Polychlorinated dibenzo-p-dioxins (also known as dioxins or PCDDS) and polychlorinated dibenzofurans (also known as furans or PCDFs)

Geographic Areas: Monitoring took place at four U.S. stations of the Integrated Atmospheric Deposition Network (IADN). The stations are located at Eagle Harbor, Michigan (Lake Superior); Sleeping Bear Dunes, Michigan and Chicago, Illinois (Lake Michigan); and Sturgeon Point, New York (Lake Erie). These stations offer coverage of three of the five lakes and a significant portion of the region from north to south and east to west. In addition, the two locations on Lake Michigan offer insight into differences between urban and rural regions.

Project Start Date: April 2004

Project Status: Completed

Synopsis: The atmospheric concentrations of PCDDs and PCDFs were measured in four sites near the shores of the Great Lakes. The sites included an urban site (Chicago, Illinois) and three rural/remote sites (Eagle Harbor, Michigan; Sleeping Bear Dunes, Michigan; and Sturgeon Point, New York). Sampling occurred every 24 days between November 2004 and December 2007. The concentration of PCDD/Fs averaged 2.3 ± 0.2 fg WHO TEQ/m3 at Eagle Harbor, 35 ± 3 fg WHO TEQ/m3 at Chicago, 7.4 ± 1.4 fg WHO TEQ/m3 at Sleeping Bear Dunes, and 13 ± 2 fg WHO TEQ/m3 at Sturgeon Point. The total concentration of the 17 toxic PCDD/F congeners showed a significant seasonal trend at all sites, except Chicago. The date of maximum concentration averaged around Dec 6 ± 35 days, which is consistent with combustion being an important source of PCDD/Fs to the atmosphere. A significant positive relationship between the logarithm of the total concentration of the 17 toxic PCDD/F congeners and the logarithm of the number of people within a 25 km radius around the sampling site was found. This suggest that urban and industrial areas act as sources of PCDDs and PCDFs to rural and remote areas across the US.

Project Contact:
Ronald A. Hites, Ph.D.
Indiana University
School of Public and Environmental Affairs
Bloomington, IN 47405
Phone: (812)855-0193
Email: [email protected]

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Evaluation of the extent and transport capabilities of PAHs within the Lake Erie watershed
Principal Investigator: Michelle Homan, Ph.D.
Institution: Gannon University
Project start date: April, 2004

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Project Title: Evaluation of the Extent and Transport Capabilities of PAHs within the Lake Erie Watershed

Synopsis: There are 42 Areas of Concern (AOCs) throughout the Great Lakes basin, 30 of which are wholly or partly within the U.S. borders. Each of these AOCs have been gradually moving toward restoration and recovery of their beneficial uses through broad-based Remedial Action Plans, which prescribe a wide range of actions, ranging from remedial dredging and clean-up to natural attenuation, depending on site-specific factors. Presque Isle Bay, in Erie, Pennsylvania, has been re-designated as an Area of Recovery and is progressing toward a recovery under a program of natural attenuation. Accurate determination of continuing contamination levels, including from atmospheric inputs, are essential in determining the recovery timeline for the bay and what additional measures, if any, are needed to speed and ensure its recovery. This project’s goal was to determine the input of polycyclic aromatic hydrocarbons (PAHs), the primary contaminants of concern in the bay, to Presque Isle Bay from the atmosphere and statistically apportion these contaminants to various likely sources.

Chemicals Studied: This project monitored eighteen PAHs: pyrene; benz(a)anthracene; chrysene; benzo(a)pyrene; benzo(b)fluoranthene; benzo(k)fluoranthene; benzo(g,h,i)perylene; dibenz(a,h)anthracene; anthracene; phenanthrene; acenaphthene; acenaphthylene; benzo(e)pyrene; fluoranthene; fluorene; ideno(1,2,3-cd)pyrene;; perylene; and coronene.

Geographic Areas: The project included three monitoring sites around Presque Isle Bay, near the shore of Lake Erie in Northwest Pennsylvania. Although the project covers only a small region, the methods and results will have very important implications to the numerous other AOCs around the region.

Project Duration: Monitoring occurred over a 12-month period, from February 2005 through January 2006. Following this, the data was be analyzed to determine loading and source contributions.

Methods Used: Gaseous and particulate air samples and wet deposition samples were taken at three sites: one in the city of Erie; one upwind of Presque Isle Bay; and one downwind of the bay. Air samples were collected by high volume samplers with quartz fiber filters and XAD-2 resin. Wet deposition samples were collected with event-based precipitation collectors. These samples were analyzed for the PAH compounds being studied. In addition to calculating total deposition to the bay, the data was analyzed with the Chemical Mass Balance model to apportion the contributions of several likely sources

Potential Results and Implications: The study has numerous important implications, including: evaluating the concentration of PAHs in particulate and gaseous form in ambient air in the Erie area; estimating the PAH fluxes into Presque Isle Bay by considering dry particle deposition, wet deposition via precipitation and gaseous air-water exchange; characterizing the potential sources of PAHs within air and precipitation samples based on the relative proportions of various species; estimating whether the potential sources of atmospheric PAHs are predominately from local or regional sources; and characterizing the transport of PAHs within the local area by comparing data between sites upwind, downwind and within the city of Erie. In addition to providing highly valuable information to the local Remedial Action Plan committees, the study is a valuable demonstration to the other Great Lakes AOCs.

Project Contact:
Michelle Homan, Ph.D.
Department of Environmental Science & Engineering
Gannon University, Box 3663
Erie, PA 16541
Phone: (814)871-5691
Email: [email protected]

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Enhanced Rates of Mercury Methylation from Sulfate Deposition: A Whole Wetland Experiment
Principal Investigator: Daniel R. Engstrom, Ph.D.
Institution: Science Museum of Minnesota
Project start date: April, 2004

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Project Title: Enhanced Rates of Mercury Methylation from Sulfate Deposition: A Whole Wetland Experiment

Chemicals Studied: Total and methyl mercury was monitored in the experimental wetland. In addition, a suite of general water chemistry parameters was monitored, including cations, anions, dissolved organics, nitrogen and sulfate.

Geographic Areas: The experiment took place at the Marcell Experimental Forest in Northern Minnesota. The results are applicable to similar ecosystems, which are common across the Great Lakes basin.

Project Start Date: April 2004

Project Status: Completed

Synopsis: This project involved a long-term, ecosystem-scale experiment in which sulfate deposition to a boreal wetland was increased in order to examine the synergistic effects of atmospheric sulfate and mercury (Hg) on production and export of the bioaccumulative neurotoxin, methylmercury (MeHg). A whole-wetland irrigation system for amending sulfate deposition through simulated rainfall was established in the fall of 2001 at the USFS Marcell Experimental Forest (MEF) in northern Minnesota. The 2-ha wetland was divided into control and experimental halves, and the experimental half was treated with a sulfate solution meant to increase annual sulfate loading by four times the current rate of atmospheric deposition. This study was conducted in 2005 and 2006 and focusedin particular on the possible chronic effects and recovery of wetlands previously impacted by elevated sulfate deposition.

In both 2005 and 2006 (and similar to previous years), peat porewater MeHg concentrations and %MeHg in the experimental treatment spiked three days after the spring (May) sulfate application, while control levels remained constant. The increase in MeHg coincided with declining sulfate concentrations, indicating Hg methylation by sulfate-reducing bacteria (SRB) as the likely process. A similar spike was not observed following the 2005 summer (July) application, because dry conditions prevented sulfate from reaching the water-table. The methylation response to the 2005 fall (October) addition was complicated by a prolonged summer drought and late-season water-table rise which regenerated sulfate from within the peat, stimulating SRB activity and Hg methylation just prior to the addition date. This response was evident in both the experimental and control sections, but was much more pronounced in the former. Drought-induced sulfate regeneration was also evident in the higher sulfate and MeHg concentrations prior to the spring addition in 2006 as compared to 2005. The actual fall-2005 sulfate addition raised MeHg concentrations in the treated section only modestly, and it may be that SRB activity and methylation were limited at this time, not by sulfate, but by carbon quality/quantity or inorganic mercury bioavailability. Severe drought returned to the MEF in 2006, drying the peat surface to such an extent that pore-waters could not be collected from most sample sites after late June. Throughout the experiment, the response of SRB Hg-methylation to sulfate addition was more pronounced in the central raised bog than in the marginal lagg, presumably because the bog is more sulfate-limited than the lagg; the bog is fed solely by atmospheric deposition whereas the lagg receives periodic inputs of sulfate from upland runoff.

Beginning with the 2006 field season a recovery treatment, in which sulfate addition was suspended to a portion of the experimental section of the wetland, was incorporated into the project design to simulate the effects of reduced sulfate deposition. Sulfate and MeHg concentrations and %MeHg declined in the recovery treatment over the spring period, while the experimental sites continued to respond to sulfate loading following the spring addition. However, the recovery section remained elevated in sulfate and Hg relative to the control for this first year of the new treatment, indicating a persistent influence of the added sulfate. Chronic effects of sulfate addition are evident in the divergence in MeHg concentrations (and %MeHg) between experimental and control treatments over the five years of the study. However, absolute MeHg concentrations vary from year to year in both treatments based on antecedent hydrological conditions and do not show a directional increase. Results of this long-term experiment imply that boreal wetlands affected for decades by high sulfate deposition will continue to experience lingering, elevated mercury methylation, especially when the effects of climate remobilize previously sequestered sulfate.

Project Contact:
Daniel R. Engstrom, Ph.D.
St. Croix Watershed Research Station
Science Museum of Minnesota
Marine on St. Croix, MN 55047
Phone: (651)433-5953
Email: [email protected]

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Bioavailability and reactivity of atmospheric mercury in surface waters of the Great Lakes Region
Principal Investigator: Christopher Babiarz, Ph.D.
Institution: University of Wisconsin
Project start date: April, 2004

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Project Title: Bioavailability and Reactivity of Atmospheric Mercury in Surface Waters of the Great Lakes Region

Chemicals Studied: Organic and inorganic mercury in both wet and dry deposition and their bioavailability.

Geographic Areas: Devils Lake and Milwaukee, Wisconsin & Lake Michigan offshore of Milwaukee — the processes (deposition and uptake by biota) are similar throughout the Great Lakes region and the results and implications are therefore applicable to the region as a whole.

Project Start Date: April 2004

Project Status: Completed

Synopsis: The investigators collected numerous samples of Lake Michigan water, urban and rural rain, and airborne particulate matter. These samples were used to conduct algal mercury uptake bioassays. The dose response curve for mercury uptake by the algal species being examined was thoroughly investigated, allowing for the use of higher algal concentrations, shorter assays and non-isotopic mercury. Field samples were collected in summer of 2004, 2005 and 2006, including storm-water runoff and a light rain shower.

The findings from this study suggest:
(a) Urban rain inhibits the bioavailability of MeHg compared with rural rain.
(b) The changing chemistry when rain is introduced into lake water affects the bioavailability with MeHg from rural rain becoming less available and MeHg from urban rain becoming more available.
(c) Urban storm-water runoff inhibits bioavailability of MeHg to algae and the effects are seen in river water that contains urban influence.
(d) Dry deposition has a fraction of MeHg that is bioavailable. Depending on the magnitude of estimates for dry deposition loading to the Great Lakes, this source could rival that of autochthonous sources.
(e) Chlamydomonas is a robust test alga for mercury bioassays. Performance is best when the initial cell count is 20K, the test waters are circum neutral (pH6.5 to 8.5), and DOC levels are moderate (less than ~5 mg/L)

Project results have been presented during the 2010-11 GLAD webinar series.

Project Contact:
Christopher Babiarz, Ph.D.
Water Science and Engineering Laboratory
University of Wisconsin
660 North Park Street
Madison, WI 53706
Email: [email protected]

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Measurement of Polybrominated Diphenyl Ether Atmospheric Concentrations and Fluxes in Lake Superior using MCCDs
Principal Investigator: Judith Perlinger, Ph.D.
Institution: Michigan Tech. University
Project start date: April, 2004

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Project Title: Measurement of Polybrominated Diphenyl Ether Atmospheric Concentrations and Fluxes in Lake Superior using MCCDs

Synopsis: Polybrominated diphenyl ethers (PBDEs) are an emerging class of chemicals of concern in the Great Lakes region and around the world. Produced as flame retardants in a wide range of consumer products, they have been detected in environmental media throughout the world, including animal and human tissues at levels that are increasing exponentially with a doubling time of a few years. Although some measurements of these chemicals have been taken in the Great Lakes region, including in air, measurements have not been sufficiently thorough to quantify loadings to the Great Lakes. This project will measure with high accuracy the amount of PBDEs depositing to Lake Superior from the atmosphere over the course of a year. The novel methods developed as part of the project will allow much higher accuracy than conventional methods and will be applicable to other chemicals and locations.

Chemicals Studied: This project will measure atmospheric concentrations of eight polybrominated diphenyl ether congeners (IUPAC numbers 28, 47, 99, 100, 153, 154, 183, and 209)

Geographic Areas: Samples will be taken at Houghton, Michigan and aboard research vessels on Lake Superior. Although the study will quantify the deposition of PBDEs only to Lake Superior, the methods developed during this project will be extremely relevant to other chemicals and lakes throughout the region.

