Accurate Structures and Rotational Constants of Steroid Hormones at DFT Cost: Androsterone, Testosterone, Estrone, ß-Estradiol, and Estriol.

A comprehensive analysis of the structural, conformational, and spectroscopic properties in the gas phase has been performed for five prototypical steroid hormones, namely, androsterone, testosterone, estrone, ß-estradiol, and estriol. The revDSD-PBEP86 double-hybrid functional in conjunction with the D3BJ empirical dispersion and a suitable triple-ζ basis set provides accurate conformational energies and equilibrium molecular structures, with the latter being further improved by proper account of core-valence correlation. Average deviations within 0.1% between computed and experimental ground state rotational constants are reached when adding to those equilibrium values vibrational corrections obtained at the cost of standard harmonic frequencies thanks to the use of a new computational tool. Together with the intrinsic interest of the studied hormones, the accuracy of the results obtained at DFT cost for molecules containing about 50 atoms paves the way toward the accurate investigations of other flexible bricks of life.

Assessment of occurrence, partitioning and ecological risk for 144 steroid hormones in Taihu Lake using UPLC-MS/MS with machine learning model.

Steroid hormones (SHs) have attracted mounting attention due to their endocrine-disrupting effects on humans and aquatic organisms. However, the lack of analytical methods and toxicity data for a large number of SHs has limited the effective management of SH contamination in the water-sediment systems. In this study, we developed a highly sensitive analytical method for the simultaneous quantification of 144 SHs to investigate their occurrence, spatial distribution and partitioning in the water and sediment in Taihu Lake. The results showed that the total concentrations of SHs in water and sediment were 366.88-998.23 ng/L (mean: 612.84 ng/L) and 17.46-150.20 ng/g (mean: 63.41 ng/g), respectively. The spatial distribution of SHs in Taihu Lake might be simultaneously influenced by the pollution sources, lake hydrodynamics, and sediment properties. The sediment-water partitioning result implied that 28 SHs were in dynamic equilibrium at the water-water interface. In addition, 22 and 12 SHs tended to spread to water and settle into sediment, respectively. To assess the ecological risk of all SHs, a robust random forest model (R2 = 0.801) was developed to predict the acute toxicity of SHs for which toxicity data were not available from publications. Risk assessment showed that SHs posed a high ecological risk throughout Taihu Lake, with the highest risk in the northwestern areas. Estrone, 17ß-estradiol and 17α-ethynylestradiol were the dominant risk contributors and were therefore recommended as the priority SHs in Taihu Lake. This work provided a valuable dataset for Taihu Lake, which would help to provide guidance and suggestions for future studies and be useful for the government to develop the mitigation and management measures.

Steroid hormones in surface water resources in China: systematic review and meta-analysis and probabilistic ecological risk assessment.

A Search was conducted in international databases including Scopus, PubMed, Embase, and Web of Science from 10 January 2005 to 15 January 2023. The risk quotient (RQ) of Estrone (E1), 17ß-E2 (E2), and Estriol (E3) on the surface water resources of China was calculated by Monte Carlo Simulation (MCS) technique. The rank order of steroid hormones based on pooled (weighted average) concentration in surface water was E3 (2.15 ng/l) > E2 (2.01 ng/l) > E1 (1.385 ng/l). The concentration of E1 in Dianchi lake (236.50.00 ng/l), 17ß-E2 in Licun river (78.50 ng/l), and E3 in Dianchi lake (103.1 ng/l) were higher than in other surface water resources in China. RQ related to E1, 17ß-E2 and E3 in 68.00%, 88.89% and 3.92% of surface water resources were high ecological risk, respectively. Therefore, carrying out source control plans for steroid hormones in surface water sources should be conducted continuously.

Critical assessment of the endocrine potential of Linalool and Linalyl acetate: proactive testing strategy assessing estrogenic and androgenic activity of Lavender oil main components.

