Multiple lines of evidence point to pesticides as stressors affecting invertebrate communities in small streams in five United States regions.

Multistressor studies were performed in five regions of the United States to assess the role of pesticides as stressors affecting invertebrate communities in wadable streams. Pesticides and other chemical and physical stressors were measured in 75 to 99 streams per region for 4 weeks, after which invertebrate communities were surveyed (435 total sites). Pesticides were sampled weekly in filtered water, and once in bed sediment. The role of pesticides as a stressor to invertebrate communities was assessed by evaluating multiple lines of evidence: toxicity predictions based on measured pesticide concentrations, multivariate models and other statistical analyses, and previously published mesocosm experiments. Toxicity predictions using benchmarks and species sensitivity distributions and statistical correlations suggested that pesticides were present at high enough concentrations to adversely affect invertebrate communities at the regional scale. Two undirected techniques-boosted regression tree models and distance-based linear models-identified which pesticides were predictors of (respectively) invertebrate metrics and community composition. To put insecticides in context with known, influential covariates of invertebrate response, generalized additive models were used to identify which individual pesticide(s) were important predictors of invertebrate community condition in each region, after accounting for natural covariates. Four insecticides were identified as stressors to invertebrate communities at the regional scale: bifenthrin, chlordane, fipronil and its degradates, and imidacloprid. Fipronil was particularly important in the Southeast region, and imidacloprid, bifenthrin, and chlordane were important in multiple regions. For imidacloprid, bifenthrin, and fipronil, toxicity predictions were supported by mesocosm experiments that demonstrated adverse effects on naïve aquatic communities when dosed under controlled conditions. These multiple lines of evidence do not prove causality-which is challenging in the field under multistressor conditions-but they make a strong case for the role of insecticides as stressors adversely affecting invertebrate communities in streams within the five sampled regions.

Chlordane exposure impairs the growth and behavior of Drosophila.

Chlordane, a previously extensively utilized insecticidal pesticide, has since been prohibited, however, owing to its limited degradability, it continues to persist significantly in soil and water reservoirs, subsequently accumulating within plant and animal organisms, representing a substantial threat to human health. Despite extensive research conducted over the past few decades to investigate the toxic effects of chlordane, there remains a notable dearth of studies focusing on its impact on sleep activity. Therefore, in this study, the effects of short-term and long-term exposure to chlordane on the activity and sleep of Drosophila were investigated. When exposed to chlordane at a concentration of 1 µM, Drosophila lost body weight, decreased body size and resulted in lipid metabolism disorders. In addition, chlordane exposure altered the arousal and sleep behaviors of Drosophila. Short-term exposure to chlordane resulted in an increase in night-time sleep duration, while long-term exposure to chlordane resulted in an increase in activity and a decrease in sleep, as evidenced by a decrease in the duration of each sleep session and the appearance of sleep fragmentation. Under conditions of long-term chlordane exposure, reactive oxygen species levels were significantly up-regulated in Drosophila. Our results suggest that long-term chlordane exposure triggers oxidative stress damage in Drosophila, leading to sleep disruption. This study offers novel insights into the harmful impacts of environmental pollutants on human sleep patterns and proposes that mitigating the presence of chlordane in the environment could potentially contribute to the reduction of global sleep disorder prevalence.

Sex-specific effects of acute chlordane exposure in the context of steatotic liver disease, energy metabolism and endocrine disruption.