Project Duration: Methodology development and testing will take place from fall of 2004 to spring of 2005. Measurements in Houghton will occur from spring of 2005 through spring of 2006. Measurements on Lake Superior will occur from spring of 2005 through fall of 2005. Data analysis and a final report will be completed by summer of 2006.

Methods Used: The project will support the construction of Multi-capillary collection devices (MCCDs) for collecting air samples at high flow rates. The MCCDs consist of a particle trap impactor, diffusion denuder, filter, and follow-up diffusion denuder through which ambient air is passed. Gaseous PBDEs collected in diffusion denuders will be thermally extracted into mini-sorbent tubes and subsequently desorbed from mini-sorbent tubes into a cooled Programmable Temperature Vaporization (PTV) inlet of a high-resolution gas chromatograph (HRGC) equipped with dual micro-electron capture detectors. Particulate-phase PBDEs will be desorbed from filters and transferred to a PTV-HRGC-mass spectrometer for analysis. Using these methods, we estimate that PBDE congener masses can be quantified in the Great Lakes region by sampling for minutes to hours rather than for days to weeks as is the case using conventional high-volume sampling or passive sampling. The short sample collection time enables micrometeorological flux measurement to be performed, which are more accurate than deposition estimation methods traditionally performed and does not require the use of unknown or uncertain parameters, such as the Henry’s law constants of PBDE congeners.

Potential Results and Implications: The novel methods being developed in the study will allow not only the first estimate of total PBDE deposition to Lake Superior, but will provide far greater accuracy than the estimates that have been made for other chemicals in the past. Accurate quantification of the flux of these chemicals into the lake is an important step toward assessing the overall impact these chemicals are having on human health and ecosystems in the region. Furthermore, the application of the methods being developed could allow more accurate and less costly quantification of deposition for PBDEs and other chemicals throughout the region.

Project Contact:
Judith Perlinger, Ph.D.
Civil and Environmental Engineering Department
Michigan Technological University
Email: [email protected]

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Source Apportionment of PBTs and Speciated PM Affecting The Great Lakes through Atmospheric Deposition
Principal Investigator: Stephanie Buehler, Ph.D.
Institution: Battelle
Project start date: April, 2004

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Project Title: Source Apportionment of PBTs and Speciated PM Affecting the Great Lakes through Atmospheric Deposition

Chemicals Studied: This project examined a large number of the contaminants monitored by the Integrated Atmospheric Deposition Network, including Great Lakes contaminants of concern such as polychlorinated biphenyls (PCBs), Polycyclic Aromatic Hydrocarbons (PAHs), and chlorinated pesticides

Geographic Areas: The IADN monitoring sites at Sleeping Bear Dunes, Michigan; Sturgeon Point, New York; and Eagle Harbor, Michigan – these monitors are located on the shores of lakes Michigan, Erie and Superior,

Project Start Date: April 2004

Project Status: Completed

Synopsis: The key element of this project was an analysis that seeked to identify pollutant sources without reliance on known emission profiles. This type of analysis is known as a source apportionment analysis. Source apportionment analyses (also known as receptor modeling when applied to air pollutants or environmental forensics when applied to groundwater contaminants) identify source categories of pollutants detected at a receptor site and apportion the detected pollutants among those source categories. For this project, the source apportionment model Positive Matrix Factorization (PMF) was used to identify source categories and apportion pollutants at receptor sites (Paatero, 2000).

The source apportionment model has been applied to a several subsets of a suite of pollutants collected across several air monitoring networks. These networks include the Integrated Atmospheric Deposition Network (IADN), the Interagency Monitoring of Protected Visual Environments (IMPROVE) network, and U.S. EPA’s PM2.5 Speciation Trends Network (STN). Together, these networks provide data on several types of air pollutants including PAH and PCB concentrations from IADN and elemental speciated PM2.5 concentrations and key PM2.5 ion measurements of nitrate and sulfate concentrations from either IMPROVE or STN. At some locations, monitors from different networks are essentially collocated (within a few miles of each other), allowing for analysis of wide suite of pollutants simultaneously. In particular, the IADN Eagle Harbor, Michigan, site is essentially collocated with the IMPROVE Isle Royale National Park (ISLE1), Michigan, site, and the IADN Chicago, Illinois, site is essentially collocated with several STN Chicago, Illinois, sites. The results from these two areas were used to aid in the source apportionment of the PAH and PCB data collected at Sturgeon Point, New York, and Sleeping Bear Dunes, Michigan, IADN sites.

The analyses of the data from the collocated sites provide insight into different aspects of the sources contributing to pollution in the Great Lakes. Paired data sets are available for the Eagle Harbor-Isle Royale sites from 2000 and, because of their rural locations, these sites are well suited to providing information about background sources. In contrast, the collocated Chicago sites, which also have paired two to three years of data, have more STN monitors and represent a more urban area. The more intensive data collection at the Chicago sites may help with identifying more local sources. The availability of several types of air pollutant data at the collocated sites presents an invaluable opportunity for establishing receptor profiles (the chemical profile after atmospheric aging), which otherwise do not exist when using speciated PM2.5 or IADN data alone.

Project Contact:
Stephanie Buehler, Ph.D.
Battelle
505 King Avenue
Columbus, OH 43201-2693
Email: [email protected]

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Monitoring Atmospheric Mercury Species in the Great Lakes
Principal Investigator: Gerald J. Keeler, Ph.D.
Institution: University of Michigan
Project start date: April, 2004

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Project Title: Monitoring Atmospheric Mercury Species in the Great Lakes

Synopsis: Since 1988, the Michigan Department of Community Health has issued a state-wide fish consumption advisory for Hg for all of Michigan’s inland lakes, for certain species of fish in three of the Great Lakes and Lake St. Clair. Many other states in the Great Lakes region have similar advisories. The atmosphere has been determined to be the most significant source of Hg to most of the region’s inland lakes and to the Great Lakes. Mercury has been and is currently being targeted as a pollutant of concern for source identification, reduction and/or elimination through a variety of state, federal and international efforts. However, significant information gaps exist that prevent effective management decisions concerning this important contaminant. In particular, temporal and spatial trends across the Great Lakes are not thoroughly established, assessment of dry deposition is lacking, and the speciation of mercury among its various forms has not been well studied in the Great Lakes region. This project is filling these important knowledge gaps through monitoring the spatial and temporal trends in speciated atmospheric Hg in both rural and urban areas in the Great Lakes.

Chemicals Studied: This study will examine concentrations of elemental and reactive (Hg(0) and Hg(II)) mercury in the gaseous and particulate phases of the atmosphere and in precipitation samples. Analysis for additional items, including particulate matter, trace elements, sulfur and nitrogen species, will allow for more thorough analysis of sources and atmospheric processes.

Geographic Areas: A series of six monitoring sites are being maintained throughout Michigan, offering considerable coverage of the Great Lakes region as a whole. The monitoring stations are at Eagle Harbor, Pellston, South Haven, Flint, Dexter and Detroit. In all, this series of monitors offers coverage of both urban and rural sites and has at least one monitor within several miles of four of the five Great Lakes.

Project Duration: Monitoring began at these locations in 2001. This project is supporting an additional two years of monitoring, which will provide data through the end of 2005. In all, these five years of monitoring data will provide a time-trend of atmospheric mercury that is unprecedented for the Great Lakes.

Methods Used: Precipitation event samples will be collected at each site by an automated sampling system at all sites. These wet deposition samples will be analyzed for mercury and trace element concentrations. Additionally, speciated ambient mercury measurements will be taken at two sites to assess elemental and reactive mercury in the gaseous and particulate phases. This ambient data will be used to estimate rates of dry deposition. In addition, the mercury and trace element data will be used to apportion mercury contributions to major source categories using statistical models, such as Positive Matrix Factorization and UNMIX.

Potential Results and Implications: This study will produce a collection of mercury data that is unprecedented in the Great Lakes region and will assist in answering a range of questions concerning the sources and processes leading to contamination of the region’s waters. Among the information that will be produced is temporal and spatial trends of mercury concentrations across the region; the speciation pattern of atmospheric mercury; the relationship between urban and rural sites; and the relative contributions of source types and regions. In all, this will provide a much clearer picture of the processes leading to contamination of the Great Lakes and inland lakes across the region.

Project Contact:
Gerald J. Keeler, Ph.D.
Air Quality Laboratory
University of Michigan
109 South Observatory St.
Ann Arbor, MI 48109-2029
Email: [email protected]

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2005

Deposition & Ambient Concentrations of PBTs (PCBs, OCs, PBDEs & Dioxins/Furans) in Support of the Lake Ontario Air Deposition Study (LOADS)
Principal Investigator: James Pagano, Ph.D.
Institution: State University of New York at Oswego
Project start date: May, 2005

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Project Title: Deposition & Ambient Concentrations of PBTs (PCBs, OCs, PBDEs & Dioxins/Furans) in Support of the Lake Ontario Air Deposition Study (LOADS)

Synopsis: The purpose of this project is to: support atmospheric trend, loading, and source-receptor studies for critical contaminants identified in the Lake Ontario LaMP; increase the capacity to monitor for pollutants of concern in the lower Great Lakes; provide additional support for the calibration and refinement of the water quality model (LOTOX2); and enhance our understanding of emerging chemicals of interest by providing continued support for the permanent air sampling station established for the Lake Ontario Atmospheric Deposition Study (LOADS) at Sterling, NY. The project involves collection of air and dry deposition samples for congener-specific PCBs, organochlorine pesticides (OCs), polybrominated diphenyl ethers (PBDEs), and dioxin/furans (PCDD/F) In addition, this project involves the collection and analysis (PCBs, OCs, and PBDEs) of salmonid eggs and muscle tissue.

Chemicals Studied: The chemicals to be studied include: polybrominated diphenyl ethers (PBDEs), a class of currently-used flame retardant chemicals that have caused concern recently due to rapidly increasing concentrations in the Great Lakes environment; dioxins and furans, a chemicals released from combustion-related and other sources that are known to have significant health impacts; polychlorinated biphenyls (PCBs), a class of chemicals banned from production in North America but still present in the Great Lakes at levels above risk thresholds; and several other chlorinated organic compounds.

Geographic Areas: Project work is being conducted within the Lake Ontario basin. Air and dry deposition samples are taken at the Sterling, New York sampling site. Fish samples are collected on the Salmon River. Related work has taken place aboard a research vessel on Lake Superior.

Project Duration: The project began in the Spring of 2005 and will conclude in the Spring of 2007.

Methods Used: Samples of ambient air (vapor and particulate) are being collected with Hi-Vol samplers and dry deposition samples collected with knife-edge surrogate surfaces every twelve days for a period of one-year at the Sterling, New York site on the southeastern shore of Lake Ontario. Samples will be analyzed for congener-specific PCBs, organochlorine pesticides (OCs), polybrominated diphenyl ethers (PBDEs), and dioxin/furans (PCDD/F). In addition, the project provides for the collection and analysis (PCBs, OCs, and PBDEs) of salmonid eggs and muscle tissue (fillet) from the New York State Altmar Fish Hatchery on the Salmon River for the 2005 and 2006 spawning runs. This information will be combined with preliminary data from the 2002, 2003, and 2004 spawning runs to determine if establishing a long-term monitoring effort using salmon eggs as an ecological indicator is warranted.

Potential Results and Implications: This work supplements and extends the sampling conducted at the IADN master site of Point Petre, by providing dry deposition PCB samples, air concentrations of PBDEs, and enhanced sampling frequency for dioxin/furans. The salmonid data will also be used to provide contaminant trend data for ongoing wildlife (mink reproductive AOC study, NYS … Great Lakes Protection Fund, SUNY Brockport and Oswego) and human health studies (ATSDR and NIEHS) currently being conducted at SUNY Oswego. The project result will be used to support current efforts to establish a mass balance model of contaminant fate and exposures for Lake Superior.

Project Contact:
James Pagano, Ph.D.
State University of New York at Oswego
Phone: (315)312-2725
Email: [email protected]

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Development and Evaluation of Passive Samples for Persistent, Bioaccumulative Toxic Pollutants (PBTs)
Principal Investigator: Thomas Holsen, Ph.D.
Institution: Clarkson University
Project start date: May, 2005

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Project Title: Development and Evaluation of Passive Samples for Persistent, Bioaccumulative Toxic Pollutants (PBTs)

Synopsis: The outcome of this project has been an inexpensive, simple to use, scientifically accepted, passive sampling device that can be deployed to obtain long-term average ambient concentrations of organic PBTs and Hg. Research was conducted to determine the ideal design of a passive sampler housing that will minimize variations in sampling rate due to wind conditions and developing a model that can be used to predict airflow within the sampler based on wind conditions.

Chemicals Studied: The sampler design developed and studied can be used with any chemical appropriate for collecting with a passive sampling media. In addition, work was done to parameterize a sampler for collecting mercury on a gold foil sheet.

Project Duration: The project began in the Spring of 2005 and concluded in early 2008.

Methods Used: Computation fluid dynamic (CFD) computer programs were used for preliminary design of sampler housings that will minimize air flow variations. Predicted results were verified by wind tunnel experiments conducted using several prototype housings. The resulting design were then field tested and validated alongside a Hi-Vol sampler.