The acyclic linear monoterpenes Linalool (Lin) and Linalyl acetate (LinAc) occur in nature as major constituents of various essential oils such as lavender oils. A potential endocrine activity of these compounds was discussed in literature including premature thelarche and prepubertal gynecomastia due to lavender product use. This study aims to follow-up on these critical findings reported by testing Lin and LinAc in several studies in line with current guidance and regulatory framework. No relevant anti-/ER and AR-mediated activity was observed in recombinant yeast cell-based screening tests and guideline reporter gene in vitro assays in mammalian cells. Findings in the screening test suggested an anti-androgenic activity, which could not be confirmed in the respective mammalian cell guideline assay. Mechanistic guideline in vivo studies (Uterotrophic and Hershberger assays) with Lin did not show significant dose related changes in estrogen or androgen sensitive organ weights and a guideline reproductive toxicity screening study did not reveal evident effects on sex steroid hormone sensitive organ weights, associated histopathological findings and altered sperm parameters. Estrous cycling and mating/fertility indices were not affected and no evident Lin-related steroid hormone dependent effects were found in the offspring. Overall, the initial concerns from literature were not confirmed. Findings in the yeast screening test were aberrant from follow-up guideline in vitro and in vivo studies, which underlines the need to apply careful interpretation of single in vitro test results to support a respective line of evidence and to establish a biologically plausible link to an adverse outcome.

Assessment of developmental toxicity and the potential mode of action underlying single and binary exposure to estrogenic endocrine disrupting chemicals in zebrafish (Danio rerio).

The current study investigated the effect of single and binary exposure to distinct xenoestrogens, including diethylstilbestrol (DES) and zearalenone (ZEN), on zebrafish embryos subjected to continuous exposure for 4 days starting from 4 h post fertilization. Noteworthy impact on cumulative mortality, hatchability, spinal and tail curvature, pericardial edema, and reduction in blood circulation were observed in DES-treated embryos, with lower incidence and intensity shown for ZEN at the same nominal concentration (3 µM). An interactive effect was seen for the combined exposure to DES and ZEN, in which deformities and circulatory failure mediated by DES were mitigated by co-treatment with low concentrations of ZEN. Similarly, ZEN-induced spinal and tail curvature, pericardial edema, and blood flow reduction declined dramatically following DES co-exposure at low concentrations. A significant counteracting effect has been observed against DES- and ZEN-induced developmental anomalies following co-treatment with an estrogen receptor (ER) antagonist, fulvestrant (FUL). The assessment of the aromatase gene (CYP19A1b) showed that DES strongly upregulated mRNA expression of CYP19A1b with a lower EC50 (1.1 × 10-3 nM) than a natural estrogen, 17ß-estradiol (2.5 nM). Similarly, ZEN induced CYP19A1b mRNA expression with an EC50 of 57 nM. Exposure to 10 or 20 µM FUL inhibited the expression of CYP19A1b induced by a single treatment of DES or ZEN. Overall, the competitive action against ER could be the main mechanism underlying the developmental toxicity induced by DES and ZEN.

Analysis and risk assessment of pharmaceutical residues in fish from three water bodies in Ghana.

Illegal mining has overshadowed pharmaceutical pollution even though exposure to pharmaceutical waste is high. Consumption of fish potentially polluted with pharmaceuticals from the rivers continues with little concern or potential threat it poses. In the present study, the residues of one antibiotic (Chloramphenicol), five hormones (progesterone, 17-beta Estradiol, Estrone, 17a-Ethynylestradiol, and one), three environmental contaminants (4-para-nonylphenol, 4-tert-octylphenol, and Bisphenol A), one barbiturate (Primidone) and one analgesic (Diclofenac sodium salt), were investigated from fish samples from the rivers Pra, Narkwa, and the Volta. The results show a high concentration of drugs in River Pra in comparison to those in Rivers Narkwa and Volta. The hazard quotients (HQs) for the environmental contaminants were all above 1, except Bisphenol A. Furthermore, the HQs from this study suggest that consumers of fish from any of the three rivers stand a hazard risk of Chloramphenicol (19), 17a-Ethynylestradiol (4), Estrone (1.366), Diclofenac sodium salt (3.29), Progesterone (4.598), 4-tert-octylphenol (87.2), and 4-para-nonylphenol (7.252), but negligible risk against E2 (0.687), Primidone (0.014), Testosterone (0.16), and Bisphenol A (0.642). Of the fish species studied, the highest concentration of all pharmaceuticals put together is found in Clarias gariepinus, Labeo senegalensis, and Chrysichthys nigrodigitatus in that order.

Deep mining of reported emerging contaminants in China's surface water in the past decade: Exposure, ecological effects and risk assessment.

