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.     

Spatial distribution of polybrominated diphenyl ethers and polybrominated biphenyls in lake trout from the Laurentian Great Lakes

Concentrations of two types of brominated flame-retardants (BFRs); polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls (PBBs) were determined in a single age class of lake trout (Salvelinus namaycush) collected from the Laurentian Great Lakes in 1997. Mean concentrations of total PBDE were highest in samples from Lake Ontario at 95+/-22 ng/g wet weight (ww) or 434+/-100 ng/g lipid weight (lw) while the lowest concentrations were observed in Lake Erie lake trout (27+/-8.6 ng/g ww, 117+/-37 ng/g lw). In all samples, the predominant PBDE congeners were 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4', 6-pentabromodiphenyl ether (BDE-100), which are the primary components of the commonly used penta-BDE formulation flame retardant. Lake trout collected from Lake Huron had the highest concentrations of PBBs (3.1+/-1.7 ng/g ww, 15+/-8.5 ng/g lw), while the lowest levels were detected in fish from Lake Superior (0.25+/-0.13 ng/g ww, 1.7+/-0.89 ng/g lw). In all lake trout samples, 2,2',4,4',5,5'-hexabromobiphenyl (BB-153), a major constituent of the flame-retardant FireMaster BP-6, was the predominant PBB congener.     

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.     

Analysis of 2,3,7,8-Tetrachlorodibenzo-p-dioxin in Great Lakes fish

In fish samples from Lake Ontario and Lake Huron 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was found at concentrations from 2 to 162 pg/g (ppt) and from 2.5 to 29 ppt respectively. Fish from the other Great Lakes (Lake Superior, Lake Michigan and Lake Erie) generally had no detectable signals for TCDD although a few samples had < 3 ppt.     

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.     

Toxaphene and other chlorinated compounds in human milk from northern and southern Canada: a comparison.

Human milk from residents of northern Canada (Keewatin) was compared to that in national surveys of southern Canada with respect to residues of toxaphene, PCBs, PCDD/PCDFs, chlordane, and several other persistent organic compounds. Concentrations of toxaphene were approximately ten-fold higher in specimens from Keewatin than from the south. Toxaphene concentrations in samples from the Great Lakes Basin collected in 1992 were not significantly (p < 0.05) different from those of the rest of Canada; however they were significantly (p < 0.05) lower than concentrations reported in a 1986 survey. Hexachlorobenzene, trans nonachlor and oxychlordane were three to five times higher in concentration in the Keewtin samples than in samples reported in the 1992 national survey. Total PCB congeners, DDTs, PCDD/PCDFs, and other chlorinated compounds were not significantly higher in northern samples.     

Levels of toxaphene congeners in fish from Danish waters

The levels of toxaphene congeners, in addition to PCB congeners and organochlorine pesticides, were determined in various fish samples from different Danish waters. While PCB-153 and p,p'-DDE show different levels depending on the fishing area, with highest levels in fish from the Western Baltic Sea, toxaphene was detected in all the samples investigated at a more constant level. The distribution of the three toxaphene congeners Parlar #26, #50 and #62 depends on the fishing area, with the Western Baltic Sea being different from the other waters by having almost equal levels of toxaphene congeners #26 and #50.     

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.     

Studies of toxaphene in technical standard and extracts of background air samples (Point Petre, Ontario) using multidimensional gas chromatography-electron capture detection (MDGC-ECD)

