Search

Long-term air monitoring data for POPs are required to determine the effectiveness of source reduction measures and factors controlling air concentrations. Air samples were collected between 1992 and 2012 at three sites with different geographical characteristics (Burnt Island, Egbert and Point Petre) in the Canadian Great Lakes Basin (GLB) using high-volume samplers and analyzed for organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). Spatial and temporal trends of gas-phase concentrations of OCPs, selected PCB congeners and ƩPCBs (84 congeners) were assessed. Egbert had the highest concentrations of some OCPs due to historical [dichlorodiphenyltrichloroethanes (DDTs), dieldrin, γ-hexachlorocyclohexane (γ-HCH)] and current (endosulfan) applications of these pesticides in the surrounding agricultural cropland. This shows that agricultural areas are a source of OCPs to the GLB. High o,p'-/p,p'-DDT ratios were determined and an increasing trend was observed at Point Petre and Burnt Island up to 2004; indicating that the GLB is influenced by dicofol-type DDT sources, which have higher o,p'-/p,p'-DDT ratios than technical DDT. Atmospheric PCB concentrations at Egbert and Point Petre are higher than those measured at Burnt Island, likely due to urban influence and greater populations. Loadings calculations suggest that the atmosphere is a source of α-endosulfan and p,p'-DDT to the lakes and the opposite is true for p,p'-DDE. Long-term decreasing trends were observed for both OCPs and PCBs; consistent with control measures implemented in North America. Atmospheric PCB concentrations are decreasing relatively slowly, with halflives in the range of 9-39 years. Chlordane, α-endosulfan, β-endosulfan, dieldrin, and DDT-related substances showed halflives in the range of 7-13 years. α-HCH and γ-HCH were decreasing rapidly in air, with halflives of 5 years. Long-term declining trends of PCBs and OCPs suggest that regulatory efforts to reduce emissions to the GLB environment have been effective, but emissions from primary and secondary sources might limit future declines., (Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.)

Loadings from Toronto, Canada to Lake Ontario were quantified and major sources and pathways were identified, with the goal of informing opportunities for loading reductions. The contaminants were polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs) and polycyclic musks (PCMs). Loadings were calculated from measured concentrations for three major pathways: atmospheric processes, tributary runoff, and wastewater treatment plant (WWTP) effluents. Although atmospheric deposition to the Great Lakes has received the greatest attention, this was the dominant loading pathway for PCBs only (17 ± 5.3 kg/y or 66% of total loadings). PCB loadings reflected elevated urban PCB air concentrations due to, predominantly, primary emissions. These loadings contribute to consumption advisories for nearshore fish. PBDE loadings to the lake, again from mainly primary emissions, were 48% (9.1 ± 1.3 kg/y) and 42% (8.0 ± 5.7 kg/y) via tributaries and WWTPs, respectively, consistent with emissions deposited and subsequently washed-off of urban surfaces and emissions to the sewage system. PAHs loadings of 1600 ± 280 kg/y (71%) from tributaries were strongly associated with vehicle transportation and impervious surfaces. PCM loadings were 83% (±140 kg/y) from WWTP final effluent, reflecting their use in personal care products. Opportunities for source reduction lie in reducing the current inventories of in-use PCBs and PBDE-containing products, reducing vehicle emissions of PAHs and use of PAHs in the transportation network (e.g., pavement sealants), and improving wastewater treatment technology.

A model has been developed to assess temporal and spatial changes in the concentration of polychlorinated biphenyl (PCB) contaminant in whole fish from Lake Huron during the years 1980 to 2004. The model uses log PCB concentration as the response variable and includes time trend, within-lake variability and dependence on age, weight and length as explanatory variables. A preliminary examination of the data revealed that some values are recorded as below detection limits (thus leading to the left censoring), and the PCB concentration appears to show declines in latter years. To this end, parametric log-location-scale regression models used in survival analysis were employed. It has been found that the Weibull model yields a better fit than the log-logistic or the log-normal models. The analysis provides strong evidence that, starting in 1996, the level of PCB concentration showed steady decline, which is most contributed by the Canadian and US governments' actions carried out earlier to reduce the load of toxic contaminants to the Great Lakes. Spatially, fish from the north of the lake is less contaminated than fish from the south. The pattern and magnitude of the estimated spatial and temporal trends can provide useful information regarding the safety of fish consumption, the setting of regularity limits, the identifiability of PCB sources and the effects of remedial actions in the future. In addition, the developed model is not restricted to the current application but could be used for the analysis of other contaminants.