Chlordane is an organochlorine pesticide (OCP) that is environmentally persistent. Although exposures to OCPs including chlordane have been associated with elevated liver enzymes, current knowledge on OCPs' contribution to toxicant-associated steatotic liver disease (TASLD) and underlying sex-specific metabolic/endocrine disruption are still widely limited. Therefore, the objective of this study was to investigate the sex-dependent effects of chlordane in the context of TASLD. Age-matched male and female C57BL/6 mice were exposed to chlordane (20 mg/kg, one-time oral gavage) for two weeks. Female mice generally exhibited lower bodyfat content but more steatosis and hepatic lipid levels, consistent with increased hepatic mRNA levels of genes involved in lipid synthesis and uptake. Surprisingly, chlordane-exposed females demonstrated lower hepatic cholesterol levels. With regards to metabolic disruption, chlordane exposure decreased expression of genes involved in glycogen and glucose metabolism (Pklr, Gck), while chlordane-exposed females also exhibited decreased gene expression of HNF4A, an important regulator of liver identity and function. In terms of endocrine endpoints, chlordane augmented plasma testosterone levels in males. Furthermore, chlordane activated hepatic xenobiotic receptors, including the constitutive androstane receptor, in a sex-dependent manner. Overall, chlordane exposure led to altered hepatic energy metabolism, and potential chlordane-sex interactions regulated metabolic/endocrine disruption and receptor activation outcomes.

Bioaccumulation of pesticide residue in earthworms collected from the agricultural soils of Kuttanad-a unique agroecosystem in India.

Earthworms encompass significant soil faunal biomass and have tremendous potential to provide vital ecosystem services. Earthworms are considered bioindicators of chemical contaminants and can provide early warnings of ecosystem deterioration. Studies pertaining to the accumulation of pesticide residues in earthworm in biomass in agrarian ecosystems are scarce. The Kuttanad agroecosystem (KAE), situated on the southwest coast of India, is one of the few regions globally supporting farming on land below the mean sea level. This investigation was conducted to assess the bioaccumulation of pesticide residues in earthworms from the KAE. The earthworms species Glyphidrilus annandalei collected from agricultural soils of the study area were analyzed for the presence of pesticides residues such as α-BHC, γ-BHC, atrazine, heptachlor, α-chlordane, γ-chlordane, 4,4-DDE, 4,4-DDD, 4,4-DDT, ß-endosulfan, and endrin ketone in their biomass. Analysis of the earthworm samples using a gas chromatograph revealed the presence of ten pesticide residues with notable concentrations (α-BHC, 0.36 ng/g; γ-BHC, 0.41 ng/g; heptachlor, 0.10 ng/g; atrazine, 0.89 ng/g; α-chlordane, 0.07 ng/g; γ-chlordane, 0.10 ng/g; 4,4-DDE, 0.05 ng/g; 4,4-DDD, 0.11 ng/g; 4,4-DDT, 0.31 ng/g; ß-endosulfan, 0.19 ng/g; and endrin ketone, 0.13 ng/g). Six groups of pesticide residues are ΣBHC, ΣDDT, atrazine, Σchlordane, endrin ketone, and ß-endosulfan were observed during bioaccumulation factor analysis, and the results show the following trend: atrazine > ΣBHC > ΣDDT > Σchlordane > Σendosulfan > Σendrin. As earthworms are a crucial component of this region's food chains, bioaccumulation of pesticide residues in earthworms can pause adverse consequences. Increasing trends in pesticide application in the KAE and bioaccumulation of pesticide residues in earthworm biomass can affect the entire food web.

Combination of slurry-bioreactors and actinobacteria consortia as strategy to bioremediate chlordane-contaminated soils.

Soil contamination caused by pesticides poses a significant environmental challenge, and addressing it requires effective solutions. Bioremediation, combining the utilization of slurry-bioreactors and microbial consortia, emerges as an appropiated strategy to tackle this issue. Therefore, this research evaluated the chlordane (CLD) removal efficiency by a Streptomyces consortium through bioaugmentation of polluted soils, and slurry-bioreactors. For that, a Streptomyces defined consortium with CLD removal abilities was inoculated in soil microcosms and soil-slurry bioreactors (SB), with (SB-TSB) and without stimulation (SB-water). In soil, CLD presence has no negative effect on consortium growth. This was supported by comparing its duplication time (7.48 ± 0.14 h) with the obtained in the biotic control (7.45 ± 0.04 h). Furthermore, 17% of pesticide removal by microbial action was detected in the treated microcosms. In SB, the microbial development was not affected by the pesticide presence. In SB-TSB, the microbial growth was higher than in SB-water. This was supported by its lesser duplication time (7.27 ± 0.17 h) with respect to the non-stimulated systems (10.88 ± 0.29 h). However, SB-water showed the highest CLD removal ability (34.8%), with a concomitant increase in the chloride ion release. In the phytotoxicity test, the vigor index showed that the bioremediation in SB-water did not exert adverse effects greater than those generated by the CLD. Indeed, the root length increased after the treatment. These findings demonstrate the versatility of the Streptomyces consortium to remediate solid and semi-solid matrices impacted with pesticides, and the advantage of using bioaugmented SB to enhance the pollutants removal and accelerating the clean-up time required.

