以QuEChERS萃取搭配極致液相層析/串聯式質譜儀分析食品中全氟碳化合物、鄰苯二甲酸酯、壬基酚及雙酚A

Advances in analytical techniques have allowed greater detection of environmental contaminants from small volumes of sample. Four methodologies were evaluated for the extraction of 53 per- and polyfluoroalkyl substances (PFASs) from eight classes in 200 µL of avian and mammal serum. Spiked serums at four concentrations (0, 0.5, 5.0 and 25 ng mL−1) were prepared by protein precipitation (PPT), enhanced matrix removal (EMR), weak anion exchange (WAX), and hydrophilic-lipophilic balance (HLB) solid-phase extraction cartridges. The extract from each methodology was analysed by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC–MS/MS), and concentrations were compared with known concentrations in the spiked media. EMR performed the best overall, with 40 of 53 compounds effectively recovered at 5 ng mL−1. Furthermore, EMR was effective overall at concentrations ranging from 0.5 to 25 ng mL−1 for 39 out of 53. Similarly, PPT was effective for 35 of 53 compounds at all spiked serum concentrations. There was a negative correlation between internal standard recovery for compounds with increasing octanol–water coefficients (Kow) for WAX (R = − 0.65, p = 0.0043) and HLB (R = − 0.62, p = 0.0077) extractions, indicating methanol may not be a suitable solvent for long-chain PFAS extraction from protein-rich tissues. EMR and PPT represent fast and effective methodologies for the extraction of PFASs from low volumes of serum which allows greater accuracy and precision that can be applied to future human and wildlife biomonitoring programmes.

Concentration, distribution, and bioconcentration of short- and long-chain perfluoroalkyl substances in the water, suspended particulate matter, and surface sediment of a typical semi-enclosed bay

In Vitro Study of Bisphenol A (BPA) in the early human placenta

The ovary is the important organ to produce oocytes. Any disorder will affect embryo production. Ovarian cancer is one of gynecologic cancers in women which can affect ovarian functions. Oestradiol (E2) may be involved in ovarian cell growth and epithelial-mesenchymal transition (EMT) for diverse functions. EMT is an important process in embryo development and tumour migration or progression. Bis-phenol A (BPA) and nonyl-phenol (NP) have an estrogenic property, which can be suspected as endocrine disrupting chemicals (EDC). In this study, it has been examined whether BPA and NP can cause EMT process and migration in BG-1 ovarian cancer cells. To confirm the effect of these EDCs, BG-1 ovarian cancer cells were cultured and treated with DMSO (0.1%), E2 (10–7 M), BPA (10–6 M) and NP (10–6 M) for 0, 6, and 24 h. The mRNAs were extracted to perform reverse-transcription (RT)-PCR and the changes in the mRNA expressions were analysed by ANOVA test. Following treatments with BPA and NP, alterations of EMT markers; that is, vimentin and E-cadherin, were examined at mRNA levels by RT-PCR. The levels of vimentin were up-regulated by E2, BPA, or NP in a time-dependent manner. In addition, transcriptional factors of EMT response, i.e. snail and slug, were enhanced by these treatments more than 2 times. BG-1 cells were exposed to these EDCs for 0, 24, and 48 h. Vimentin and snail proteins were induced by E2, BPA, or NP, while the expression of E-cadherin was decreased by them. To reveal that this EMT response is affected by oestrogen receptor (ER), the cells were treated with these EDCs in the presence of an ER antagonist, ICI 182 780 (10–6 M). Treatment with ICI 182 780 reversed EDC-induced alteration of these EMT markers, E-cadherin, vimentin, and snail. Since EMT response can cause metastasis, a scratch assay was performed to show migration caused by BPA or NP. BPA or E2 enhanced migratory capability of these BG-1 cells. Taken together, these results indicate that BPA and NP, potential EDC, may have an ability to influence ovarian cancer metastasis via regulating snail and slug genes in ER-positive ovarian cancers. In a future study, their effects in inducing EMT and migration will be tested in a xenograft mouse model.This work was supported by a grant from the Next-Generation BioGreen 21 Program (no. PJ009599), Rural Development Administration, Republic of Korea.