The identification and management of high-risk contaminants have raised great concern from governments. Facing the growing amount of data on the occurrence of emerging contaminants (ECs) in surface water, a deep mining and quality control strategy was developed to integrate data on all reported ECs in Chinese surface water over the past decade, and an exposure and effect database was further built. In addition, multilevel risk characterization was carried out to prioritize high-risk areas, contaminants and endpoints. A total of 1038 ECs, mainly pharmaceutical and personal care products (PPCPs) and industrial chemicals, were curated, with concentrations ranging from 0.02 pg/L to 533 µg/L. For individual risk, all the provinces had acceptable risks except for Henan, which was characterized with a medium chronic risk. Nine ECs, including 4-nonylphenol and estrone, dominated individual risks. Conversely, for multisubstance risk, 76.20% and 73.87% of aquatic organisms were affected acutely and chronically at the national level, with acute and chronic risks exceeding the safety threshold of 5% in 11 and 19 provinces, respectively. Nineteen ECs, including sitosterol and chyfluthrin, dominated the multisubstance risk. In addition, 9 MoAs mainly inducing electron transfer inhibition, neurotoxicity and narcosis toxicity are high-risk endpoints. The study revealed the ecological risk status and key risk entities of Chinese surface waters, which provided the latest data to support the control of ECs in China.

Harnessing microbial phylum-specific molecular markers for assessment of environmental estrogen degradation.

Steroidal estrogens are ubiquitous contaminants that have garnered attention worldwide due to their endocrine-disrupting and carcinogenic activities at sub-nanomolar concentrations. Microbial degradation is one of the main mechanisms through which estrogens can be removed from the environment. Numerous bacteria have been isolated and identified as estrogen degraders; however, little is known about their contribution to environmental estrogen removal. Here, our global metagenomic analysis indicated that estrogen degradation genes are widely distributed among bacteria, especially among aquatic actinobacterial and proteobacterial species. Thus, by using the Rhodococcus sp. strain B50 as the model organism, we identified three actinobacteria-specific estrogen degradation genes, namely aedGHJ, by performing gene disruption experiments and metabolite profile analysis. Among these genes, the product of aedJ was discovered to mediate the conjugation of coenzyme A with a unique actinobacterial C17 estrogenic metabolite, 5-oxo-4-norestrogenic acid. However, proteobacteria were found to exclusively adopt an α-oxoacid ferredoxin oxidoreductase (i.e., the product of edcC) to degrade a proteobacterial C18 estrogenic metabolite, namely 3-oxo-4,5-seco-estrogenic acid. We employed actinobacterial aedJ and proteobacterial edcC as specific biomarkers for quantitative polymerase chain reaction (qPCR) to elucidate the potential of microbes for estrogen biodegradation in contaminated ecosystems. The results indicated that aedJ was more abundant than edcC in most environmental samples. Our results greatly expand the understanding of environmental estrogen degradation. Moreover, our study suggests that qPCR-based functional assays are a simple, cost-effective, and rapid approach for holistically evaluating estrogen biodegradation in the environment.

Electrochemical degradation of 17α-ethinylestradiol: Transformation products, degradation pathways and in vivo assessment of estrogenic activity.

Conventional water treatment methods are not efficient in eliminating endocrine disrupting compounds (EDCs) in wastewater. Electrochemical Advanced Oxidation Processes (eAOPs) offer a promising alternative, as they electro-generate highly reactive species that oxidize EDCs. However, these processes produce a wide spectrum of transformation products (TPs) with unknown chemical and biological properties. Therefore, a comprehensive chemical and biological evaluation of these remediation technologies is necessary before they can be safely applied in real-life situations. In this study, 17α-ethinylestradiol (EE2), a persistent estrogen, was electrochemically degraded using a boron doped diamond anode with sodium sulfate (Na2SO4) and sodium chloride (NaCl) as supporting electrolytes. Ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry was used for the quantification of EE2 and the identification of TPs. Estrogenic activity was assessed using a transgenic medaka fish line. At optimal operating conditions, EE2 removal reached over 99.9% after 120 min and 2 min, using Na2SO4 and NaCl, respectively. The combined EE2 quantification and in vivo estrogenic assessment demonstrated the overall estrogenic activity was consistently reduced with the degradation of EE2, but not completely eradicated. The identification and time monitoring of TPs showed that the radical agents readily oxidized the phenolic A-ring of EE2, leading to the generation of hydroxylated and/or halogenated TPs and ring-opening products. eAOP revealed to be a promising technique for the removal of EE2 from water. However, caution should be exercised with respect to the generation of potentially toxic TPs.