Chlorinated persistent organic pollutants in human breast milk in the Miyagi Prefecture disaster-affected area 1 year after the Great East Japan Earthquake of 2011.

BACKGROUND: In the Great East Japan Earthquake of 11 March 2011, an earthquake and accompanying tsunami struck the Tohoku region of northeastern Japan. Buildings collapsed and the tsunami spread waste, including hazardous materials. This study aimed to determine the concentrations of persistent organic pollutants (POPs) in the breast milk of mothers living in the disaster-affected area of Sendai 1 year after the earthquake. Temporal trends in the POPs concentrations were evaluated by comparison with previous studies. METHODS: One hundred breast milk samples were obtained from lactating mothers at a hospital in Sendai in 2012. The results were compared with those from other years to examine whether there were changes in the POPs concentrations after the earthquake. We measured polychlorinated biphenyls (PCBs) and organochlorine pesticides, such as chlordanes, using gas chromatography-mass spectrometer (GC-MS) with negative chemical ionization, and dichlorodiphenyl trichloroethane (DDT) and its metabolites using GC-MS with electron impact ionization. RESULTS: The mean total PCBs (11 congeners), total chlordane, and total DDT concentrations were 76.2 ng/g lipid, 39.8 ng/g lipid, and 73.5 ng/g lipid, respectively. For the samples collected in 2012, the concentrations of POPs in breast milk showed minimal changes compared with results from previous years for samples collected at the same hospital in Sendai. CONCLUSIONS: Our study demonstrates that 1 year after the earthquake and tsunami, the concentrations of chlorinated POPs in breast milk had not changed substantially.

Application of hollow fiber-protected liquid-phase microextraction combined with GC-MS in determining Endrin, Chlordane, and Dieldrin in rice samples.

This paper introduces a novel and minimized sample preparation technique based on hollow fiber-protected liquid-phase microextraction that can be used in joint with gas chromatography-mass spectrometry (GC-MS) detection to extract three organochlorine pesticides-Endrin, Chlordane, and Dieldrin-from rice samples. To that end, a single-walled carbon nanotube (SWCNT) and a proper ionic liquid (IL) were ultrasonically dispersed and injected into the lumen of hollow fiber as the extraction phase for preconcentrating and extracting the target analytes from the rice samples. The effects of the type of nanoparticles, ILs, and desorption solvent on the efficiency of extracting the analytes were investigated based on the one-factor-at-a-time (OFAT) approach. In addition, other parameters influencing the extraction procedure were optimized using an experimental design that decreased the number of experiments, reagent consumption, and costs. Under optimized conditions, the limits of detection and quantification in determining mentioned pesticides varied between 0.019-0.029 and 0.064-0.098 ng mL-1, respectively. The calibration graphs to measure Endrin, Chlordane, and Dieldrin were linear over the concentration range of 0.064-13.2, 0.098-16.7, and 0.092-11.4 ng mL-1, respectively. The relative standard deviations for inter-day and intra-day analysis were below 7.06 and 4.75% for the triplicate determination of three organochlorine pesticides. Besides, the relative recoveries and standard deviations of Endrin, Chlordane, and Dieldrin for analyzing several Iranian rice samples were between 86.0-92.9% and 4.5-5.8%, respectively. The results were compared with other similar works in literature, proving that the proposed method is efficient and useful for routine monitoring of organochlorine compounds in food samples.

