Glucocorticoid hormones in relation to environmental exposure to bisphenols and multiclass pesticides among middle aged-women: Results from hair analysis.

Bisphenols and pesticides have been shown to alter circulating glucocorticoids levels in animals, but there is limited human data. Moreover, measurements from biological fluids may not be able to reflect long-term status of non-persistent pollutants and glucocorticoids due to the high variability in their levels. Using hair analysis, we examined the associations between glucocorticoid hormones and environmental exposure to multi-class organic pollutants among a healthy female population aged 25-45 years old. Concentrations of four glucocorticoids, four polychlorinated biphenyl congeners (PCBs), seven polybrominated diphenyl ether congeners (PBDEs), two bisphenols and 140 pesticides and their metabolites were measured in hair samples collected from 196 Chinese women living in urban areas. Due to the low detection frequency of some pollutants, associations were explored only on 54 pollutants, i.e. PCB 180, bisphenol A, bisphenol S and 51 pesticides and their metabolites. Using stability-based Lasso regression, there were associations of cortisol, tetrahydrocortisol, cortisone, and tetrahydrocortisone with 14, 10, 13 and 17 biomarkers of exposure to pollutants, respectively, with bisphenol S, p,p'-dichlorodiphenyldichloroethylene, diethyl phosphate, 3,5,6-trichloro-2-pyridinol, thiamethoxam, imidacloprid, fipronil, tebuconazole, trifluralin, pyraclostrobin and 1-(3,4-dichlorophenyl)-3-methylurea being associated with at least three of the four hormones. There were also associations between cortisone/cortisol molar ratio and pollutants, namely dimethyl phosphate, 3-methyl-4-nitrophenol, carbofuran, λ-cyhalothrin, permethrin, fipronil, flusilazole, prometryn and fenuron. Some of these relationships were confirmed by single-pollutant linear regression analyses. Overall, our results suggest that background level of exposure to bisphenols and currently used pesticides may interfere with the glucocorticoid homeostasis in healthy women.

The Roles of Diet and Habitat Use in Pesticide Bioaccumulation by Juvenile Chinook Salmon: Insights from Stable Isotopes and Fatty Acid Biomarkers.

Stable isotopes (SI) and fatty acid (FA) biomarkers can provide insights regarding trophic pathways and habitats associated with contaminant bioaccumulation. We assessed relationships between SI and FA biomarkers and published data on concentrations of two pesticides [dichlorodiphenyltrichloroethane and degradation products (DDX) and bifenthrin] in juvenile Chinook Salmon (Oncorhynchus tshawytscha) from the Sacramento River and Yolo Bypass floodplain in Northern California near Sacramento. We also conducted SI and FA analyses of zooplankton and macroinvertebrates to determine whether particular trophic pathways and habitats were associated with elevated pesticide concentrations in fish. Relationships between DDX and both sulfur (δ34S) and carbon (δ13C) SI ratios in salmon indicated that diet is a major exposure route for DDX, particularly for individuals with a benthic detrital energy base. Greater use of a benthic detrital energy base likely accounted for the higher frequency of salmon with DDX concentrations > 60 ng/g dw in the Yolo Bypass compared to the Sacramento River. Chironomid larvae and zooplankton were implicated as prey items likely responsible for trophic transfer of DDX to salmon. Sulfur SI ratios enabled identification of hatchery-origin fish that had likely spent insufficient time in the wild to substantially bioaccumulate DDX. Bifenthrin concentration was unrelated to SI or FA biomarkers in salmon, potentially due to aqueous uptake, biotransformation and elimination of the pesticide, or indistinct biomarker compositions among invertebrates with low and high bifenthrin concentrations. One FA [docosahexaenoic acid (DHA)] and DDX were negatively correlated in salmon, potentially due to a greater uptake of DDX from invertebrates with low DHA or effects of DDX on FA metabolism. Trophic biomarkers may be useful indicators of DDX accumulation and effects in juvenile Chinook Salmon in the Sacramento River Delta.

[Exposure characteristics and health risk assessment of 97 typical chemical pollutants in human serum].

