Modeling transport and deposition of contaminants to ecosystems of concern: a case study for the Laurentian Great Lakes

Transfer efficiency (TE) is introduced as a model output that can be used to characterize the relative ability of chemicals to be transported in the environment and deposited to specific target ecosystems. We illustrate this concept by applying the Berkeley-Trent North American contaminant fate model (BETR North America) to identify organic chemicals with properties that result in efficient atmospheric transport and deposition to the Laurentian Great Lakes. By systematically applying the model to hypothetical organic chemicals that span a wide range of environmental partitioning properties, we identify combinations of properties that favor efficient transport and deposition to the Lakes. Five classes of chemicals are identified based on dominant transport and deposition pathways, and specific examples of chemicals in each class are identified and discussed. The role of vegetation in scavenging chemicals from the atmosphere is assessed, and found to have a negligible influence on transfer efficiency to the Great Lakes. Results indicate chemicals with octanol-water (K(ow)) and air-water (K(aw)) partition coefficients in the range of 10(5)-10(7) and 10(-4)-10(-1) combine efficient transport and deposition to the Great Lakes with potential for biaccumulation in the aquatic food web once they are deposited. A method of estimating the time scale for atmospheric transport and deposition process is suggested, and the effects of degrading reactions in the atmosphere and meteorological conditions on transport efficiency of different classes of chemicals are discussed. In total, this approach provides a method of identifying chemicals that are subject to long-range transport and deposition to specific target ecosystems as a result of their partitioning and persistence characteristics. Supported by an appropriate contaminant fate model, the approach can be applied to any target ecosystem of concern.     

BETR North America: a regionally segmented multimedia contaminant fate model for North America

We present the Berkeley-Trent North American contaminant fate model (BETR North America), a regionally segmented multimedia contaminant fate model based on the fugacity concept. The model is built on a framework that links contaminant fate models of individual regions, and is generally applicable to large, spatially heterogeneous areas. The North American environment is modeled as 24 ecological regions, within each region contaminant fate is described using a 7 compartment multimedia fugacity model including a vertically segmented atmosphere, freshwater, freshwater sediment, soil, coastal water and vegetation compartments. Inter-regional transport of contaminants in the atmosphere, freshwater and coastal water is described using a database of hydrological and meteorological data compiled with Geographical Information Systems (GIS) techniques. Steady-state and dynamic solutions to the 168 mass balance equations that make up the linked model for North America are discussed, and an illustrative case study of toxaphene transport from the southern United States to the Great Lakes Basin is presented. Regionally segmented models such as BETR North America can provide a critical link between evaluative models of long-range transport potential and contaminant concentrations observed in remote regions. The continent-scale mass balance calculated by the model provides a sound basis for evaluating long-range transport potential of organic pollutants, and formulation of continent-scale management and regulatory strategies for chemicals.     

Assessment of environmental endocrine disruptors in bald eagles of the Great Lakes

Environmental endocrine disruption in wildlife has primarily focused on estrogenic/androgenic end points and their antagonists. We describe here the work that has occurred within the Great Lakes of North America that has used the bald eagle (Haliaeetus leucocephalus) as a sentinel species of the effects of environmental toxicants, including endocrine disruption. Our data suggests that population level effects of hormone disrupting chemicals, not necessarily estrogen/androgen mimics and their antagonists, have been associated with reproductive and teratogenic effects observed in the bald eagle population within the Great Lakes Basin. Additional laboratory and field studies are necessary to further clarify the role of environmental endocrine disruptors on reproduction in avian populations. The use of sea eagles (Haliaeetus spp.) as biosentinels of pollution in other regions of the world is also discussed.     