Quantitative analysis of the minimum days of dietary survey to estimate dietary pesticide exposure: Implications for dietary pesticide sampling strategy.

Populations are exposed to pesticides through diet on a daily basis. However, there is no research guiding how to evaluate dietary pesticide exposure, and researchers used 1-day, 3-days, 7-days or even longer dietary survey to evaluate without any consensus. It is important for dietary pesticide evaluation to identify the minimum survey days. To increase knowledge of this, a data combination was applied between a two-wave consecutive repeated-measures study in Baoding City and the Fifth China Total Diet Study. Further policy consistency on pesticides were evaluated to explain its credibility. We computed the sensitivity and specificity to evaluate how well different days of dietary survey classify participants with high exposure, and calculated the minimum days required to estimate the participant-specific mean at different acceptable error range. With 1 day of dietary survey, the classification sensitivity was low (<0.6) for total HCH, endosulfan, chlordane, cyhalothrin, allethrin, and prallethrin; that for the other pesticides was high sensitivity (≥0.6). Sensitivity increased as the number of days increased, and the maximum marginal sensitivity increase (≥0.039) occurred from 1 to 2 days for all pesticides except phenothrin, whose maximum marginal sensitivity increase (0.042) occurred from 2 to 3 days. The specificity increased gradually from 0.8 to 0.9 from 1 to 7 days. Under the acceptable error range of 0.5%, 3-28 days were required for participant-specific mean estimation and 1-7 days were required when acceptable error range was shrunk in 1%. Only 1 day was enough if 5% error range was acceptable. In conclusion, 3 days in the study period was cost-effective to distinguish high exposure group, and it rose to 7 when estimating participant-specific mean from a conservative perspective. This study can serve as a reference to determine the minimum survey days for epidemiological studies employing dietary surveys.

Nationwide assessment of atmospheric organochlorine pesticides over a decade during 2008-2017 in South Korea.

Long-term nationwide atmospheric monitoring of organochlorine pesticides (OCPs) was performed in South Korea during 2008-2017. Their occurrences, seasonal and temporal variability, sources, and effect of ambient temperature were investigated. The OCPs are pronounced with a mean concentration of total OCPs ranging from 5.2 to 256 pg/Sm3. However, a decrease of 54 % was observed in the mean concentration of total OCPs from 2008 to 2017 associated with regulatory actions. OCP concentrations did not show any variations between the different site types, and OCPs were ubiquitously present at all site types. The mean concentration of total OCPs in summer was two-fold higher than in winter. The concentrations of DRINs, DDTs, ENDOs, and HCHs were significantly higher in summer, but the concentrations of chlordane and heptachlor were higher in winter. The diagnostic ratios identified major sources as ongoing sources, past use, and atmospheric transport. Clausius Clapeyron plots strongly suggested the re-emission of α-endosulfan, ß-endosulfan, α-HCH, and ß-HCH, and ΔHsa (enthalpy of surface air exchange) values suggested the influence of the transport and/or new sources on aldrin, dieldrin, and chlordane. The occurrence of OCPs due to re-emissions, ongoing sources, and long-range atmospheric transport could be a challenge towards the complete phase-out of OCPs in South Korea.

Persistent organic pollutants in air from Asia, Africa, Latin America, and the Pacific.

In support of the United Nations Environment Programme (UNEP) global monitoring plan under the Stockholm Convention concentrations of persistent organic pollutants (POPs) were determined during two years in air from 42 countries in Asia, Africa, Latin America, and the Pacific by using polyurethane foams installed in passive samplers. The compounds included were polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenylethers (PBDEs), one polybrominated biphenyl and hexabromocyclododecane (HBCD) diastereomers. Total-DDT and PCBs were the highest in concentrations in about 50% of the samples, which shows their high persistency. Total DDT in air from the Solomon Islands ranged from 200 to 600 ng/polyurethane foam disk (PUF). However, at most locations, a decreasing trend is observed for PCBs, DDT and most other OCPs. Patterns varied per country with e.g. elevated dieldrin in air from Barbados and chlordane in air from the Philippines. A number of OCPs, such as heptachlor and its epoxides, some other chlordanes, mirex and toxaphene have decreased down to almost undetectable levels. PBB153 was hardly found and penta and octa--mix related PBDEs were also relatively low at most locations. HBCD and the decabromodiphenylether were more prominent at many locations and may even still increase. To draw more holistic conclusions more colder climate countries should be included in this program.