Potential Results and Implications: The outcome of this project is an inexpensive, simple to use, scientifically accepted, passive sampling device that can be deployed to obtain long-term average ambient concentrations of organic PBTs and mercury. This development will directly assist states and other stakeholders in making informed decisions about how to assess and reduce the deposition and impacts of the contaminants being addressed because passive samplers will allow more information about atmospheric concentrations of PBTS to be obtained at lower costs. The deployment of these samplers in and around urban areas would give much better estimates of air concentration gradients leading directly to better deposition estimates. Deployed at new or existing sites outside of urban areas they will give clearer signals of long-term average concentrations that can be used in current and new models of atmospheric fate and transport. Passive samplers deployed near suspected sources can be used to determine if concentrations in an area are elevated, and can be used to verify emission factors in conjunction with dispersion models. Similarly passive samplers deployed at strategic locations can be used to verify atmospheric and multi-media modeling.

Project Contact:
Clarkson University
Dr. Thomas Holsen
Phone: (315)268-3851
Email: [email protected]

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Source Profiles and Estimates for PCB Air Emissions From Electrical Transformers-II
Principal Investigator: William Mills, Ph.D.
Institution: University of Illinois at Chicago
Project start date: May, 2005

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Project Title: Source Profiles and Estimates for PCB Air Emissions from Electrical Transformers-II

Synopsis: PCBs remain a chemical of concern through out the Great Lakes. Atmospheric deposition from the IADN and other sampling indicates that concentrations in urban areas are greater than in rural areas, which are greater than in remote areas. Monitoring within the Chicago urban area indicates that identifiable source regions exist. Other work has shown that the environment surrounding source regions responds quickly to destruction of PCBs. A number of potential sources have been hypothesized. Since electrical equipment is the largest single use of PCBs and there are indications that, at least under storage conditions, PCB transformers may be responsible, at least in part for these elevated air concentrations. This project is an extension to previous work which conducted preliminary sampling in the vicinity of PCB transformers in order to provide source characterization and emissions estimates. The goal of the project is to: i) produce emissions estimates which can be used to rank the relative importance of transformers relative to other PCB sources; and ii)produce source profiles which might prove useful in identifying potential sources during air monitoring.

Chemicals Studied: Polychlorinated biphenyls were used extensively for numerous purposed between the 1940s and the 1970s, when their production and most uses were banned in North America. Among remaining uses are electrical transformers that were previously in existence and which are operated as “closed systems.” The toxicological effects of PCBs are numerous and well studied. Concentrations found in many sport fish caught in the Great Lakes exceed established risk thresholds for human consumption of these fish. As a result, PCBs are a prevalent cause of fish consumption advisories within the basin.

Geographic Areas: The study is being conducted within the Chicago urban area, with specific focus on several industrial facilities suspected of being significant remaining sources of PCB emissions.

Project Duration: The extended project work began in the Spring of 2005 and will conclude in the Spring of 2007.

Methods Used: Additional targeted sampling and analysis is being in order to address the uncertainties in the data from the previous project. This data is required in order to address limitations in the previous project data and to obtain emissions estimates and source profiles from additional potential sources. In particular, additional stored samples are being obtained through passive sampling, surface wipes and other methods. In addition, preserved samples are being analyzed to expand the data set and for quality control purposes.

Potential Results and Implications: Successful identification of remaining discrete sources of PCBs within the Chicago urban area is the first step needed to successfully eliminate these sources. Monitoring data suggests that the rate of PCB decline in the region’s fish has slowed significantly and nearly stopped. Models suggest that further reductions in the upcoming years will require finding and eliminating continuing sources of these chemicals. Although PCBs are capable of long-range transport, evidence suggests that many remaining sources are within the region, particularly within or near Chicago.

Project Contact:
William Mills , Ph.D.
University of Illinois at Chicago
Phone: (312)413-1085
Email: [email protected]

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2006

Great Lakes Charter Captain Mortality Study
Principal Investigator: Lynda Knobeloch, Ph.D.
Institution: Wisconsin Department of Health and Family Services
Project start date: April, 2006

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Project Title: Great Lakes Charter Captain Mortality Study

Chemicals Studied: This study assessed the blood levels of several pollutants known to be present at high levels in many sport fish in the Great Lakes region. These include methylmercury, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and dichlorodiphenyldichloroethylene (DDE, a persistent metabolite of DDT). Methylmercury is a form of mercury that can be produced in the environment from other mercury forms, accumulates in wildlife and human and has known adverse health impacts. PCBs are an industrial chemical that were used in numerous applications in the middle of the 20th century. Although banned from production in the U.S. and Canada, use of these chemicals remains in some “closed-system” applications. DDT was formerly used as a pesticide in North America and is still used in some parts of the world. PBDEs are currently used as a flame retardant in a wide range of commercial products, including consumer electronics and furniture, among many others.

Geographic Areas: The study includes a more than 4000 people from Wisconsin, Ohio, Michigan, Illinois and Indiana. When they began to participate in this study in 1993, these individuals were either licensed to conduct Charter Fishing operations, were frequent anglers or were infrequent consumers of Great Lakes fish.

Project Start Date: April 2006

Project Status: Completed

Synopsis: This project assessed the mortality rates and causes among an existing, well-defined cohort of frequent and infrequent consumers of Great Lakes sportfish. This research examined both the beneficial effects of a diet that includes freshwater and marine fish, as well as the adverse health effects of chronic exposure to persistent, bioaccumulative atmospheric contaminants of the Great Lakes basin on human health among an aging population. This work evaluated age at death and causes of death among 2,542 frequent and 1,664 infrequent Great Lakes fish consumers. More than 3,000 members of this cohort, which includes Great Lakes charter captains, anglers, and non-anglers who were residing or fishing in the Great Lakes Basin in 1993-1994, are men over the age of 50 years. The results of this study suggesting possible linkages between sport fish consumption and measurable health outcomes.

Project results have been presented during the 2010-11 GLAD webinar series.

Project Contact:
Linda Knobeloch, Ph.D.
Wisconsin Department of Health and Family Services
Phone: (608)266-0923
Email: [email protected]

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Monte Carlo Based Multi-Media Fate Model for the Great Lakes Ecosystem
Principal Investigator: Mario Citra, Ph.D.
Institution: Syracuse Research Corporation, Environmental Science Center
Project start date: April, 2006

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Project Title: Monte Carlo Based Multi-Media Fate Model for the Great Lakes Ecosystem

Chemicals Studied: The model is designed to be used with a wide range of persistent organic compounds. Such compounds include well-known high priority chemicals such as polychlorinated biphenyls PCBs), toxaphene, hexachlorobenzene (HCB), dichlorodiphenyltrichloroethane (DDT), as well as chemicals that have become of increasing concern in recent years, such as the polybrominated diphenyl ethers (PBDEs). Given the Monte Carlo method that is used to handle uncertainty, this model is well suited for application to organic chemicals for which there is incomplete knowledge of chemical properties and environmental concentrations.

Geographic Areas: Lakes Huron, Ontario, Michigan, Erie, and Superiod

Project Start Date: April 2006

Project Status: Completed

Synopsis: This project has produced an online, interactive modeling application for predicting the fate of chemicals within the Great Lakes environment. This easy-to-use application allows users to determine several important factors relating to how chemicals behave once they have been released into the Great Lakes environment. These include:
(i) Where in the environment does the chemical tend to accumulate (such as in water, soils, sediments, air or fish)?
(ii) How long is the chemical retained in the Great Lakes environment before it degrades or is transported to another region?
(iii) What concentration in the environment would be produced by a given level of emission?
(iv) What is the potential for a chemical to travel to the Great Lakes region from far away?

By providing this capability through an online interface that is easy to access and use, the model gives users a powerful tool for answering questions about the behavior of a given chemical in the Great Lakes system. The modeling program may be run with as little input as the chemical’s Chemical Abstract Service (CAS) identification number (of which 33 million are available) although more detailed characteristics may be used as well. The model’s ease of use and availability over the Internet make it a great tool for use in educational settings.

While much information can be generated by the model without specifying chemical quantities, knowing how much of a chemical is emitted into the environment allows the user to obtain even more information, such as predicted concentrations in air, water, soils, sediments and fish. It also allows the user to determine the likelihood that a certain concentration known to be a high-risk level would be exceeded. The users can also enter their own emissions information or the website also includes links to pesticide application data from the CropLife Foundation and air emissions data from the Great Lakes Regional Toxic Air Emissions Inventory, which together provide useful release information on more than 350 toxic substances.

The standard version of the model provides the easiest option , or for less advanced users there is also a version that allows the use of Monte Carlo statistical techniques to assess the uncertainty in the models predictions. This option allows users to enter a range of possible values for important variables, rather than entering a single value. The model then computes the likelihood of possible outcomes given that range of inputs. For example, rather than simply predicting that a given chemical’s concentration in water would be 2 grams per liter, the results might say it is 90% likely that the concentration would be between 0.5 and 5 grams per liter, with a most like value of 2. Examples are given on the model’s website to assist users in choosing a range of values.

The model is configured to represent each of the five Great Lakes basins (Huron, Ontario, Michigan, Erie, and Superior). The user is able to choose which of these five they would like to use as the basis for the model. The program then automatically loads the proper environmental characteristics for that lake basin (such as area and depth of surface water). By modeling with the same inputs but different lake basins selected, comparisons can be made as to how chemicals might behave differently in the different basins. Although the model allows the selection of individual lake basins, the geography within each basin model is not specific enough to allow release points to be defined. Rather, the air and water of each basin are modeled as a single, well-mixed, box.

Potential applications include investigating the behavior of new or unstudied chemicals; comparing emissions and monitoring data; and calculating expected concentrations of chemicals in the environment or the likelihood that such concentrations will exceed known risk values.

Project Contact:
Mario J. Citra, Ph.D.
Syracuse Research Corporation, Environmental Science Center
Phone: (315)452-8406
Email: [email protected]

The Model Website: http://glad.syrres.com/

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Emissions of Brominated Flame Retardants (BFRs) from Industrial and Commercial Sources in the Great Lakes Region
Principal Investigator: Stuart Batterman, Ph.D.
Institution: University of Michigan School of Public Health
Project start date: April, 2006

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Project Title: Emissions of Brominated Flame Retardants (BFRs) from Industrial and Commercial Sources in the Great Lakes Region

Chemicals Studied: Brominated flame retardants

Geographic Areas: Great Lakes Region

Project Start Date: April 2006

Project Status: Completed

Synopsis: This project has determined emission rates for brominated flame retardants from numerous building types. Included in the study are 12 residential buildings, 10 commercial buildings and 10 industrial buildings. The sponsored research group determined building air flow rates and made multiple measurements of brominated flame retardants in air and dust samples within the buildings and the air outside the buildings. This information was used to determine the rate of efflux of these compounds from the building. Numerous building characteristics have been determined and the emission rates were assessed for potential trends with certain building characteristics. The emission rates determined during the project provided a much needed estimate of the overall input of these chemicals to the region’s air from buildings. Inclusion of multiple building types and characteristics has allowed the range of building emission rates to be explored.

Project Contact:
Stuart A. Batterman, P.D.
University of Michigan School of Public Health
Phone: 734-763-2417
Email: [email protected]

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Sources of Atmospheric Mercury Deposited in the Great Lakes: Receptor vs. Source Oriented Modeling
Principal Investigator: Gerald J. Keeler, Ph.D.
Institution: University of Michigan Air Quality Laboratory
Project start date: April, 2006

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Project Title: Sources of Atmospheric Mercury Deposited in the Great Lakes: Receptor vs. Source Oriented Modeling

Synopsis: This project will support numerous modeling activities aimed at determining source regions and source types of mercury depositing within the Great Lakes region. Among the model types to be used are receptor based methods such as positive matrix factorization, back-trajectory calculation, determination of potential source contribution functions and quantitative transport bias analysis. These methods will allow determination of the likely origin of mercury concentrations and mercury deposition measured at several monitoring stations within the region. These analyses will be complemented by source-oriented modeling of mercury transport, reaction and deposition within the region using the Community Multiscale Air Quality model. Use of these complementary modeling methods will provide a robust assessment of the origin of mercury deposition within the region. In addition, this project will support continued monitoring of event-based mercury precipitation levels at six sites and speciated ambient mercury levels at two sites.

Chemicals Studied: The study will focus on mercury, a substance of high concern within the Great Lakes region due to its high toxicity and tendency to accumulate at high levels within fish. Both the monitoring and modeling approaches used will allow differentiation among the various mercury species commonly found in the atmosphere and in the region’s waters.

Geographic Areas: The modeling approaches will be applied to cover a range including the entire Great Lakes region. Both the receptor-oriented and source-oriented modeling activities will be based largely upon data collected at six monitoring stations throughout the state of Michigan, as well as data obtained at partnering sites within the Great Lakes region and northeastern United States.

Project Duration: The project will begin in the Spring of 2006 and extend through the Fall of 2007.

Methods Used: Several receptor modeling and source apportionment approaches will be used. Data that will support these assessments includes that from a previous GLAD project, as well as from other sources. Multivariate statistical techniques, such as positive matrix factorization (PMF) and UNMIX will be used to segregate several principal components of the measured mercury and trace metal concentrations. The results from this analysis will be paired with back-trajectories (as determined by HYSPLIT) to assess regional contributions of these principal source profiles. Quantitative transport bias analysis (QTBA) will also be used to determine geographic gradients in source contributions.

Source-oriented modeling will also be conducted, using a modification of the Community Multiscale Air Quality (CMAQ) model. This work will be used to predict mercury transport, transformation and deposition from know sources. These predictions can then be compared to observations to assess the validity of model outcomes. Alternate scenarios, such as the removal of a certain set of sources, can also be assessed with this methodology.

