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Nowadays, two of the endocrine disrupting compounds (EDCs) in the group of alkylphenols (APs), nonylphenol (4-NP) and octylphenol (4-t-OP), have attracted great scientific and regulatory attention mainly due to concerns about their aquatic toxicity and endocrine disrupting activity. This paper investigated the occurrence, distribution behavior, fate, and removal of 4-NP and 4-t-OP in liquid and solid phases of three full-scale wastewater treatment plants (WWTPs) with different treatment technologies comparatively. In this context, (i) advanced biological WWTP, (ii) wastewater stabilization pond (WSP), and (iii) constructed wetland (CW) were utilized. In all three investigated WWTPs, the concentrations of 4-NP (219.9-19,354.4 ng/L) in raw wastewater were higher than those of 4-t-OP (13.9-2822.4 ng/L). Within the scope of annual average removal efficiencies, 4-NP was treated highly in advanced biological WWTP (93.5 %), while it was almost not treated in WSP (3.1 %) and treated with negative removal (<0 %) in CW. While 4-t-OP was treated at a similar removal rate (93.5 %) to 4-NP in advanced biological WWTP, it was treated moderately in WSP (52.5 %) and very poorly in CW (12.4 %). It has been determined that the most important removal mechanism of both 4-NP and 4-t-OP in WWTPs is biodegradation, followed by sorption onto sewage sludge. According to the mass balance performed in advanced biological WWTP, the biodegradation rates for 4-NP and 4-t-OP were found to be 70.4 % and 86.6 %, respectively, while the sorption onto sewage sludge were determined to be 23.3 % and 6.8 %. One of the critical findings obtained within the scope of the study is that while the concentrations of both metabolites, especially 4-NP, in wastewater and sewage sludge, decreased considerably under aerobic conditions, on the contrary, their concentrations increased significantly under anaerobic conditions. Both compounds were detected at higher concentrations in primary sludge compared to secondary sludge in advanced biological WWTP, while in WSP, they were determined at higher concentrations in anaerobic stabilization pond sludge compared to facultative stabilization pond sludge. Besides, it was also determined that the sorption behavior of these alkylphenols is much more dominant than desorption., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Alkylphenols (APs) may cause gestational diabetes mellitus (GDM) in pregnant women by impairing glucose metabolism through endocrine disruption. However, the current literature has limited epidemiological evidence on the association between APs exposure and the risk of GDM, especially the lack of evidence on joint exposure. Thus, we evaluated the effect of exposure to APs during early pregnancy on the risk of GDM. The study involved 2035 pregnant women from Guangxi Zhuang Birth Cohort (GZBC) in China. Poisson regression model, restricted cubic spline (RCS), Bayesian kernel machine regression (BKMR), and quantile g-computation (Qgcomp) were conducted to evaluate the effects of serum APs levels on the risk of GDM in pregnant women. For each Ln-unit increase in the serum nonylphenol (NP) of pregnant women, the adjusted relative risk (RR) for GDM risk was 1.12 (95 % CI: 1.00, 1.24). After sex stratification, the effect was more pronounced among pregnant women carrying female fetuses（RR=1.22; 95 % CI: 1.09, 1.38). The serum 4-t-octylphenol (4-T-OP) of the medium-exposure (adjusted RR = 3.25: 95 % CI: 1.30, 8.12) and high-exposure groups (adjusted RR = 2.90: 95 % CI: 1.15, 7.31) were related to a significantly increased risk of GDM in pregnant women carrying female fetuses only when compared to the low-exposure group. A reverse U-shaped nonlinear association was found between 4-n-octylphenol (4-N-OP) and 4-n-nonylphenol (4-N-NP) concentrations and GDM risk, and it was more susceptible in pregnant women carrying female fetuses. The Qgcomp and BKMR models showed that exposure to APs mixtures was correlated with an elevated risk of GDM in pregnant women carrying female fetuses (adjusted OR = 1.90: 95 % CI: 1.07, 3.38). Exposure to APs during early pregnancy may have potential fetal sex-specific effects on the risk of GDM, with pregnant women carrying female fetuses being