[Pollution Characteristics and Risk Assessment of Typical Endocrine Disrupting Chemicals in Drains Flowing into the Yellow River of Ningxia].

Solid-phase extraction and ultra-high performance liquid chromatography-mass spectrometry were used to detect and analyze the contamination of nine typical endocrine disrupting chemicals (EDCs) in drains flowing into the Yellow River of Ningxia. Sources of these EDCs were analyzed, and their risks were assessed. The results showed that EDCs were detected in drains at all 33 sampling sites, with total concentrations （ΣEDCs） of 82.28-1730.09 ng·L-1. Among phenolic compounds, bisphenol A (BPA) and nonylphenol (NP) were two that were more commonly detected EDCs, with the detection rates above 90%; estrone (E1) and estriol (E3) were more commonly detected estrogenic compounds, both with detection rates of 79%. On a spatial scale, the average concentrations of ΣEDCs in the drains in Shizuishan and Yinchuan were much higher than those in Wuzhong and Zhongwei. Concentrations of ΣEDCs at the sampling sites before flowing into Yellow River ranged from 82.28 to 979.82 ng·L-1. The source analysis showed that industrial wastewater and domestic sewage were two primary sources for BPA, whereas industrial wastewater was the primary source for OP. The primary sources of E1 and E3 were livestock and poultry breeding wastewater and domestic sewage, respectively. Risk assessment results showed that EDCs in drains flowing into the Yellow River posed low or moderate ecological risk but high risk for estrogenic activity at all sampling sites.

Comprehensive assessment of estrogenic activities of parabens by in silico approach and in vitro assays.

Parabens are ubiquitous pollutants in the environment and humans due to their wide applications in food, pharmaceuticals, and personal care products. Although the estrogenic activity of some parabens has been confirmed, the underlying mechanisms and the structure-estrogenic activity relationship are still largely unclear. Here, we systematically used in silico and in vitro approaches to investigate the estrogenic potency of typical parabens, including methyl-, ethyl-, propyl-, iso-propyl-, butyl-, iso-butyl- and benzyl-paraben. Molecular dynamics simulations and binding free energy calculations were combined to investigate the atomic-level mechanism of paraben binding to estrogen receptors (ERs). Computational analysis showed that ER were the targets of tested parabens and kept a stable agonist conformation. The calculated total binding free energies suggested that van der Waals interactions were the major driving forces for paraben-ER interaction and correlated with the structure of paraben side chains. In in vitro assays, paraben with an aromatic side chain, benzyl-paraben, showed the strongest estrogenic activity at 0.01 µM and the EC50 at 0.796 ± 0.307 µM, on par with levels commonly detected in human organs. Among tested parabens with an alkyl side chain, the estrogenicity increased as the side chain length increased from 1 to 4, but no significant difference appeared between parabens with isomeric alkyl side chains (propyl- vs isopropyl and butyl- vs iso-butylparaben). The estrogenic activity of parabens was significantly related to the calculated binding energies (R2 = 0.94, p = 0.0012), depending on the side chains of parabens. Our findings provide a significant mechanism for parabens to disrupt estrogenic function and considerations for structural optimization from the perspective of environmental protection.

A critical review on the distribution and ecological risk assessment of steroid hormones in the environment in China.

During past two decades, steroid hormones have raised significant public concerns due to their potential adverse effects on the hormonal functions of aquatic organisms and humans. Considering China being a big producer and consumer of steroid hormones, we summarize the current contamination status of steroid hormones in different environmental compartments in China, and preliminarily assess the associated risks to ecological systems. The results show that steroid hormones are ubiquitously present in Chinese surface waters where estrogens are the most studied steroids compared with androgens, progestogens and glucocorticoids. Estrone (E1), 17ß-estradiol (17ß-E2) and estriol (E3) are generally the dominant steroid estrogens in Chinese surface waters, whereas for the other steroids, androsterone (ADR), epi-androsterone (EADR), progesterone (PGT), cortisol (CRL) and cortisone (CRN) have relatively large contributions. Meanwhile, the investigations for the other environmental media such as particles, sediments, soils and groundwater have been limited, as well as for steroid conjugates and metabolites. The median risk quotients of most steroid hormones in surface waters and sediments are lower than 1, indicating low to moderate risks to local organisms. This review provides a full picture of steroid distribution and ecological risks in China, which may be useful for future monitoring and risk assessment. More studies may focus on the analysis of steroid conjugates, metabolites, solid phase fractions, analytical method development and acute/chronic toxicities in different matrices to pursue a more precise and holistic risk assessment.

