Legacy Organochlorine Pesticides Research Articles

A Decade of Data and Hundreds of Analytes: Legacy and Emerging Chemicals in North American Herring Gull Plasma

Between 2010 and 2021, 199 herring gull serum samples were collected from Lake Michigan, Lake Huron, and Lake Erie, including two Areas of Concern: Saginaw Bay and the River Raisin. They were analyzed for 21 polybrominated diphenyl ether congeners, 10 non-PBDE flame retardants, 85 polychlorinated biphenyls, 17 legacy organochlorine pesticides, and 36 per- and polyfluoroalkyl substances. Σ36PFAS, Σ85PCB, Σ21PBDE, and Σ17Pesticide concentrations comprised 41-74%, 17-50%, 3-4%, and 5-9% of the total concentration, respectively. Median concentrations of the chemical groups ranged from 81.5 – 129 ng/g ww for PFAS, 26.3 – 158 ng/g ww for PCBs, 4.26 – 8.89 ng/g ww for PBDEs, and 8.08 – 23.0 ng/g ww for pesticides. The regional concentrations of all four classes of compounds are significantly decreasing when sites are combined with halving times of 11.3 ± 4.8, 8.2 ± 4.3, 5.9 ± 3.1, and 8.3 ± 4.2 years for Penta-BDE mixture, ΣDDTs, Σ85PCBs and Σ36PFAS, respectively. These results suggest that while PFAS has emerged as the dominant group of chemicals in the plasma, legacy pollutants continue to represent a threat to herring gulls and wildlife in the Great Lakes basin. PCBs were the largest contributor to the chemical load in plasma of birds whose colonies are located near the River Raisin, and continue to pose a threat to herring gulls within the two Areas of Concern.

A Decade of Data and Hundreds of Analytes: Legacy and Emerging Chemicals in North American Herring Gull Plasma

Between 2010 and 2021, 199 herring gull serum samples were collected from Lake Michigan, Lake Huron, and Lake Erie, including two Areas of Concern: Saginaw Bay and the River Raisin. They were analyzed for 21 polybrominated diphenyl ether congeners, 10 non-PBDE flame retardants, 85 polychlorinated biphenyls, 17 legacy organochlorine pesticides, and 36 per- and polyfluoroalkyl substances. Σ36PFAS, Σ85PCB, Σ21PBDE, and Σ17Pesticide concentrations comprised 41-74%, 17-50%, 3-4%, and 5-9% of the total concentration, respectively. Median concentrations of the chemical groups ranged from 81.5 – 129 ng/g ww for PFAS, 26.3 – 158 ng/g ww for PCBs, 4.26 – 8.89 ng/g ww for PBDEs, and 8.08 – 23.0 ng/g ww for pesticides. The regional concentrations of all four classes of compounds are significantly decreasing when sites are combined with halving times of 11.3 ± 4.8, 8.2 ± 4.3, 5.9 ± 3.1, and 8.3 ± 4.2 years for Penta-BDE mixture, ΣDDTs, Σ85PCBs and Σ36PFAS, respectively. These results suggest that while PFAS has emerged as the dominant group of chemicals in the plasma, legacy pollutants continue to represent a threat to herring gulls and wildlife in the Great Lakes basin. PCBs were the largest contributor to the chemical load in plasma of birds whose colonies are located near the River Raisin, and continue to pose a threat to herring gulls within the two Areas of Concern.

Sediment-water exchange and risk assessment of pesticidal persistent organic pollutants in Bharathappuzha and Periyar Riverine region along the Arabian Sea.