A series of experiments were conducted among the laboratories participating in the Integrated Atmospheric Deposition Network (IADN) monitoring program to evaluate comparability of the reported persistent organic pollutant concentrations. This quality assurance activity is essential because a variety of methods are currently used for sample collection, extraction, and analysis by the IADN laboratories. The experiments included analyses of a common reference standard (CRS), analyses of split samples, and analyses of samples collected with co-located samplers at the Point Petre IADN measurement station. The analytes included polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), and polychlorinated biphenyls (PCBs). For virtually all compounds, the laboratories produced generally comparable results for the CRS samples, the split samples and the co-location samples, although some differences were observed. Analysis of the methods may pinpoint areas where variations in the methods will result in the differences observed in the reported data. These differences can be due to the field sampling process, the analytical method, field blank values, or a combination of all these factors. This study points out the importance of QA activities at every step of an environmental monitoring process so that areas where improvements may be needed or where inconsistencies may exist can be identified.

Archived suspended sediment samples collected over the period 1980-2002 at Niagara-on-the-Lake in the Niagara river were analyzed to assess temporal trends in contaminants associated with historical industrial activities in the watershed (PCDDs/PCDFs, DLPCBs), compared to more modern industrial chemicals (PBDEs). The temporal trends for PCDDs/PCDFs and DLPCBs were generally similar, and showed a general trend toward decreasing concentrations, which was presumably due to implementation of control measures in the Niagara river watershed, including the remediation of hazardous waste facilities. The temporal trend in PBDEs contrasted with those of PCDDs/PCDFs and DLPCBs. Prior to 1988, PBDEs (sum of 16 congeners including deca-BDE) were generally detected at low-ppb concentrations, but showed a trend toward increasing concentrations over the period 1980-1988. After 1988, PBDE concentrations in the Niagara river showed a more rapidly increasing trend to a maximum of approximately 35 ng/g in 1995, with deca-BDE as the predominant congener detected. Samples collected over the period February 2003 to March 2004 at the head and mouth of the Niagara river were also analyzed for PBDEs; in all cases PBDE concentrations were higher at the mouth of the river at the outflow to Lake Ontario, indicating the Niagara river watershed is a source of PBDE contamination to Lake Ontario. However, PBDE concentrations in suspended sediments of the Niagara river were comparable to, or lower than, concentrations in bottom sediments in other industrialized/urbanized areas of the world. Based on these comparisons of global PBDE bottom sediment concentrations, the Niagara river watershed does not appear to be a significant local source of PBDEs to Lake Ontario, and concentrations in suspended sediments appear to be indicative of general PBDE contamination from a contamination of local, regional, and continental sources.

The majority of analytical results in the Greenland AMAP (Arctic Monitoring and Assessment Programme) are produced by laboratories that participate regularly in performance studies. This makes it possible to judge the quality of the results based on the objective measurements made by independent assessors. AMAP laboratories participated, while analysing the AMAP samples, in the QUASIMEME laboratory performance study programme, and in two other smaller laboratory performance study programmes. Here is a system presented where the laboratory performance studies are used to calculate a constant error and a proportional error for each analyte. The calculations are performed by the trial and error method that sets the proportional and the constant error so that the 95%, the 68.2%, and the 50% confidence limits fit as well as possible with the data. The constant error is roughly the same as the detection limit defined as the highest concentration where zero is inside the 95% confidence interval. The relative errors of the trace analyses, i.e. the relative deviation of the result obtained by the AMAP laboratory from the assigned value, are in most of the cases less than 25% which is regarded as acceptable by the QUASIMEME. Usually the errors, especially for trace elements, are less than 12.5%, while errors for trace organics below 1 microg kg(-1) may rise to 50% or more.

Recently, there has been an increase in studies focusing on an emerging class of organic contaminants, hydroxylated PCBs (OH-PCBs) and chlorinated phenolic compounds (CPCs) in the environment, particularly in northern regions of Europe and Canada. Since information for fish from the Great Lakes are scarce, we determined the blood plasma concentrations of OH-PCB congeners, pentachlorophenol (PCP), 2,3,4,5-tetrachlorophenol (TCP), and 4-hydroxyheptachlorostyrene (4-OH-HpCS) for lake trout (Savelinus namaycush) collected from two of the Great Lakes, Lake Ontario and Lake Superior, and two regional lakes, Lake Champlain and Lake Opeongo. PCP was the dominant CPC in lake trout (105-658 pg/g of plasma). Detectable concentrations of 2,3,4,5-TCP and 4-OH-HpCS were found in all lake trout (2.6-101 and 0.4-27 pg/g, respectively). Highest concentrations were found in trout from Lake Ontario and Lake Superior. Sixteen OH-PCBs were quantified, with 4-OH-CB187 having the highest concentration in all samples (10-173 pg/g of plasma). Unexpectedly, highly chlorinated OH-PCBs such as 4'-OH-CB199 (mean 21.4 and 74.4 pg/g), 4,4'-diOH-CB202 (18.3 and 27.7 pg/g), and 4'-OH-CB208 (24.5 and 34.7 pg/g) were found in lake trout from Lake Ontario and Lake Superior, respectively. Future studies to delineate the sources and impacts of CPCs in the Great Lakes catchment are needed.

