Incidence of chlorinated benzenes and chlorinated ethylenes in Lake Ontario Herring Gulls

Great Lakes Herring Gulls (Larus argentatus) and their eggs have proven to be useful integrators on a lakewide basis of high molecular weight, relatively involatile organochlorine pollutants such as PCRs. A search for relatively volatile organochlorine compounds by GC/MS also revealed the presence of tri- and tetrachloroethylene, and isomers of di-, tri-, tetra-, penta- and hexachlorobenzene in the body lipid of adult Herring Gulls from Lake Ontario. Analysis of pooled eggs from colonies throughout the Great Lakes in 1978 showed that pentachlorobenzene and hexachlorobenzene were ubiquitous contaminants at levels from 14–50 ng/kg and 90–350 ng/kg, respectively. Hexachlorobenzene levels were 2–3 times higher in Lake Ontario than the other lakes, whereas pentachlorobenzene was more evenly distributed geographically. Levels of 1,2,3,4-tetra-, 1,2,4,5-tetra- and 1,2,4-trichlorobenzene near the detection limit of 10–20 ng/kg were found in a few samples.     

Mercury levels in Great Lakes herring gull (Larus argentatus) eggs, 1972-1992

Since 1971, the herring gull (Larus argentatus) has been used as a sentinel species for monitoring the levels of persistent contaminants in the Great Lakes ecosystem. In this study, 21 herring gull colonies in the Great Lakes and connecting channels were sampled during 1972-1976, 1981-1983, 1985 and 1992. For each year, 10 eggs (usually) were collected from each colony site and analyzed for total mercury (microg/g, wet wt). Results indicated that eggs from Lake Ontario displayed the highest lake-wide mercury levels (0.28-0.73 microg/g), followed by Lake Superior (0.21-0.50 microg/g). Lake Erie typically displayed the lowest mercury levels (0.18-0.24 microg/g). Overall, mercury levels ranged from 0.12 microg/g in 1985 to 0.88 microg/g in 1982 for Channel Shelter Island (Lake Huron) and Pigeon Island (Lake Ontario), respectively. Generally, all colony sites showed peak egg mercury levels in 1982. A significant decline in egg mercury levels was observed in five colony sites for the period 1972-1992 and in three different colony sites for the period 1981-1992. Mercury levels in the eggs of herring gulls for the period of this study were below levels associated with acute toxic effects in this species but were within a range, for certain years, which potentially reduces hatchability in other avian species.     

Investigation of spatial trends and neurochemical impacts of mercury in herring gulls across the Laurentian Great Lakes

Herring gulls (Larus argentatus) bioaccumulate mercury (Hg) but it is unknown whether they are exposed at levels of neurological concern. Here we studied brain tissues from gulls at five Great Lakes colonies and one non-Great Lakes colony during spring of 2001 and 2003. Total brain Hg concentrations ranged from 0.14 to 2.0 μg/g (dry weight) with a mean of 0.54 μg/g. Gulls from Scotch Bonnet Island, on the easternmost edge of the Great Lakes, had significantly higher brain Hg than other colonies. No association was found between brain Hg concentration and [3H]-ligand binding to neurochemical receptors (N-methyl-d-aspartate, muscarinic cholinergic, nicotinic cholinergic) or nicotinic receptor α-7 relative mRNA expression as previously documented in other wildlife. In conclusion, spatial trends in Hg contamination exist in herring gulls across the Great Lakes basin, and herring gulls accumulate brain Hg but not at levels associated with sub-clinical neurochemical alterations.     

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.     

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.     