Assessment of decadal changes in sediment contamination in a large connecting channel (Detroit River,North America)

Concentrations of selected heavy metals (Cd, Cu, Hg, Pb, Zn) and organic contaminants (PCBs, PAHs) were investigated in samples from the Detroit River (Great Lakes, North America) in 1999 and 2008/09 collected using a stratified random sampling design. Getis–Ord geospatial analysis was used to further establish locations of areas demonstrating significantly high and low contaminant concentrations in the river. Based on the stratified random sampling design, a majority of the examined metals and organic contaminants demonstrated little or no trends with respect to regional sediment concentrations and river-wide mass balances over the investigated time interval. The Getis–Ord analysis revealed local scales of contaminated and clean areas which did not conform to the original strata used in the geostatistical sampling design. It is suggested that geospatial analyses such as Getis–Ord be used in the design of future sediment quality surveys to refine locations of strata that can simultaneously address sediment recovery over system-wide, regional and local spatial scales.     

Trends of brominated diphenyl ethers in fresh and archived Great Lakes fish (1979-2005)

While few environmental measurements of brominated diphenyl ethers (BDEs) were completed prior to the mid-1990s, analysis of appropriately archived samples might enable the determination of contaminant trends back to the introduction of these chemicals. In this paper, we first investigate the stability of BDEs in archived frozen and extracted fish samples, and then characterize trends of these chemicals in rainbow smelt (Osmerus mordax) and lake trout (Salvelinus namaycush) in each of the Great Lakes between 1979 and 2005. We focus on the four most common congeners (BDE-47, 100, 99 and 153) and use a change-point analysis to detect shifts in trends. Analyses of archived fish samples yielded precise BDE concentration measurements with only small losses (0.8% per year in frozen fish tissues, 2.2% per year in refrigerated extracts). Trends in fish from all Great Lakes showed large increases in BDE concentrations that started in the early to mid-1980s with fairly consistent doubling times (generally 2-4 years except in Lake Erie smelt where levels increased very slowly), though concentrations and trends show differences by congener, fish species and lake. The most recent data show that accumulation rates are slowing, and concentrations of penta- and hexa-congeners in trout from Lakes Ontario and Michigan and smelt from Lake Ontario started to decrease in the mid-1990s. Trends in smelt and trout are evolving somewhat differently, and trout concentrations in the five lakes are now ranked as Michigan>Superior=Ontario>Huron=Erie, and smelt concentrations as Michigan>Ontario>Huron>Superior>Erie. The analysis of properly archived samples permits the reconstruction of historical trends, congener distributions, biomagnification and other information that can aid the understanding and management of these contaminants.     

Embryonic abnormalities and organochlorine contamination in double-crested cormorants (Phalacrocorax auritus) and Caspian terns (Hydroprogne caspia) from the upper Great Lakes in 1988

Persistent organochlorine contaminants including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were determined in eggs with normal and deformed embryos collected in 1988 from different colonies during an epizootiological survey of double-crested cormorants (Phalacrocorax auritus) and Caspian terns (Hydroprogne caspia) from the upper Great Lakes. PCBs and p,p'-DDE were found in the highest concentrations in eggs of both species. The residue pattern of PCB isomers and chlordane compounds suggested that double-crested cormorants have greater metabolic capacity to degrade contaminants than Caspian terns. According to the toxicity evaluation using the 2,3,7,8-TCDD equivalents (TEQs) approach, non-ortho coplanar PCBs contributed much more toxicity than PCDDs and PCDFs. Total TEQ of dioxin-like compounds was likely associated with occurrence of live-deformed embryos in double-crested cormorants eggs. The toxic effects of these contaminants were also estimated in Caspian tern eggs, where elevated levels of coplanar PCBs, PCDDs and PCDFs were observed in concordance with increased rate of anomalies in eggs during a breeding season in the Great Lakes.     

Pharmaceuticals and personal care products found in the Great Lakes above concentrations of environmental concern