more susceptible., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Concerns regarding man-made organic chemicals pervading our ecosystem and having adverse and detrimental effects upon organisms, including man, have now been studied for several decades. Since the 1970s, some environmental pollutants were identified as having endocrine disrupting affects. These endocrine disrupting chemicals (EDC) were initially shown to have estrogenic or anti-estrogenic properties and some were also shown to bind to a variety of hormone receptors. However, since the 1990s it has also been identified that many of these EDC additionally, have the ability of causing abnormal alterations in Ca 2+ signalling pathways (also commonly involved in hormone signalling), leading to exaggerated elevations in cytosolic [Ca 2+ ] levels, that is known to cause activation of a number of cell death pathways. The major emphasis of this review is to present a personal perspective of the evidence for some types of EDC, specifically alkylphenols and brominated flame retardants (BFRs), causing direct effects on Ca 2+ transporters (mainly the SERCA Ca 2+ ATPases), culminating in acute cytotoxicity and cell death. Evidence is also presented to indicate that this Ca 2+ ATPase inhibition, which leads to abnormally elevated cytosolic [Ca 2+ ], as well as a decreased luminal ER [Ca 2+ ], which triggers the ER stress response, are both involved in acute cytotoxicity., (© 2024 The Author(s). FEBS Open Bio published by John Wiley & Sons Ltd on behalf of Federation of European Biochemical Societies.)

This study describes the development of an acid induced dispersive liquid-liquid microextraction method based on the in situ formation of hydrophobic deep eutectic solvents for the extraction of bisphenol A and alkylphenols from environmental water and beverage samples. Hydrochloric acid altered the hydrophilic-hydrophobic state of fatty acid salts to obtain hydrophobic fatty acids, which formed hydrophobic deep eutectic solvents with analytes in situ to extract the analytes. Under optimized conditions, the limits of detection and limits of quantitation were 0.03-0.1 μg L -1 and 0.12-0.3 μg L -1 , the intraday and interday relative standard deviations were less than 3.9 %, and the enrichment factor was 29-32. The recoveries of bisphenol A and alkylphenols were 95.9-104.9 % and 86.9-105.0 %, respectively. The extraction process used only hydrochloric acid and fatty acid salts, and the extraction process required less than 1 min. This method has the advantages of simplicity, speed, low cost and environmental friendliness., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

A solid-phase microextraction (SPME) Arrow and high-performance liquid chromatography-UV detector (HPLC-UV, detection at 225 nm) based method was developed for the selective determination of nine alkylphenols (APs) in milk. The functionalized mesoporous UiO-66 (4-meso-UiO-66) was utilized as the new coating material, which was synthesized by post-modification of pore-expanded UiO-66-NH 2 by an esterification reaction with 4-pentylbenzoic acid. It was fully characterized by X-ray photoelectron spectroscopy (XPS), fourier transformation infrared spectrometry, nitrogen sorption-desorption test, scanning electron microscopy, transmission electron microscopy, and X-ray diffractometer. The characterization results showed the ester groups and benzene rings were introduced into the 4-meso-UiO-66, and the mesoporous structure was predominant in the 4-meso-UiO-66. The extraction mechanism of 4-meso-UiO-66 to APs is the synergistic effect of Zr-O electrostatic interaction and the size exclusion effect resulting from XPS, selectivity test, and nitrogen sorption-desorption test. The electrospinning technique was utilized to fabricate the 4-meso-UiO-66 coated SPME Arrow and polyacrylonitrile (PAN) was used as the adhesive. The mass rate of 4-meso-UiO-66 to PAN and the electrospinning time were evaluated. The extraction and desorption parameters were also studied. The linear range of this method was 0.2-1000 μg L -1 with a coefficient of determination greater than 0.9989 under the optimal conditions. The detection limits were 0.05-1 μg L -1 , the inter-day and intra-day precision (RSD) were 2.8-11.5%, and the recovery