This project will also support the continued collection of event-based wet deposition samples as six locations throughout Michigan (Grand Rapids, Flint, Detroit, Dexter, Pellston and Eagle Harbor), as well as the high temporal resolution measurement of speciated atmospheric mercury at the Detroit and Dexter sites.

Potential Results and Implications: The results of the various modeling approaches will provide much-needed information regarding the sources of mercury to regional deposition and their relative contributions. In combination, these techniques will provide an important knowledge base for informing policy decisions within the region and beyond regarding the reduction of mercury deposition. Continued support of monitoring activities will further enhance the regional information base for future analysis and modeling activities.

Project Contact:
Gerald J. Keeler, Ph.D.
University of Michigan Air Quality Laboratory
Phone: 734-936-1836
Email: [email protected]

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Accumulation and High Resolution Event-scale Washoff of Mercury Species from Urban Systems
Principal Investigator: Brian Branfireun, Ph.D.
Institution: University of Toronto at Mississauga
Project start date: April, 2006

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Project Title: Accumulation and High Resolution Event-scale Washoff of Mercury Species from Urban Systems

Synopsis: Researchers will examine in detail the dynamics of mercury being washed off of urban surfaces during rain events. Several rain events will be examined in the Toronto metropolitan area. For each event, the rainfall and runoff dynamics over a surface will be studied by high-frequency water sampling, rain gauging and measurement of numerous water quality parameters. Water samples will be assessed for total, reactive and methyl mercury. Mercury in samples will also be assessed for bioavailability. The outcomes of this study will include a much improved understanding of the dynamics leading to mercury washoff during rain events, will be applicable to other urban areas in the region, and may have significant implications for efforts to reduce mercury flows into urban waterways, as well as the Great Lakes.

Chemicals Studied: The study will focus on mercury, a substance of high concern within the Great Lakes region due to its high toxicity and tendency to accumulate at high levels within fish. The analysis approaches used will allow differentiation among the various mercury species commonly found in the atmosphere and in the region’s waters.

Geographic Area: The studies will take place in the Toronto metropolitan area and the results will be broadly applicable to other urban areas throughout the region, as well as elsewhere in the world.

Project Duration: The project will begin in the Spring of 2006 and will complete in the Spring of 2007.

Methods Used: During several rain events, a high-frequency acoustic Doppler flow meter will be used to characterize the flow of precipitation over an urban surface. Simultaneously, a high-frequency water quality meter will be used to determine the chemical characterization of the water and frequent samples will be taken at high frequency for mercury (inorganic and methyl) analysis. In addition, the surface will sampled for mercury content before and after the rain event and frequent rain samples will be analyzed to allow determination of the relative contribution of wet-deposited and dry-deposited mercury in the urban rain runoff. Finally, the samples will be assessed to determine the reactivity and availability of the mercury for uptake by biota and ultimately accumulation in the food chain.

Potential Results and Implications: This study will provide essential information for determining relative origin of mercury in urban rainwater. It will distinguish between previously deposited mercury that is washed off an urban surface and that depositing with the rain event itself. In addition, it will provide a thorough temporal profile of the mercury and related water quality dynamics during an urban rain event. Finally, the project will provide an assessment of the relative reactivity and bioavailability of mercury from such rain events, which is important for assessing its eventual accumulation in the aquatic food chain.

Project Contact:
Brian Branfireun, Ph.D.
University of Toronto at Mississauga
Phone: (905)569-4649
Email: [email protected]

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Development of a Great Lakes Screening Model for Emerging Chemicals
Principal Investigator: Deborah Swackhamer, Ph.D.
Institution: University of Minnesota
Project start date: April, 2006

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Project Title: Development of a Great Lakes Screening Model for Emerging Chemicals

Synopsis: Researchers will develop a multi-media model of chemical fate and exposure within the basin. Among other things, this model will be applicable as a screening tool for chemicals of emerging concern to identify potential high-risk compounds. The region’s air, water, soils, sediments, food chains and other media will be modeled as part of an integrated system. The model will be suitable for modeling organic chemicals with a wide range of parameters.

Chemicals Studied: The model will be broadly applicable to those chemicals that can be modeled with a fugacity-type approach. This includes most organic chemicals, but excludes most metals. While applicable to well-studied chemicals, the screening-level model will be particularly applicable to chemicals of emerging concern, for which there is limited physio-chemical or environmental information available.

Geographic Areas: The geography modeled will be representative of the entire Great Lakes basin, making the model broadly applicable throughout the region

Project Duration: The project will begin in the Spring of 2006 and will conclude in the Summer of 2008.

Methods Used: A multi-compartmental model of the Great Lakes basin (GLMOD) will be created for application in determining the transport, fate and exposure of chemicals within the region. The model will contain numerous compartments for air, water, soils, sediments and biota, each segmented to represent the geography of the Great Lakes region. This multi-media model will be used to inform a multi-media risk assessment model, taking account of common chemical exposure pathways within the basin. The resulting model will be applied to PCBs, a well studied compound to assess its validity and accuracy and then applied to a group of chemicals of emerging concern to make predictions regarding the transport and exposure of these chemicals.

Potential Results and Implications:
The need for a model of this type within the region is significant. In addition to application to well-studied chemicals, the ability to predict exposures of newly recognized chemical risks has been a well recognized need, including by the Great Lakes Regional Collaboration’s Toxic Pollutant Strategy Team. Developing the ability to model chemical exposures will improve the ability to screen chemicals and identify risks earlier and therefore avoid pollution-related health risks.

Project Contact:
Deborah Swackhamer, Ph.D.
University of Minnesota
Phone: (612)624-9282
Email: [email protected]

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Modeling Fine PM, PAHs and Mercury Over the Great Lakes Airshed Using CMAQ
Principal Investigator: Sherri Mason, Ph.D.
Institution: State University of New York at Fredonia
Project start date: April, 2006

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Project Title: Modeling Fine PM, PAHs and Mercury Over the Great Lakes Airshed Using CMAQ

Synopsis: Under this project, researchers will model the atmospheric transport and transformation of several contaminants in the air of the Great Lakes region. In addition to mercury, researchers will focus on transport and deposition of particulate matter and several polycyclic aromatic hydrocarbons (PAHs). Working closely with researchers and regulators at the state level, the university-based project will develop and apply a modeling framework for use in predicting mercury concentrations and deposition rates. These results will be compared to observed levels for purposes of assessing and validating the model.

Chemicals Studied: The study will focus on mercury, PAHs and particulate matter. Mercury is substance of high concern within the Great Lakes region due to its high toxicity and tendency to accumulate at high levels within fish. PAHs are a class of many compounds, emitted primarily from combustion sources, many of which are persistent enough to deposit and bioaccumulate to high levels. In this study, several PAH compounds will be modeled as surrogates for the class as a whole. Particulate matter includes all solids suspended in the atmosphere. As many persistent toxic chemicals are present in particulate matter, conclusions made regarding this contaminant will have implications for many chemicals of concern.

Geographic Areas: The geography covered in the model will focus on the northeastern U.S. and Great Lakes region, with a particular focus on the portion of New York State in proximity to Lake Erie and Lake Ontario.

Project Duration: The project will begin in the Spring of 2006 and will extend through the Fall of 2007.

Methods Used: Atmospheric modeling of pollutant emission, transports and deposition will be done using the U.S. EPA’s Models-3/CMAQ modeling system. Recent updates for mercury, PAHs and hazardous air pollutants will be included, as will recent updates to photochemical reaction rates. The model will use a mixture of emissions and meteorology data from 2001-2003. Emissions will be processed with the SMOKE system and meteorology with MM5. Model results will be validated against observed concentrations from several monitoring stations in the region.

Potential Results and Implications: The results of this modeling study will provide valuable information regarding the transport and deposition of mercury, PAHs and other pollutants within the region. In combination with other GLAD modeling activities, this project will help determine the best approach for future efforts to predict pollutant transport and deposition with atmospheric models.

Project Contact:
Sherri Mason, Ph.D.
State University of New York at Fredonia
Phone: (716)673-3347
Email: [email protected]

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Assessing Methods of Alleviating Impacts from Mercury on Human Health and the Environment in the Great Lakes Basin
Principal Investigator: Kevin Crist, Ph.D.
Institution: Ohio University
Project start date: April, 2006

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Project Title: Assessing Methods of Alleviating Impacts from Mercury on Human Health and Environment in the Great Lakes Basin

Chemicals Studied: Mercury

Geographic Areas: The Great Lakes Region

Synopsis: The purpose of this project was to conduct regional-scale modeling analysis to provide an improved understanding of the fate and transport of mercury within the Great Lakes region. The research team developed a comprehensive budget of elemental mercury (Hg0), reactive gaseous mercury (RGM), particulate mercury (Hgp), and mercury wet deposition across the Great Lake region, including sources, sinks, atmospheric lifetimes, burdens, and advective fluxes. Updated emissions inventories for global and continental emissions were investigated to support the regional-scale modeling. Using the updated global emissions inventory, global modeling was conducted to provide initial and boundary conditions for the regional chemical transport modeling (CTM). The regional chemical transport modeling (MM5-SMOKE-CMAQ) was performed to provide an improved understanding of the fate and potential ecological impacts of mercury in the Great Lakes region. Water-air exchange flux calculations were also performed to simulate and improve understanding of how local, regional, and global emissions of mercury cycle through the atmospheric and aquatic environment in the Great Lakes basin.

To strengthen the initial findings and provide a more sound approach, a more in-depth modeling study was conducted with updated emissions and enhancements to the treatment of mercury chemistry in the chemical transport model. The U.S. EPA MODELS-3 (MM5-SMOKE-CMAQ4.7.1) was utilized to simulate mercury deposition and transport for the year 2005 with 36-km grid domain which included a 148 by 112 grid array over the United States, Southern Canada, and Northern Mexico. Simulations included: a base case and three sensitivity evaluations including: zero-out runs of point sources (PT-IPM), Chinese emissions, and global background concentrations.

In general, the global background concentrations had the highest contribution to the RGM deposition in the Great Lakes (27-97%). However, a significant impact of PM-IPM on wet deposition to Lake Erie, Lake Huron, and southern tip of Lake Michigan was observed. High PM-IPM contributions to the wet and dry RGM deposition were observed during the winter season on the Great Lakes with maximum influence in Lake Erie. A high localized PM-IPM impact on wet and dry RGM deposition to Lake Erie was observed throughout the year, varying from 2 to 58%. RGM deposition to Lake Superior was mostly influenced by global contributions, varying from 75-97%, predominantly in the fall season. Other lakes also observed high global contributions except Lake Erie. Chinese emissions contributed 0.05-9% to RGM deposition in the Great Lakes with maximum effect on wet deposition in winter.

Sensitivity analysis on net loading to the Great Lakes was also conducted. Chinese emissions, PM-IPM emissions, and global background concentrations were used as individual scenarios to assess the percent change in net mercury loadings when the individual source contributions change by seasons. The change in the net loading is most sensitive to the global background with a maximum of 214% increase due to global contributions. The PM-IPM sources showed the least sensitivity with net percent change ranging from 1.8 to 12.4%. Chinese emissions results in a maximum change of 21.4% in Lake Superior and a minimum of 2.3% change in Lake Ontario in spring 2005.

Project Contact:
Kevin Crist, Ph.D.
Ohio University
Phone: (740)593-4751
Email: [email protected]

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Measurement and Modeling of PBT Transport in Lake Superior
Principal Investigator: Judith Perlinger, Ph.D.
Institution: Michigan Technological University
Project start date: April, 2006

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Project Title: Measurement and Modeling of PBT Transport in Lake Superior

Synopsis: This project will continue the development and application of novel methods for the direct determination of pollutant deposition to the Great Lakes. The micrometeorological methods used collect air samples at multiple heights above the lakes over short timeframes and use temperature differences to determine the rate of pollutant movement to or from the lake. Methods will be fully developed for polybrominated diphenyl ethers, polychlorinated biphenyls, and other chlorinated organic compounds. Preliminary results have indicated that such direct measurements of deposition can differ by 1-2 orders of magnitude from deposition rates calculated from on-shore concentration measurements. These measurements will be used to inform creation of one-dimensional models of pollutant deposition to the lakes. These new methods will be applied to better understand the physical-chemical processes involved in deposition and how parameters such as increasing fetch across the lakes affect deposition rates.

Chemicals Studied: The measurement techniques will be applied to polybrominated diphenyl ethers (PBDEs), a class of currently-used flame retardant chemicals that have caused concern recently due to rapidly increasing concentrations in the Great Lakes environment. In addition, polychlorinated biphenyls (PCBs), a class of chemicals banned from production in North America but still present in the Great Lakes at levels above risk thresholds, will be examined, as will other chlorinated organic compounds.

Geographic Areas: The measurements will take place largely aboard a research vessel on Lakes Superior. Some shore-based measurements will be taken as well, also near Lake Superior.

Project Duration: The project will begin in the Spring of 2006 and extend through the Spring of 2008.

Methods Used: Sampling will be done with newly-developed multi-capillary collection devices (MCCDs). The MCCDs consist of fused silica columns and allow for faster sample collection and improve sample analysis. With the low sampling times achieved by the MCCDs, a direct deposition measurement technique can be used in which concentrations are measured at two heights above the lake and sensible heat flux is used as a surrogate to determine the rate of contaminant transfer. Using these methods, the uncertainty in estimates of deposition are decreased by more than an order of magnitude. Preliminary results show differences in calculated depositions compared to conventional methods of up to or more than an order of magnitude.