Rapid industrial and agricultural developments in China have led to the wide use and discharge of chemical products and pesticides, resulting in extensive residues in environmental media. These residues can enter the human body through various pathways, leading to high exposure risks and health hazards. Because the human body is exposed to a variety of chemical pollutants, accurately quantifying the exposure levels of these pollutants in the human body and evaluating their health risks are of great importance. In this study, the serum concentrations of 97 typical chemical pollutants of 60 adults in central China were simultaneously determined using solid-phase extraction coupled with gas chromatography-tandem mass spectrometry (SPE-GC-MS/MS). In this method, 200 µL of a serum sample was mixed with 10 µL of an isotope-labeled internal standard solution. The sample was vortexed and refrigerated overnight at 4 ℃. Each sample was then deproteinized by the addition of 200 µL of 15% formic acid aqueous solution and vortexed. The serum sample was loaded into a preconditioned Oasis® PRiME HLB SPE cartridge and rinsed with 3 mL of methanol-water (6∶1, v/v). The SPE cartridge was subsequently vacuumed. The analytes were eluted with 3 mL of dichloromethane followed by 3 mL of n-hexane. The eluent was concentrated to near dryness under a gentle nitrogen stream and reconstituted with 100 µL of acetone. The samples were determined by GC-MS/MS and separated on a DB-5MS capillary column (30 m×0.25 mm×0.25 µm) with temperature programming. The column temperature was maintained at 70 ℃ for 2 min, increased at a rate of 25 ℃/min to 150 ℃, increased at a rate of 3 ℃/min to 200 ℃, and then held for 2 min. Finally, the column temperature was increased at a rate of 8 ℃/min to 300 ℃ and maintained at this temperature for 8 min. The samples were detected in multiple-reaction monitoring (MRM) mode and quantitatively analyzed using the internal standard method. Multiple linear regression models were used to analyze the effects of demographic characteristics, lifestyle habits, and diet on the concentrations of the chemical pollutants in the serum samples, and known biomonitoring equivalents (BEs) and human biomonitoring (HBM) values were combined to compute hazard quotients (HQs) and hazard indices (HIs) and evaluate the health risks of single and cumulative exposures to the chemical pollutants. The results showed that the main pollutants detected in human serum were organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The detection rates of eight pollutants, including hexachlorobenzene (HCB) (100%), pentachlorophenol (PCP) (100%), p,p'-dichlorodiphenylene (p,p'-DDE) (100%), PCB-138 (100%), PCB-153 (98.3%), ß-hexachlorocyclohexane (ß-HCH) (91.7%), fluorene (Flu) (85.0%), and anthracene (Ant) (75.0%), were greater than 70%. The serum levels of ß-HCH were higher in females than in males, and age was positively correlated with exposure to p,p'-DDE, PCB-138, PCB-153, and ß-HCH. Increased exposure levels to p,p'-DDE and ß-HCH may be associated with a high frequency of meat intake, whereas increased exposure level to PCP may be associated with a high frequency of vegetable intake. The serum HQ of PCP was greater than 1 in 6.7% of the samples, and no risk was observed for HCB and p,p'-DDE exposure in the study population. Approximately 28.3% of the study subjects had HI values greater than 1. Overall, the general adult population in this region is widely exposed to a wide range of chemical pollutants, and gender, age, and diet are likely to be the main factors influencing the concentration of chemical pollutants. The health risk of single and compound exposures to chemical pollutants should not be ignored.

Zooplankton taxa repository of DDTtot and sumPCB14: Seasonal and decadal variations in Lake Maggiore.

Lake Maggiore has been the subject of a monitoring program on persistent organic pollutants (DDTs and PCBs) since 1996 when DDT contamination was first detected. In this context, in 2009 we started to estimate the concentration of DDTtot (Dichlorodiphenyltrichloroethane, sum of p,p'-DDT, o,p'-DDT, p,p'-DDD, o,p-DDD, p,p-DDE, o,p-DDE) and sumPCB14 (polychlorinated biphenyls 18, 28, 31, 44, 52, 101, 118, 149, 138, 153, 170, 180, 194 and 209) in zooplankton pelagic organisms preyed on by zooplanktivorous fish (size fraction ≥450 µm). We evaluated taxa specific repositories of DDTtot and sumPCB14, their seasonal variation, their changes over the period 2009-2021 and the potential contribution of different taxa in transferring toxicants to whitefish, based on the Ivlev's Electivity Index. The repository of both POPs was generally higher in spring. A decrease in the zooplankton Standing Stock Biomass (SSB) drove a decline in the zooplankton DDTtot repository over the last six years (2016-2021 SSBmean = 12.5 mg m-3; 2009-2015; SSBmean = 30 mg m-3), despite the concentration being broadly constant during this period. The sumPCB14 repository was generally characterized by lower values during the last six years, but the difference with the previous period was not so marked. Daphnia and cyclopoids were the major contributors to the repository; however, when the whitefish selectivity index was applied, the role of carnivorous Bythotrephes was more important to the detriment of cyclopoids, particularly in summer and winter. Our results are useful to elaborate predictive models on the transfer of POPs along the food chain and highlight not only the importance of freshwater zooplankton in toto, but also that different taxa can have different roles. The increasing importance of microphagous zooplankton, driven by water warming and extended thermal stratification, underlines the need for future studies on the role of small zooplankton as carriers of POPs in freshwater lakes.