was 83.6%-112%. The reusability study showed that the extraction performance of this new SPME Arrow could be maintained after 80 adsorption-desorption cycles. This method showed excellent applicability for the selective determination of APs in milk., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Environmental phenolic chemicals, due to their widespread occurrence and potent estrogenic properties, pose a risk to human exposure. The phenolic organic contaminants alkylphenols (APs) and alkylphenol polyethoxylates (APEs) are used in various household applications, and they may enter to the environment during production and use, potentially appearing in indoor dust. However, little is known about the levels of environmental phenolics in indoor environments. In this study, five of these compounds namely octylphenol (OP), 4-Octylphenol Monoethoxylate (4-OPME), 4-tert-octylphenol (4-t-OP), 4-n-nonylphenol (4-n-NP) and nonylphenol diethoxylate (di-NPE) were analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in household dust samples (n = 148) collected from Ankara, the capital of Turkiye. OP and 4-OPME was not present in any of the analyzed samples. The median concentrations of the 148 settling dust samples were 35, 520, and 1910 ng g -1 dust for 4-t-OP, 4-n-NP, and di-NPE, respectively. An assessment of the human (children and adults) exposure pathway to APs and APEs, which are recognized as endocrine-disrupting chemicals found in residential dust, revealed that it was approximately 3 times higher for children than for adults at both moderate and heavy exposure levels. The association between chemical exposure, house characteristics, and family lifestyle was investigated using a multivariate logistic regression model. According to the results of this model, while the high concentrations measured for 4-t-OP were not found to be associated with any of the household parameters, high levels of 4-n-NP and di-NPE were associated with the frequency of house cleaning, repairs made during the previous year, residential type, the number of occupants, flooring materials, and the purchase of new household items within the past year. This study provides a basis for prioritizing toxicology and exposure studies for EDCs and mixtures and may offer new tools for exposure assessment in health studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Background: While prenatal exposure to alkylphenols (APs) has been demonstrated to be associated with neurodevelopmental impairments in animals, the evidence from epidemiological studies remains limited and inconclusive. This study aimed to explore the link between AP exposure during pregnancy and the intelligence quotient (IQ) of preschool children., Methods: A total of 221 mother-child pairs from the Guangxi Zhuang Birth Cohort were recruited. Nonylphenol (NP), 4-tert-octylphenol (4-T-OP), 4-n-nonylphenol (4-N-NP), and 4-n-octylphenol were measured in maternal serum in early pregnancy. Childhood IQ was evaluated by the Fourth Edition of Wechsler Preschool and Primary Scale of the Intelligence at 3 to 6 years of age. The impact of APs on childhood IQ were evaluated by generalized linear models (GLMs), restricted cubic spline (RCS), and Bayesian kernel machine regression (BKMR)., Results: In GLMs, prenatal exposure to NP and the second tertile of 4-T-OP exhibited an inverse association with full-scale IQ (FSIQ) (β = -2.38; 95% CI: -4.59, -0.16) and working memory index (WMI) (β = -5.24; 95% CI: -9.58, -0.89), respectively. Prenatal exposure to the third tertile of 4-N-NP showed a positive association with the fluid reasoning index (β = 4.95; 95% CI: 1.14, 8.77) in total children, as well as in girls when stratified by sex. A U-shaped relationship between maternal 4-T-OP and WMI was noted in total children and girls by RCS (all P nonlinear < 0.05). The combined effect primarily driven by NP, of maternal AP mixtures at concentrations above the 50th percentile exhibited an inverse trend on FSIQ in total children and girls in BKMR., Conclusions: Prenatal exposure to various APs affects IQ in preschool children, and there may be nonmonotonic and sex-specific effects. Further investigation across the population is required to elucidate the potential neurotoxic effects of APs., (© 2024. The Author(s).)