Potential Results and Implications: The improved accuracy in deposition estimates obtained by these methods have significant ramifications for further scientific or policy development efforts that depend upon estimates of contaminant deposition to the lake. Improved certainty regarding the amount of chemicals entering the lakes from the atmosphere will significantly increase the ability to establish accurate mass balance models for the lakes, to estimate recovery trajectories of the lakes from chemical impairments, and other efforts.

Project Contact:
Judith Perlinger, Ph.D.
Michigan Technological University
Phone: (906)487-3641
Email: [email protected]

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2007

Changes in Mercury Methylation in a Boreal Wetland Previously Enriched in Sulfate: Synergistic Effects of Atmospheric Deposition and Water-level Fluctuations
Principal Investigator: Daniel R. Engstrom, Ph.D.
Institution: Science Museum of Minnesota
Project start date: April, 2007

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Project Title: Changes in Mercury Methylation in a Boreal Wetland Previously Enriched in Sulfate: Synergistic Effects of Atmospheric Deposition and Water-level Fluctuations

Chemicals Studied: Total and Methyl Mercury

Geographic Areas: The Marcell Experimental Forest in Northern Minnesota and Similar Ecosystems

Project Start Date: April 2007

Project Status: Completed

Synopsis: This project builds on a long-term ecosystem-scale experiment in which sulfate deposition to a boreal wetland was increased in order to examine the synergistic effects of atmospheric sulfate and mercury on methylmercury production. This previous work, funded by the EPA STAR and GLAD programs, established a whole-wetland irrigation system for amending sulfate deposition through simulated rainfall. Results from the first four years of the experiment showed a consistent increase in mercury concentration and export from the wetland following sulfate addition, although the response differed markedly depending on the season of application. The focus of the project was on possible chronic effects and recovery (i.e., reduction in mercury methylation) of this sulfur-enriched wetland with the cessation of sulfate addition and to address the effect of water-table fluctuations on mercury methylation and the recovery of wetlands previously impacted by elevated sulfate deposition.

Pore-water mercury and sulfate results for 2007 and 2008 show very clear trends that reflect both recovery of the S6 peatland from chronic sulfate enrichment and the added effect of water-table drawdown and peat oxidation during several years of recurring mid-summer droughts at Marcell Experimental Forest (MEF). Extended periods of pre-addition sampling in spring and fall 2007 provide strong evidence for sulfate regeneration by oxidation of organic-sulfur stores in the peat during periods of water-table drawdown and subsequent release to pore-waters during rebound. The released sulfate stimulates mercury methylation, raising pore-water concentrations in a manner similar to that following experimental sulfate addition. This natural methylation response was observed in control and recovery treatments as well as in the experimental section. Experimental sulfate additions following prolonged water-table fluctuations, especially those in fall, produced only a muted response in MeHg levels, presumably because sulfate was not limiting microbial methylation at these times. The role of hydrologic fluctuations in stimulating sulfate regeneration and mercury methylation was confirmed by water-table manipulations in experimental mesocosms.

Results from the 2007 and 2008 field seasons indicate a relatively rapid re-establishment of baseline sulfate and MeHg concentrations in peat pore-waters following the cessation of experimental sulfate addition. Although seasonal hydrologic fluctuations induced sulfate regeneration and mercury methylation, the intensity of these events lessened dramatically over time. In 2007 MeHg and sulfate concentrations in the recovery section tended to be intermediate between control and experimental concentrations, but by fall of 2008 there were few, if any significant differences between control and recovery concentrations despite a water-table rise that elevated experimental MeHg and sulfate. It thus appears that new sulfate inputs are more available to drive methylation events than pre-existing stores and that sulfur reactivity diminishes over time. These results suggest that reductions in atmospheric sulfate loading should be met with a relatively rapid decline in MeHg production in boreal wetlands.

Project Contact:
Daniel R. Engstrom, Ph.D.
St. Croix Watershed Research Station
16910 152nd St. North
Marine on St. Croix, MN 55047
Phone: (651) 433-5953
Email: [email protected]

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Urban Sources and Loadings of Toxics to Lake Ontario from an Integrated Measurements and Modeling Approach
Principal Investigator: Miriam Diamond, Ph.D.
Institution: University of Toronto
Project start date: April, 2007

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Project Title: Urban Sources and Loadings of Toxics to Lake Ontario from an Integrated Measurements and Modeling Approach

Chemicals Studied: The project is studying polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons(PAHs) and synthetic musk compounds

Geographic Areas: Toronto urban area (Lake Ontario) — the results are informative for other urban areas bordering the Great Lakes, including Chicago, Detroit, Cleveland, Milwaukee, Rochester and others.

Project Start Date: April 2007

Project Status: Completed

Synopsis: This project quantified legacy and emerging chemical loadings from the Greater Toronto Area (GTA) – the major urban centre on Lake Ontario. The type of source categories included: atmospheric deposition, tributary loadings, urban runoff, and municipal wastewater treatment plant effluents. A variety of samples have been collected including: air, precipitation, surface waters, and other environmental components in and around the GTA. These were analyzed for a wide range of toxic chemicals (PCBs, PAHs, PBDEs, and musks). The results of these analyses have been and continue to be used to construct models of the origin and fate of these chemicals within the urban environment and their transfer from a coastal city (e.g., Toronto) to the adjacent lake. Statistical analysis and atmospheric and multi-media modeling approaches have been used to assess the sources and their relative importance in terms of loadings to the lake. The results from this project significantly improve the current understanding of the fate of legacy and emerging chemicals, particularly within a Great Lakes urban environment.

Project Contact:
Miriam Diamond, Ph.D.
University Of Toronto
Department of Earth Sciences
100 St. George Street
Toronto, Ontario M5S 3G3
Phone: (416) 978-1586
Email: [email protected]

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Development of Techniques to Directly Measure Mercury Dry Deposition
Principal Investigator: Thomas Holsen, Ph.D.
Institution: Clarkson University
Project start date: April, 2007

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Project Title: Development of Techniques to Directly Measure Mercury Dry Deposition

Chemicals Studied: Mercury [elemental and reactive, Hg(0) and Hg(II)] in the gaseous and particulate stmospheric dry deposition

Project Start Date: April 2007

Project Status: Completed

Synopsis: As part of this project, several surrogate surfaces designed to directly measure Hg dry deposition were investigated. Static water surrogate surfaces (SWSS) containing deionized or acidified water or salt solutions, and a knife-edge surrogate surface (KSS) using quartz fiber filters (QFF), KCl-coated and gold-coated quartz fiber filters (QFF) were evaluated as a means to directly measure Hg dry deposition. Collocated samples agreed well with each other except for deionized water samples. Of the SWSS solutions tested, acidified BrCl solution was found to measure the largest Hg deposition probably because of its ability to oxidize deposited Hg0. However, gold-coated QFFs collected the greatest amount of mercury, probably because of the fast amalgamation between gaseous mercury (Hg0 and RGM) and the gold surface. The study concludes that dry deposition measurements made with acidified aqueous solutions in the SWSS and gold-coated QFF would likely overestimate the net Hg0 deposition (deposition minus reemission) to most natural water bodies but may be similar to the total Hg0 input.

Project Contact:
Thomas M. Holsen, Ph.D.
Clarkson University
P.O. Box 5710
Potsdam, NY 13699-5710
Phone: (315) 268-3851
Email: [email protected]

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Speciated Atmospheric Mercury: Sources and Transport Across Southern Lake Michigan
Principal Investigator: Gerald J. Keeler, Ph.D.
Institution: University of Michigan Air Quality Laboratory
Project start date: April, 2007

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Project Title: Speciated Atmospheric Mercury: Sources and Transport Across Southern Lake Michigan

Chemicals Studied: Mercury (Hg)

Geographic Areas: Holland, Michigan & Chicago, Illinois

Project Duration: April 2007

Project Status: Completed

Synopsis: As part of this study, to better characterize the impact of Chicago/Gary sources on southwest Michigan, during summer 2007 speciated atmospheric Hg concentrations have been measured at two locations (Chicago, IL and Holland, MI). Due to the different behaviors of reactive and elemental forms of Hg, such measurements are useful for understanding atmospheric Hg chemistry and to help to differentiate between impacts from local and regional source. The addition of event-based precipitation sampling and monitoring of criteria gases and meteorological parameters at these two locations provided a complete framework for examining the impact of Chicago/Gary sources on southwest Michigan. The data collected as part of this study offers valuable insight into the ways in which the Chicago urban area impacts southwestern Michigan, and inferentially southern Lake Michigan.

As a result of this project, it is evident that sources in the Chicago/Gary urban area have a measurable impact on Holland, MI. Back-trajectory cluster analysis demonstrated that during the southwesterly air flow, Hg concentrations in Holland, MI were substantially elevated relative to other transport directions with median Hg0, Hgp, and RGM concentrations enhanced by 6 percent, 9 percent, and >3 times, respectively. It appears that elevated ambient Hg concentrations in Chicago are predominantly the result of direct emission from major local sources, whereas the elevated concentrations in Holland, MI during the south-southwesterly air flow may be the result of a combination of direct emission and photochemical Hg(II) production. Furthermore, detailed exploration of the speciated Hg data and meteorological conditions revealed specific episodes in which ambient Hg was transported from Chicago/Gary point sources to Holland, MI. The impact of this transport could also be observed in recorded Hg wet deposition amounts, with five of the ten highest Hg wet deposition concentrations measured during the southwesterly transport conditions.

Project Contact:
Gerald J. Keeler, Ph.D.
University of Michigan
School of Public Health
3003 S. State Street
Ann Arbor, MI 48109-1274
Phone: (734) 936-1836
Email: [email protected]

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Toxic Air Emissions From Outdoor Wood Fired Boilers
Principal Investigator: Sukh Sidhu, Ph.D.
Institution: University of Dayton Research Institute
Project start date: April, 2007

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Project Title: Toxic Air Emissions From Outdoor Wood Fired Boilers

Chemicals Studied: Particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), poly chlorinated dibenzo dioxins/furans (PCDD/Fs)

Geographic Areas: Great Lakes region

Project Start Date: April 2007

Project Status: Completed

Synopsis: This study was conducted in an attempt to help fill an existing information gap regarding emissions data from outdoor wood-fired boilers (OWB) and to assess the impact of emissions from OWBs on the Great Lakes region. The study entailed both a lab scale analysis using the Cone Calorimeter Test Facility at University of Dayton Research Institute (UDRI) and a simulated field study using the U.S. EPA outdoor wood-fired hydronic-heater (OWHH) test facility at Research Triangle Park, NC. The study provides quantitative emissions data including: particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), poly chlorinated dibenzo dioxins/furans (PCDD/Fs), and other pollutants of concern from combustion of woods commonly used in the Great Lakes region as well as other types of wood/fuel commonly used in OWBs. As a result, the emissions data/emission factors for four types of wood (i.e., red oak, ash wood, sugar maple, and pine) and wood pellets have been generated.

Project Contact:
Sukh Sidhu
University of Dayton
Research Institute
300 College Park
Dayton, Ohio 45469-0104
Phone: (937) 229-3605
Email: [email protected]

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2008

Mechanistic Coupling of Atmosphere-Vegetation-Surface Water Transfers of Mercury along an Urban-Rural Gradient
Principal Investigator: Brian Branfireun, Ph.D.
Institution: University of Toronto
Project start date: May, 2008

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Project Title: Mechanistic Coupling of Atmosphere-Vegetation-Surface Transfers of Mercury Along an Urban-Rural Gradient

Chemicals Studied: Gaseous Elemental Mercury (GEM) Particulate mercury (PM) and Reactive Gaseous Mercury (RGM)

Geographic Areas: Two forested study sites along an urban (Mississauga,Ontario) and rural (Dorset, Ontario) gradient

Project Start Date: May 2008

Project Status: Completed

Synopsis: The focus of this research was on the role of the forest canopy in the accumulation and delivery of mercury (Hg) to the soil Hg pool and more particularly on the role of atmospheric Hg speciation on deposition. An urban-rural gradient was examined from Mississauga to Dorset, Ontario, to determine the role of locally emitted Hg: RGM, and PM on deposition. GEM concentrations were similar at both sites, and PM and RGM concentrations were greater at the urban location. Seasonal accumulation of Hg on foliar surfaces was dominated by GEM measurements to be similar at the urban (8.74 ng cm-2) and rural (9.80 ng cm-2) locations. Increased PM and RGM concentrations at the urban location resulted in a transient upper canopy Hg pool, and throughfall enrichment at the urban site. This is likely a result of the exposure of the upper canopy to turbulent air and therefore higher RGM and PM concentrations.