Occurrence and sources of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in surficial sediments of Lakes Superior and Huron

Concentrations and congener profile patterns of 2378-substituted PCDD/Fs and DLPCBs in offshore, nearshore and tributary sediments of Lakes Superior and Huron are reported, and spatial trends and source contributions assessed. PCDD/F concentrations ranged from 5 to 18 000 pg/g dw (Lake Superior) and 3 to 6100 pg/g dw (Lake Huron); DLPCBs ranged from 9 to 11 000 pg/g dw (Lake Superior) and 9 to 27 000 pg/g dw (Lake Huron). Our analysis indicated atmospheric deposition is a primary source to depositional areas of both lakes; however, greater PCDD/F and DLPCB concentrations were observed at several nearshore and tributary sites, and were attributed to corresponding land use in the watershed. Statistical analysis and pattern comparison suggested that industrial inputs mainly associated with wood treatment plants, pulp and paper mills, mining operations, and chlorine-based chemical manufacturing also contributed to contamination by PCDD/Fs and DLPCBs in certain nearshore and offshore areas of Lakes Superior and Huron.     

Polybrominated diphenyl ethers (PBDE) in serum: findings from a US cohort of consumers of sport-caught fish

Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in foams, fabrics and plastics, and are common contaminants of household air and dust and bioaccumulate in wildlife, and are detectable in human tissues and in fish and animal food products. In the Great Lakes Basin sport fish consumption has been demonstrated to be an important source of PCB and DDE exposure. PBDEs are present in the same sport fish but prior to our study the contribution to human PBDE body burdens from Great Lakes sport fish consumption had not been investigated. This study was designed to assess PBDE, PCB and 1,1-bis(4-chlorophenyl)-2,2-dichloroethene (DDE) serum concentrations in an existing cohort of 508 frequent and infrequent consumers of sport-caught fish living in five Great Lake states. BDE congeners 47 and 99 were identified in the majority of blood samples, 98% and 62% respectively. summation operatorPBDE levels were positively associated with age, hours spent outdoors, DDE, summation operatorPCB, years of sportfish consumption, and catfish and shellfish intake, and negatively associated with income and recent weight loss. Other dietary components collected were not predictive of measured summation operatorPBDE levels. In multivariate models, summation operatorPBDE levels were positively associated with age, years consuming sport fish, shellfish meals, and computer use and negatively associated with recent weight loss. Having summation operatorPBDE levels in the highest quintile was independently associated with older age, male gender, consumption of catfish and shellfish, computer use and spending less time indoors. summation operatorPCB and DDE were strongly associated suggesting common exposure routes. The association between summation operatorPBDE and summation operatorPCB or DDE was much weaker and modeling suggested more diverse PBDE sources with few identified multi-contaminant-shared exposure routes. In our cohort Great Lakes sport fish consumption does not contribute strongly to PBDE exposure.     

Trends of TCDD and related compounds in the Great Lakes: The Lake Ontario ecosystem

The Laurentian Great Lakes represent 20 percent of the surface fresh water of the world. They are unique because of their long flushing times (in excess of 175 years for Lake Superior), their relatively short mixing times and their consequent propensity to accumulate persistent chemicals and respond very slowly to decreased chemical loadings. Lake Ontario, as the last lake in the system, receives the drainage from the other four Great Lakes in addition to significant chemical contributions from within its drainage basin particularly from its main tributary, the Niagara River.

This paper evaluates environmental levels of TCOD and related compounds within the Lake Ontario ecosystem by considering temporal trends, the application of mass loading principles for large lake ecosystems and the examination of a holistic ecosystem perspective on exposure routes.     

Determination of perchlorate in selected surface waters in the Great Lakes Basin by HPLC/MS/MS

Surface water samples were collected from 55 sites in the Great Lakes Basin and analyzed for the presence of perchlorate using HPLC/MS/MS with an isotopically enriched internal standard. Sites included areas impacted by heavy industry, urbanization, agriculture and atmospheric deposition. Perchlorate was detected at several of the sites at concentrations close to the method detection limit (0.2 microg/l). Despite these low concentrations, its presence was confirmed by sample concentration and determination of the isotopic ratio of perchlorate. The presence of perchlorate at two of the sites was related to a fireworks display which had occurred prior to sampling. The other detections of perchlorate were in rivers/creeks draining watersheds which had high density livestock and crop farming activity. We suspect the two are related. To our knowledge, these are the first reported concentrations of perchlorate in Canadian surface waters.     