Endocrine-disrupting compounds (EDCs) such as natural and synthetic hormones as well as phenolic industrial chemicals are considered contaminants of emerging concern in environmental waters. While EDCs carried through rivers may impact ecosystem health and productivity, these compounds are still not widely studied nor regulated. In the present study, we report the occurrence of EDCs in urban rivers in Mega Manila, namely, the Marikina, Pasig, Angat, and Pampanga Rivers that drain into Manila Bay. Endocrine-disrupting compounds may have reached these rivers through domestic wastewater and industrial effluents. Water samples from the rivers were extracted by solid-phase extraction before instrumental analysis using a liquid chromatograph coupled to a mass spectrometer. The analytical method exhibited good linear response (>99% in the concentration range of 1-50 µg/L) and low instrument detection limits (0.14-1.46 µg/L) for the hormones estrone (E1), estradiol, ethinylestradiol, progesterone, and testosterone, and the industrial chemicals bisphenol A, nonylphenol, and octylphenol. Of the hormones, E1 was detected up to 11 ng/L. Bisphenol A, nonylphenol, and octylphenol were measured up to 54, 1878, and 62 ng/L, respectively. Endocrine-disrupting compounds are not yet monitored in water bodies in the Philippines and there are no local guidelines yet on occurrence, pollution prevention, and mitigation. Environ Toxicol Chem 2024;43:259-266. © 2023 SETAC., (© 2023 SETAC.)

Humans are exposed to various bisphenols, alkylphenols and nitrophenols through dietary intake, food packaging and container materials, indoor and outdoor air/dust. This study aimed to evaluate exposure of Japanese pregnant women to environmental phenols by measuring target compounds in urine samples. From a cohort of the Japan Environment and Children's Study, 4577 pregnant women were selected. Bisphenol A (BPA), bisphenol S (BPS), bisphenol F (BPF), bisphenol AF (BPAF), para-nitrophenol (PNP), 3-methyl-4-nitrophenol (PNMC), branched 4-nonylphenol (4-NP), linear 4-nonylphenol and 4-tert-octylphenol (4-t-OP) were analysed using a high-performance liquid chromatograph coupled to a triple-quadrupole mass spectrometer. The urinary metabolite data were combined with a questionnaire to examine the determinants of phenol exposure by machine learning. The estimated daily intake (EDI) and hazard quotient (HQ) of BPA were calculated. PNP (68.2%) and BPA (71.5%) had the highest detection frequencies, with median concentrations of 0.76 and 0.46 μg/g creatinine, respectively. PNMC, BPS, BPF and 4-NP were determined in 24.9%, 11.9%, 1.3% and 0.4% of samples, respectively, whereas BPAF (0.02%) and 4-t-OP (0.02%) were only determined in a few samples. The PNP concentrations measured in this study were comparable with those reported in previous studies, whereas the BPA concentrations were lower than those reported previously worldwide. The EDI of BPA was 0.014 μg/kg body weight/day. Compared with the tolerable daily intake set by the German Federal Institute for Risk Assessment, the median (95th percentile) HQ was 0.044 (0.2). This indicates that the observed levels of BPA exposure pose a negligible health risk to Japanese pregnant women. Determinants of bisphenol and nitrophenol exposure could not be identified by analysing the questionnaire solely, suggesting that biological measurement is necessary to assess exposure of pregnant women to bisphenols and nitrophenols. This is the first study to report environmental phenol exposure of Japanese pregnant women on a nationwide scale., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Municipal wastewater treatment plant (WWTP) effluent is a primary source of pharmaceuticals and personal care products (PPCPs) to the marine environment, as most of these compounds are not fully removed during the treatment process. Continual discharge from WWTPs into coastal areas may act as a stressor by continually exposing organisms to a suite of PPCPs. To quantify organismal exposure to PPCP mixtures, we conducted a 12-week lab experiment that exposed Pacific oysters to effluent from two Oregon coastal WWTPs of different discharge capacities (permitted as <1 million gallons/day and >1 million gallons/day; or < or >3.785 million liters/day) at a dilution of 25 %. Composite samples of weekly collected effluent and a subset of freeze-dried oysters from experiment week 12 were analyzed for PPCPs. Though challenges with food availability inhibited our ability to confidently identify effects of the contaminants on growth and fitness, the experiment allowed us to examine uptake of contaminants from effluent into an estuarine bivalve of commercial importance. We detected 30 PPCPs and three alkylphenols in effluent and 13 PPCPs and four alkylphenols in oyster tissue, indicating high rates of release from secondary treatment