Combined effects of organochlorine pesticides on type 2 diabetes mellitus: Insights from endocrine disrupting effects of hormones.

Association between organochlorine pesticides (OCPs) exposure and type 2 diabetes mellitus (T2DM) remains contradictory, and the evidence is mostly focused on a single exposure. Here, we assessed the associations between individual and combined OCPs exposure and T2DM, and explored the underlying mechanism of sex hormones and the methylation levels of sex hormone receptors in above associations. A case-control study with 1812 participants was performed. Gas chromatography mass spectrometry, liquid chromatography-tandem mass spectrometry, and pyrosequencing were used to measure plasma OCPs, serum sex hormones, and whole blood methylation levels of sex hormone receptors, respectively. Generalized linear models were used to analyze the relationships between OCPs, sex hormones, the methylation levels of sex hormone receptors, and T2DM. Quantile based g-computation (QGC) and Bayesian Kernel Machine Regression (BKMR) were employed to assess the combined OCPs exposure. The roles of sex hormones and the methylation levels of their receptors were evaluated by moderating mediation models. After adjusting for covariates, each unit (2.718 ng/ml) increase in p,p'-DDE was associated with a higher risk of T2DM in males (odds ratio (OR) and 95% confidence interval (CI): 1.066 (1.023, 1.112)). QGC and BKMR showed a positive combined effect in the associations of OCPs mixtures on T2DM among premenopausal females, and positive effects but not statistically significant among males and postmenopausal females. p,p'-DDE was the largest contributor for the positive associations. Furthermore, testosterone mediated 21.149% of the associations of p,p'-DDE with T2DM moderated by the androgen receptor methylation (ARm) located in CpG island 1. Individual and mixtures of OCPs exposure were positively linked to elevated risk of T2DM. Testosterone and ARm may participate in the related processes of OCPs with T2DM, providing new insights into the adverse endocrine effects caused by OCPs and specific pathways for the etiology and control of diabetes.

Selected pesticidal POPs and metabolites in the soil of five Vietnamese cities: Sources, fate, and health risk implications.

Large quantities of organochlorine pesticides (OCPs) have been used in tropical regions. The fate processes and risks of these legacy contaminants in the tropics are poorly understood. Herein, we investigated the occurrence of three classes of widely used OCPs and their metabolites in surface and core soil from five cities across Vietnam with a prevalent tropical monsoon climate and a long history of OCP application. We aimed to elucidate migration potentials, degradation conditions, and transformation pathways and assess current health risks of these contaminants. Generally, the concentrations of OCPs and metabolites in the soil core were slightly lower than those in surface soil except for hexachlorocyclohexane (HCH) isomers. 2,2-bis(4-chlorophenyl)-1,1,1-trichloroethane (p,p'-DDT), 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (p,p'-DDE), the sum of dicofol and 4,4'-dichlorobenzophenone (p,p'-DBP), and 2,2-bis(4-chlorophenyl)-1,1-dichloroethane (p,p'-DDD) were the most abundant compounds in both surface and core soils. A uniform distribution of HCHs (the sum of α-, ß-, γ-, and δ-HCH) at trace levels was found in almost all soils, serving as evidence of the lack of recent use of HCH pesticides. Higher concentrations of DDTs (the sum of DDT, DDD, and DDE) were observed in north-central Vietnamese soil, whereas appreciable concentrations of ENDs (the sum of α- and ß-endosulfan and endosulfan sulfate) were only found in southern Vietnamese soils. Empirical diagnostic ratios indicated residuals of DDTs were mainly from technical DDT rather than dicofol, whereas aged HCHs could be explained by the mixture of lindane and technical HCH. Both historical applications and recent input explain DDTs and ENDs in Vietnamese soil. Total organic carbon performs well in preventing vertical migration of more hydrophobic DDTs and ENDs. The dominant transformation pathway of DDT in surface soil followed p,p'-DDE→2,2-bis(4-chlorophenyl)-1-chloroethylene or p,p'-DDMU→1,1-bis(4-chlorophenyl)ethylene or p,p'-DDNU→p,p'-DBP, whereas the amount of p,p'-DDMU converted from p,p'-DDD and p,p'-DDE is similar in soil core. Non-cancer risks of OCPs and metabolites in all soils and cancer risks of those chemicals in core soils were below the safety threshold, whereas a small proportion of surface soil exhibited potential cancer risk after considering the exposure pathway of vegetable intake. This study implied that organic matter in non-rainforest tropical deep soils still could hinder the leaching of hydrophobic organic contaminants as in subtropical and temperate soils. When lands with a history of OCP application are used for agricultural purposes, dietary-related risks need to be carefully assessed.