Project Contact:
Dr. Brian A. Branfireun
Associate Professor
Dept. of Geography at Mississauga
3359 Mississauga Road North, Mississauga Ontario, Canada L5L 1C6
Phone: (905) 569-4649
Email: [email protected]

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Integrating Multimedia Measurements of Mercury in the Great Lakes Basin
Principal Investigator: David Evers, Ph.D.
Institution: BioDiversity Research Institute
Project start date: May, 2008

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Project Title: Integrating Multimedia Measurements of Mercury in the Great Lakes Region (2008)

Enhancement of the Great Lakes Mercury Project: Integrating Multimedia Measurements of Mercury in the Great Lakes Region (2009)

Chemicals Studied: Mercury & methylmercury

Geographic Areas: Great Lakes Basin

Project Start Date: May 2008 & August 2009

Project Status: Completed

Synopsis: These complementary projects resulted in collection and analysis of a wide verity of regional mercury data and development of important informational products answering key scientific questions regarding mercury cycling in the Great Lakes region. Outcomes include (1) analysis of mercury exposure and effects in fish and wildlife, (2) spatial gradients of mercury including the identification of biological mercury hotspots, (3) temporal trends of mercury, and (4) summary of policies concerning mercury in the Great Lakes region.

Project Contact:
David C. Evers
Executive Director/Chief Scientist
BioDiversity Research Institute
Phone: (207) 839-7600
Email: [email protected]

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Mercury Dry Deposition Measurement Intercomparison and Workshop
Principal Investigator: Frank Marsik, Ph.D.
Institution: University of Michigan
Project start date: May, 2008

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Project Title: Mercury Dry Deposition Measurement Intercomparison and Workshop

Chemicals Studied: Mercury

Geographic Areas: N/A

Project Start Date: May 2008

Project Status: Completed

Synopsis: As part of this project, the Mercury Dry Deposition Measurement Intercomparison Workshop was held at the University of Michigan Matthei Botanical Gardens in Ann Arbor, MI, on August 4-13, 2008 and the Mercury Dry Deposition Measurement Workshop was held in the Department of Atmospheric, Oceanic, and Space Sciences on the University of Michigan’s North Campus on August 6-7, 2008. The overall goals of these GLAD funded events were:
(a) evaluation of currently utilized sampling approaches used in the quantification of mercury dry deposition;
(b) quantification of the variability between mercury dry deposition estimates obtained from the approaches used during the intercomparison;
(c) presentation of previous mercury dry deposition measurement results and interpretations by workshop participants using their respective approaches;
(d) identification of mercury dry deposition measurement research needs and opportunities for collaboration between participants, and
(e) an opportunity for interaction between scientists, federal/state/local policymakers, and private industry representatives.

The following observations can be made from the results of this project:
1. Under low ambient mercury concentrations, the mercury dry deposition rates quantified with different measurement approaches were generally in good agreement, with most estimates ranging from 0.0 to 0.5 ng/m2/hr. The upper limit of this range would equate to an annual deposition of approximately 4 ug/m2. These results would suggest that peer-reviewed published estimates of mercury dry deposition derived from these measurement approaches can be viewed as comparable, without significant methodological biases. The approaches for which consistent biases were observed have been highlighted.

2. The variability in the mercury dry deposition estimates obtained were attributed to a number of factors including: (i) differences in the sampler designs pertaining to the forms of mercury believed to be sampled by a given approach, (ii) the efficiency with which a given mercury species is “collected” by a given approach, (iii) differences in the ability for different sample media to “retain” collected mercury (e.g., potential for loss of collected mercury by volatilization under sunny conditions), and (iv) differences in the analytical methods applied to samples (e.g., direct thermal desorption into Tekran, Incorporated Model 2537A, laboratory-based cold vapor atomic fluorescence spectroscopy).

3. In studies where varying meteorological conditions are expected the UMAQL Adjusted-TSS and UNR CEM samplers maybe the most appropriate approaches for unattended sampling over extended periods of time, as these two approaches appear not to be impacted by adverse meteorological conditions (strong winds or rain). When compared directly these two approaches were in good agreement and the differences in the mercury dry deposition rates from the University of Michigan Air Quality Laboratory (UMAQL) Adjusted-TSS and University of Nevada – Reno (UNR) CEM samplers were not found to be statistically significant.

4. Given that the UMAQL TSS and UNR CEM measurement approaches were developed for use during extended and unattended sampling situations, the other sampling approaches compared in this study are more appropriate for use in short-term, process-based and/or source attribution study applications. As an example, a given measurement site can be impacted by different source regions (and thus by different natural and anthropogenic sources) on a day-to-day basis. As a result, if a particular study seeks to obtain a better understanding of the relative impact of different sources or source-types on the mercury deposition to an given site or area, short-term measurements (four to 24- hours) would be required to insure that the deposition at a give site over the sampling period was not impacted by different source regions (such as would be the case if a two-day sampling period experienced flow from the north for one day and from the south for the second day).

Project Contact:
Dr. Frank J. Marsik
University of Michigan Air Quality Lab
Dept. of Atmospheric, Oceanic and Space Sciences
2455 Hayward Avenue, Ann Arbor, Michigan 48109
Phone: (734) 763-5369
Email: [email protected]

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Characterization of PBT Emissions from Burning of Agricultural Plastics and Identification of Alternate Methods for Disposing / Recycling Agriculture Plastics
Principal Investigator: Sukh Sidhu, Ph.D.
Institution: University of Dayton
Project start date: May, 2008

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Project Title: Characterization of PBT Emissions from Burning of Agricultural Plastics and Identification of Alternate Methods for Disposing/Recycling Agriculture Plastics

Chemicals Studied: Polychlorinated diobenzo dioxins and furans (PCDD/Fs), particulate matter(PM), polyaromatic hydrocarbons (PAHs) and other pollutants of emerging concern, such as PBDEs

Geographic Areas: N/A

Project Start Date: May 2008

Project Status: Completed

Synopsis: This study was conducted by the UDRI in collaboration with the U.S. EPA Research Triangle Park, NC. The purpose of the study was to help fill existing information gaps on emissions data from the open burning of agriculture plastics and to develop a viable method to characterize and quantify emissions from open burning to the Great Lakes region. The study entailed both a lab scale study using the Cone Calorimeter Test Facility at UDRI and a simulated field study using the Open Burn Test Facility (OBTF) at EPA-RTP. The study provides quantitative emissions data on PM, PAHs, PCDD/Fs, and other pollutants of concern from combustion of agricultural plastics commonly used in the great lakes region. The emissions data/emission factors for three types of agricultural plastics: polypropylene (nursery pots), polyethylene (silage bags), and high density polyethylene (HDPE Jars) were derived as a result of this study.

The emission factors obtained using the cone calorimeter for the various types of agricultural plastics was compared to the emission factors data provided by the U.S. EPA using the OBT facility. The study shows that the cone calorimeter system can be used to obtain emission factors to compare different samples and to predict emission factors from open burning. The cone tests show that polypropylene nursery pots has the highest emission factors for most of the emissions characterized. Except for PM (where differences were observed due to the sampling methods), the emission factors from OBTF and cone calorimeter are similar in magnitude and within experimental uncertainty.

Project Contact:
Sukh Sidhu, Ph.D.
University of Dayton Research Institute
300 College Park, Dayton, Ohio 45469-0141
Phone: (937) 229-3605
Email: [email protected]

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Time Trend of Mercury in Precipitation
Principal Investigator: Michael Sydor, Ph.D.
Institution: University of Minnesota
Project start date: May, 2008

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Project Title: Time Trend of Mercury in Precipitation

Chemicals Studied: Mercury

Geographic Areas: Great Lakes states/provinces and 7 other states

Project Start Date: May 2008

Project Status: Completed

Synopsis: The purpose of this project was to examine atmospheric wet deposition data from 29 monitoring sites in the US and Canada (23 of which are located in the states/province bordering the Great Lakes) to assess mercury concentration time trends in rain from 1996 to 2007. Considering all sites together, rate-adjusted volume weighted mercury concentrations for rain events showed a statistically significant decline for all time periods evaluated. The average decrease across all time periods is approximately 2.2% per year. When considering only Great Lake sites, the decrease is 2.4% per year. Non-Great Lake sites tended to have a smaller decrease with less statistical significance.

Regional comparisons of time trends were difficult because of the different amounts of data available for each region. However, the westernmost sites exhibited a larger decline (-2.7% per year) in measured mercury concentrations than those in the east (-1.5% per year). All time periods showed a statistically significant decline in the west while only the 2001-2007 period was significant in the east.

Standardized mercury concentrations (events equally weighted) qualitatively showed the same results as volume weighted values. However, large variations in concentrations observed for very low volume events resulted in less statistical significance. Changes in mercury concentrations were -1.2% per year and -1.5% per year for all sites and Great Lake sites, respectively.

Project Contact:
Michael Sydor
University of Minnesota Duluth
10 University Drive, Duluth, Minnesota 55812
Phone: (218) 736-7205
Email: [email protected]

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2009

Mercury Speciation Monitoring to Aid the Investigation of Sources and Transport of Mercury Impacting Lake Michigan and Lake Superior
Principal Investigator: Mark Allen
Institution: Wisconsin Department of Natural Resources
Project start date: August, 2009

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Project Title: Mercury Speciation Monitoring to Aid the Investigation of Sources and Transport of Mercury Impacting Lake Michigan and Lake Superior

Chemicals Studied: Mercury: elemental, oxidized, and particulate-bound

Geographic Areas: Lake Michigan and Lake Superior

Project Start Date: August 2009

Project Status: Completed

Synoposis: As part of this project the states of Michigan, Minnesota, and Wisconsin have modified and upgraded the analytical and the support systems on their Mobile Mercury Monitoring Trailer. The trailer was originally purchased and developed in 1999; the original analyzers measured only elemental mercury. With the upgrade, one analyzer in the trailer laboratory can now measure two additional forms of mercury: gaseous oxidized mercury and particulate bound mercury. The capacity to measure additional forms of mercury improves the ability to identify local source signatures (e.g., coal fueled power plants) or study mercury transport, thus extending the range of projects for which the trailer can be used.

Project results have been presented during the 2012 GLAD webinar series.

Project Contact:
Mark Allen, M.S.
Wisconsin Department of Natural Resources
Phone: (608) 266-8049
Email: [email protected]

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Neurochemical Biomarkers to Assess Health Effects of Toxic Substances to Great Lakes Wildlife
Principal Investigator: Niladri Basu, Ph.D.
Institution: University of Michigan
Project start date: August, 2009

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Project Title: Neurochemical Biomarkers to Assess Health Effects of Toxic Substances to Great Lakes Wildlife

Chemicals Studied: Mercury, PBDEs

Geographic Areas: Great Lakes Region

Project Start Date: August 2009

Project Status: Completed

Synopsis: The specific aims of this project included:
(1) Exposure Assessment: to determine tissue mercury and PBDE levels in river otters and bald eagles from several Great Lakes states, with a focus on animals collected from existing statewide monitoring programs in Michigan and Wisconsin
(2) Health Assessment: to determine river otter and bald eagle health status by means of neurochemical biomarker studies on key receptors (muscarinic, glutamate) and enzymes (monoamine oxidase, cholinesterase) in physiologically important brain regions
(3) Risk Characterization: to determine if there is a statistical association between mercury and PBDE exposure and alterations in neurochemical biomarkers
(4) Education and Capacity Building: to build capacity among academic researchers and government/state managers and to disseminate results to scientific and regulatory communities.

Collection of Bald Eagles: Tissues (i.e., whole brain, liver, muscle, fur/feather) were obtained from 149 individual bald eagles. Because of the quality of tissue, none of the brains were separated into areas of physiological importance, rather they were analyzed in whole. For each eagle, the liver was obtained, and for many the muscle and feather were received. For all the eagles received, mercury (total) has been analyzed on nearly all brains and livers. Methylmercury has been analyzed in nearly all liver and brain samples. In a subset of 46 eagles, 15 different metals/elements were measured in both liver and brain. In a subset of 33 eagles from Michigan, a suite of PBDEs were measured in the liver. Four neurochemical biomarkers were measured in a majority of brain tissues. Tissue quality and certain QA/QC criteria did not permit all results to be of the highest quality (this is an innate hurdle in postmortem biomarker studies involving wild animals).

This study demonstrates that many bald eagles in the Great Lakes region accumulate substantial levels of Hg and provides evidence that Hg is associated with neurochemical changes. Similar changes have been identified in mink (Basu et al. 2007b), otters (Basu et al. 2007a), polar bears (Basu et al. 2009a), loons, and eagles (Scheuhammer et al. 2008), but the relevance of these subclinical changes is unknown. Considering that Hg is known to affect learning, memory, and motor coordination (Evers et al. 2008; Bennett et al. 2009; Spalding et al. 2000; Kenow et al. 2010), which are in part regulated by glutamate and GABA (Scholes 1965, Gibbs et al. 2008), changes in these neurotransmitters may impact ecologically important behaviors in wildlife. Future work should focus on identifying a threshold for Hg’s subclinical effects on the brain and clarifying the relationship between subclinical changes and relevant behavioral changes.

Collection of River Otters: Tissues (e.g., brain, liver, fur, muscle) from 107 otters harvested on a 3-year cycle between the 2009- 2010 were collected by the Wisconsin DNR. Brains (n=107) were dissected into three regions (brain stem, occipital cortex, cerebellum). In a subset of 20 otters, 10 brain regions were also dissected to increase understanding of regional differences in mercury distribution. Total mercury analyses have been performed in nearly all dissected brain regions, as well as muscle, fur and liver samples. In a subset of 35 otters, a suite of PBDEs were measured in the liver. Two key neurochemical biomarkers were measured in each brain region for half the otters. Tissue quality and certain QA/QC criteria did not permit all results to be of the highest quality (this is an innate hurdle in postmortem biomarker studies involving wild animals).