Considering the extensive agricultural practices along the perennial rivers, viz. Periyar and Bharathappuzha of Kerala in the southwest coast of India, the first comprehensive surveillance of new and legacy organochlorine pesticides (OCPs) in surface sediment was conducted. Further, the sediment-water exchange fluxes have been elucidated. Mean concentrations of total HCH, DDT and endosulfan were 0.84ng/g, 0.42ng/g and 0.30ng/g for Bharathappuzha Riverine sediment (BRS) and 1.08ng/g, 0.39ng/g and 0.35ng/g for Periyar Riverine sediment (PRS). The dominance α-HCH and β-HCH isomers in PRS and BRS reflect the ongoing use of technical HCH in Kerala. The calculated KSW in both rivers was very low in comparison with other Indian rivers. The average log K'OC for all the detected OCPs in both the rivers was lower than the predicted log KOC in equilibrium indicating the higher adherence of OCPs to sediment. Furthermore, fugacity fraction (fs/fw) was < 1.0 for all OCPs confirming the net deposition of OCPs into the sediment. Sediment concentrations for each of the OCPs in PRS and BRS did not surpass the threshold effect level and probable effect level as stipulated by the Canadian Council of Ministry of the Environment Guidelines. In addition, all the sites of both rivers had sediment quality guideline quotient (SQGQ) values below 0.1 indicating the absence of significant biological and ecological risks.

New and legacy pesticidal persistent organic pollutants in the agricultural region of the Sultanate of Oman

Comprehensive air and surface soil monitoring was conducted for new and legacy organochlorine pesticides (OCPs) to fill the knowledge and data gap on the sources and fate of pesticidal persistent organic pollutants (POPs) in the Sultanate of Oman. DDTs in agricultural soil samples ranged from 0.013 to 95.80 ng/g (mean: 8.4 ± 25.06 ng/g), with a median value of 0.07 ng/g. The highest concentration was observed at Shinas, where intensive agricultural practice is prevalent. The dominance of p,p′-DDT in soil and air reflected technical DDT formulation usage in Oman. Among newly enlisted POPs, pentachlorobenzene had the maximum detection frequency in air (47%) and soil (41%). Over 90% of sites reflected extensive past use of hexachlorobenzene. Major OCP isomers and metabolites showed net volatilisation from the agricultural soil, thereby indicating concurrent emission and re-emission processes from the soil of Oman. However, the cleansing effect of oceanic air mass is the possible reason for relatively lower atmospheric OCP levels from a previous study. Although DDT displayed maximum cancer risk, the level is below the permissible limit. DDT primarily stemmed from obsolete stock and inadequate management practices. Hence, we suggest there is a need for DDT regulation in Oman.

Legacy and current-use pesticides in Western Canadian mountain air: Influence of pesticide sales, source proximity, and altitude

Large amounts of pesticides are applied in agriculture in Canada and around the world. A considerable fraction can be dispersed in the atmosphere and deposited in non-target ecosystems. Our knowledge of the factors controlling the movement of pesticides in the atmosphere is still limited. In order to investigate the atmospheric distribution of pesticides under the influence of diverse environmental variables, we deployed XAD-2 resin-based passive air samplers (PAS) at multiple elevations of four mountains across Southern British Columbia and derived annually averaged concentrations of twelve current-use pesticides (CUPs) and five legacy organochlorine pesticides (OCPs) in air. The four mountains have similar altitude and latitude but vary in their proximity to source regions. Hexachlorobenzene, endosulfan I, and simazine were most abundant with median concentrations exceeding 50 pg/m3. While concentrations were generally lower than elsewhere in Canada, especially in agricultural regions, they varied greatly across the four mountains. Remote Mount Anderson had lower CUP levels than the other three mountains. CUP concentrations correlated well with regional pesticide sales, with two distinct spatial patterns becoming apparent. The OCP concentrations in the air of the four mountains were relatively uniform. CUP concentrations in air usually decreased with increasing altitude, when under the strong influence of ground-level sources. Source proximity and altitude appear to play a much more important role than precipitation and vegetation cover in the distribution of pesticides in the atmosphere. This study also highlights the value of a good registration system for pesticide sales for explaining environmental concentration variability.

Alterations of Systemic and Hepatic Metabolic Function Following Exposure to Trans-nonachlor in Low and High Fat Diet Fed Male Sprague Dawley Rats.