Polychlorinated dibenzodioxins and dibenzofurans in human adipose tissue samples from five Ontario municipalities

Human adipose tissue samples obtained during autopsies in 5 Canadian municipalities within the Great Lakes basin were analysed for polychlorinated dibenzodioxins and dibenzofurans using gas chromatography-high resolution-mass spectrometry. The mean congener values for male and female donors in each municipality are comparable with previously reported data. No significant differences in congener levels between male and female and between municipalities were detected. A positive correlation between congener level and age was observed for several congeners as well as for the total congener concentration expressed as its 2378-TCDD toxic equivalent.     

Historical record of polychlorinated dibenzo-p-dioxins and dibenzofurans in Swiss lake sediments

Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were found in annually laminated sediments from Lakes Zurich, Baldegg, and Lugano in Switzerland. Octachlorodibenzo-p-diox in (OCDD) predominated, averaging approximately 1.3 ppb. The congener distribution indicated that combustion was the source of PCDD and PCDF in these sediments. In these dated sediment cores, we found that PCDD and PCDF were absent from the sediments before about 1945, but increased thereafter.     

Determination of potential sources of PCBs and PBDEs in sediments of the Niagara River

Sediments from Niagara River, an important waterway connecting two of the Great Lakes (Lake Erie to Lake Ontario), were analyzed for 14 congeners of polychlorinated biphenyls (PCBs) and 9 congeners of polybrominated diphenyl ethers (PBDEs) using accelerated solvent extraction and gas chromatography/mass spectrometry. Total concentrations of PCBs ranged from 1.7 to 124.6 ng/g were PCBs 138 and 153 were found in all samples. All sites but one showed PBDE in sediments with total concentrations as high as 148 ng/g, suggesting that PBDE is becoming an important class of POP. A land-use and coverage map was used to trace potential localized sources of PCB and PBDE contamination. Results indicate that the highest levels of PCBs and PBDEs were found in sediments collected from areas closest to the discharge locations of municipal wastewater treatment plants (WWTP) and local industries. This is the first study that suggests the importance of WWTP discharges as a potential source of PBDE contamination in the Great Lakes.     

滇池污染状况及其综合治理

滇池污染已引起各级政府和市民的广泛关注,被列为“九五”国家“三湖”、“三河”重点治理项目之一。对滇池污染及治理的研究始于８０年代初期,迄今为止已取得了大量的研究成果,找到了一些比较有效的治理技术,本文将分析滇池主要污染问题,简述滇池污染的治理项目,对效果进行简要分析并对治理措施进行讨论。     

The Characterization of Ozone Data for Sites Located in Forested Areas of the Eastern United States

Six years (1978-1983) of ozone monitoring data from sites located within six forested areas were examined. Areas that experienced the lowest to the highest ozone exposures were located in (1) northern New England/New York and upper Great Lakes, (2) New York/Pennsylvania/Maryland, (3) southeastern/southern, and (4) New Jersey pinelands. In general, higher ozone concentrations were observed in 1978, 1980 and 1983 as compared to the other three years examined. Ozone concentrations varied considerably within the areas. Recommendations for additional ozone monitoring sites are made. A concentrated effort should be made to examine ozone monitoring data from subsequent years (1984, 1985, and 1986) to explore whether the 6-year period 1978 through 1983 is representative of the annual variability of ozone concentrations over eastern forested areas. To better understand the relationship between ozone exposure and possible forest effects, we recommend that the temporal distributions of elevated ozone concentrations over a growing season be examined. The occurrence of elevated ozone levels during specific growth periods during a season may be an important aspect that biologists may wish to explore.     

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.     