Dichlorodiphenyltrichloroethane (DDT) and Dichlorodiphenyldichloroethylene (DDE) levels in air and surface sea waters along the Antarctic Peninsula.

Persistent organic pollutants (POPs) are widespread worldwide, even reaching polar regions. Among POPs, dichlorodiphenyltrichloroethane (DDT) and their metabolites have been reported scarcely in the Antarctic environment. Here we report the levels of p,p'-DDT, o,p'-DDT, p,p'-DDE, and o,p'-DDE in air and water samples collected during austral summer 2009. The levels found ranged from 0.25 to 4.26 pg m-3 in the atmospheric samples while in the water samples ranged from 0.07 to 0.25 pg L-1. These concentrations were within the range of the reported concentrations in the last 20 years in Antarctica. However, the source ratio showed that most of p,p'-DDT comes from fresh applications and Dicofol formulations. The back-trajectories estimated for the air masses revealed that most of the p,p'-DDT came from the continental Antarctic peninsula and surrounding waters. The diffusive exchange direction showed that Antarctic surface waters are the final sink of the studied compounds during the survey period.

Circulating organochlorine pesticide levels, genetic predisposition and the risk of incident type 2 diabetes.

Persistent organochlorine pesticide (OCP) has been associated with type 2 diabetes (T2D), and genetic polymorphism might modify such an association. However, prospective evidence remains scarce. We conducted a nested case-control study comprising 1006 incident diabetic cases and 1006 matched non-diabetic controls [sex and age (±5 years)] from 2008 to 2013 (mean follow-up period: ∼4.6 years) based on the Dongfeng-Tongji cohort in Shiyan City of China, determined baseline levels of nineteen OCPs, and examined the associations of circulating OCPs, both individually and collectively, with incident T2D risk. We also constructed overall genetic risk score (GRS) based on 161 T2D-associated variants and five pathway-specific cluster GRSs based on established variants derived from the Asian population. Compared with the first quartile of serum ß-BHC levels, the multivariable-adjusted ORs (95% CIs) of incident T2D risk in the second, third, and fourth quartiles were 0.98 (0.70-1.39), 1.43 (0.99-2.07), and 1.75 (1.14-2.68), respectively (FDR-adjusted Ptrend = 0.03). A positive association was observed between serum OCP mixture and incident T2D risk and can be largely attributed to ß-BHC. Furthermore, serum ß-BHC and p,p'-DDE showed significant interactions with the GRS for lipodystrophy, a T2D-related pathway representing fat redistribution to viscera, on T2D risk (Pinteraction < 0.05). In conclusion, higher circulating OCP levels were independently associated with an increased risk of T2D, with ß-BHC possibly being the major contributor. Genetic predisposition to T2D-related morbidity, such as visceral adiposity, should be considered when assessing the risk of T2D conferred by OCPs.

Exposure to Organochlorine Pesticides and Female Breast Cancer Risk According to Molecular Receptors Expression: a Systematic Review and Meta-analysis of Epidemiological Evidence.

PURPOSE OF REVIEW: Organochlorine pesticides (OCP) have been proposed as potential mammary carcinogens since they interact with steroid signaling pathways. However, the epidemiological results are not conclusive. Most studies have evaluated breast cancer (BC) as a single entity without considering the different molecular expressions, including estrogen receptor (ER), progesterone receptor (PR), and HER2, that could differ in their association with these contaminants. Hence, we assessed the association between biological concentration of OCP and BC, according to its molecular receptor expression, based on a systematic review and meta-analysis. RECENT FINDINGS: Of the 141 articles eligible for full-text review, nine met the inclusion criteria. The way in which molecular expression was reported was heterogeneous; therefore, the inclusion of studies in the meta-analysis was limited to eight articles. A negative association was identified for ß-hexachlorocyclohexane and trans-nonachlor with ER + tumors and between hexachlorobenzene and ER - tumors. No associations were observed for p,p'-dichlorodiphenyldichloroethylene, cis-nonachlor, and dieldrin, and it was not possible to evaluate the associations between OCP with HER2 expression or triple-negative tumors due to lack of data. The results suggest that some OCP might be associated with BC depending on the expression of ER. However, the evidence is not conclusive due to the scarce data. We identified several methodological aspects to fill the gaps in knowledge and increase the comparability among studies.

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in adipose tissue of women from Grand Tunis and their association with demographic factors and dietary habits.