The overall prevalence of metabolic diseases such as type 2 diabetes (T2D) and associated co-morbidities have increased at an alarming rate in the United States and worldwide. There is a growing body of epidemiological evidence implicating exposure to persistent organic pollutants (POPs), including legacy organochlorine (OC) pesticides and their bioaccumulative metabolites, in the pathogenesis of metabolic diseases. Therefore, the goal of the present study was to determine if exposure to trans-nonachlor, a bioaccumulative OC pesticide contaminant, in concert with high fat diet intake induced metabolic dysfunction. Briefly, male Sprague Dawley rats were exposed to trans-nonachlor (.5 or 5 ppm) in either a low fat (LFD) or high fat diet (HFD) for 16 weeks. At 8 weeks of intake, trans-nonachlor decreased serum triglyceride levels in LFD and HFD fed animals and at 16 weeks compared to LFD fed animals. Interestingly, serum glucose levels were decreased by trans-nonachlor (5 ppm) in LFD fed animals at 16 weeks. Serum free fatty acids were increased by trans-nonachlor exposure (5 ppm) in LFD fed animals at 16 weeks. HFD fed animals displayed signs of hepatic steatosis including elevated liver triglycerides, liver enzymes, and liver lipid peroxidation which were not significantly altered by trans-nonachlor exposure. However, there was a trans-nonachlor mediated increase in expression of fatty acid synthase in livers of LFD fed animals and not HFD fed animals. Thus, the present data indicate exposure to trans-nonachlor in conjunction with LFD or HFD intake produces both diet and exposure dependent effects on lipid and glucose metabolism.

Contamination characteristics, spatial distribution and ecological-health risk assessment of legacy and current-use pesticides: a case study in the Beibu Gulf

With the prohibition of conventional organochlorine pesticides (OCPs), the extensive use and continuous release of current-use pesticides (CUPs), such as organic amine pesticides (OAPs) and organophosphate pesticides (OPPs), in agriculture and mariculture activities have raised global attention. In this study, the occurrence and distribution of 36 pesticides from above 3 categories were investigated in seawater and sediment in Beibu Gulf, a typical subtropical agricultural and maricultrual zone. Results showed that pesticides were widely present in this region with the total concentration ranging from 0.36 to 21.07 ng/L in seawater and from 0.02 to 9.73 ng/g dw in sediment. OAPs and OPPs were the most abundant categories contributing 74% and 66% to the total pesticides burden in seawater and sediment, respectively, revealing the current-use pesticides as substitutes of legacy organochlorine pesticides (OCPs) were mainly used in surrounding areas. For both seawater and surface sediment, the spatial distribution of pesticides concentrations showed generally seaward decreasing trends, suggesting that anthropogenic activities at coastal areas have an important impact on pesticides pollution. Source identification indicated OCPs in some seawater samples might be from mixture of antifouling paint and dicofol usage, while history residues are main sources of OCPs in sediment. OAPs, especially for cyflufenamid and kresoxim-methyl, mainly come from agricultral and maricultural sewage input, and OPPs were speculated from currency transportation from surrounding areas. Ecological risk assessment showed that OPPs posed moderate to even high risks in most seawater sites. It appears that crustaceans are the most sensitive trophic species to OPPs among aquatic organisms, followed by fish. According to the results of health risks proposed by the major aquatic products in Beibu Gulf (fish and shrimp), the selected pesticides pose no health risk to humans. Nevertheless, OCPs made the highest contribution to the total HQ values. Comprehensively considering the evaluation results of both ecological and health risks, more attention should be given on OPPs and OCPs pollution in the Beibu Gulf.

Occurrence of legacy organochlorine pesticides in small mammals from two mountainous National Parks in southeastern Brazil

In southeastern Brazil, particular altitudinal grassland ecosystems, known as campos de altitude, occur at mountainous summits that host an outstanding level of biodiversity and endemism. However, despite being environmentally protected areas, several studies have shown their susceptibility to the impacts of climate change and airborne pollution. Previous studies highlighted that organochlorine pesticides (OCPs), present higher atmospheric concentrations along altitudinal gradients and can be locally deposited. On top of that, formerly used OCPs are still detected in the atmosphere on those mountaintops, long after their phase-out. Nevertheless, the potential bioaccumulation of OCPs by endemic species has not yet been assessed. Thus, we aimed to investigate the occurrence of OCPs in terrestrial subalpine wildlife and to establish a baseline for further in-depth studies on OCPs, or similar hazardous chemicals, in these endangered environments. In summary, 28 OCP congeners were investigated in 49 liver samples of ten small mammal species collected in 2013 and in 2016. Chemical analyses were based on gas chromatography coupled with electron capture negative ionization mass spectrometry (GC/ECNI-MS). Additional stable isotope analyses (δ 15 N and δ 13C) were performed to elucidate the role of trophic position on OCP bioaccumulation. Mirex, heptachlor, hexachlorobenzene, chlordane, and hexachlorocyclohexane congeners were the most frequently detected OCPs (59–97% of all samples). Regarding OCP contents in liver tissues, Mirex was also dominant. The atmospheric transport from secondary sources was assumed to be the origin of OCPs in the studied environment and their occurrence and difference between the two sampling sites are in good agreement with previous atmospheric monitoring. Further studies are needed to evaluate the exposure of campos de altitude endemic organisms to other airborne hazardous chemicals and to assess the potential toxicity posed by contaminant mixtures.