and significant potential for marine organism exposure to and uptake of PPCPs in rural coastal areas., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Elise Granek reports financial support was provided by USGS-PSU Partnership. Amy Ehrhart reports financial support was provided by Sigma Xi Grants in Aid of Research. Amy Ehrhart reports financial support was provided by Edward D. and Olive C. Bushby Scholarship from Portland State University., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Parabens and alkylphenols pose serious hazards to human health, yet there are few studies on their exposure profiles and health risks in rural Chinese populations. In this study, 804 participants were selected from the Henan Rural Cohort in mid-eastern China. The plasma levels of parabens (methylparaben, ethylparaben, propylparaben, butylparaben (BuP)) and alkylphenols (4-tert-butylphenol (4-t-BP), 4-tert-octylphenol (4-t-OP)) were analyzed via liquid chromatography-tandem mass spectrometry. Linear regression models were used to investigate factors that may influence pollutant exposure levels. The correlation between contaminants was assessed using Spearman's correlation. The human contaminant intake was estimated using the estimated daily intake (EDI). The health risk was assessed using the hazard quotient (HQ). The detection frequency of four parabens and two alkylphenols exceeded 75%, with median concentrations of 0.444, 0.067, 0.078, 0.053, 8.810, and 6.401 ng/mL, respectively. Significant correlations were observed between parabens, as well as between 4-t-BP and 4-t-OP. Regarding gender, paraben concentrations were higher in women than in men, except for BuP. The EDI for pollutants except 4-t-OP was lower than their respective tolerable/acceptable daily intake. In total, 85.70% of participants had 4-t-OP HQ > 1. A widespread exposure to parabens and alkylphenols among the rural population was found. The high health risks of alkylphenol exposure indicate that alkylphenols should be used with caution.

In this study, the spatial distribution characteristics of nine alkylphenols (APs) in the Yongding River and Beiyun River were analyzed. The differences in the concentrations and spatial distribution patterns of nine APs were systematically evaluated using principal component analysis (PCA). The relationships between the concentration distribution patterns and the risks associated with nine APs were investigated under various categories of land use conditions in the region. The results demonstrated that the APs were widely present in both rivers, and the pollution risks associated with the APs were more severe in the Yongding River than in the Beiyun River. The results show that the contamination risks associated with 4-NP were the most serious in the two rivers, with detection percentages of 100% and 96.3%, respectively. In the Yongding River, the APs showed a tendency of low concentration levels in the upper reaches and high levels in the middle and lower regions. Meanwhile, the overall concentration levels of the APs in the Beiyun River were relatively high. However, despite the differences between the upper and middle regions of the Yongding River, the distribution pattern of the APs in the Beiyun River was basically stable. The concentration levels and risk quotient of the APs were negatively correlated with the vegetation cover land use type and positively correlated with the cropland and unused land use types within 500 m, 1 km, and 2 km. The purpose of this study was to provide theoretical data support and a basis for AP pollution risk evaluations in the Yongding River and Beiyun River.

Alkylphenols (APs) represent one of the highest exposure levels among endocrine disrupting chemicals (EDCs) in the South China Sea (SCS) due to their extensive use as plastic additives. The concerns about EDCs, including APs, have been reiterated since the surge in plastic waste from the COVID-19 response, but far less is known about the response of AP loadings in the SCS to emerging public policies and activities, including the COVID-19 pandemic. Here, we used cetaceans as bioindicators for monitoring two major APs, 4-nonylphenol (4-NP) and 4- tert -octylphenol (4-t-OP), in nine stranded cetacean species ( n = 110) in the SCS between 2004 and 2021. Prior to the COVID-19, APs loads showed decreasing temporal trends for finless porpoises and humpback dolphins, most likely due to China's restrictions on AP use or a shift in dominant prey species. Unexpectedly, AP loads continued to decline after the COVID-19 outbreak, probably due to a temporal-lag response of marine AP fluxes to the pandemic. The health risk assessments based on hormone biomarkers and toxicity thresholds suggest the potential adverse effects of APs on cetaceans, while recent declines in APs, though limited, may mitigate the detrimental impacts.