Dichlorodiphenyl trichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB) and polychloronated biphenyls (PCBs) were measured in 25 woman adipose tissues collected in 2016 from Grand Tunis, Tunisia. p,p'-DDE, p,p'-DDT, HCB and ß-HCH were the dominant organochlorine pesticides (OCPs) in decreasing order in all samples. The total OCP levels varied from 79 to 343 ng g-1 lipid with a median value of 189 ng g-1 lipid and DDTs contributed approximately 88% to sum OCP. The ratio of p,p'-DDT/p,p'-DDE across all samples is below one, which suggests mainly historic exposure but may indicate some recent exposure to the banned pesticide. The median concentration of PCBs was 109 ng g-1 lipid and ranged between 27 and 204 ng g-1 lipid. PCB-153, PCB-180, PCB-138 and PCB-170 were the most abundant congeners, which contributed about 78% of the total PCBs. Spearman analysis showed that dominant organochlorine compounds (OCs) are highly positive correlated except for PCB-28/31, indicating that women from Tunis are exposed via similar routes. Inhalation exposure could be a possible pathway for the uptake of the less chlorinated congeners. We found positive and statistically significant association with subjects age for HCB (r = 0.517; p = 0.009) and PCBs (r = 0.65; p = 0.001) levels and a weak age-dependent accumulation was found for HCHs (r = 0.375; p = 0.065) and DDTs (r = 0.388; p = 0.056). The concentrations of OC subgroups were not associated with BMI, parity and residence. No association was observed between fish, red/white meat, milk and dairy products consumption and levels of HCB, HCHs and PCBs. DDTs levels were significantly correlated only with milk (p = 0.048) and milk products (p = 0.047) intake.

Review of DDT, DDE, DDD, DDMU and DDMS Toxicity Data for Organisms Used in Estuarine and Marine Sediment Toxicity Tests.

The open literature was searched for laboratory toxicity data for marine/estuarine organisms exposed to dichlorodiphenyltrichloroethane (DDT) and its degradation products of dichlorodiphenyldichloroethylene (DDE), dichlorodiphenyldichloroethane (DDD), dichlorodiphenylchloroethylene (DDMU), and dichlorodiphenylchloroethane (DDMS). The goal of the review was to determine water-column toxicity values that could be used for porewater-based assessment of sediment toxicity. Data for individual compounds (and isomers thereof) in this group were very limited; most available data were for mixtures of multiple compounds, some defined and others undefined. Further, the majority of relevant studies involved exposure to spiked or field-contaminated sediment (rather than waterborne exposure), which requires inferring concentration in porewater from bulk sediment. Comparing data on the basis of effect concentrations for water or inferred concentration in sediment pore water, the lower reported effect concentrations were in the range of 0.05 to 0.1 µg/L, generally in studies of longer duration and/or evaluating sub-lethal effects. Because field exposures are generally to mixtures of these compounds in varied proportions, additional data on chemical-specific toxicity would aid in pore-water based toxicity assessment for marine/estuarine sediments contaminated with DDT-related chemicals.

Age at menarche and chemical exposure: per- and polyfluoroalkyl substances (PFAS), dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), and polychlorinated biphenyls (PCBs).

CONTEXT: Humans are now exposed to a multitude of chemicals throughout the life course, some of which may affect growth and development owing to their endocrine-like activity. OBJECTIVE: To assess the relationship of suspect toxicants to maturation, specifically to age at menarche. METHODS: We conducted two systematic reviews of age at menarche and PFOA, PFOS, PCBs and DDE/DDT based on publications indexed by pubmed. RESULTS: 16 unique reports were identified. Most studies of PFOA and PFOS reported either no association or delays in the age at menarche; only one reported an earlier age. Studies of DDT and DDE were more mixed. Reports on PCBs varied by PCB congener group with an equal number of them reporting delays and no association but one an acceleration. Sources of variation in results include the timing of exposure assessment (prenatal vs. postnatal), level of the toxicant, and sample size. No obvious pattern to the variation in results could be tied to those sources of variation. CONCLUSION: The absence of consistent evidence from multiple reports of earlier age at menarche suggests that these toxicants may not be responsible for accelerated sexual maturation in girls. However, human populations naturally vary in the variety and levels of exposure, making the comparison of studies difficult. Further, studies vary in methodology, complicating aggregation of results and generalisations.