Vertical profiles of legacy organochlorine pesticides in sediment cores from lake Nakaumi, Japan

Two sediment core samples from the brackish Lake Nakaumi in Japan were analyzed to determine the historical profiles of organochlorine pesticides (OCPs). It was observed that from the 1940s to 2005, the vertical distribution of OCPs in sediment cores reflected the temporal trend of pesticide usage in Japan. Dichlorodiphenyltrichloroethane (DDT) and its metabolites were predominant, with concentrations of 0.008–8.27 ng g−1 dry weight, and their contribution to ΣOCPs was over 58%. The results also confirmed that the DDTs in the sediment cores originated from past input. Further, even though hexachlorocyclohexanes were the most used OCP in Japan, their residual concentrations were lower than those of DDTs and chlordane related compounds (CHLs). The concentrations of CHLs were 0.163–1.539 ng g−1 dry weight, whereas hexachlorobenzene (HCB), drins, heptachlor, and mirex showed very low concentrations. Interestingly, although HCB was never registered as a pesticide in Japan, it was detected in both core samples. This HCB contamination might be attributed to pentachlorophenol. Additionally, the hierarchical cluster analysis results corresponding to both sediment cores could be classified under four groups based on a similarity of over 50%. The results also showed that the OCP burden in Lake Nakaumi for the past 60 years was 130 kg and 1153 kg at Honjo and at the center of Lake Nakaumi, respectively. Overall, the results of this study indicate that the distribution of OCPs in Lake Nakaumi reflects the trend of pesticide usage in Japan.

Seasonal variations in air concentrations of 27 organochlorine pesticides (OCPs) and 25 current-use pesticides (CUPs) across three agricultural areas of South Africa

For decades pesticides have been used in agriculture, however, the occurrence of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPs) is poorly understood in Africa. This study investigates air concentrations of OCPs and CUPs in three South African agricultural areas, their spatial/seasonal variations and mixture profiles.Between 2017 and 2018, 54 polyurethane foam-disks passive air-samplers (PUF-PAS) were positioned in three agricultural areas of the Western Cape, producing mainly apples, table grapes and wheat. Within areas, 25 CUPs were measured at two sites (farm and village), and 27 OCPs at one site (farm). Kruskal-Wallis tests investigated area differences in OCPs concentrations, and linear mixed-effect models studied differences in CUPs concentrations between areas, sites and sampling rounds.In total, 20 OCPs and 16 CUPs were detected. A median of 16 OCPs and 10 CUPs were detected per sample, making a total of 11 OCPs and 24 CUPs combinations. Eight OCPs (trans-chlordane, o,p’-/p,p’-dichlorodiphenyldichloroethylene (DDE)/dichlorodiphenyltrichloroethane (DDT), endosulfan sulfate, γ-hexachlorocyclohexane and mirex) and two CUPs (carbaryl and chlorpyrifos) were quantified in all samples. p,p’-DDE (median 0.14 ng/m3) and chlorpyrifos (median 0.70 ng/m3) showed the highest concentrations throughout the study. Several OCPs and CUPs showed different concentrations between areas and seasons, although CUPs concentrations did not differ between sites. OCPs ratios suggest ongoing chlordane use in the region, while DDT and endosulfan contamination result from past-use.Our study revealed spatial and seasonal variations of different OCPs and CUPs combinations detected in air. Further studies are needed to investigate the potential cumulative or synergistic risks of the detected pesticides.