The monitoring of pharmaceuticals and personal care products (PPCPs) has focused on the distribution in rivers and small lakes, but data regarding their occurrence and effects in large lake systems, such as the Great Lakes, are sparse. Wastewater treatment processes have not been optimized to remove influent PPCPs and are a major source of PPCPs in the environment. Furthermore, PPCPs are not currently regulated in wastewater effluent. In this experiment we evaluated the concentration, and corresponding risk, of PPCPs from a wastewater effluent source at varying distances in Lake Michigan. Fifty-four PPCPs and hormones were assessed on six different dates over a two-year period from surface water and sediment samples up to 3.2 km from a wastewater treatment plant and at two sites within a harbor. Thirty-two PPCPs were detected in Lake Michigan and 30 were detected in the sediment, with numerous PPCPs being detected up to 3.2 km away from the shoreline. The most frequently detected PPCPs in Lake Michigan were metformin, caffeine, sulfamethoxazole, and triclosan. To determine the ecological risk, the maximum measured environmental concentrations were compared to the predicted no-effect concentration and 14 PPCPs were found to be of medium or high ecological risk. The environmental risk of PPCPs in large lake systems, such as the Great Lakes, has been questioned due to high dilution; however, the concentrations found in this study, and their corresponding risk quotient, indicate a significant threat by PPCPs to the health of the Great Lakes, particularly near shore organisms.     

Spatial and temporal trends in surface water and sediment contamination in the Laurentian Great Lakes

Data from recent sediment and surface water surveys have been collated and mapped to illustrate the spatial distribution of contaminants across the entire Great Lakes basin. Information from historical surveys, together with data from surface water monitoring programs in three major connecting channels, has also been collated in order to evaluate temporal trends. In general, Lakes Superior and Michigan exhibited the lowest levels of sediment contamination while Lake Ontario had the highest. Contaminants such as gamma-HCH (lindane) and dieldrin were ubiquitous in surface waters across the entire basin, which was indicative of atmospheric sources. The distribution of other compounds including hexachlorobenzene, octachlorostyrene and mirex indicated the presence of local sources within the watersheds of the connecting channels. Surficial sediment contamination was found to have decreased markedly since the late 1960s and 1970s. Similarly, surface water contamination decreased over the period 1986-1997 with concentrations of dieldrin, hexachlorobenzene, octachlorostyrene and mirex reduced by over 50%. However, the spatial distributions of both sediment and surface water contamination indicate that further effort is warranted in reducing local sources of contaminants, particularly in Lake Ontario.     

Perfluoroalkyl chemicals in vacuum cleaner dust from 39 Wisconsin homes

Perfluoroalkyl chemicals (PFCs) have been used as surfactants and stain repellants in a variety of consumer products for more than 50 years and there is growing concern regarding their persistence and toxicity. Human exposure to these chemicals is essentially universal in North America and researchers have linked them to a variety of health problems ranging from higher rates of cancer, to developmental and reproductive problems, and higher cholesterol levels. Major exposure pathways are food and water ingestion, dust ingestion via hand to mouth transfer. In an effort to assess residential exposure, the Wisconsin Department of Health Services tested vacuum cleaner contents from thirty-nine homes for 16 perflouroalkyl chemicals. PFOS, PFOA, PFHxS, PFHpA and PFNA were found in all of the vacuum dust samples and dust from eight homes contained all 16 PFCs included in our analysis. The most commonly detected compounds were perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS) and perfluorooctanoic acid (PFOA) which together made up 70% of the total PFC residues in dust from these homes. Summed PFC concentrations in these dust samples ranged from 70 to 2513 ng/g (median 280 ng/g). Our investigation suggests that these chemicals may be ubiquitous contaminants in US homes.     

Validation and use of in vivo solid phase micro-extraction (SPME) for the detection of emerging contaminants in fish

A variety of emerging chemicals of concern are released continuously to surface water through the municipal wastewater effluent discharges. The ability to rapidly determine bioaccumulation of these contaminants in exposed fish without sacrificing the animal (i.e. in vivo) would be of significant advantage to facilitate research, assessment and monitoring of their risk to the environment. In this study, an in vivo solid phase micro-extraction (SPME) approach was developed and applied to the measurement of a variety of emerging contaminants (carbamazepine, naproxen, diclofenac, gemfibrozil, bisphenol A, fluoxetine, ibuprofen and atrazine) in fish. Our results indicated in vivo SPME was a potential alternative extraction technique for quantitative determination of contaminants in lab exposures and as well after exposure to two municipal wastewater effluents (MWWE), with a major advantage over conventional techniques due to its ability to non-lethally sample tissues of living organisms.     