Individual and mixtures of polychlorinated biphenyls and organochlorine pesticides exposure in relation to metabolic syndrome among Chinese adults.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are commonly detected in humans due to their persistence and bioaccumulation, and are suspected risk factors for metabolic syndrome (MetS). However, most studies have focused on individual rather than combined exposure. We explored the associations between individual and combined PCBs/OCPs exposure and MetS to better assess the health effects of PCBs and OCPs. This cross-sectional study included 1996 adults from Wuhan, China. A total of 338 participants fulfilled criteria for MetS. Eight PCBs and OCPs were detected in >50 % of the samples. Most of the hexachlorocyclohexanes (HCHs) in the serum were derived from the recent environmental input of lindane, while the high levels of dichlorodiphenyltrichloroethane (DDTs) were mainly due to historical use. Multivariate linear regression analyses revealed that ß-HCH, p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE), PCB-52, PCB-153, and PCB-180 were positively correlated with increased odds of MetS. The profiles of the PCBs and OCPs associated with the different components of MetS were distinct. Furthermore, quantile-based g computation (qgcomp) analyses showed that PCB and OCP mixtures were positively associated with the risk of MetS, and p,p'-DDE was the largest contributor to our model. These findings suggest that PCB and OCP concentrations, both individually and as mixtures, are associated with MetS risk. Prospective studies are needed to confirm these results.

A Study of Headspace Solid-Phase Microextraction in the Analysis of 54 Hydrophobic Pollutants in Remote Alpine Lake Waters with an Emphasis on Analyte Recovery and Storage Time.

Commercially available headspace solid-phase microextraction (HS-SPME) fibers have been used for years to extract pesticides and polychlorinated biphenyls from aqueous samples at the expected ultratrace levels (picograms per liter or parts per quadrillion) in alpine lakes. Several variables of the HS-SPME technique have been adequately evaluated, including water temperature, pH, salt content, fiber type and coating thickness, length of fiber-sample exposure, and liquid immersion versus headspace exposure; but surprisingly, analyte recovery as a function of analyte concentration and storage time has not been included in previous studies, which can be important for remote sampling sites. Seven hydrophobic chlorinated pollutants were identified in alpine lake water (out of 54 analyzed); but recovery using the common SPME technique was found to be inconsistent as the analyte concentration decreases, and the recovery trend as a function of concentration varies on a compound-to-compound basis that could result in a large underestimation of analyte concentrations in field samples. Of the 54 compounds surveyed, o,p'-dichlorodiphenyltrichloroethane (DDT), p,p'-DDT, p,p'-dichlorodiphenyldichloroethylene (DDE), o,p'-DDE, chlorthal-dimethyl, endosulfan I, γ-hexachlorocyclohexane, heptachlor, and trans-nonachlor were generally measured at concentrations between 1 and 150 pg/L (parts per quadrillion). No study to date has evaluated this commonly used but unstandardized technique for analyte recovery as a function of analyte concentration or storage time of aqueous samples. Environ Toxicol Chem 2023;42:1199-1211. © 2023 SETAC.

Pesticide Residues and Effect of Household Processing in Commonly Consumed Vegetables in Jimma Zone, Southwest Ethiopia.

The long-term and indiscriminate use of pesticides has resulted in serious health effects. Aside from that, developing countries do not have any monitoring systems in place to prevent the consumption of high levels of pesticides in foods. Therefore, this study aimed to determine pesticide residues and the effect of processing in commonly consumed vegetables in the southwestern part of Ethiopia. In total, 12 samples of 1 kg of each type of vegetable were collected from selected markets. Moreover, as a solution to pesticide residue problems in vegetables, the effect of different processing methods such as washing, peeling, boiling, and their cumulative effect was studied. In the analytical procedure, the modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction with florisil as a cleanup sorbent was used and the identification of pesticides was done by using gas chromatography with an electron capture detector (GC-ECD). The parent p,p'-DDT was detected at a concentration of 0.015 mg/kg in potato samples from the Serbo market and a concentration of 0.516, 0.232, 0.174, and 1.512 mg/kg in Merkato, Kochi, Serbo, and Shebe onion samples, respectively. P`p-DDT is detected at a high concentration compared to its metabolites (p,p'-DDE and p,p'-DDD), which is an indication of recent use. DDT and its metabolites, other organochlorines (lindane, γ-chlordane, dimethachlor, and heptachlor), and pyrethroids (cypermethrin and deltamethrin) exceeded the recommended limits by FAO and WHO in multiple samples of potato, onion, and cabbage. The processing result showed that washing, boiling, and the combination of the two revealed a 100% reduction in o,p'-DDT, and p,p'-DDT pesticides detected in cabbage. In conclusion, multiple residues were detected in the three vegetables studied, indicating that pesticides were applied intensively. Pesticide levels were reduced by home processing procedures, which is important for consumer safety.

Assessment of organohalogenated pollutants in breast milk from the Czech Republic.