Perinatal exposure to pesticides alters synaptic plasticity signaling and induces behavioral deficits associated with neurodevelopmental disorders.

Increasing evidence from animal and epidemiological studies indicates that perinatal exposure to pesticides cause developmental neurotoxicity and may increase the risk for psychiatric disorders such as autism and intellectual disability. However, the underlying pathogenic mechanisms remain largely elusive. This work was aimed at testing the hypothesis that developmental exposure to different classes of pesticides hijacks intracellular neuronal signaling contributing to synaptic and behavioral alterations associated with neurodevelopmental disorders (NDD). Low concentrations of organochlorine (dieldrin, endosulfan, and chlordane) and organophosphate (chlorpyrifos and its oxon metabolite) pesticides were chronically dosed ex vivo (organotypic rat hippocampal slices) or in vivo (perinatal exposure in rats), and then biochemical, electrophysiological, behavioral, and proteomic studies were performed. All the pesticides tested caused prolonged activation of MAPK/ERK pathway in a concentration-dependent manner. Additionally, some of them impaired metabotropic glutamate receptor-dependent long-term depression (mGluR-LTD). In the case of the pesticide chlordane, the effect was attributed to chronic modulation of MAPK/ERK signaling. These synaptic alterations were reproduced following developmental in vivo exposure to chlordane and chlorpyrifos-oxon, and were also associated with prototypical behavioral phenotypes of NDD, including impaired motor development, increased anxiety, and social and memory deficits. Lastly, proteomic analysis revealed that these pesticides differentially regulate the expression of proteins in the hippocampus with pivotal roles in brain development and synaptic signaling, some of which are associated with NDD. Based on these results, we propose a novel mechanism of synaptic dysfunction, involving chronic overactivation of MAPK and impaired mGluR-LTD, shared by different pesticides which may have important implications for NDD.

Amyotrophic Lateral Sclerosis-Associated Persistent Organic Pollutant cis-Chlordane Causes GABAA-Independent Toxicity to Motor Neurons, Providing Evidence toward an Environmental Component of Sporadic Amyotrophic Lateral Sclerosis.

Amyotrophic lateral sclerosis (ALS) is an incurable neurodegenerative disease characterized by the death of upper and lower motor neurons. While causative genes have been identified, 90% of ALS cases are not inherited and are hypothesized to result from the accumulation of genetic and environmental risk factors. While no specific causative environmental toxin has been identified, previous work has indicated that the presence of the organochlorine pesticide cis-chlordane in the blood is highly correlated with ALS incidence. Never before tested on the motor system, here, we show that cis-chlordane is especially toxic to motor neurons in vitro- and in vivo-independent of its known antagonism of the GABAA receptor. We find that human stem-cell-derived motor neurons are more sensitive to cis-chlordane than other cell types and their action potential dynamics are altered. Utilizing zebrafish larvae, we show that cis-chlordane induces motor neuron and neuromuscular junction degeneration and subsequent motor deficits in a touch-evoked escape response. Together, our work points to cis-chlordane as a potential sporadic ALS exacerbating environmental pollutant.

Health risk of consuming Sphoeroides spp. from the Navachiste Lagoon complex due to its trace metals and organochlorine pesticides content.

