Identification of organochlorines and organobromines in coals

Four Chinese bituminous coals were extracted with CS₂, n-hexane, benzene, methanol, acetone, tetrahydrofuran (THF) and THF/methanol (1: 3 vol/vol) mixed solvent sequentially. The resulting 28 extracts were analyzed with GC/MS. Six organochlorines (OCs) and two organobromines (OBs) were identified in eight extracts from the coals. Our experiments provide, for the first time, the information on the molecular structure of OCs and OBs in coals.     

Determination of organochlorine pesticides in shrimp by gas chromatography–mass spectrometry using a modified QuEChERS approach

Pacific white shrimp (Litopenaeus vannamei) collected during dry and rainy seasons from three different states in Malaysia were analyzed for nine organochlorine pesticides (OCPs) (α-HCH, β-HCH, γ-HCH, δ-HCH, trans-chlordane, cis-chlordane, p,p′-DDE, p,p′-DDD and p,p′-DDT) using QuEChERS sample preparation method and GC–MS SIM with split/splitless injection mode. The efficiency of combination of primary and secondary amine (PSA) and octadecyl (C18) at 25 mg of PSA and 25 mg of C18 per mL of shrimp extract as the clean-up sorbent to remove matrix interferences was evaluated. By combining PSA and C18, matrix interferences such as gamma-tocopherol and cholesterol were not able to be eliminated. Good separation and high recoveries which ranged from 90 to 105% with associated RSD < 15% were obtained for all OCPs at 3–75 ng/g. No significant difference in recoveries due to seasonal variation for studied OCPs, except for α-HCH, β-HCH, δ-HCH and p,p′-DDT were obtained. The limits of detection and quantification ranged from 0.3 to 4.5 ng/g and 3 to 15 ng/g, respectively. The linearity for matrix matched standard calibrations was >0.99.     

Solar photocatalytic degradation of some hazardous water-soluble pesticides at pilot-plant scale

The technical feasibility and performance of photocatalytic degradation of six water-soluble pesticides (cymoxanil, methomyl, oxamyl, dimethoate, pyrimethanil and telone) have been studied at pilot-plant scale in two well-defined systems which are of special interest because natural solar UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. TiO(2) photocatalysis tests were performed in a 35L solar pilot plant with three Compound Parabolic Collectors (CPCs) under natural illumination and a 75L solar pilot plant with four CPC units was used for homogeneous photocatalysis tests. The initial pesticide concentration studied was 50 mg L(-1) and the catalyst concentrations employed were 200 mg L(-1) of TiO(2) and 20 mg L(-1) of iron. Both toxicity (Vibrio fischeri, Biofix) and biodegradability (Zahn-Wellens test) of the initial pesticide solutions were also measured. Total disappearance of the parent compounds and nearly complete mineralization were attained with all pesticides tested. Treatment time, hydrogen peroxide consumption and release of heteroatoms are discussed.     

Organochlorine residues in two seal species from Western Iceland

Harbour seals and grey seals from Faxaflói (Western Iceland) were analyzed for contamination with organochlorines (HCB, PCBs, p,p′-DDT, p,p′-DDE, chlordanes and the enantiomers of α-HCH). Although the values strongly varied, both harbour seals and grey seals on average showed comparable levels of PCBs, p,p′-DDT, p,p′-DDE and α-HCH, as well as chlordanes (ΣCD). Differences were measured in the HCB content of the seal species. The HCB/α-HCH ratio in harbour seals was <1 and in grey seals >1. The results from seals on Iceland were compared with data derived from seal samples of the Antarctic, the Arctic (Spitzbergen) and the North Sea (Germany) in order to give an insight into the global distribution of pollution with chlorinated organics.     

Spatial and temporal trends and effects of contaminants in the Canadian Arctic marine ecosystem: a review

Recent studies have added substantially to our knowledge of spatial and temporal trends of persistent organic pollutants and heavy metals in the Canadian Arctic marine ecosystem. This paper reviews the current state of knowledge of contaminants in marine biota in the Canadian Arctic and where possible, discusses biological effects. The geographic coverage of information on contaminants such as persistent organochlorines (OCs) (PCBs, DDT- and chlordane-related compounds, hexachlorocyclohexanes, toxaphene) and heavy metals (mercury, selenium, cadmium, lead) in tissues of marine mammal and sea birds is relatively complete. All major beluga, ringed seal and polar bear stocks along with several major sea bird colonies have been sampled and analysed for OC and heavy metal contaminants. Studies on contaminants in walrus are limited to Foxe Basin and northern Québec stocks, while migratory harp seals have only been studied recently at one location. Contaminant measurements in bearded seal, harbour seal, bowhead whale and killer whale tissues from the Canadian Arctic are very limited or non-existent. Many of the temporal trend data for contaminants in Canadian Arctic biota are confounded by changes in analytical methodology, as well as by variability due to age/size, or to dietary and population shifts. Despite this, studies of OCs in ringed seal blubber at Holman Island and in sea birds at Prince Leopold Island in Lancaster Sound show declining concentrations of PCBs and DDT-related compounds from the 1970s to 1980s then a levelling off during the 1980s and early 1990s. For other OCs, such as chlordane, HCH and toxaphene, limited data for the 1980s to early 1990s suggests few significant declines in concentrations in marine mammals or sea birds. Temporal trend studies of heavy metals in ringed seals and beluga found higher mean concentrations of mercury in more recent (1993/1994) samples than in earlier collections (1981–1984 in eastern Arctic, 1972–1973 in western Arctic) for both species. Rates of accumulation of mercury are also higher in present day animals than 10–20 years ago. Cadmium concentrations in the same animals (eastern Arctic only) showed no change over a 10-year period. No temporal trend data are available for metals in sea birds or polar bears. There have been major advances in knowledge of specific biomarkers in Canadian Arctic biota over the past few years. The species with the most significant risk of exposure to PCBs and OC pesticides may be the polar bear which, based on comparison with EROD activity in other marine mammals (beluga, ringed seal), appears to have elevated CYP1A-mediated activity. The MFO enzyme data for polar bear, beluga and seals suggest that even the relatively low levels of contaminants present in Arctic animals may not be without biological effects, especially during years of poor feeding.     