Preliminary project results have been presented during the 2010-11 GLAD webinar series.

PBDE results are to be summarized in: Basu, N., Dornbos, P., Chernyak, S., Batterman, S. 2012. PBDE congener profiles in river otters and bald eagles from two Great Lakes States (Manuscript in Preparation).

Niladri Basu, Ph.D.
Assistant Professor
Dept. of Environmental Health Sciences
University of Michigan
Phone: (734) 764-9490
Email: [email protected]

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Resolving the Cause of the Recent Rise of Fish-Mercury Levels in the Western Great Lakes
Principal Investigator: Daniel Engstrom, Ph.D.
Institution: Science Museum of Minnesota
Project start date: August, 2009

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Project Title: Resolving the Cause of the Recent Rise of Fish Mercury Levels in the Western Great Lakes Region

Chemicals Studied: Mercury

Geographic Areas: Western Great Lakes Region

Project Start Date: August 2009

Project Status: Completed

Synopsis: This study examined recent trends in fish-mercury (Hg) levels for inland lakes of the western Great Lakes region to determine which factor(s) are responsible for an observed upturn in fish-Hg and whether atmospheric Hg inputs to area lakes have risen or not.

An evaluation of fish-Hg records from 115 lakes in northeastern Minnesota confirms previous observations of a decline in standardized-length predator fish mercury concentrations beginning in the early 1980s and a reversal of that trend in the mid-1990s. A statistical evaluation of watershed characteristics and lake-water chemistry does not point to any variables that could explain annual percentage change (APC) in fish-Hg for individual lakes. APC fish-Hg was not correlated with factors known to influence delivery or production of methyl-Hg (MeHg) such as land cover, wetland area, lake-DOC, or -pH. An analysis of sediment-core records of Hg inputs from 39 area lakes showed generally modest changes for the period of record (1980-2010) with decreases in Hg concentration in 41% of lakes and increases in 18%. Hg accumulation rates showed the opposite trend with increases in 41% of lakes and decreases in 15%. A similar pattern was observed when the time period was divided into two intervals (1980-1995 and 1995-2010).

Changes in sediment Hg were significantly correlated with lake geometry ratio (GR), a metric for lake stratification, with shallow polymictic lakes tending to decrease in Hg concentration and increase in Hg accumulation over time; deeper dimictic lakes showed the opposite pattern. The antipathetic relationship between Hg concentration and accumulation appeared to be driven by an increasing flux of organic matter to the sediments, possibly driven by greater watershed export of dissolved organic carbon (DOC) or increasing lake productivity.

While watershed land-cover was only weakly correlated with APC in sediment Hg, other factors suggest that the increases in sediment Hg accumulation were driven by greater export of Hg from catchment soils and not changes in atmospheric Hg deposition. Although atmospheric Hg deposition may have declined over this time period, it was not evident against a backdrop of rising Hg inputs from the large pool of Hg stored in terrestrial soils. The absence of strong predictors of APC fish-Hg, including detailed sediment-core Hg records, likely stems from the infrequency of fish-Hg measurements which limits the reliability of trend data for any individual lake.

Project Contact:
Dr. Daniel R. Engstrom
Director
Science Museum of Minnesota
St. Croix Watershed Research Station
Phone: (651) 433-5953
Email: [email protected]

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Enhancement of the Great Lakes Mercury Project: Integrating Multimedia Measurements of Mercury in the Great Lakes Region
Principal Investigator: David Evers, Ph.D.
Institution: BioDiversity Research Institute
Project start date: August, 2009

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Project Title: Integrating Multimedia Measurements of Mercury in the Great Lakes Region (2008)

Enhancement of the Great Lakes Mercury Project: Integrating Multimedia Measurements of Mercury in the Great Lakes Region (2009)

Chemicals Studied: Mercury & methylmercury

Geographic Areas: Great Lakes Basin

Project Start Date: May 2008 & August 2009

Project Status: Completed

Synopsis: These complementary projects resulted in collection and analysis of a wide verity of regional mercury data and development of important informational products answering key scientific questions regarding mercury cycling in the Great Lakes region. Outcomes include (1) analysis of mercury exposure and effects in fish and wildlife, (2) spatial gradients of mercury including the identification of biological mercury hotspots, (3) temporal trends of mercury, and (4) summary of policies concerning mercury in the Great Lakes region.

Project Contact:
David C. Evers
Executive Director/Chief Scientist
BioDiversity Research Institute
Phone: (207) 839-7600
Email: [email protected]

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Effects of Climate Change on Mercury Cycling and Bioaccumulation in the Great Lakes Region
Principal Investigator: Reed Harris
Institution: Reed Harris Environmental Ltd.
Project start date: August, 2009

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Project Title: Effects of Climate Change on Mercury Cycling and Bioaccumulation in the Great Lakes Region

Chemicals Studied: Methylmercury (MeHg)

Geographic Areas: Great Lakes Basin

Project Start Date: August 2009

Project Status: Completed

Synopsis:The current understanding of links between climate change and mercury (Hg) is inadequate for policy makers to have a sound scientific basis for decisions regarding Hg management. A study has therefore been carried out to provide a preliminary analysis of the potential for climate change to influence Hg cycling and bioaccumulation in aquatic systems in the Great Lakes region. A combination of mechanistic modeling and experimental work in the laboratory was used. Climate-related factors that were studied for potential influences on Hg included temperature, hydrology, Hg export from terrestrial systems, in-lake water quality, trophic factors and atmospheric Hg deposition.

Using literature estimates of potential changes to these factors in the 21st century, mechanistic modeling predicted significant changes to Hg cycling. Warmer temperatures predicted to occur in the Great Lakes region produced significantly higher fish Hg concentrations in simulations, through a combination of effects on methylation and fish bioenergetics. Temperature effects need to more fully consider issues associated with short term versus long term sustainability of increased decomposition. Experimental studies carried out as part of this study also suggest that methylation may not increase as much with temperature as commonly assumed. Reduced watershed flow that is predicted to occur widely in the Great Lakes region, and faster fish growth associated with warmer temperatures are predicted to tend towards lower fish Hg concentrations using a size standard. Climate-related changes to DOC have the potential to significantly alter Hg cycling and bioaccumulation, but the magnitude and direction changes to DOC are not clear and may vary among ecosystems. Potential changes to the duration of ice cover, thermal stratification, and the depth of the thermocline in lakes that stratify were less significant in simulations. These factors require additional study, and should be considered jointly in combination with oxygen depletion that may arise due to changes in stratification patterns. Additional climate-related factors affecting Hg in ecosystems need to be addressed, including system productivity, sedimentation, pH, sulfate, food web changes and extreme events. These additional factors need to be considered to adequately estimate the overall effects of climate change on fish Hg concentrations. The magnitude of change predicted for some factors (e.g. up to 50% increases due to warmer temperatures) is comparable to benefits that may emerge from Hg emission controls in North America. As a result, programs designed to monitor the benefits of Hg emissions controls in the Great Lakes region should also be designed to consider climate change effects.

Project Contact:
Reed Harris, P.E.
Reed Harris Environmental Ltd.
Phone: (905) 339-0763
Email: [email protected]

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2010

Multiple Toxic Chemical Exposures at the Aamjiwnaang First Nations Reserve
Principal Investigator: Niladri Basu, Ph.D.
Institution: University of Michigan
Project start date: August, 2010

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Project Title: Multiple Toxic Chemical Exposures at the Aamjiwnaang First Nations Reserve

Chemicals Studied: Metals, PFCs, PAHs

Geographic Areas: Lake Huron and Lake Erie corridor

Project Start Date: August 2010

Project Status: Completed

Synopsis: As part of this project a number of environmental pollutants were measured in biomarker samples from 43 mother-child pairs living in the Aamjiwnaang region. Pollutants measured included various metals, polycyclic aromatic hydrocarbons (PAH), perfluorinated chemicals (PFC), brominated flame retardants (BFR), polychlorinated biphenyls (PCB), and organochlorine pesticides (OCP). Potential sources of these chemicals are industries, the general environment, and home. Despite some limitations of our study, the findings show that mothers and children in the Aamjiwnaang region are exposed to a number of environmental pollutants. Some exposures trended higher than the average Canadian; notable chemicals include cadmium, possibly mercury, some perfluorinated chemicals (PFCs), some polychlorinated biphenyls (PCBs), hexachlorohexane (HCH) , and DDT.

Recommendations:
(i) There is a need for a rigorous epidemiological study to comprehensively assess and characterize pollutant exposures and potential human health effects in relation to the various sources in the Aamjiwnaang region (including broader Lambton County). Such a study should build upon this project and be focused on both occupational and environmental exposures. In particular, it should consider children’s exposure and health.
(ii) There is a need for an enhanced and expanded ecological research study to monitor environmental quality on spatial and temporal scales. Such a study should include several monitoring sites (more than currently being tracked by various organizations), each site should be monitored regularly (several times per year) and over many years, and monitoring sites should include both ecological sites as well as human communities. Such a study would better help resolve pertinent source-fate-exposure pathways.
(iii) There is a need to support an independent oversight panel that may provide objective and expert guidance concerning environmental public health risks in the Aamjiwnaang region in relation to pollutant exposures.

Project Contact:
Niladri Basu, Ph.D.
Assistant Professor
Dept. of Environmental Health Sciences
University of Michigan
Phone: (734) 764-9490
Email: [email protected]

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How Effective are our Chemical Management Policies in Reducing Lake Ontario Fish Contaminant Burdens?
Principal Investigator: Miriam Diamond, Ph.D.
Institution: University of Toronto
Project start date: August, 2010

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Project Title: How Effective are Our Chemical Management Policies in Reducing Lake Ontario Fish Contaminant Burdens?

Chemicals Studied: PCBs and PBDEs

Geographic Areas: Lake Ontario

Project Start Date: August 2010

Project Status: Completed

Synopsis: This project explored the effect of regulatory actions aimed at controlling releases of Persistent Organic Pollutants (POPs) in relation to Lake Ontario fish concentrations. This was accomplished by measuring concentrations of PCBs, PBDEs and “novel” flame retardants (NFRs) in outdoor air in Toronto. Data were gathered on fish concentrations in Lake Ontario. Finally, a modeling framework was assembled that aimed to connect the inventory of PCBs and PBDEs with concentrations in outdoor air, nearshore Lake Ontario water, sediment and fish.

The half-lives of PCBs in air, sediment and fish from the Great Lakes now range from 10 to 20 years. The half-lives were quicker just after the first round of PCB regulations were passed in the 1970s. As discussed by Salamova et al. (2013), the rates of decrease in air and fish are roughly tracking each other. Unfortunately, the lack of disclosure of information on the magnitude of PCB stock does not allow to disentangle the factors attributing to this decrease – whether the decrease is controlled by primary emissions or the slow rate of decrease of the mass of PCBs cycling in the Great Lakes environment.

The inventories of penta- and octaBDE have been estimated to be decreasing since 2004 with a half-life of 4 years (Abbasi et al. in prep.). In comparison, Salamova and Hites (2011) found that PBDE air concentrations at all US IADN sites were decreasing with half-lives of ~10 years, 6.6 and ~5 years for gas and particle phases and precipitation, respectively, including BDE-209. BDE-209 concentrations were stable over time but the half-lives of BDE-47 in gas and particle phases and precipitation were 6.3, 7 and ~5 years, respectively. These half-lives are slower than the ~1-3 y half-lives for BDE-47 and -99 and 4 years for sum of PBDEs in gas plus particle phases reported by Venier and Hites (2008). Salamova and Hites (2011) attributed the faster half-lives from air measurements taken in 2005-2006 (as reported by Venier and Hites 2008) to reflect the immediate effect of the cessation of PBDE production in the US. In comparison, Abbasi et al. (in prep) have estimated that the half-life of decaBDE in products has an estimated half-life of 23 years from 2008 to 2013, after which it is assumed to accelerate to 7-11 years. PBDE concentrations in large predatory fish are decreasing with a half-life of ~5 to 13 years in Lake Ontario. As with PCBs, the rate of decrease of PBDEs in air, sediment and fish appear to be tracking each other. However, as the concentrations of PBDEs decrease, the concentrations of NFRs are increasing.

Project Contact:
Miriam Diamond, Ph.D.
University Of Toronto
Department of Earth Sciences
100 St. George Street
Toronto, Ontario M5S 3G3
Phone: (416) 978-1586
Email: [email protected]

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Measurement and Modeling of the Contribution of Atmospheric Particulate Deposition to the Fluorinated Surfactants Burden in Great Lakes Sediments
Principal Investigator: David Ellis, Ph.D.
Institution: Trent University
Project start date: August, 2010

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Project Title: Measurement and Modeling of the Contribution of Atmospheric Particulate Deposition to the Fluorinated Surfactants Burden in Great Lakes Sediments.

Chemicals Studied: Perfluorinated carboxylic acids (C7 – C14)

Geographic Areas: Lake Ontario

Project Start Date: August 2009

Project Status: Completed

Synopsis: The anthropogenically-derived and potentially toxic class of chemicals, known as perfluorinated carboxylic acids, is ubiquitous in the Great Lake’s environment and has been shown to bioaccumulate. As such, these chemicals have been classified as emerging priority chemicals for study by U.S. and Canadian government agencies. They have been observed at higher than expected concentrations in the sediments of the Great Lakes with the cause of these elevated concentrations being yet unknown. Atmospheric particulate matter, through the sedimentation processes, contributes significantly to the composition of bottom sediments. Atmospheric particulate matter over the Great Lakes has been shown to contain considerable levels of perfluorinated carboxylic acid (PFOA). This project aimed to establish the contribution due to the atmospheric deposition of particulate matter to the overall burden of PFOA (C7 – C14) within lake sediments. This research has been conducted through field measurements, laboratory experimentation, and environmental modeling.