4-Nonylphenol (4-NP), an environmental pollutant with potent ecotoxicological effects, has been discovered in significant quantities in glacial ice and snow of the Sierra Nevada Mountain Range, CA. Photolysis of 4-NP is suspected to be a major, if not the sole, breakdown pathway in snow. However, the photolysis process has yet to be characterized in detail for this unique environment. This study therefore seeks to (1) confirm the presence of the major photolysis product within snowpack and snowmelt samples from the Palisade Glacier, CA, (2) determine key photolysis parameters through laboratory assays in snow analogs, and (3) compute environmentally relevant photolysis rates in snowpack via a spectral solar irradiance model parameterized for the Palisade Glacier. The primary photooxidation product of 4-NP, 4-nonylcatechol (4-NC), was synthesized and characterized by NMR and GC-MS for use as a reference standard in the detection of 4-NC in environmental samples. 4-NP was detected in all snowpack (n = 4) and snowmelt (n = 5) samples, with concentrations of 1.05 (± 0.11) μg L -1 and 1.28 (± 0.12) μg L -1 , respectively. 4-NC was detected in all snowmelt outflow samples and all but one snow samples (88 % detection frequency) but was below the limit of quantification for the given method. All samples were collected during a sampling regime at the Palisade Glacier in August of 2021. Quantum yields of photolysis at the 277 nm absorption band were determined to be 0.36 (±0.06) and 0.21 (±0.06) in ultrapure water and liquid snow, respectively. Under clear sky conditions at the Palisade Glacier, half-lives for 4-NP are estimated to range from 235 to 251 h (9.8-10.5 days) based on assays conducted in liquid snowmelt and irradiance modeling. These results suggest that the photolysis of 4-NP, and hence the production of 4-NC, is occurring at significant rates within the snowpack where 4-NC is inevitably released to downstream catchment areas via snowmelt. 4-NC is significantly more toxic than its precursor, thereby raising amplified concerns for downstream human and wildlife populations. Furthermore, the ubiquity of 4-NP among the Earth's environments presents this as an issue of potentially global concern., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The investigation into the degradation of alkylphenol pollutants (APs) has become a hotspot due to their harmful effects on the environment and human health. In this study, microbial electrolysis cells (MECs) were used to degrade nonylphenol (NP) and 4-tert-octylphenol (4-tert-OP). The study found that the degradation rates of NP and 4-tert-OP for a 6-day period were 83.6% and 96.3%, respectively, which were 30.53% and 26.7% higher than those of the group without applied voltage. The double layer area in the degradation of 4-tert-OP was larger than that of NP, and the resistance exhibited by 4-tert-OP (87.47 Ω) in MEC was lower than that of NP (99.42 Ω). Meanwhile, NP had a greater effect on the bioenzyme activity than 4-tert-OP. GC-MS analysis showed that the degradation pathways of both pollutants mainly included oxidation and hydroxylation reactions. Furthermore, the microbial community analysis indicated that the main functional bacteria in NP degradation were Citrobacter, Desulfovibrio and Advenella, and those in 4-tert-OP degradation were Stenotrophomonas, Chryseobacterium, Dokdonella, and the key microbiomes underlying the cooperative relationship. The biotoxicity test indicated that the toxicity of residual substances was significantly reduced. Therefore, the MEC system is efficient and environmentally friendly and has broad application prospects in phenol refractory organics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Phenols are significant environmental endocrine disruptors that can have adverse health effects on exposed individuals. Correlating phenol exposure to potential health implications requires the development of a comprehensive and sensitive analytical method capable of analyzing multiple phenols in a single sample preparation and analytical run. Currently, no such method is available for multiple classes of phenols due to electrospray ionization (ESI) limitations in concurrent ionization and lack of sensitivity to certain phenols, particularly alkylphenols. In this study, we investigated the influence of mobile phase compositions in ESI on concurrent ionization and analytical sensitivity of liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) during the analysis of multiple classes of phenols, and we propose a comprehensive and sensitive analytical method for various classes of phenols (i.e., bisphenols, parabens, benzophenones, chlorophenols, and alkylphenols). The proposed method was affected by 0.5 mM ammonium fluoride under methanol conditions. It enabled the concurrent ionization of all the phenols and significantly improved the