Development of a fast screening method for the direct determination of chlorinated persistent organic pollutants in fish oil by high-resolution continuum source graphite furnace molecular absorption spectrometry

The occurrence of persistent organic pollutants (POPs), mainly organochlorine pesticides and polychlorinated biphenyls, was directly associated with several diseases and environmental endocrine disrupting. In the aquatic environment, POPs can accumulate in fish lipoid tissues due to their high hydrophobicity, and become this way one of the main sources of human exposure to POPs through the consumption of fish meat and oil as Omega-3 source. Chlorine might serve as a proxy for the presence of POPs, and a fast screening of chlorine in a complex matrix, such as fish oil, could provide substantial information about the contamination with POPs. Therefore, a method has been developed in this work for the determination of total chlorine in fish oil samples via molecular absorption of the strontium mono-chloride molecule in the gas phase using high-resolution continuum source graphite furnace molecular absorption spectrometry. The effect of zirconium as permanent chemical modifier in the pyrolysis and vaporization stages was optimized in order to avoid the need for any kind of sample preparation prior to the determination of total chlorine, using just a dilution with 1-propanol. The accuracy has been evaluated using micro-coulometric titration after sample combustion, and the values were statistically in agreement (95% confidence level) between both techniques. The method has been applied for the determination of total chlorine in five different fractions of a commercial pooled marine fish oil sample collected from the Pacific Ocean, where the majority of the fish is Peruvian anchovy (Engraulis ringens), two commercial oils from Brazil and three Omega-3 supplements acquired in Germany. The limit of detection of the procedure is 1.8 ng Cl absolute or 0.9 μg g⁻¹ Cl in the fish oil. The time required for a single determination is less than 5 min, and less than 15 min for a triplicate determination.     

Organ-specific accumulation and elimination patterns of PCBs in adult seabass (Dicentrarchus labrax)

The present study quantifies and explains the differences between measured organ-specific polychlorinated biphenyls (PCBs) accumulation and elimination kinetics in seabass (Dicentrarchus labrax), comparing these results with calculations using the generic model OMEGA. Specimens of approximately 250 g were selected and fed with contaminated food with PCBs 18, 44, 49, 52, 101, 105, 118, 138, 180 and 187. The OMEGA model was applied using a measured biomass (re)production coefficient and the food ingestion coefficient. It produced estimations of total body concentrations within a factor between 1.5 and 7.0 times of the measured and it also reproduced the general trend of the PCB concentrations during the experiment. This study allows us to confirm that internal distribution of PCBs is slow, producing significant differences in the tissues elimination rate constants and consequently in tissues bioaccumulation factors (BAF). The distribution of PCBs within the organism was slower than reported before, due to the bigger body size and the high lipid content of these fish.     

Organochlorine contaminants in endangered Steller sea lion pups (Eumetopias jubatus) from western Alaska and the Russian Far East

Investigations into the cause of the Steller sea lion population decline have focused on numerous factors, including exposure to toxic contaminants such as organochlorines (OCs). OCs, such as polychlorinated biphenyls (PCBs), 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, or dichlorodiphenyltrichloroethane (DDT), have been associated with various biological effects in marine mammals. We measured these compounds in whole blood of free-ranging Steller sea lion pups in order to determine the extent and magnitude of contamination across their geographical range. Of 212 pups analyzed for OCs, 76 pups (36 females and 40 males) were from western Alaska and the other 136 (63 females and 73 males) were from the Russian Far East. Concentrations of summation SigmaPCBs in the whole blood of pups from western Alaska ranged from 0.21 to 13 ng/g wet weight with a mean of 2.1+/-0.27 ng/g wet weight. In the Russian animals, summation SigmaPCB concentrations in the whole blood of pups ranged from 0.33 to 36 ng/g wet weight with a mean of 4.3+/-0.44 ng/g wet weight. summation SigmaDDT concentrations in the whole blood of pups from western Alaska ranged from 0.18 to 11 ng/g wet weight with a mean of 1.6+/-0.23 ng/g wet weight. In Russia, summation SigmaDDT in the whole blood of pups ranged from undetectable to 26 ng/g wet weight with a mean of 3.3+/-0.36 ng/g wet weight. Average OC concentrations were significantly higher in the blood of Russian animals compared to western Alaska (for PCBs and DDTs, p<0.001) and in both areas females had higher concentrations than males. Male pups from western Alaska had significantly lower levels of summation SigmaPCBs and summation SigmaDDT when compared to male pups from Russia (for PCBs and DDTs p<0.001). Female pups from western Alaska were significantly lower in summation SigmaPCBs than Russian female pups (for PCBs p=0.009) as were female pups for summation SigmaDDT levels between areas (for DDTs p=0.026). OC contaminants data indicate that Steller sea lion pups have measurable concentrations of these synthetic chemicals. While any physiological effect and the specific role these chemicals may have in either the decline or the failure of the endangered Steller sea lion population to recover needs to be further investigated, this study indicates specific areas and animals that may be most at risk.     