MDGC-ECD procedures have been used to provide insight into the compositional complexity of some of the specific peaks or clusters observed in the gas chromatographic analysis of a technical toxaphene standard, with reference to individual toxaphene congeners (Parlar # components) that are flow commercially available. These investigations have focussed initially upon those peaks and clusters recently identified (Shoeib. M., Brice, K.A., Hoff, R., 1999. Chemosphere 39, 849-871) as dominant constituents of background ambient air. Multiple electron-capturing components have been found to be present in all the species studied: the available individual toxaphene congeners have been matched against these components where possible. In similar fashion, the responses obtained in equivalent gas chromatographic elution windows from the analysis of typical processed air sample extracts have been investigated, with the results showing clear differences relative to the patterns found in the technical toxaphene standard. In most cases, the air sample shows reduced complexity with fewer components present in the cluster. Also, the presence of interfering responses (due to PCBs and other organochlorines) is quite apparent and significant, showing that major problems and errors could arise when using single-column GC-ECD procedures for quantitation of toxaphene in environmental samples. The presence of certain of the Parlar species in the air samples has been confirmed and in most cases these represent the dominant toxaphene component found in the targeted cluster. Furthermore, the persistence of certain congeners in the atmospheric samples appears to be strongly dependent upon chemical structure, since the congeners in question possess an alternating exo-endo chlorine substitution pattern around the six-membered ring in the bornane skeleton. Such persistence is probably the result of lower metabolization of toxaphene residues in soils, water and sediments leading to a similar pattern in the atmosphere following volatilization.     

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.     

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.     

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.     

PCBs in sediments of the Great Lakes--distribution and trends, homolog and chlorine patterns, and in situ degradation

A region-wide data analysis on polychlorinated biphenyls (PCBs) in the sediment of the Great Lakes reveals a total accumulation of approximately 300 ± 50 tonnes, representing a >30% reduction from the 1980s. Evidence of in situ degradation of sediment PCB was found, with estimated t_1/2 of 11 and 17 years, at two open water locations in Lake Ontario. The relative abundance of heavy homologs as well as para-chlorines decreases with increasing depth, while the opposite is true for medium and light homologs and ortho-chlorines. In Lake Michigan, the vertical pattern features enrichment of heavier congeners and reduction of ortho-chlorines in deeper sediment layers, opposite to the trend in Lake Ontario. PCBs decrease log-linearly with increasing latitude and longitude. Air deposition of PCBs to lake sediment decreases at about 0.077 ng cm⁻² yr⁻¹ per degree latitude (N) for the geographic region extending from the Great Lakes to within the Arctic Circle.     

Status and changes of water quality in typical near-city zones of three East African Great Lakes in Tanzania

Environmental Science and Pollution Research - Tanzania is the only country bordering all three transboundary East African Great Lakes, i.e., Lake Victoria, Lake Tanganyika, and Lake Nyasa (Lake...     

Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

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.     

Record of PCB congeners, sorbents and potential toxicity in core samples in Indiana Harbor and Ship Canal

Indiana Harbor and Ship Canal (IHSC) is an active navigational system that serves a heavily industrial area of southern Lake Michigan. We have determined the amount of polychlorinated biphenyls (PCBs), congener distributions, sorbent types and potential for dioxin-like PCB toxicity from two IHSC sediment cores. Vertical distributions of ΣPCBs (sum of 161 individual or coeluting congeners) ranged from 410 to 91000 and 1800 to 41000 ng g(-1) dry weight (d.w.) for cores 1 and 2, respectively. Core 1 showed its highest accumulation rate for the year ～1979 and exhibits a strong Aroclor 1248 signal in sediments accumulating over the last 60 years. It appears that from the late 1930s until the beginning of the 1980s there was a large and constant input of PCBs into this system. This pattern differs from lake cores from the Great Lakes region which commonly exhibit a rapid increase, a peak, followed by a sharp decrease in the PCB accumulation rates. Core 2 also has a strong Aroclor 1248 signal in the top layers, but deeper layers show evidence of mixtures of Aroclors and/or weathering processes. High levels of black carbon as a fraction of total organic carbon were found in both cores (median ～30%), which reflect the long history of local combustion sources. No strong relationship was found between ΣPCB concentration and sorbents. Both cores contain dioxin-like PCBs that are highest in concentration below the surface. The high levels of PCBs in the deep sediments are of concern because of plans to dredge this system.     