This biomonitoring survey brings new information on the occurrence of a total of 94 organohalogenated pollutants in 231 human breast milk samples collected in 2019 and 2021 from women living in two regions of the Czech Republic (Karvina and Ceske Budejovice). This study aimed to evaluate the concentrations of 6 indicator polychlorinated biphenyls (PCBs), 10 organochlorine pesticides (OCPs), 34 halogenated flame retardants (HFRs), 29 perfluoroalkyl and polyfluoroalkyl substances (PFAS) and 15 polychlorinated naphthalenes (PCNs). PCBs, OCPs, most of HFRs and PCNs were identified/quantified by gas chromatography coupled to (tandem) mass spectrometry (GC-MS(/MS)), while PFAS, hexabromocyclododecane isomers (HBCD), brominated phenols, and tetrabromobisphenol A (TBBPA) by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The mean value of the sum of the 6 indicator PCBs was 123.12 nanogram per gram of lipid weight (ng g-1 lw). Hexachlorobenzene (HCB), ß-hexachlorocyclohexane (ß-HCH) and p,p'-dichlorodiphenyl-dichloroethylene (p,p'-DDE) were the most abundant OCPs, detected in 100 % (mean 11.8 ng g-1 lw), 94.8 % (mean 6.1 ng g-1 lw) and 100 % (mean 101.5 ng g-1 lw) of samples, respectively. PCN congeners 20, 52 and 66 were detected in <1 % of the samples. The HFRs concentrations were relatively low compared to the levels of OCP; The detection rate of polybrominated diphenyl ethers (PBDEs, # 47, 99 and 153) ranged 21-68 % with a mean concentrations of 0.34 ng g-1 lw - 0.42 ng g-1 lw. PFAS concentrations were also low, with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) dominant in this group (means of 22 pg ml-1 and 21 pg ml-1, respectively). Our results confirmed the long-term trend of declining levels of banned POPs in Czech mothers. The amounts of PCBs and OCPs were higher in older breastfeeding primiparous women.

Validation of a Modified QuEChERS Method for the Determination of Selected Organochlorine Compounds in Honey.

Honey is considered to be a health-promoting food product. Therefore, it is assumed that it should be free of contaminants. Although the use of organochlorine pesticides (OCPs) was banned a few decades ago in developed countries, persistent organic pollutants (POPs) are still detected in various environmental and biological matrices, including food. These contaminants exhibit toxic properties and bioaccumulate in some food chains. The validation of a modified QuEChERS extraction method was successfully performed for o,p'-DDT, o,p'-DDE, o,p'-DDD, p,p'-DDT, p,p'-DDE, p,p'-DDD, heptachlor and dieldrin. 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153) was used as an internal standard. The modification involved changing the solvent from acetonitrile to n-hexane after extraction. Quantitation was carried out using gas chromatography with an electron capture detector (µECD). The mean recovery values for o,p'-DDT, o,p'-DDE, o,p'-DDD, p,p'-DDT, p,p'-DDE, p,p'-DDD and dieldrin, spiked at 2.9 ng/g and 20 ng/g, ranged from 64.7% to 129.3%, and, for heptachlor spiked at 5.6 ng/g and 20 ng/g, ranged from 68.0% to 88.3%. The relative standard deviation (RSD) for these concentrations did not exceed 20%, and the within-laboratory reproducibility was below 20%, except o,p'-DDE and p,p'-DDT, which were 25.2% and 20.7%, respectively. This modified QuEChERS extraction method for selected organochlorine compounds was demonstrated as effective for routine testing in honey.

Typical organic contaminants in hair of adult residents between inland and coastal capital cities in China: Differences in levels and composition profiles, and potential impact factors.

The growing of urbanization, industrialization, and agricultural production have resulted in the increasing contamination of typical organic contaminants (OCs) in China. However, data on differences in exposure characteristics of typical OCs between the coastal and inland cities among residents in China are limited. In this study, hair samples were collected from adult residents in 10 and 17 provincial capital cities in coastal and inland China, respectively, to investigate the differences in the levels and composition profiles of typical OCs. The potential factors impacting the human exposure to OCs were also examined based on the relationship among the hair OC levels and the population characteristics and statistical indicators. The median concentrations of dichlorodiphenyltrichloroethane's (DDTs), polybrominated diphenyl ethers (PBDEs), and organophosphorus flame retardants (PFRs) in hair of coastal urban residents were 3.64, 5.58, and 268 ng/g, respectively, while their concentrations in samples from inland urban residents were 1.84, 3.85, and 202 ng/g, respectively. Coastal residents showed significantly higher hair OC concentrations than inland residents (p < 0.05). BDE209 and p,p'-DDE were the predominant chemicals for PBDEs and DDTs, respectively, in both coastal and inland cities. Tris(2-chloroisopropyl) phosphate (TCIPP) was the dominant PFR in coastal residents' hair, while triphenyl phosphate (TPHP) was the major PFR in inland residents' hair, possibly owing to the different usages of the PFRs. Significant gender differences were observed in the levels and composition profiles of OCs (p < 0.05). The levels of p,p'-DDE and TCIPP were significantly related to the gross domestic product (GDP), gross secondary industry product, and the per capita consumption of aquatic products (p < 0.05). This study provides scientific data for evaluating human exposure to OCs in urban residents at a large scale and its associations with statistical indicators including urbanization, industrialization, agricultural production, and diet in China.