Co-occurrence of phthalate esters and perfluoroalkyl substances affected bacterial community and pathogenic bacteria growth in rural drinking water distribution systems

The aim of this study was to assess the soil-water partitioning behavior of a wider range of per- and polyfluoroalkyl substances (PFASs) onto soils covering diverse soil properties. The PFASs studied include perfluoroalkyl carboxylates (PFCAs), perfluoroalkane sulfonates (PFSAs), fluorotelomer sulfonates (FTSs), nonionic perfluoroalkane sulfonamides (FASAs), cyclic PFAS (PFEtCHxS), per- and polyfluoroalkyl ether acids (GenX, ADONA, 9Cl-PF3ONS), and three aqueous film-forming foam (AFFF)-related zwitterionic PFASs (AmPr-FHxSA, TAmPr-FHxSA, 6:2 FTSA-PrB). Soil-water partitioning coefficients (log Kd values) of the PFASs ranged from less than zero to approximately three, were chain-length-dependent, and were significantly linearly related to molecular weight (MW) for PFASs with MW > 350 g/mol (R2 = 0.94, p < 0.0001). Across all soils, the Kd values of all short-chain PFASs (≤5 -CF2- moieties) were similar and varied less (<0.5 log units) compared to long-chain PFASs (>0.5 to 1.5 log units) and zwitterions AmPr- and TAmPr-FHxSA (∼1.5 to 2 log units). Multiple soil properties described sorption of PFASs better than any single property. The effects of soil properties on sorption were different for anionic, nonionic, and zwitterionic PFASs. Solution pH could change both PFAS speciation and soil chemistry affecting surface complexation and electrostatic processes. The Kd values of all PFASs increased when solution pH decreased from approximately eight to three. Short-chain PFASs were less sensitive to solution pH than long-chain PFASs. The results indicate the complex interactions of PFASs with soil surfaces and the need to consider both PFAS type and soil properties to describe mobility in the environment.

Prenatal exposure to perfluroalkyl substances and children's IQ: The Taiwan maternal and infant cohort study.

The purpose of this study was to give a worldwide overview of the concentrations of typical estrogenic endocrine disrupting chemicals (EDCs) in the effluent of sewage plants and then compare the concentration distribution of the estrogenic EDCs in ten countries based on the survey data of the estrogenic EDCs research. The concentrations of three main categories (totally eight kinds) of estrogenic EDCs including steroidal estrogens (estrone (E1), estradiol (E2), estriol (E3) and 17α-ethynylestradiol (EE2)), phenolic compounds (nonylphenol (NP) and bisphenol A (BPA)) and phthalate esters (dibutyl phthalate (DBP) and dibutyl phthalate (2-ethylhexyl) phthalate (DEHP)) in the effluents of sewage plants reported in major international journals over the past decade were collected. The statistics showed that the concentration distributions of eight kinds of EDCs were in the range of ng·L−1 to μg·L−1. The concentrations of steroidal estrogens mainly ranged within 50.00 ng·L−1, and the median concentrations of E1, E2, E3 and EE2 were 11.00, 3.68, 4.90 and 1.00 ng·L−1, respectively. Phenolic compounds and phthalate esters were found at μg·L−1 level (some individual values were at the high level of 40.00 μg·L−1). The median concentrations of BPA, NP, DBP and DEHP were 0.06, 0.55, 0.07 and 0.88 μg·L−1, respectively. The concentrations of phenolic compounds and phthalate esters in the effluents were higher than that of steroids estrogens. The analysis of the concentration in various ten countries showed that steroids estrogens, phenolic compounds and phthalate esters in sewage plant effluents were detected with high concentration in Canada, Spain and China, respectively.

Groundwater contamination by per- and polyfluoroalkyl substances (PFAS) is an emerging threat to drinking water quality, highlighting the need for effective treatment solutions. This study investigated subsurface flow constructed wetlands for treating groundwater contaminated with PFAS. The wetlands used a peat, biochar, and lightweight expanded clay aggregate (LECA) filter substrate, planted with either tufted sedge (Carex elata), fiber hemp (Cannabis sativa Futura 75), or an intercropping of the two Salix clones S. Wilhelm and S. Loden. The experiment was conducted under field conditions in Sweden, during one growing season, using PFAS-contaminated groundwater impacted by landfill leachate. The study showed accumulation of PFAS in all plant species and the peat and biochar part of the filter substrate, with short-chain PFAS and perfluoroalkyl carboxylates (PFCAs) dominating when considering the whole plants (57% and 77% of ƩPFAS, respectively) and long-chain PFAS and perfluoroalkyl sulfonates (PFSAs) dominating in the peat and biochar filter substrate (77% and 54% of ƩPFAS, respectively). Sorption to the filter substrate was shown to be the primary mechanism for PFAS removal. The highest plant PFAS concentrations were found in leaves, followed by roots, for all species. There was a difference in the PFAS composition profile when comparing different plant tissues, with PFCAs dominating in leaves (84% of ƩPFAS) and PFSAs dominating in roots (66% of ƩPFAS). All plant species were determined to have an above-ground tissue/water phase concentrations >10/1 for C3-PFCA (PFBA). This was also observed for C. sativa with C4- and C7-PFCAs (PFPeA, PFOA), and C4- and C5-PFSAs (PFBS, PFPeS), for C. elata with C8-PFSA (L-PFOS), and for S. Loden with PFPeA. ∑PFAS phytoextraction potential from landfill leachate-impacted groundwater (mg/ha yr) was estimated to be 940±670 for C. sativa, 390±310 for S. Loden, 330±160 for S. Wilhelm, and 160±56 for C. elata.