The Navachiste complex (NAV) is impacted by neighbored human activities and is located in the southwestern coastal zone of the Gulf of California. The study determines the trace metal (TM) and organochlorine pesticides (OCP) health risk content in the edible tissue of Sphoeroides spp. from NAV. The daily intakes (EDI), target hazard quotient (THQ), hazard index (HI), and carcinogenic and non-carcinogenic risks were calculated. Twenty OCP and seven TM were detected. Cd, Cu, Fe, Mn, Pb, and Zn were above MRLs. The γ‒Chlordane was the most frequent OCP. The highest average concentration was for α‒HCH, followed by γ‒chlordane. With the high ratios of γ‒HCH, p, p'‒ DDD and p, p'‒DDD, and the absence of p, p'‒ DDT, the higher ratios for dieldrin and endrin than for aldrin, α‒ chlordane, γ‒chlordane, heptachlor, and heptachlor epoxide indicates historical contamination. In contrast, the residual products of methoxychlor, endosulfan, and its isomers indicate endosulfan's recent use. The TM EDI, THQ > 1 (at 120 g day-1), and the ILCR (> 1 × 10-6) were above minimum levels, showing a high-risk potential for cancer development in the long term.

Teratogenic Effects of Organohalogen Contaminants Extracted from Whale Bacon in a Whole-Rat-Embryo Culture System.

Marine foods can be contaminated with organochlorines and the risk to human beings who consume these foods needs to be evaluated. We examined the teratogenic effects of contaminants extracted from whale bacon on rat embryos using a whole-embryo culture system. Embryonic day 11.5 embryos were cultured for 48 h with organohalogens extracted from whale bacon at low (polychlorinated biphenyls (PCBs): 0.32 ppm, dichlorodiphenyltrichloroethanes (DDTs): 0.16 ppm, chlordanes (CHLs): 0.02 ppm) and high (PCBs: 2.15 ppm, DDTs: 1.99 ppm, CHLs: 0.20 ppm) doses. The levels of organohalogen compounds in cultured embryos were determined. The organochlorine contaminants extracted from whale products were readily transferred to the cultured rat embryos. The number of heartbeats, yolk sac circulation score, and embryonic body circulation score of embryos did not change during the culture period in either exposure group. Cultured embryos treated with the low-dose contaminated medium for 48 h showed abnormalities of the mandible, and craniofacial or forelimb hematomas with an incidence of 50%. All embryos treated with the high-dose medium showed craniofacial abnormalities and cleft lip, and limb abnormalities and hematomas. These results indicate that the organohalogen contaminants in whale bacon may be teratogenic in a dose-dependent manner. Further studies are necessary to determine the dose-effect relationship.

Metabolomic profiling to assess the effects of chlordanes and its bioaccumulation characteristics in chicken embryo.

Although chlordane-related compounds (CHLs) have been regulated, a variety of CHLs are still identified and detected in wild birds and eggs. Embryo is one of fragile periods and is very susceptible to toxic effects of pollutants. In this study, the fate of CHLs during embryo development and degradation of CHLs in neonatal chick were investigated. During embryo development, CHLs were mainly distributed to the liver and muscle, in which trans-nonachlor and an octachlorochlordane (MC5) were hardly metabolized and showed the high persistence, implying a greater risk to birds' offspring. CHLs with the lower Kow were found to be higher uptake efficiency in embryo, implying contaminants with the lower lipophilicity may contribute to their transport to embryo. Furthermore, the effects of CHLs on the metabolome of neonatal chicks was evaluated. The ether lipid metabolism and glycerophospholipid metabolism were found to be significantly affected, which may disturb the angiogenesis and endothelial cell migration in embryogenesis. Taken together, the lipophilicity of contaminants might be a main factor influencing their transport to embryo, and metabolomics results improve understanding of the effects of CHLs on embryo.

Volatile organic compounds in water matrices: Recent progress, challenges, and perspective.