Development of current ambient background threshold values for sediment quality parameters in U.S. lakes on a regional and statewide basis

For the first time, background threshold values have been developed for a large suite of sediment quality parameters from 969 lakes spanning the conterminous United States (U.S.). These values provide a statistical basis for estimating current ambient background, which refers to chemical and physical (e.g., grain size) concentrations derived from natural and/or widespread diffuse anthropogenic sources (e.g., nonpoint sources like atmospheric deposition and land runoff). Surficial sediment quality data, collected based on the randomized, probability-based sampling design of the 2017 National Lakes Assessment (NLA) study, were utilized for this effort. These data included 16 metal(loid)s, 25 polycyclic aromatic hydrocarbons (PAHs), 53 polychlorinated biphenyl (PCB) congeners, 27 legacy organochlorine pesticides and metabolites, total organic carbon (TOC), and grain size parameters. The data were analyzed based on different geographic areas, including: 10 U.S. Environmental Protection Agency (EPA) Regions, two major ecoregions bisecting the State of Minnesota (i.e., Temperate Plains and Upper Midwest), and for Minnesota. Hypothesis testing of 47 sediment quality parameters was performed on three geographic areas bisecting Minnesota, and there were many statistically significant (p < 0.05) differences between geographic pairs that included Minnesota. Background threshold values were calculated for parameters with >20% detects using 95% one-sided upper tolerance limit (UTL) with 95% coverage (UTL95-95) values. The UTL95-95 represents the value below which 95% of the population values are expected to fall with 95% confidence. These values were compared to matching sediment quality guidelines for the protection of benthic organisms, both with and without potential outliers removed. Applications and limitations of the UTL95-95 values are discussed. Jurisdictions within the continental U.S. could use these same publicly available sediment quality data to calculate UTL95-95 values for specific geographic areas, and other countries could design similar probabilistic field studies to determine current ambient background of sediment quality parameters in lake sediments.

Seasonal Variation of Legacy Organochlorine Pesticides (OCPs) From East Asia to the Arctic Ocean

AbstractLarge‐scale field investigations of seven legacy organochlorine pesticides (OCPs) in the surface seawater and atmosphere from East Asia to the high Arctic Ocean were completed in 2016 and 2017. Seawater OCP (Σ7OCPs) concentrations displayed rapid and significant seasonal variations during mid‐late summer. The ocean is the most significant atmospheric‐OCP source region for the Arctic, and feedback affects the middle‐ or low‐latitude regions of the Northern Hemisphere. The legacy OCP concentrations in the Arctic Ocean were shown to gradually decrease with distance from water masses originating in the Bering Sea and the landmass of Alaska. This study is the first updated investigation of OCPs along the North Pacific Ocean to the Arctic Ocean transect in the past decade. It provides updated field data on the global fate of OCPs in a region undergoing rapid climate change.

Agrochemicals in freshwater systems and their potential as endocrine disrupting chemicals: A South African context.

South Africa is the largest agrochemical user in sub-Saharan Africa, with over 3000 registered pesticide products. Although they reduce crop losses, these chemicals reach non-target aquatic environments via leaching, spray drift or run-off. In this review, attention is paid to legacy and current-use pesticides reported in literature for the freshwater environment of South Africa and to the extent these are linked to endocrine disruption. Although banned, residues of many legacy organochlorine pesticides (endosulfan and dichlorodiphenyltrichloroethane (DDT)) are still detected in South African watercourses and wildlife. Several current-use pesticides (triazine herbicides, glyphosate-based herbicides, 2,4-dichlorophenoxyacetic acid (2,4-D) and chlorpyrifos) have also been reported. Agrochemicals can interfere with normal hormone function of non-target organism leading to various endocrine disrupting (ED) effects: intersex, reduced spermatogenesis, asymmetric urogenital papillae, testicular lesions and infertile eggs. Although studies investigating the occurrence of agrochemicals and/or ED effects in freshwater aquatic environments in South Africa have increased, few studies determined both the levels of agricultural pesticides present and associated ED effects. The majority of studies conducted are either laboratory-based employing in vitro or in vivo bioassays to determine ED effects of agrochemicals or studies that investigate environmental concentrations of pesticides. However, a combined approach of bioassays and chemical screening will provide a more comprehensive overview of agrochemical pollution of water systems in South Africa and the risks associated with long-term chronic exposure.