[Occurrence Characteristics and Health Risk Assessment of Endocrine Disrupting Chemicals in Groundwater in Wuxi-Changzhou].

The concentrations of 22 endocrine disrupting chemicals, including 4 categories of sex hormones, progesterones, glucocorticoids, and phenolic hormones, in groundwater of Wuxi-Changzhou were analyzed using solid-phase extraction and ultra-performance liquid chromatography tandem mass spectrometry. The results indicated that 20 EDCs were detected, among which bisphenol A (BPA), estrone (E1), estradiol (E2), and 17α-ethinyl estradiol (EE2) were the main components with detection ratios greater than 90%, followed by estriol (E3) and methyl-prednisolonel (Meprednl), which had detection rates 67.7% and 48.4%, respectively. The average concentration of BPA was the highest (4.95 ng·L-1), followed by that of Meprednl, E2, prednisolone (Prednl), testosterone propionate (TES-pro), and megestrol-acetate (MA; 2.84, 0.71, 0.64, 0.58, and 0.53 ng·L-1, respectively). The total concentration in each site ranged from 0.38 to 147.35 ng·L-1. The sites with higher concentration were mainly distributed in the Xinbei District, Liyang City, and the Zhonglou District of Changzhou City. The potential sources were analyzed by a principal component analysis (PCA) combining the point sources near sample sites. The results showed that domestic sewage, aquaculture, and industrial wastewater were the main sources, following by medical wastewater. A non-carcinogenic risk assessment showed a low risk of EDCs in the groundwater of the study area, and the risk of drinking water was greater than that of skin exposure. EE2 had the highest non-carcinogenic risk and is suggested to be monitored in priority.

Occurrence and risk assessment of steroid estrogens in environmental water samples: A five-year worldwide perspective.

The ubiquitous occurrence of steroid estrogens (SEs) in the aquatic environment has raised global concern for their potential environmental impacts. This paper extensively compiled and reviewed the available occurrence data of SEs, namely estrone (E1), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2), estriol (E3), and 17α-ethinyl estradiol (EE2), based on 145 published articles in different regions all over the world including 51 countries and regions during January 2015-March 2020. The data regarding SEs concentrations and estimated 17ß-estradiol equivalency (EEQ) values are then compared and analyzed in different environmental matrices, including natural water body, drinking and tap water, and wastewater treatment plants (WWTPs) effluent. The detection frequencies of E1, 17ß-E2, and E3 between the ranges of 53%-83% in natural water and WWTPs effluent, and the concentration of SEs varied considerably in different countries and regions. The applicability for EEQ estimation via multiplying relative effect potency (REPi) by chemical analytical data, as well as correlation between EEQbio and EEQcal was also discussed. The risk quotient (RQ) values were on the descending order of EE2 > 17ß-E2 > E1 > 17α-E2 > E3 in the great majority of investigations. Furthermore, E1, 17ß-E2, and EE2 exhibited high or medium risks in water environmental samples via optimized risk quotient (RQf) approach at the continental-scale. This overview provides the latest insights on the global occurrence and ecological impacts of SEs and may act as a supportive tool for future SEs investigation and monitoring.

Multi-approach assessment for the evaluation of spatio-temporal estrogenicity in fish from effluent-dominated surface waters under low instream flow.