Modeling the atmospheric transport and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in North America

The atmospheric fate of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was simulated for the year 2000 in North America using a SMOKE/CMAQ-based chemical transport model that was modified for this purpose. The 1999 USEPA emission inventories of PCDD/Fs and criteria pollutants were used. The 1995 Canadian emission inventory of criteria pollutants and the 1995 Canadian area source emissions for PCDD/Fs were used with the 2000 Canadian point source emissions. Modifications to CMAQ involved coupling it with dual organic matter (OM) absorption and black carbon (BC) adsorption models to calculate PCDD/F gas–particle partitioning. The model satisfactorily reproduced the particle bound fractions at all rural sites for which there were measured data and across the whole domain, the modeled vs. measured differences in particle bound fractions were less than 20% for nearly all congeners. The model predicted ambient air PCDD/F concentrations were also consistent with measurements. Simulated deposition fluxes were within 58% of direct measurements. PCDD/F atmospheric depositions to each of the Great Lakes were estimated for the year 2000. The results indicate that approximately 76% of the total deposition of PCDD/Fs to the Great Lakes (in W-TEQ, or toxic equivalent units as defined by the World Health Organization) is attributed to PCDD/Fs absorbed into OM in aerosol. For all of the lakes, more than 92% of all deposition is particle phase wet deposition and only 5–8% is particle phase dry deposition. Wet deposition from the gas phase is negligible. Of the 17 toxic PCDD/F congeners, the Cl_4–5DD/F compounds contribute approximately 70% to the total atmospheric deposition to the Great Lakes. The seasonal changes in the PCDD/F deposition flux track variations in ambient temperature.     

Organochlorine contaminants in eggs of Common Terns from the Canadian Great Lakes, 1981

To determine if contaminant levels in Common Terns had changed over the last decade, we collected and analyzed eggs from four nesting colonies on the three lower Great Lakes during 1981. DDE and PCBs were detected in every egg from the four colonies. Dieldrin, mirex and trans-nonachlor were detected in more than 45% of the eggs. Seven other organochlorine contaminants (DDD, DDT, hexachlorobenzene, oxychlordane, cis-chlordane, cis-nonachlor and toxaphene) were detected in less than 25% of the eggs. Eggs from the Lake Ontario colony were generally the most heavily contaminated. Comparisons of DDE and PCB data with earlier studies of Common Terns indicated that contaminant levels in eggs from the four sampled colonies, or nearby sites, have decreased by up to 80-90% from 1969-1973 to 1981. Interspecies comparisons showed that Common Tern eggs have lower organochlorine residue levels than eggs of Caspian Terns or Herring Gulls. Dietary variation and migratory status are possible explanations for the differences in residue levels among species. Eggshell thickness, log-PCBs, and log-DDE were not significantly intercorrelated. Elevated contaminant levels in the early 1970s might be at least partly responsible for the decline of the Great Lakes Common Tern population over the past decade. Stabilization of population numbers during the early 1980s suggests that organochlorine pollution levels have been reduced to a point where they are no longer an important factor in the population dynamics of this species on the Great Lakes.     

New trends in the analytical determination of emerging contaminants and their transformation products in environmental waters

Since the so-called emerging contaminants were established as a new group of pollutants of environmental concern, a great effort has been devoted to the knowledge of their distribution, fate and effects in the environment. After more than 20 years of work, a significant improvement in knowledge about these contaminants has been achieved, but there is still a large gap of information on the growing number of new potential contaminants that are appearing and especially of their unpredictable transformation products. Although the environmental problem arising from emerging contaminants must be addressed from an interdisciplinary point of view, it is obvious that analytical chemistry plays an important role as the first step of the study, as it allows establishing the presence of chemicals in the environment, estimate their concentration levels, identify sources and determine their degradation pathways. These tasks involve serious difficulties requiring different analytical solutions adjusted to purpose. Thus, the complexity of the matrices requires highly selective analytical methods; the large number and variety of compounds potentially present in the samples demands the application of wide scope methods; the low concentrations at which these contaminants are present in the samples require a high detection sensitivity, and high demands on the confirmation and high structural information are needed for the characterisation of unknowns. New developments on analytical instrumentation have been applied to solve these difficulties. Furthermore and not less important has been the development of new specific software packages intended for data acquisition and, in particular, for post-run analysis. Thus, the use of sophisticated software tools has allowed successful screening analysis, determining several hundreds of analytes, and assisted in the structural elucidation of unknown compounds in a timely manner.     