Atmospheric legacy organochlorine pesticides and their recent exchange dynamics in the Northwest Pacific Ocean

The occurrence and air–sea gas exchange of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), and chlordanes were determined in the Northwest Pacific Ocean (NWP) in spring to elucidate their current pollution status and fate. ΣHCHs, ΣDDTs, and Σchlordanes in air (sum of gaseous and aerosol phase) ranged from 9.37 to 102, from 1.73 to 12.8, and from 0.24 to 14.9 pg/m3, respectively, with their dissolved levels being 30.7–518, 7.10–80.5, and 0.25–7.10 pg/L, respectively. HCHs, DDTs, and chlordanes cause substantial contamination of the air and seawater of the East China Sea (ECS), indicating significant OCP inputs from China. Isomer ratios of HCHs and DDTs provided a fingerprint of East Asian emissions of legacy OCPs, with the pollution profiles of HCHs and DDTs dominated by lindane and combined dicofol-type and weathered technical DDTs, respectively. The former result is consistent with the apparent decline in air α-HCH levels over the ECS. Different from still net deposition of gaseous α- and γ-HCH in the NWP, outgassing of trans-chlordane, cis-chlordane, and DDTs other than dicofol-sourced o,p′-DDT was indicated. This observation attributes to intensive historical usage of technical HCHs and the prevalence of lindane pollution in East Asia, and demonstrates the transitioning role of seawater as a source for residual OCPs in the East Asia-NWP region. Significant subcooled liquid vapor pressure-based relationships for legacy OCPs were identified mainly in marine air masses; these were different from land-sourced polybrominated diphenyl ethers, and suggested a heterogeneous role of ocean- and land-based sources in atmospheric partitioning of these pollutants.

Organic pollutants in indoor dust from Ecuadorian Amazonia areas affected by oil extractivism

Fifty-five household dust samples collected within six settlements surrounding oil production complexes along the Ecuadorian Amazonia were analysed to evaluate the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs), phthalates, alkylphenols (APs), bisphenol A (BPA), nicotine, organophosphorus flame retardants (OPFRs), polychlorinated biphenyls (PCBs), legacy organochlorine pesticides (OCs) and organophosphorus pesticides. Studied areas are mainly affected by gas flares emissions and oil spilling coming from extractivist operations and pesticides used in agriculture. Median ΣPAHs values ranged from 739 to 1182 ng g−1 and up to 52% of the PAH dust concentrations were associated to petrogenic activities from crude oil extraction, according to diagnostic ratios. ΣPAHs and toxic equivalents based on benzo[a]pyrene concentration (ΣTEQBaP, ng g−1) suggested similar toxicities among the different areas. Individual lifetime cancer risk (ILCRdust) was calculated for ingestion and dermal contact exposure routes and a non-acceptable total carcinogenic risk of up to 10−4 (one case per ten thousand people) was found for newborns from 0 to 3 years-old in Pimampiro area. Plasticisers and OPFRs were present in dust at maximum median concentrations of 332,507 ng g−1 (DEHP), 5,249 ng g−1 (DBP), 1,885 ng g−1 (BPA), 871 ng g−1 (TBOEP) and 122 ng g−1 (TEHP). Some dust samples from Ecuadorian houses had high maximum levels of legacy and modern pesticides such as chlorpyrifos (up to 44,176 ng g−1), 4,4′-DDT (12,958 ng g−1), malathion (34,748 ng g−1) and α+β-endosulfan (10,660 ng g−1) attributed to inappropriate use and storage of the pesticides. Finally, nicotine was seldom detected (36 ng g−1). The sources and risks of these compounds are discussed based on the activities carried out in the study areas and attending to an additional non-cancer risk assessment which showed high hazard quotients (HQ) and hazard indexes (HI) for DEHP, DBP, 4,4′-DDT, malathion, chlorpyrifos, naphthalene and benzo[a]pyrene in newborns and children up to 16 years-old.