Simple SummaryIn this study, 70 male albino rats were allocated to the control group (GI) and were given 1 mL of ethanol; G, II, and G III were treated with 100 mg/Kg of each of BPA and NP, G IV and G V were treated with 25 mg/Kg of each of BPA and NP, G VI was given a mixture of a high dose of BPA and NP, and G VII was given a mixture of a low dose of BPA and NP. A significant elevation in the TNF Alpha, TNF Beta, and Caspase 3 serum was recorded individually and in the groups treated with high doses. In conclusion, exposure to BPA and NP strongly impacts antioxidants, immune-inflammatory mediators, and testicular tissue architecture. Furthermore, the data from this investigation support the idea that exposure to BPA and NP in daily life has multiple damages.This investigation was conducted to demonstrate the potential impacts of different doses of Bisphenol A (BPA) or Nonylphenol (NP) and their mixtures on some biological activities in male albino rats. Seventy male albino rats were allocated to the control group (GI) and were given 1 mL of ethanol. G II and G III were given 100 mg/kg of each of BPA and NP, G IV and G V were given 25 mg/kg of each of BPA and NP, G VI was given a high dose of BPA and NP, and G VII was given a low dose of BPA and NP. All animals were treated orally for 60 days. Serum biomarkers of oxidative stress, antioxidants, immune-inflammatory mediators, and apoptotic markers were determined, as well as a histopathological examination of the testis at the end of the experimental period. The results obtained showed a pronounced increase in malondialdehyde (MDA), protein carbonyl (PC), and 4-hydroxynonenol (4-HNE), concomitant with a significant reduction in serum Superoxide dismutase (SOD), catalase enzyme (CAT), and total antioxidant capacity (TAC) in all treated groups. A significant elevation in TNF Alpha, TNF Beta, and Caspase 3 serum was recorded individually and in the groups treated with high doses. The disturbance is represented by histological damage in the testis in the germinal epithelium and a decrease in spermatozoa inside the lumen of seminiferous tubules. The effects on testis tissues were dose-dependent, pronounced in mixture doses, and remarkable in higher doses. In conclusion, exposure to BPA and NP strongly impacts antioxidants, immune-inflammatory mediators, and testis tissue architecture. Furthermore, the data from this investigation support the idea that exposure to BPA and NP in daily life has multiple damages.

Per- and polyfluoroalkyl substances (PFAS) are toxic and persistent compounds widely distributed in the environment and accumulate in top predators, including seabirds. Because of the biomagnification potentials of some PFAS, diet is thought to be a key exposure route for PFAS. However, other factors such as habitat use, may mask interspecific differences in PFAS exposure expected from trophic structure. Among seabirds, gulls are generalists that forage in both terrestrial and marine habitats, making them relevant models to concurrently investigate the influence of foraging habitats and trophic position on PFAS exposure. We combined plasma PFAS concentrations with GPS tracking and stable isotopes to define foraging habitats (δ13C; δ34S; GPS) and trophic positions (δ15N) in three sympatric gull species breeding in France (Isle of Ré). In herring gulls (Larus argentatus), long-chain perfluoroalkyl carboxylic acids (PFCAs) were positively correlated with high trophic resources from marine habitats. We found compound- and sex-dependent relationships between PFAS concentrations and stable isotope values in lesser black-backed gulls (Larus fuscus), while no association was found with habitat use. No association was found between PFAS levels and stable isotopes in great black-backed gulls (Larus marinus). Our study suggests that coastal habitat could be a source of PFCA contamination and highlights that the influence of habitat use on gull exposure to PFAS varied depending on species, sex, and compounds.