Total toxaphene and specific congeners in fish from the Yukon, Canada

Toxaphene is one of the major persistent organic pollutants with global environmental impacts. We have measured total toxaphene and specific congeners concentrations in 19 fish samples collected from the Yukon, Canada using gas chromatography coupled to ion trap MS/MS. The total toxaphene concentrations ranged from 42 to 242 ng/g (mean = 107+/-61 ng/g). The sum of the three specific congeners (Parlar 26, 50 and 62) was within 10-55 ng/g. The ratio of the sum of the three congeners to the total toxaphene varied between 8% and 25% in the fish samples but the ratio may be species specific. Our results suggest that consumption of these Yukon fish should have minimal risk of toxaphene exposure.     

A gas chromatography/high-resolution mass spectrometry (GC/HRMS) method for determination of polybrominated diphenyl ethers in fish

A method for the determination of polybrominated diphenyl ethers (PBDEs) in biota for routine analysis is described. The mass spectroscopic (MS) evaluation of 23 brominated diphenyl ethers, under electron ionization and electron capture negative ion conditions using magnetic sector and quadrupole mass spectrometers, showed that high-resolution mass spectrometry (HRMS) under electron ionization conditions was the most reliable technique, with high selectivity and adequate sensitivity. The instrument detection limit for this method ranged for individual congeners between 4.8 and 0.1 pg for 3-bromodiphenyl ether (BDE-2) and 2,3',4,4'-tetrabromodiphenyl ether (BDE-66), respectively, and method detection limit for each homologue group ranged between 5 pg/g for salmon certified reference material (CRM) and 93 pg/g for lake trout CRM. The effectiveness of this method was evaluated by analyzing the occurrence of PBDEs in commercially available CRMs comprising Lake Ontario lake trout, Pacific herring, and sockeye salmon. The average coefficients of variation for the replicate analyses of PDBEs in several tissue samples were: 25% for lake trout, 36% for Pacific herring, and 34% for sockeye salmon. The average deviations in the inter-laboratory study were: 14% for lake trout, 15% for Pacific herring, and 37% for sockeye salmon. Results indicated that the described method, based on gas chromatography/high-resolution mass spectrometry, is reliable for determining PBDE concentrations in biological tissues.     

Air concentrations of polybrominated diphenyl ethers (PBDEs) in 2002–2004 at a rural site in the Great Lakes

Atmospheric PBDEs were measured on a monthly basis in 2002–2004 at Point Petre, a rural site in the Great Lakes. Average air concentrations were 7.0 ± 13 pg m^?3 for Σ₁₄BDE (excluding BDE-209), and 1.8 ± 1.5 pg m^?3 for BDE-209. Concentrations of 3 dominant congeners (i.e., BDE-47, 99, and 209) were comparable to previous measurements at remote/rural sites around the Great Lakes, but much lower than those at urban areas. Weak temperature dependence and strong linear correlations between relatively volatile congeners suggest importance of advective inputs of gaseous species. The significant correlation between BDE-209 and 183 implies their transport inputs associated with particles. Particle-bound percentages were found greater for highly brominated congeners than less brominated ones. These percentages increase with decreasing ambient temperatures. The observed gas/particle partitioning is consistent with laboratory measurements and fits well to the Junge–Pankow model. Using air mass back-trajectories, atmospheric transport to Point Petre was estimated as 76% for BDE-47, 67% for BDE-99, and 70% for BDE-209 from west–northwest and southwest directions. During the same time period, similar congener profiles and concentration levels were found at Alert in the Canadian High Arctic. Different inter-annual variations between Point Petre and Alert indicate that emissions from other regions than North America could also contribute PBDEs in the Arctic. In contrast to weak temperature effect at Point Petre, significant temperature dependence in the summertime implies volatilization emissions of PBDEs at Alert. Meanwhile, episodic observations in the wintertime were likely associated with enhanced inputs through long-range transport during the Arctic Haze period.