Background levels of polycyclic aromatic hydrocarbons and legacy organochlorine pesticides in wheat sampled in 2017 and 2018 in Poland

Both polycyclic aromatic hydrocarbons (PAHs) and legacy organochlorine insecticides (OCPs), including DDT, are dangerous chemical contaminants. The aims of this study were to (i) determine background levels of PAHs and legacy OCPs for wheat samples collected in 2017 and 2018 in Poland, (ii) identify differences between levels in wheat harvested in various regions of Poland, (iii) evaluate differences in contamination sources manifested by the profiles of the identified chemicals, (iv) identify possible correlations between different classes of chemicals present in wheat, and (v) assess the health risks associated with the presence of PAHs and OCPs in Polish wheat. Average concentrations found in the samples were 0.09 ± 0.03 μg kg−1 for benzo[a]pyrene (BaP) (formerly used as a single PAH marker), 0.43 ± 0.16 for the more recently introduced collective PAH 4 marker (benzo[a]anthracene + benzo[a]pyrene + chrysene + benzo[b]fluoranthene), and 1.07 ± 0.68 μg kg−1 for DDT and its metabolites. The PAH profiles indicated contamination from combustion-related emission sources (liquid fossil fuels, coal, biomass). Health risks associated with the presence of PAHs and OCPs in cereals were assessed using the margin of exposure (MOE) approach. The MOE values calculated based on the highest concentrations found in this study exceeded 50,000 for both BaP and PAH 4. The calculated worst-case scenario value for DDT and metabolites was as low as 0.3% of the respective tolerable daily intake (TDI) value. Assessment of dietary risk has shown that the presence of the two contaminant classes in Polish wheat grains is of low concern.

Residues of legacy organochlorine pesticides and DDT metabolites in highly consumed fish from the polluted Guanabara Bay, Brazil: distribution and assessment of human health risk

Organochlorine (OCP) pesticides were determined in samples of sardine (Sardinella brasiliensis), whitemouth croaker (Micropogonias furnieri), and mullet (Mugil liza) from Guanabara Bay (state of Rio de Janeiro, Brazil). OCP concentrations and fish consumption were linked with acceptable daily intake values in order to assess the human health risk for the Brazilian population. The total concentrations of OCPs (Σ OCP) was 6.6 ng/g f.w., 7.5 ng/g f.w., and 2.8 ng/g f.w. for sardines, corvina, and mullet, respectively. There was a significant difference (P < 0.05) among the species related to o,p’-DDD and o,p’-DDT concentrations. Both DDT-related compounds were 5 and 76 times more abundant in sardines than in whitemouth croaker and mullet. Newly discovered DDT metabolite, o-Cl-DDMU, was frequently detected in the fish. None of the samples exceeded the maximum limits for acceptable levels of OCP residues. According to the data of average intake of Brazilian population, none of three species exceeded toxicological parameter. The investigated fishes are considered as safe for human consumption in regard to exposure of the studied OCPs. However, fish may be a intake source of OCP metabolites such as o-Cl-DDMU whose toxicity is still unknown.

Sediment-associated organopollutants, metals and nutrients in the Nechako River, British Columbia: a current study with a synthesis of historical data

The flow-diverted Nechako River is the second largest tributary of the Fraser River which drains 25% of mainland British Columbia, Canada. The watershed provides critical reproductive habitats for anadromous chinook salmon (Oncorhynchus tshawytscha) and sockeye salmon (O. nerka) and year-round habitat for the endangered Nechako white sturgeon (Acipenser transmontanus) population. In this study, the chemical quality of sediment in the upper Nechako River and its major tributaries was examined for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), legacy organochlorine (OC) pesticides, polycyclic aromatic hydrocarbons (PAHs), organophosphorus and phenoxy acid herbicides, polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs), labile (exchangeable) metals/metalloids, and major nutrients (N and P). ΣPCB and ΣPBDE were detected in channel bottom sediments at all Nechako River and tributary sites; hexachlorobenzene (HCB) and 4,4′-DDE (dichlorodiphenyldichloroethylene) were also detected at most sites. Organophosphorus and phenoxy acid herbicides were not detected in any samples. While ΣPCB, ΣPBDE, HCB, and 4,4′-DDE concentrations in bottom sediments were always well below provincial and federal guidelines for the protection of aquatic life, concentrations of total labile As (AsT), CrT, CuT, FeT, MnT, NiT, and ZnT in suspended and/or bottom sediments often exceeded provincial threshold effect levels (TEL) and, in some cases, approached or exceeded probable effect levels. Distinct CuT, NiT, PbT and ZnT concentration maxima in suspended sediments were linked to road and urban densities. Historical PCDD, PCDF and PAH data show that concentrations in bottom sediment samples were highest at a site in the lower Nechako River between Miworth and the City of Prince George where PCDD and PCDF concentrations exceeded the interim federal TEL. Nitrogen and P concentrations in bottom sediments were negatively correlated with water velocity and sediment texture; the evidence suggests that reductions in velocity resulting from the 1952 diversion of the Nechako River have increased the nutrient content of bottom substrates.