Volatile organic compounds (VOCs) are a group of organic compounds that have a molecular structure containing carbon and their chemical properties allow them to be easily converted to steam and gas and remain for a long period of time and have diverse effects on the environment. The purpose of this study is determination of the concentration of VOCs such as alachlor, anthracene, benzene, bromoform, chloroform, heptachlor, isophorone, tetrachloroethylene, γ -chlordane, toluene, etc. in water matrices. The results showed that among studies conducted on VOCs, the concentration of tetrachloroethylene, m,p-xylene, and toluene were at the top in water matrices, and the lowest average concentrations were found in chloroform, anthracene, and butyl benzyl phthalate. In terms of VOC concentrations in water matrices, China was the most polluted country. Moreover, the data analysis indicated that China was the only country with carcinogenic risk. A Monte-Carlo simulation showed that although the averages obtained were comparable to the acceptable limits, for heptachlor, the maximum carcinogenic risk is achieved at a level that is slightly over the limit, only 25% from the population being exposed.

The impact of climate sensitive factors on the exposure to organohalogenated contaminants in an aquatic bird exploiting both marine and freshwater habitats.

To assess how climate-sensitive factors may affect the exposure to organochlorines (OCs) and perfluoroalkyl substances (PFASs), we monitored concentrations in eggs of the common goldeneye (Bucephala clangula) over two decades (1999-2019) in central Norway. The goldeneye alternates between marine and freshwater habitats and is sensitive to climate variation, especially due to alterations in ice conditions which may affect feeding conditions. We assessed how biological factors such as diet (stable isotopes δ13C and δ15N), the onset of egg laying, and physical characteristics such as winter climate (North Atlantic Oscillation: NAOw) influenced exposure. We predicted compounds to show different temporal trends depending on whether they were still in production (i.e. some PFASs) or have been banned (i.e. legacy OCs and some PFASs). Therefore, we controlled for potential temporal trends in all analyses. There were declining trends for α- and γ-hexachlorocyclohexane (HCH), oxychlordane, cis-chlordane, cis-nonachlor, p,p'-dichlorodiphenyltrichloroethane (p.p'-DDT) and less persistent polychlorinated biphenyl (PCB) congeners (e.g. PCB101). In contrast, the dominant compounds, such as p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and persistent PCB congeners, were stable, whereas hexachlorobenzene (HCB) increased over time. Most OCs were positively related to δ15N, suggesting higher exposure in birds feeding at upper trophic levels. Chlordanes and HCB were positively associated with δ13C, indicating traces of marine input for these compounds, whereas the relationships to most PCBs were negative. Among PFASs, perfluorooctanesulfonamide (PFOSA) and perfluorohexane sulfonic acid (PFHxS) declined. Most PFASs were positively associated with δ13C, whereas there were no associations with δ15N. Egg laying date was positively associated to perfluoroheptanesulfonic acid (PFHpS), perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), suggesting that some of the PFAS load originated from the wintering locations. Although NAOw had little impact on the exposure to organohalogenated contaminants, factors sensitive to climate change, especially diet, were associated with the exposure to OHCs in goldeneyes.

Widespread pesticide contamination of drinking water and impact on cancer risk in Brazil.

Pesticides, which are associated with endocrine dysfunction, immunological dysregulation, and cancer, are widespread sources of drinking water contamination. The state of Paraná has a population of 11 million, is the second largest grain producer in Brazil and is a leading consumer of pesticides. In this study, we analyzed the extent of drinking water contamination from 11 proven, probable, or potentially carcinogenic pesticides (alachlor, aldrin-dieldrin, atrazine, chlordane, DDT-DDD-DDE, diuron, glyphosate-AMPA, lindane-γ-HCH, mancozeb-ETU, molinate, and trifluralin) in 127 grain-producing municipalities in the state of Paraná. Extensive contamination of drinking water was found, including legacy pesticides such as aldrin-dieldrin (mean 0.047 ppb), DDT-DDD-DDE (mean: 0.07), chlordane (mean: 0.181), and lindane-HCH (mean: 2.17). Most of the municipalities were significantly above the maximum limits for each one of the currently allowed pesticides (67% for alachlor, 9.44% for atrazine, 96.85% for diuron, 100% for glyphosate-AMPA, 80.31% for mancozeb-ETU, 91.33% for molinate, and 12.6% for trifluralin). Ninety-seven percent of municipalities presented a sum of all pesticides at levels significantly above (189.84 ppb) the European Union preconized limits (<0.5 ppb). Using the mean pesticide concentration in water (ppb), the exposed population for each municipality, and the benchmark cancer risk for pesticides, we estimated the minimum number of cancer cases attributable to pesticide-contaminated drinking water during the period (total of 542 cases). More than 80% were attributed to mancozeb-ETU and diuron. Glyphosate-AMPA and diuron-attributable cases strongly correlated with the total cancer cases in the same period (R = 0.8117 and 0.8138, respectively) as well as with breast cancer cases (R = 0.7695 and 0.7551, respectively). Water contamination was significantly correlated with the sum of the estimated cancer cases for all 11 pesticides detected in each city (R = 0.58 and p < 0.0001). These findings reveal extensive contamination of drinking water in the state of Paraná and suggest that contamination may increase the risk of cancer in this region.