Current practices employed by most wastewater treatment plants (WWTP) are unable to completely remove endocrine disrupting compounds (EDCs) from reclaimed waters, and consistently discharge these substances to receiving systems. Effluent-dominated and dependent surface waters, especially during low instream flows, can increase exposure and risks to aquatic organisms due to adverse biological effects associated with EDCs. Given the ecological implications that may arise from exposure to such compounds, the present a multi-approach study examined spatio-temporal estrogenic potential of wastewater effluent to fish in East Canyon Creek (ECC), Utah, USA, a unique urban river with instream flows seasonally influenced by snowmelt. Juvenile rainbow trout (Oncorhynchus mykiss) were caged at different upstream and downstream sites from an effluent discharge during the summer and fall seasons. In the summer, where approximately 50% of the streamflow was dominated by effluent, fish from the upstream and a downstream site, located 13 miles away from the effluent discharge, presented significantly elevated concentrations of plasma vitellogenin (VTG). Similarly, significantly high 17ß-estradiol to 11-ketotestosterone ratios were measured in the summer across all sites and time points, compared to the fall. In the laboratory, juvenile fish and primary hepatocytes were exposed to concentrated effluent and surface water samples. Quantification of VTG, although in significantly lower levels, resembled response patterns observed in fish from the field study. Furthermore, analytical quantification of common EDCs in wastewater revealed the presence of estriol and estrone, though these did not appear to be related to the observed biological responses, as these were more significant in sites were no EDCs were detected. These combined observations suggest potential estrogenicity for fish in ECC under continuous exposures and highlight the advantages of following weight-of-evidence (WoE) approaches for environmental monitoring, as targeted analytically-based assessments may or may not support the identification of causative contaminants for adverse biological effects.

A Simple, Low Cost, Sensitive, and Portable Electrochemical Immunochromatography Sensing Device to Measure Estrone-3-Sulfate.

In livestock production, point-of-care testing (POCT) technology that enables easy on-site analysis of sex hormones is desired to improve reproductive efficiency. In this context, low-molecular-weight endogenous steroids are particularly important for perinatal management. Therefore, we attempted to use a simple method that combines electrochemical techniques with immunochromatography to measure estrone-3-sulfate (E1S), one of the low-molecular-weight endogenous steroids that is an estrogen ester. The limit of detection (LOD) for E1S achieved by electrochemical immunochromatography was 570.5 ng/mL, which was one to two orders of magnitude lower than that of small molecule compounds analyzed by other POCT techniques (Primpray et al., Anal. Chim. Acta, 2019). In addition, it was indicated by a colorimetric analysis that the sensitivity of the electrochemical immunochromatographic technique could be enhanced by improving the method of application of the antibodies on the nitrocellulose membrane and the contact between the electrochemical detector and the nitrocellulose membrane.

Assessment of water contamination and health risk of endocrine disrupting chemicals in outdoor and indoor swimming pools.

The occurrence of endocrine disrupting chemicals (EDCs) in swimming pool waters has been scarcely investigated. In this study, the concentrations of 20 EDCs (4 phenols, 6 estrogens, 4 progestogens, 5 androgens, and 1 pharmaceutical) in 40 outdoor and indoor swimming pools in Changsha, China were investigated. Out of them, two phenols (bisphenol A and 4-tert-octylphenol), three estrogens (17ß-estradiol, 17ɑ-ethinlestradiol (EE2), and hexestrol), one pharmaceutical (caffeine), and two progestogens (progesterone and levonorgestrel) were detected in the collected samples. The androgens were not detected. Bisphenol A and caffeine were the dominant EDCs at concentrations of ND-23.22 ng/L and ND-39.08 ng/L, respectively. The levels of caffeine were significantly higher in indoor swimming pools (11.15 ng/L in average) than those in outdoor pools (1.90 ng/L in average) (p < 0.05), owing to the less sun's UV radiation and less use of sunscreens containing caffeine. The progestogens (progesterone and levonorgestrel) and estrogens (17ß-estradiol and hexestrol) were only detected in outdoor swimming pools. The detection frequencies and concentrations of bisphenol A and caffeine in downtown pools were significantly higher than those in outskirt pools. Besides, the correlations between the concentrations of EDCs and water quality parameters evaluated by the Spearman correlation analysis implied that residual chlorine had strong oxidant capable to bisphenol A and suggested that caffeine could be a potential indicator of organic contamination in swimming pool water. Finally, a quantitative risk assessment revealed that non-athletic child and athletic adult female were vulnerable subpopulations. The EDItotal of EE2 for athletic child, non-athletic female, non-athletic male, and non-athletic child were higher than ADIEE2 adopted by Australia and the EDItotal of EE2 for athletic female and athletic male were higher than ADIEE2 adopted by the United States.

Bioaccumulation, metabolism, and risk assessment of phenolic endocrine disrupting chemicals in specific tissues of wild fish.