Recently reported quantification of the atmospheric sampling artifact for PFOA was applied to existing gas and particle concentration measurements. Specifically, gas phase concentrations were increased by a factor of 3.5 and particle-bound concentrations by a factor of 0.1. The correlation constants in two particle-gas partition coefficient estimation equations were determined for multiple studies with and without correcting for the sampling artifact. Correction for the sampling artifact gave correlation constants with improved agreement to those reported for other neutral organic contaminants, thus supporting the application of the suggested correction factors for perfluorinated carboxylic acids (PFCAs). Applying the corrected correlation constant to a recent modeling study improved model agreement with corrected and reported atmospheric concentrations over the Great Lakes.

A large volume particulate sampling campaign was conducted during the summer of 2011 in Toronto in close proximity to Lake Ontario. Samples that were collected were extracted and analyzed for their PFCA concentrations as a function of time and carbon chain length. Results indicated that, for particulate bound long chain PFCAs (C6 and greater), concentrations are all within an order of magnitude of one another and that their concentrations did not differ significantly over the time frame investigated. Particulate concentrations may indicate a decline in atmospheric contamination due to the C8 PFCA, PFOA with an increase in the C4 PFCA since 2007. This observation would be consistent with changes in industrial practices over that period. Laboratory studies employing the collected particulate showed that, when the particulate enters a body of water, all PFCAs, except C5 and PFOA, that were atmospherically sorbed are effectively stripped from particles in the first few meters of water. Experimental results are consistent with two potential mechanisms for particulate binding. They are consistent with a previously unrecognized binding to soot carbon that could be described as irreversible with regard to transfer to water from the particle. Results indicate that C5 and PFOA tightly bind with a constant concentration to a fraction of air particulate.

A generic model was developed for the process of chemical transfer to lake sediments through the deposition of atmospheric particulate. The model considers the processes of lake sedimentation as a result of both organic particulate in the water column and atmospheric particulate. It considers a chemical bonding to a soot particle in which the species is lost from the particle following a first order process. Through the use of this model it was shown that the deposition of atmospheric particulate and subsequent sedimentation processes explain the elevated PFOA concentrations observed in the sediments in the Lake Ontario. This project clearly illustrates that there is a need to fully understand the nature of binding of organic contaminants to soot carbon in the atmosphere as this plays a crucial role in sediment contamination.

Project Contact:
David A. Ellis, Ph.D.
Trent University
Chemistry Department
1600 West Bank Drive
Peterborough, ON K9J 7B8
Phone:(705) 748 1011 ext. 7898
Email: [email protected]

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Ambient Mercury Speciation Measurements for Tracking the Progress of Emission Reduction Strategies in the Lake Ontario Basin
Principal Investigator: Dirk Felton, P.E.
Institution: New York State Department of Conservation
Project start date: August, 2010

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Project Title: Ambient Mercury Speciation Measurements for Tracking the Progress of Emission Reduction Strategies in the Lake Ontario Basin

Chemicals Studied: Mercury (elemental, reactive gaseous, and particle-bound)

Geographic Areas: Lake Ontario Basin

Project Start Date: August 2010

Project Status: Completed

Synopsis: The main objective of this project was to continue operation and maintenance of a mercury wet-deposition sampler and speciated Tekran system at a site on the shores of Lake Ontario, downwind of coal-fired facilities in the Ohio River Valley, western New York, and Ontario. This was done to track the progress of in- and out-of-state emissions reductions; monitoring data of ambient speciated (elemental, reactive gaseous, and particle-bound) mercury concentrations and wet-deposition in Rochester, New York will be used together with earlier measurements initiated in 2008 to establish a baseline against which to track progress of current and planned emission reduction strategies in support of future planning efforts

Project Contact:
Dirk Felton, P.E.
New York State Department of Environmental Conservation
Division of Air Resources, Bureau of Air Quality Surveillance
Phone: (518) 402-8508
Email: [email protected]

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Mercury Wet-Deposition Monitoring in Indiana
Principal Investigator: Donna Kenski, Ph.D.
Institution: Lake Michigan Air Directors Consortium
Project start date: August, 2010

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Project Title: Mercury Wet-Deposition Monitoring in Indiana

Chemicals Studied: Mercury

Geographic Areas: Indiana

Project Start Date: August 2010

Project Status: Completed

Synopsis: This project continued operation of two out of five Mercury Deposition Network monitoring sites in Indiana, Indiana Dunes (IN34) and Clifty Falls (IN21), for measuring atmospheric mercury wet deposition. These sites provide valuable data for understanding the spatial pattern and temporal trend of mercury deposition in the Great Lakes region. The data can be obtained from the National Atmospheric Deposition Program (NADP) website.

As part of this project, a regional mercury monitoring network assessment was also conducted by LADCO and USGS. Data from mercury wet-deposition monitoring sites (from 1996 to 2010) operated in the Great Lakes region were evaluated with spatial and statistical techniques with the intent of determining an optimized design for long-term monitoring. This evaluation rated geographic representativeness of selected sites based on 21 factors that included characteristics of the locations of the monitoring sites and available mercury data. Site ratings were based on area, population, mercury emissions, co-located monitoring, and locations in protected natural areas, urban areas, and Great Lakes watersheds. Weekly mercury concentrations in precipitation and wet deposition were used to determine long-term averages and significant temporal trends. Site ratings were based on the magnitude of these mercury averages and trends. Gaps were identified in the regional distribution of mercury monitoring sites with respect to mapped areas of high density annual mercury emissions and high average weekly mercury-wet deposition. It was determined that a minimum of 20 sites in a representative and relatively uniform geographic distribution have the potential to detect anticipated changes in mercury-wet deposition resulting from reductions in mercury emissions.

Project Contact:
Donna Kenski, Ph.D.
Data Analyst
Lake Michigan Air Directors Consortium (LADCO)
Phone: 847-720-7883
Email: [email protected]

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Using Passive Samplers to Detect Legacy and Emerging Organic PBTs in Lake Superior and their Air-Water Exchange
Principal Investigator: Rainer Lohmann, Ph.D.
Institution: University of Rhode Island
Project start date: August, 2010

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Project Title: Using passive samplers to detect legacy and emerging organic PBTs in Lake Superior, and their air-water exchange

Chemicals Studied: PAHs, PCBs, organochlorine pesticides, PBDEs, new chemicals of concern.

Geographic Areas: Lake Superior

Project Start Date: August 2010

Project Status: Completed

Synopsis: The purpose of this project was to enhance the 2011 Coordinated Science and Monitoring Initiative intensive field program in the Lake Superior watershed by deploying passive polyethylene samplers in the atmosphere and surface water along nine coastal stations and mid-lake to: (i) uniquely enhance measurements of the spatial variability of atmospheric concentrations of persistent bioaccumulative toxics around the lake; (ii) assess whether Lake Superior is volatilizing or absorbing gas-phase PBTs to derive fluxes and loading to the lake; and (iii) screen for halogenated emerging contaminants of concern across the lake. A total of 60 individual passive polyethylene samplers were deployed in surface water and surface air at 16 sites around Lake Superior (6 coastal US, 3 open water/air and 7 coastal Canadian sites) and analyzed for the: 22 polycyclic aromatic hydrocarbons, 25 legacy organochlorine pesticides, 18 polychlorinated biphenyl congeners, 12 polybrominated diphenylethers and screened for emerging persistent, bioaccumulative and toxic compounds.

PAHs: In general, net deposition was observed for Welcome Isle, Sault St Marie, Pt Aux Pins, Ontonagon and Duluth, while evaporation was more prevalent for the open lake sites, Sturgeon Bay, Marquette and Michipicoten Bay. For pyrene, net deposition was observed for most coastal sites, with net evaporation for the open lake sites. For phenanthrene, net deposition was observed for all southern coastal sites, with only few sites displaying net evaporation (Sturgeon Bay, open Lake site 113 and eastern lake site 23).

Organochlorine pesticides (OCPs): Most OCPs displayed net evaporation, particularly a-HCH, HCB, heptachlor-epoxide, trans-chlordane and p,p’-DDE. Cis-chlordane displayed mostly net deposition, same for o,p’-DDT/p,p’-DDD. Endosulfan was the only pesticide for which net deposition was observed, either because it was present only in the atmosphere and below detection limit in the water (n=20), or because the gradient was strongly favoring net deposition

PCBs: The majority of PCBs appear to be evaporating or in equilibrium in Lake Superior, with a few notable exceptions. CB206 has a high air-water ratio, indicating deposition, however, CB206 is also present at some of the lowest concentrations in both air and water samples. Ontonagon and Marquette appear to have the highest deposition gradients, especially for CB18, 28, 44, 52, 105, and 118.

PBDEs: Air-water exchange gradients of the freely dissolved BDE congeners were generally favoring net deposition and increased with increasing molecular weight of the BDEs. For BDE 47 and higher, even smallest gradients were still favoring net deposition.

Emerging PBTs: This study was not able to confirm the presence of the following in any of the samples: bromopentafluorobenzene; 3,5-dichlorotrifluoropyridine; 3,4-dichlorobenzotrifluoride; pentachloropyridine; 2,4,6-tritertbutylphenol; 1,1-bis-dimethylphenylethane; dibutyl chlorendate; antidechlorane plus.

Publications supported by this award:
1. Lohmann, R. A critical review of low-density polyethylene’s partitioning and diffusion coefficients for trace organic contaminants and implications for its use as a passive sampler, Environmental Science & Technology 2012, 46, 606-618.

2. Khairy and Lohmann, Sources and Seasonal Trends of Vapor Phase PAHs in a Major Developing Urban City Using Passive Polyethylene Air Samplers, Environmental Science & Technology 2012, 46, 3990-3998.

3. Khairy, M.A. and Lohmann, R. Field Calibration of Polyethylene Passive Air Samplers for Organochlorine Pesticides, Environmental Science & Technology, submitted August 2012.

Project Contact:
Rainer Lohmann, Ph.D.
Associate Professor
Graduate School of Oceanography, University of Rhode Island
Phone: (401) 874-6612
Email: [email protected]

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Impacts of Forest Biomass Harvesting on the Mobility and Bioaccumulation of Mercury in the Western Great Lakes Region
Principal Investigator: Carl Mitchell, Ph.D.
Institution: University of Toronto – Scarborough
Project start date: August, 2010

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Project Title: Impacts of Forest Biomass Harvesting on the Mobility and Bioaccumulation of Mercury in the Western Great Lakes Region

Chemicals Studied: Mercury

Geographic Areas: Western Great Lakes Region

Project Start Date: August 2010

Project Status: Completed

Synopsis: This project set out to take a realistically scaled, field-based manipulative approach to directly address how intensification of biomass harvesting for “advanced biofuel” (specifically cellulosic-based ethanol) production will affect the mobility of mercury between forest and susceptible low-lying wetland systems or whether these practices will augment the bioaccumulation of mercury by susceptible organisms. Three established <1 hectare upland forest-peatland field plots at the Marcell Experimental Forest in northern Minnesota have been intensively hydrologically instrumented. As part of this project, one of the plots has been clearcut without biomass removal, one has been clearcut with intensive biomass removal, and the third has been unaltered for control comparison. Prior to and following forest harvesting, an enriched stable isotope of mercury was added to the plots so that the movement of contemporary mercury deposition could be traced throughout all ecological compartments in relation to the experimental treatments. Changes in mercury mobility, mercury methylation, and bioaccumulation have been examined by hydrological sampling, stable isotope incubations of soils, and sampling of peatland invertebrates.

Forest harvesting has a significant impact on mercury mobility between upland forests in the western Great Lakes region and adjacent low-lying wetlands. Specifically, significantly elevated fluxes of mercury in runoff have been observed when either clearcutting or clearcutting with additional removal of biomass was conducted. The increased flux is not related to an increased mobilization of mercury from soil storage, but rather due to overall increased runoff, which results from these practices.

Contrary to the proposed hypotheses, biomass harvesting did not worsen the increased mercury flux compared to regular clearcutting practices. In fact, impacts from clearcutting + biomass harvesting were always less than from clearcutting alone. Although runoff fluxes of mercury were increased as a result of forest harvesting, this did not translate into augmented methylmercury production in an adjacent wetland, nor did it have any effect on the bioaccumulation of mercury in the predominant peatland macroinvertebrate taxa. From a management perspective, even given this relatively short-term post-impact data, it is safe to conclude that increased forest harvesting intensity related to biomass harvesting, at least in the means by which it was conducted for this study, will have no further deleterious effects on mercury mobility, methylation, or bioaccumulation than do existing clearcutting practices. From a mercury pollution perspective at this time, no amendments are being recommended to existing best management practices for forestry that are required to specifically address the issue of harvesting forest biomass for fuel production.

Project Contact:
Dr. Carl Mitchell, Ph.D.
Assistant Professor
Dept. Physical and Environmental Sciences
University of Toronto – Scarborough
Phone: (416) 208-2744
Email: [email protected]

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