Spatio-temporal variations and ecological risks of organochlorine pesticides in surface waters of a plateau lake in China.

Qilu Lake is one of the 9 plateau lakes in Yunnan, China, with a lake surface altitude of 1796.62 m above sea level. In spite of the importance and agriculturally-intensive phenomenon in Qilu Lake Basin, few studies have provided a modern evaluation of pesticide residues and potential effects to local aquatic organisms. The primary goal of this study was to determine the spatio-temporal variations of organochlorine pesticides (OCPs) in this area, and to further assess the related ecological risks. Of the 25 OCPs analyzed, 14 were detected, and the concentrations of ∑25OCPs were highest in the upstream of rivers, followed by regions close to the lake shore, and the lowest concentrations were found in Qilu Lake in every season except winter. The concentrations of ∑25OCPs were the highest in summer, and the lowest in winter. OCP concentrations in spring and in autumn were similar. 4,4'-DDD, γ-HCH, HCB, trans-chlordane, and cis-chlordane were 5 OCPs with relatively high risk in Qilu Lake Basin. Interestingly, higher OCP concentrations do not necessarily correspond to higher ecological risk levels. Low predicted no-effect concentration (PNEC) values and relatively high toxicity of these OCPs led to their high risk quotient (RQ) values. This work further illustrated that although OCPs have been banned for many years, they were still frequently detected in surface waters, and caused risks to aquatic animals.

A comprehensive evaluation of organic micropollutants (OMPs) pollution and prioritization in equatorial lakes from mainland Tanzania, East Africa.

A lack of understanding the fate of highly toxic organic micropollutants (OMPs) in the equatorial lakes of Tanzania hinders public awareness for protecting these unique aquatic ecosystems, which are precious water resources and stunning wildlife habitats. To address this knowledge gap, the occurrence of 70 anthropogenically-sourced OMPs, including phthalates (PAEs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), was investigated in the water and sediment of 18 lakes in Tanzania. Similar residue concentrations were found in both compartments, showing higher pollution of PAEs ranging from 835.0 to 13,153.1 ng/L in water and 244.6-8691.8 ng/g dw in sediment, followed by PAHs, while OCPs and PCBs were comparatively lower. According to the multi-criteria scoring method for prioritization, the final OMP priority list for the lake environment in Tanzania comprised 25 chemicals, specifically 5 PAEs (DEHP, DIBP, DBP, DCHP and DMPP), 6 PCBs (PCB153, PCB105, PCB28, PCB156, PCB157 and PCB167), 6 PAHs (BaP, BaA, BbF, Pyr, DahA and InP) and 8 OCPs (cis-chlordane, trans-chlordane, p,p'-DDD, p,p'-DDE, p,p'-DDT, endrin, methoxychlor and heptachlor epoxide), suggesting the key substances for conventional monitoring and pollution control in these equatorial lakes, with an emphasis on PAEs, especially DEHP, due to the top priority and endocrine disruptor properties.