Association between exposure to perfluoroalkyl substances (PFAS) and endometriosis in the ENDEA case-control study

Multivariate optimization of low-temperature cleanup followed by dispersive solid-phase extraction for detection of Bisphenol A and benzophenones in infant formula

Bisphenol A (BPA), nonylphenol (NP), and octylphenol (OP) are common environmental phenolic endocrine disruptors and widely used industrial chemicals that have garnered significant attention due to their potential to disrupt endocrine functions. These compounds are known to interfere with hormonal activities, particularly those related to estrogen, and are linked to the onset and progression of breast cancer. This study aims to systematically investigate the potential relationship between BPA, NP, and OP and breast cancer risk, along with their underlying molecular mechanisms, by synthesizing data from multiple databases. We initially acquired the chemical structures and SMILES representations of BPA, NP, and OP from the PubChem database. Subsequently, we utilized multiple databases, including the Comparative Toxicogenomics Database (CTD), SEA, and Swiss Target Prediction, t0 estimate their probable biological targets. The predicted targets were standardized and consolidated to form a comprehensive target database. Breast cancer-related targets were subsequently identified from the GeneCards and DisGeNET databases, and their overlap with the targets of BPA, NP, and OP was analyzed to pinpoint potential breast cancer risk targets. To elucidate the functional pathways involved, we conducted Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) enrichment analyses using the DAVID database. This analysis offered insights into the molecular pathways influenced by BPA, NP, and OP in the context of breast cancer. Additionally, we utilized machine learning algorithms, specifically Least Absolute Shrinkage and Selection Operator (LASSO) regression and Support Vector Machine (SVM), to identify nuclear targets linked to BPA, NP, and OP-induced breast cancer. These nuclear targets were further validated through differential expression analysis and Receiver Operating Characteristic (ROC) curve analysis using the GEO dataset GSE42568. We also performed a Single Gene Gene Set Enrichment Analysis (GSEA) to investigate the potential regulatory mechanisms of these nuclear genes in breast cancer. The infiltration of immune cells in breast cancer tissues was analyzed using single-sample gene set enrichment analysis (ssGSEA), and the correlation between nuclear targets and immune cell infiltration was examined. Finally, molecular docking and molecular dynamics simulations were conducted to assess the binding affinity and stability of BPA, NP, and OP with their nuclear targets. In this study, we integrated network toxicology, machine learning and multi-omics validation, and identified for the first time that BPA, NP and OP may induce breast cancer through 156 common targets; among them, MAOA, MGLL, ADRA2A, RPN2, GF1R and CTSD were identified as the key causative genes, with a diagnostic efficacy of 0.80–0.94 AUC. Mechanistically, these genes are concentrated in the GPCR/MAPK/JNK, sphingolipid, and prolactin signaling pathways, which regulate the Wnt/TGF-β/chemokine network and dramatically modify the immunological infiltration of nine classes of M0-M2 macrophages and CD4⁺ T cells. Molecular docking and kinetic simulations suggested the strong affinity of BPA for MGLL, and the complex was stabilized with ≥ 3 hydrogen bonds. In conclusion, phenolic endocrine disruptors may cause breast cancer through the “multi-target-immune microenvironment-metabolic reprogramming” axis, and MAOA, MGLL, ADRA2A, and RPN2 may serve as new targets for early detection and management.

Phthalates (PAEs), bisphenol A (BPA), and oestrogenic compounds have become major concerns due to their endocrine-disrupting effect. However, few studies related to the occurrence of PAEs, BPA, and oestrogen in food and compost from different growth age livestock have been conducted. In this study, faeces, urine and food samples were collected from a typical livestock (cow) and a special livestock (pigeon) from concentrated animal feeding operations (CAFOs). The daily total oestrogen excretion of a single cow ranged from 192 μg/day to 671 μg/day, which was significantly higher than that of a single pigeon (0–0.01 μg/day). Conjugated oestrogens represented 22.0–46.0% of the total oestrogens excreted from cow faeces and 80.7–91.8% of those from cow urine, indicating that the form of the excreted oestrogens depends on the livestock species and type of excrement. BPA was all detected in all livestock manure and food, and the concentration in pigeon was 9.2–40.2 ng/g and 23.1 ng/g respectively, while that in cattle was 50.5–72.0 ng/g and 41.1 ng/g respectively. The results indicated that the food is significant sources of BPA entering the process of cow and pigeon breeding. Diethyl phthalate (DEP) was detected at high frequency in pigeon faeces samples, suggesting that pigeons were highly exposed to these plasticisers. The total oestradiol equivalent quantity (EEQt) of livestock origin in aquatic environments was estimated to be 2.99 ng/L, which was higher than the baseline hazard value (1 ng/L) (Xu et al., 2018). The study provides data on the emissions and sources of PAEs, BPA, and oestrogenic compounds from different livestock in CAFOs and demonstrates that food is a significant source of BPA entering livestock.