Multimedia emissions inventory of polychlorinated biphenyls for the U.S. Great Lakes states

Polychlorinated biphenyls (PCBs) were banned in the United States in 1979, and since then a significant decline in their release to the environment has been observed. This decline has now reached a plateau. Several new regulatory programs have been put in place to further reduce PCB emissions/releases. However, our ability to measure the effectiveness of these regulatory/voluntary programs and to support regional fate/transport and source/receptor modeling efforts depend on reliable emission information. In this study, we attempt to improve the emission inventory for PCBs by compiling and analyzing the multimedia total PCB emission/release data reported for the U.S Great Lakes states for each year from 1990 to 2000. Although Toxic Release Inventory (TRI), National Emissions Inventory (NEI), Great Lakes Regional Air Toxic Emissions Inventory (GLRATEI), and Integrated Atmospheric Deposition Network (IADN) data formed the basis of estimating air emissions, we used the TRI, National Response Center (NRC), and PCB transformer inventory data to estimate PCB releases to land. We used the Permit Compliance System and NRC data to obtain estimates of PCB discharges to water systems in the Great Lakes states. The Remedial Action Plans for each area of concern were the primary source for estimating PCB loads of dredged sediments. On the basis of the NEI, IADN, and GLRATEI data, the total air emissions within the decade were approximately 126 t. The regionwide discharges to water systems and releases to land in the form of landfills and accidental spills in 1990-2000 were estimated as approximately 170 and 3225 t, respectively. We estimated that approximately 1.3 million t of PCB-contaminated sediment were removed or targeted for removal in five lakes of the U.S. portion of the Great Lakes basin. We stress that these estimates were based on reported amounts and the unreported PCB releases/emissions could result in significantly higher estimates.     

Bench-scale testing of selected remediation alternatives for contaminated sediments

The Assessment and Remediation of Contaminated Sediments (ARCS) Program within the U.S. Environmental Protection Agency's Great Lakes National Program Office (GLNPO) contained a component for demonstrating and evaluating sediment remediation technologies. Toward this end, bench-scale tests of solvent extraction, thermal desorption, and wet air oxidation technologies were conducted. Contaminated sediments were tested from the Grand Calumet River, Indiana; Buffalo River, New York; Saginaw River, Michigan; and Ashtabula River, Ohio. The primary contaminants of concern in these sediments were polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs). The solvent extraction tests were conducted with sediments from the Grand Calumet, Buffalo, and Saginaw rivers. The thermal desorption studies were conducted with sediments from the Grand Calumet, Buffalo, and Ashtabula rivers. The wet air oxidation testing was performed with the Grand Calumet River sediment. Raw sediment contaminant concentrations ranged from 0.32-21.9 mg/kg dry mass for PCBs and 2.70-266 mg/kg dry mass for PAHs. PCB removal or destruction efficiencies ranged from approximately 6-99%. PAH removal or destruction efficiencies ranged from 65-99%. Mass balance closures ranged from 40-99% for solids; 59-139% for water; 29-3500% for oil; 16-129% for PCBs; and 69-3170% for PAHs.     