Phenolic endocrine disrupting chemicals (EDCs) may pose a great hazard to wildlife and humans, owing to their ubiquitous presence in the environment and potential bioaccumulation ability. We investigated the bioaccumulation, metabolism, and human health risks of six phenolic EDCs, including bisphenol A (BPA), 4-tert-octylphenol (4-t-OP), 4-nonylphenol (4-NP), estrone (E1), 17ß-estradiol (E2), and 17α-ethinylestradiol (EE2), in wild fish from the Pearl River system, South China. Except EE2, the other five EDCs were detected in at least one of the four fish tissues (bile, liver, plasma, and muscle). The concentrations of BPA and 4-NP were greater than those of 4-t-OP, E1, and E2 in all tissues. The median values of log bioaccumulation factors for EDCs at the range of 3.86-4.52 in bile, 2.06-3.16 in liver, 2.69-3.87 in plasma, and 1.34-2.30 in muscle, indicating a higher bioaccumulation potential in fish bile than in other tissues. Greater levels of glucuronide/sulfate conjugated EDCs were found in fish bile and liver than in the plasma and muscle, suggesting that the liver and bile played an important role in the metabolism and excretion of phenolic EDCs in fish. The calculated hazard quotient values were below 1 for each compound, implying low risk to human health by intake of edible fish.

Endocrine-disrupting compounds in the Xiangjiang River of China: Spatio-temporal distribution, source apportionment, and risk assessment.

Endocrine-disrupting compounds (EDCs) were seasonally investigated in the surface water of the Xiangjiang River (south China) in order to understand their spatio-temporal distribution, source apportionment, and ecological risks. The occurrence of 21 EDCs were determined with liquid chromatography-tandem mass spectrometry in the water samples collected along the river over four seasons, and the results were statistically analyzed. The concentrations of progestagens, androgens, estrogens ranged from not detected (ND) to 98.3 ng L-1; while the concentrations of alkylphenols ranged from 0.8 to 3.1 × 103 ng L-1; and that of caffeine ranged from 0.1 to 49.8 ng L-1. The detection frequencies of bisphenol A, 4-tert-octylphenol, 4-n-nonylphenol, estrone, and 17ß-estradiol were 95-100% during the four sampling campaigns. The seasonal and spatial variation trend of EDCs in the Xiangjiang River was noticeable. The concentration of EDCs in Yueyang section (downstream) was the highest in winter, while the concentration in Yongzhou (upstream) section was the lowest in spring. The concentration of EDCs in the Xiangjiang River was significantly correlated with the levels of the total organic carbon, water temperature, and dissolved oxygen. Source analysis indicated that untreated sewage was the major source of EDCs. Furthermore, the potential risks of EDCs in the surface water to aquatic organisms were assessed with the risk quotient method (European Commission, 2003), and the results indicated the highest ecological risk of 17ß-estradiol in the Xiangjiang River.

Steroidal and phenolic endocrine disrupting chemicals (EDCs) in surface water of Bahe River, China: Distribution, bioaccumulation, risk assessment and estrogenic effect on Hemiculter leucisculus.

This study investigated selected steroidal and phenolic endocrine disrupting compounds (EDCs) in the surface water of the Bahe River (China) using gas chromatography mass spectrometry (GC-MS). Their effect on the wild sharpbelly Hemiculter leucisculus was investigated. The concentrations of 4-t-octylphenol, nonylphenol, bisphenol-A, estrone, 17 ß-estradiol, 17 α-Ethinylestradiol, and estriol were up to 126.0, 634.8, 1573.1, 55.9, 23.9, 31.5, and 5.2 ng L-1 in the surface water, and up to 26.4, 103.5, 146.9, 14.2, 9.3, 13.8, and 1.3 ng g-1 in the fish muscle tissue, respectively. High estrogen equivalent levels and hazard quotients were found in the middle and lower reaches of the river, and the pollution in these regions caused enhanced growth conditions, inhibition of gonad growth, and suppression of spermatogenesis in H. leucisculus. The up-regulation of Vitellogenin mRNA expression in male fish, collected from relatively heavily EDCs contaminated areas, indicates a potential estrogenic effect. The differential expression profiles of genes related to steroidogenesis at all sampling sites suggests that these endpoints may play an important role for the pollution monitoring of estrogenic EDCs in the Bahe River.