Concentrations of legacy and new contaminants are related to metabolite profiles in Hudson Bay polar bears

There are very few metabolomics assessments based on field accumulated, uncontrolled contaminant exposures in wildlife, particularly in the Arctic. In the present study, targeted metabolomics and contaminant data were analyzed together to assess potential influences of contaminant exposure on the hepatic metabolome of male polar bears (n = 29) from the southern and western Hudson Bay (SHB and WHB respectively), Canada. The 29 metabolites identified as important in the differentiation of the two subpopulations after partial least squares discriminant analysis (PLS-DA) included phosphatidylcholines (PCs), acylcarnitines (ACs; involved in β-oxidation of fatty acids), and the fatty acid (FA) arachidonic acid (ARA). Perfluorinated alkyl substances, polybrominated diphenyl ethers, dichlorodiphenyldichloroethylene (p,p′-DDE) and some highly chlorinated ortho-polychlorinated biphenyl congeners were greater in the SHB bears and were consistently inversely correlated with discriminating ACs and PCs between the subpopulations. The concentrations of discriminatory, legacy organochlorine pesticides along with one tetrachlorobiphenyl were greater in the WHB and were directly correlated with the VIP-identified ACs and PCs. ARA, glycerophospholipid and several amino acid metabolic pathways were identified as different between subpopulations and/or were impacted. ARA is an important, conditionally essential, dietary n-6 FA and is also part of the inflammation response, and elevated concentrations in the SHB could be related to differences in chronic contaminant exposure and/or differences in diet and/or season, among a number of possible explanations. Dietary tracers (stable isotopes of carbon and nitrogen) were correlated with some discriminatory metabolites, supporting the hypothesis that dietary variation was also an important factor in the differentiation of the subpopulations. The results suggest linkages between contaminant exposure in Hudson Bay polar bears and elements of the hepatic metabolome, particularly those related to lipid metabolism.

Linking organochlorine exposure to biomarker response patterns in Anurans: a case study of Müller's clawed frog (Xenopus muelleri) from a tropical malaria vector control region.

Organochlorine pesticides are highly persistent in aquatic ecosystems. Amphibians, specifically anurans, play an intricate part in the aquatic food web, and have very permeable skin which makes them prone to bioaccumulation of persistent pollutants. In this study the bioaccumulation of various legacy organochlorine pesticides (OCPs)-including dichlorodiphenyltrichloroethane (DDT), currently used for malaria vector control (MVC)-was assessed along with a set of biomarker responses in Müller's clawed frog Xenopus muelleri collected from the lower Phongolo River floodplain in South Africa. Possible relationships between bioaccumulation and biomarkers (of exposure, oxidative stress biomarkers, and cellular energy allocation) alongside their temporal changes were investigated. The OCP concentrations showed a significant increase over time for the duration of the study. The increase correlated negatively with rainfall from the region. DDT levels were well below expected effects levels with p,p-DDE being the main contributing metabolite. The results of this study indicate OCPs actively accumulate at sub-lethal levels in aquatic frogs from the study area, while showing possible relations towards some of the biochemical stress responses measured. Most notable were negative relationships indicated between p,p-DDE and acetylcholinesterase, malondialdehyde, and carbohydrates and protein energy availability. Levels of DDT were not found to be significantly higher than other legacy pesticides in the frog tissue, although evidence of newly introduced DDT in the frog tissue was found. Further investigation about sub-lethal effects of these pesticides on anurans is required to gain better insight into their full impact on animal livelihood.