Organochlorine pesticides and polycyclic aromatic hydrocarbons in serum of Beijing population: Exposure and health risk assessment.

Organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants, but large-scale human biomonitoring and health risk assessment data on these contaminants remain limited. In this study, concentrations of 6 OCPs and 5 PAHs were determined by GC-MS/MS in 1268 human serum samples which were collected from the participants in 2017 Beijing Chronic Disease and Risk Factor Surveillance. The detection frequencies of OCPs and PAHs ranged from 64.7 % to 96.5 % and 89.4 % to 99.6 %, respectively. The most abundant contaminants in OCPs and PAHs were pentachlorophenol (PCP) and pyrene (Pyr) with median concentrations reaching up to 3.13 and 8.48 µg/L, respectively. Nonparametric tests were employed to assess the correlations among contaminants levels, demographic characteristics (age, gender, body mass index, residence) and serum biochemical indexes. Significantly higher serum levels of all PAHs were observed in suburb residents than that in urban residents (P < 0.001). Binary logistic regression analysis demonstrated that exposure to benzo(a)pyrene (OR 2.17 [1.29, 3.63]), phenanthrene (OR 1.06 [1.02, 1.11]), fluoranthene (OR 1.04 [1.02, 1.07]) and Pyr (OR 1.02 [1.01, 1.03]) might increase the occurrence of hyperglycemia, and exposure to hexachlorobenzene (HCB) (OR 1.53 [1.05, 2.22]) and pentachlorobenzene (OR 1.14 [1.02, 1.27]) were positively associated with hyperlipidemia. Furthermore, the hazard quotients (HQs) for serum HCB, PCP and p,p'-dichlorodiphenyldichloroethylene were calculated based on health-based guidance values to predict health risks. 0.2 % and 4.3 % of serum samples showed HQ values exceeding 1 for HCB and PCP, respectively, in case of the non-carcinogenic risk, while 23.1 % of HQs for HCB were above 1 in case of the carcinogenic risk for a risk level 10-5. Our study reveals that the body burden of the Beijing general population relative to OCPs and PAHs was nonnegligible. The past exposure of HCB and PCP might adversely affect the health status of the Beijing population.

First WHO/UNEP survey of the current concentrations of persistent organic pollutants in human milk in Morocco.

The presence of persistent organic pollutants (POPs) in human milk is an indicator of the level of these substances in the environment and enables evaluation of the potential exposure of breastfed children. POPs concentrations in a Moroccan human milk pooled sample (59 donors) were determined for the first time by the WHO reference laboratory to provide a baseline and allow monitoring of the future trends for those persistent organohalogen compounds. Eighty-one different POPs, including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and dioxins and furans (PCDD/Fs) were identified and quantified by using gas chromatography (GC) with an electron capture detector (ECD) and confirmed by gas chromatography-mass spectrometry (GC/LRMS). The obtained results showed that the sum of DDT (sum of o,p'-DDD, p,p'-DDD, o,p'-DDE, p,p'-DDE, o,p'-DDT, and p,p'-DDT) was 237.9 ng/g, representing 94.0% of all detected OCPs levels, with a dominance of p,p'-DDE, and p,p'-DDT. Cis-heptachlor epoxide, HCB, and HCH were found at much lower levels. PCB indicator level was 60.7 ng/g of lipid, with the dominance of PCB 138, PCB 153, and PCB 180, presenting 98.3% of the total. Among the 25 PBDE congeners quantified, BDE-47, BDE-153, BDE-197, and BDE-207 were the dominant congeners account for 15.4% of the total concentration of PBDE (1.3 pg/g lipid). The lipid-adjusted level of PCDD/Fs and dl-PCBs expressed in Toxic Equivalents (TEQs: 6.65 pg/g) were lower in comparison to those found in the other countries. In summary, detected POPs levels in Moroccan human milk were much lower compared to the other countries, reflecting the effectiveness of the compliance with Stockholm Convention requirements on eliminating or reducing emissions of selected POPs. Continued monitoring is needed for these compounds, for which this is the first data available, provided by the WHO/UNEP survey in Morocco.