Samples of spruce needles, snowpack, and sediment were analyzed in the area around the Alberta Special Waste Treatment Centre (ASWTC) near Swan Hills, Canada, in 1997 and 1998, following a major accidental release of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in October 1996. The PCB concentrations in spruce needles and snow were mostly elevated to the east of the plant and contained congeners that were not present at upwind or distant sites. Several years of annual vegetation monitoring data indicated that PCB emissions increased prior to the reported accident. Within 3 km of the plant, there was a predominance of higher chlorinated congeners penta-, hexa-, hepta-, and octachlorobiphenyls in white spruce (Picea glauca) needles and snow. Polychlorinated biphenyl congener patterns varied seasonally in spruce needles, likely influenced by temperature effects on the volatilization and of particle-bound and vapor phase PCBs in the forest canopy. The similarity of deposition patterns in snow and needles in 1997 and 1998 suggested the PCBs in the surrounding area were derived by long-term fugitive releases of PCBs rather than an accidental release. In addition, hexachlorobenzene, a combustion by-product of chlorinated organics in waste incinerators, was not measured at elevated concentrations in spruce needles or snow east of the facility and, when detected, was not correlated with PCB concentrations. A radiometrically dated sediment core from nearby Chrystina Lake (AB, Canada) showed a gradual increase in annual PCB flux during the early years of operation of the ASWTC, followed by a higher PCB flux in 1997, indicating that the lake may have been directly contaminated by the accidental release.

Planktonic copepods (Calanus glacialis and C. hyperboreus; n = 37) and water (n = 19) were collected to examine the spatial distribution and bioaccumulation of organochlorine contaminants (OCs) in the Alaskan and Canadian Arctic. The rank order of total OC (sigma OC) group concentrations in Calanus samples was toxaphene > or = sigma polychlorinated biphenyls (PCBs) > sigma hexachlorcyclohexane (HCH) > sigma DDT > sigma chlordane-related compounds (CHLOR) > sigma chlorobenzenes (ClBz). The dominant analyte was alpha-HCH in all water and zooplankton samples. The most abundant toxaphene congener in water and zooplankton samples was the hexachlorobornane B6-923. Organochlorine contaminant group concentrations in Alaskan zooplankton and water samples were lower than those in samples collected from sites in the eastern Canadian Arctic. Comparison of PCB and toxaphene congener profiles in zooplankton and water samples suggests that biotransformation by cytochrome P-4502B isozymes is low in Calanus, and limited phase I metabolism may occur. The log relationship of bioaccumulation factor (log BAF) versus octanol-water partition coefficient (log Kow) relationship was near 1:1 for OCs within the log Kow range of 3 to 6. A curvilinear model provided a better relationship between these two variables when OC compounds with log Kow > 6 were included. These results suggest that hydrophobic OCs (log Kow 3-6) in Calanus species are at equilibrium with the water concentrations and that physical partitioning, rather than biotransformation, is the major factor governing OC profiles in marine zooplankton.

A variety of commercial surfactants were tested to determine their effect on polychlorinated biphenyl (PCB) transformation by Pseudomonas LB400. Initial tests determined that most surfactants were fully or partially able to solubilize the PCB congeners 2,5,2'-chlorobiphenyl (CBP), 2,4,2',4'-CBP, 2,3,5,2',5'-CBP and 2,4,5,2',4',5'-CBP, at concentrations above the surfactants' critical micelle concentration (CMC). Surfactants were also found to have no negative effect on bacterial survival, as cell numbers were the same or higher after incubation in the presence of surfactants than after incubation without surfactants. A comparison of the extent of biotransformation of single PCB congeners by the bacterium revealed that, at surfactant concentrations above the CMC, the presence of an anionic surfactant promoted while nonionic surfactants inhibited PCB transformation, compared to a control with no surfactant. The rates of transformation of PCB congeners were also higher in the presence of the anionic surfactant compared to the control. The inhibitory effects of a nonionic surfactant, Igepal CO-630 at a concentration above its CMC, on transformation of 2,4,5,2',5'-CBP could be eliminated by diluting the surfactant/PCB solution to a concentration close to the surfactant CMC.

Resting cells of Pseudomonas strain LB400, grown on biphenyl, transformed 80, 50 and 17% of Aroclor 1242, 1254, and 1260, respectively. Resting cells grown on glucose or glycerol also transformed these polychlorinated biphenyl (PCB) mixtures to the extent of 60, 35, and 9% for Aroclors 1242, 1254, and 1260, respectively. Time courses of the transformation of the separated individual congeners in the Aroclors were plotted and used to determine the transformation rate constants (k). By analysis of the rate constants, it was concluded that the order of degradation of the different congeners in an Aroclor were similar regardless of the growth substrate. In general, k values for the conversion of a particular congener were lower for cells grown on glucose or glycerol compared with cells grown on biphenyl. Generally, k values for the transformation of the same congener in different Aroclors were not the same: rate constants had highest values for the congener in Aroclor 1242 and lowest values in Aroclor 1260. The data allowed congeners to be grouped according to their relative rates of degradation. The ratio of k values for transformation of individual congeners in Aroclors by cells grown on biphenyl and glucose were not constant.