Organochlorine pesticides in the ambient air of Chiapas, Mexico

Organochlorine (OC) pesticides were measured in the ambient air of Chiapas, Mexico during 2000-2001. Concentrations of some OC pesticides (DDTs, chlordanes, toxaphene) were elevated compared with levels in the Great Lakes region, while those of other pesticides were not (hexachlorocyclohexanes, dieldrin). While this suggests southern Mexico as a source region for the former group of chemicals, comparably high levels have also been reported in parts of the southern United States, where their suspected sources are soil emissions (DDTs, toxaphene) and termiticide usage (chlordane). Ratios of p,p'-DDT/p,p'-DDE and trans-chlordane/cis-chlordane/trans-nonachlor (TC/CC/TN) in Chiapas suggest a mixture of fresh and weathered sources, while congener profiles of toxaphene suggest emission of old residues from soils. This is supported by air parcel back trajectory analysis, which indicated that air masses over Chiapas at the time of sampling had previously passed over areas of continuing or recent use of some OC pesticides as well as areas of past use.     

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.     

PCDDs/PCDFs and coplanar PCBs in eels (Anguilla anguilla) from different areas of the rivers Havel and Oder in the state of Brandenburg (Germany)

In 1996 forty-nine eels were caught from different locations along the rivers Oder (Hohenwutzen and Schwedt) and from 11 locations along the Havel river. They were analysed for PCDDs/PCDFs and the coplanar PCBs (PCB 77, PCB 126, PCB 169). Their contribution to 2,3,7,8-TCDD equivalents were estimated. In case of PCDDs/PCDFs these amounted between 1.8 and 15.2 pg/g fat (mean 6.1 pg/g; median 5.2 pg/g), in case of coplanar PCBs between 2.4 and 170.5 pg/g fat (mean 47.7 pg/g; median 36.1 pg/g). Lakes which are associated with but not directly located at the main stream of the river Havel contributed much less to contamination of the eels than the river segments situated in the more urbanised or industrialised sites along the main river.     

Chemical indicators of anthropogenic impacts in sediments of the pristine karst lakes

The anthropogenic impact on the pristine karst lakes was investigated using combination of specific parameters, including multielemental analysis of major inorganic constituents (Al, K, Fe) and trace metals (Li, Ag, Cd, Sn, Pb, Bi, Cr, Co, Ni, Cu, Zn and Sb), polycyclic aromatic hydrocarbons (PAHs) and anionic surfactants of linear alkylbenzene sulfonate (LAS) type. The study was performed in the Plitvice Lakes National Park, situated in a sparsely populated area of the northwestern Dinarides, central Croatia. Dated cores of recent sediments from the two biggest lakes, Lake Prosce and Lake Kozjak, were analysed for the selected contaminants using highly specific methods, involving inductively coupled plasma mass spectrometry (ICP/MS), gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). The concentration of inorganic constituents reflected primarily the geological background of the area as well as geomorphological and geochemical characteristics of the Plitvice Lakes. Due to the higher terrigenous input, the concentration of all elements was significantly higher in the Lake Prosce. The concentration of toxic metals was relatively low in both lakes, except for Cd (>1 mg kg⁻¹) and Pb (up to 40 mg kg⁻¹). The vertical profiles of these metals suggested that elevated concentrations of Cd were of natural origin, derived from the erosion of the Jurassic dolomite bedrock, while Pb was predominately of recent anthropogenic origin. A similar distribution pattern, suggesting the same prevailing mechanism of input, was observed for pyrolytic PAHs. The characteristic diagnostic PAH ratios revealed that higher PAHs prevailingly originated from the combustion of biomass and fossil fuels. LAS, which represent highly specific indicators of untreated wastewaters, were found in rather high concentrations in the recent sediment layers (up to 4.7 mg kg⁻¹), suggesting that contaminated household and hotel wastewaters reach the Lakes, very probably by leaking through the porous karst rocks.     

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.