Toxaphene congeners in the Canadian Great Lakes basin: temporal and spatial food web dynamics

Samples of a top predator fish species, lake trout (Salvelinus namaycush) and predominant forage species including smelt (Osmerus mordax), alewife (Alosa pseudoharengus), slimy sculpin (Cottus cognatus), deepwater sculpin (Myoxocephalus quadricornis) and lake herring (Coregonus artedii) were, collected from throughout 4 of the 5 Great Lakes (Superior, Huron, Erie and Ontario) (Fig. 1). Lake trout were also collected from three isolated lake systems (Lakes Nipigon, Simcoe and Opeongo), all located within the basin. All the samples were analysed for body burdens of total toxaphene and 22 toxaphene congeners. In addition, from each of the Great Lakes sites samples of major invertebrate dietary items, which included Mysis relicta, Diporeia hoyi and plankton, were similarly analysed. Whole lake trout samples, archived at -80 degrees C, were reanalysed to determine historical trends of toxaphene congeners plus carbon and nitrogen stable isotope signatures. The Lake Superior food web consistently had the highest levels of total toxaphene of all the Great Lakes monitored. The primary source of toxaphene to Lake Superior has been identified as atmospheric transport and deposition from sites in the southern US, Mexico and Central America (Hoff, R.M., Strachan, W.M.J., Sweet, C.W., Chan, C.H., Shackelton, M., Bidleman, T.F., Brice, K.A., Burnison, D.A., Cussion, S., Gatz, D.F., Harlin, K., Schroeder, W.H., 1996. Atmospheric deposition of toxic chemicals to the Great Lakes: A review of data through 1994. Atmospheric Environ. 30, 3505-3527). Of the offsystem lakes surveyed. Lake Nipigon, situated due north of Lake Superior and with a Lake Basin area of about 6% of Lake Superior (Hendendorf, C.E., 1982. J. Great Lakes Res. 8(3), 379-412) had total toxaphene levels in lake trout equivalent to about 50% of those found in lake trout from Lake Superior. Temporal trend toxaphene congener analysis was conducted on archived whole fish samples collected over the period 1980 through to the 1990's. Initially a nonachlorobornane congener (Parlar #50) was predominant, with congeners #40, #62 and #21 being the next most prominent in the 1980 samples. Samples from the 1990's showed a significant decline in the presence of lower chlorinated congeners #40 and #21. Analysis of total toxaphene in food webs, indicated elevated levels in lower trophic level species such as Diporeia and Cottus sp. which have a benthic association. The stable isotope temporal trend 13C signature identified a significant shift in the lake trout diet over the period 1993 to 1996.     

Organochlorine insecticides, polychlorinated biphenyls, and metals in water, sediment, and green frogs from southwestern Michigan.

In an attempt to explain the etiology of frog deformities and population declines, many possible causative factors have been examined, including the input of synthetic chemicals into aquatic systems, where frogs spend much of their lives, including their entire developmental stages. Deformities in populations of green frogs in wetlands of southwestern Michigan that are influenced by agricultural, urban, or industrial inputs were assessed in this study. Of the 1445 green frogs (Rana clamitans) examined, only four (0.3%) exhibited morphological deformities. This deformity rate is less than the recognized background level of deformities for this species, which is approximately 1%. Concentrations of organochlorine insecticides, polychlorinated biphenyls (PCBs), and metals were determined in water, sediment, frog eggs, tadpoles, and adult green frog tissues. Concentrations of all individual organochlorine insecticides in tissue were less than 6 ng/g, wet wt. Concentrations of sigmaPCBs in tissue did not exceed 100 ng/g, wet wt. Concentrations of toxic metals were less than the limits of detection. Because no significant numbers of green frog deformities were observed in this region, it can be assumed that at these low concentrations, physical malformations in green frogs should not be observed. Significance of study. This study provides information on the incidence of deformities in green frog populations in southwestern Michigan and offers background data on chemical residues in green frogs and their environment.     

Environmental contaminants in four eider species from Alaska and arctic Russia

Population declines in four species of eider; common (Somateria mollissima), king (Somateria spectabilis), spectacled (Somateria fischeri) and Steller's (Polysticta stelleri), have raised concerns about exposure to contaminants. Livers and kidney tissues were collected from eiders in Alaska and Russia for organic and elemental analyses. Results showed that organochlorine and many elemental levels were below toxic thresholds; however, in many cases, cadmium, copper, lead and serenium appeared high relative to other waterfowl and may warrant concern. With the exception of lead, local anthropogenic sources for these elements are not known. Although adverse physiological responses have not been documented in eiders, these four elements cannot be ruled out as contaminants of potential concern for some eider species.