Abandoned Mid-Canada Radar Line sites in the Western James region of Northern Ontario, Canada: a source of organochlorines for First Nations people?

The potential exists for human exposure to polychlorinated biphenyls (PCBs) and other contaminants originating from abandoned Mid-Canada Radar Line (MCRL) sites in sub-arctic Canada. We examined patterns of differences with respect to body burden of organochlorines (lipid-adjusted) between residents of the Ontario First Nations of Fort Albany (the site of MCRL Site 050) and Kashechewan (no radar base) and Hamilton (an industrial, southern Ontario community) to assess whether the presence of Site 050 influenced organochlorine body burden with respect to the people of Fort Albany. PCBs (Aroclor 1260 and summation operator14 PCBs congeners [CBs]) and DDE in the plasma of Fort Albany and Kashechewan subjects were elevated relative to Hamilton participants. PCB and DDE-plasma levels in First Nation women were of comparable magnitude to those reported for Inuit women living in the west/central Northwest Territories. Significantly lower DDE/DDT ratios observed for Fort Albany indicates exposure to higher levels of DDT compared to Kashechewan. The probable source of DDT exposure for Fort Albany people is the DDT-contaminated soil surrounding buildings of Site 050. The results of the correspondence analysis (CA) indicated that people from Hamilton had relatively higher pesticides and lower CB body burdens, while people from Fort Albany and Kashechewan exhibited relatively higher CBs and lower pesticide levels (CA-1). The separation of Fort Albany and Kashechewan from Hamilton was also clear using questionnaire data (i.e., plotting dietary principal component [PC]-1 scores against PC-2); PC-1 was correlated with the consumption of a traditional diet. Separation of Kashechewan and Albany residents occurred because the people of Kashechewan ate more traditional meats and consumed shorebirds. Only one significant relationship was found between PC analysis and contaminant loadings; PC-1 versus CA-3 for Kashechewan. The presence of Site 050 on Anderson Island appears to have influenced organochlorine body burden of the people of Fort Albany. ANCOVA results revealed that it was not activity on Anderson Island that was important, but activity on Site 050 was the influential variable. When these results are considered with the DDE/DDT ratio data and the CB 187 results (Fort Albany and Kashechewan residents differed significantly), the findings are suggestive that Site 050 did influence organochlorine body burden of people from Fort Albany.     

Levels and trends of organochlorines and brominated flame retardants in ivory gull eggs from the Canadian Arctic, 1976 to 2004

The ivory gull (Pagophila eburnea) is a circumpolar marine bird which has recently been listed as an endangered species in Canada. To determine whether contaminants may be playing a role in the population decline of this species, ivory gull eggs collected in 1976, 1987 and 2004 from Seymour Island in the Canadian Arctic were analyzed for organochlorines, polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs. This study also provides the first account of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs) and polybrominated biphenyls (PBBs) in ivory gulls. The most quantitatively abundant legacy organochlorines found in the ivory gull eggs were p,p'-DDE, SigmaPCB and oxychlordane. Concentrations of the organochlorines analyzed either decreased or showed little change between 1976 and 2004. Concentrations of SigmaPCDD in ivory gull eggs were greater than SigmaPCDF, and the non-ortho PCBs (primarily PCB-126) contributed the largest fraction to the total TEQ value in all years sampled. Concentrations of PCDDs, PCDFs and SigmaTEQ decreased from 1976 to 2004. In contrast, concentrations of the PBDEs steadily increased between 1976 and 2004 driven primarily by increases in BDE-47. Although concentrations of the persistent chlorinated compounds (i.e. organochlorine pesticides, PCBs, PCDDs, PCDFs) reported in this study were below published toxicological threshold values for eggs of wild birds, we cannot rule out the possibility of synergistic/additive, sublethal effects. Very few studies have been carried out to evaluate the exposure-effect relationship of the persistent brominated compounds in avian species. Given the scarcity of information on toxicity threshold levels for PBBs and PBDEs in avian species, coupled with the trend toward increasing concentrations in ivory gulls, continued monitoring and further toxicological studies of these compounds are warranted.