analytical sensitivity for bisphenols and alkylphenols, which typically have poor ionization efficiency. This method, combined with a "dilute and shoot" approach, allowed us to simultaneously quantify 38 phenols with good chromatographic behavior and sensitivity. Furthermore, the method was successfully applied to the analysis of 61 urine samples collected from aquatic (swimming) and land (indoor volleyball and outdoor football) athletes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Killer whales ( Orcinus orca ) have been deemed one of the most contaminated cetacean species in the world. However, concentrations and potential health implications of selected 'contaminants of emerging concern' (CECs) and new persistent organic pollutants (POPs) in endangered Southern Resident and threatened Bigg's (Transient) killer whales in the Northeastern Pacific (NEP) have not yet been documented. Here, we quantify CECs [alkylphenols (APs), triclosan, methyl triclosan, and per- and polyfluoroalkyl substances (PFAS)] and new POPs [hexabromocyclododecane (HBCCD), PFOS, PFOA, and PFHxS] in skeletal muscle and liver samples of these sentinel species and investigate in utero transfer of these contaminants. Samples were collected from necropsied individuals from 2006 to 2018 and analyzed by LC-MS/MS or HRBC/HRMS. AP and PFAS contaminants were the most prevalent compounds; 4-nonylphenol (4NP) was the predominant AP (median 40.84 ng/g ww), and interestingly, 7:3-fluorotelomer carboxylic acid (7:3 FTCA) was the primary PFAS (median 66.35 ng/g ww). Maternal transfer ratios indicated 4NP as the most transferred contaminant from the dam to the fetus, with maternal transfer rates as high as 95.1%. Although too few killer whales have been screened for CECs and new POPs to infer the magnitude of contamination impact, these results raise concerns regarding pathological implications and potential impacts on fetal development and production of a viable neonate. This study outlines CEC and new POP concentrations in killer whales of the NEP and provides scientifically derived evidence to support and inform regulation to mitigate pollutant sources and contamination of Southern Resident killer whale critical habitat and other marine ecosystems.

Many chemicals, including many endocrine disruptors (EDCs) are known to leach out from various plastic consumer products and waste, and are widespread in the environment. EDCs are a large group of contaminants that can interfere with hormonal metabolism or function. In addition, there are in the literature implications of contribution by EDCs in tumor progression, the last stage of carcinogenesis driven by cells with a metastatic phenotype. The process of epithelial cells losing their apical-basal polarity and cell-to-cell contacts, and acquiring migration and invasive properties typical of mesenchymal cells is called epithelial-mesenchymal transition (EMT). It is essential for tumor progression. In human cells, plastic-related EDCs, (phthalates, bisphenol A, and the alkylphenols: nonylphenol and octylphenol) reduce epithelial E-cadherin, and increase mesenchymal N-cadherin and extracellular matrix metalloproteinases. These changes are hallmarks of EMT. In xenograft mouse studies, EDCs increase migration of cells and metastatic growth in distant tissues. Their contribution to EMT and tumor progression, the topic of this review, is important from public health perspective, because of the ubiquitous exposure to these EDCs. In this mini-review we also discuss molecular mechanisms associated with EDC-induced EMT and tumor progression., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Stormwater and snowmelt runoff is known to contribute to the deterioration of quality of urban surface waters. Vehicular traffic is recognised as a major source of a wide range of pollutants to urban runoff, including conventional pollutants, such as suspended solids and metals, and those referred to as 'contaminants of emerging concern'. The aim of this study was to investigate the contribution of selected metal(loid)s (Cd, Cr, Cu, Ni, Pb, Pd, Sb, W, Zn), polycyclic aromatic hydrocarbons (PAHs), nonylphenols, octylphenols and -ethoxylates, phthalates and bisphenol A (BPA) from vehicular traffic by sampling urban roadside snow at eight sites, with varying traffic intensities, and one control site without direct impacts of traffic. Our results confirmed that vehicles and traffic-related activities were the sources of octylphenols, BPA and phthalates as well as the metal(loid)s Sb and W, infrequently reported in previous studies. Among metal(loid)s, Cu, Zn and W occurred in the highest concentrations (up to 1.2 mg/L Cu, 2.4 mg/L Zn and 1.9 mg/L W), while PAHs and phthalates occurred in the highest concentrations among the trace organic pollutants (up to 540 μg/L phthalate diisononyl phthalate). Among the phthalates, di-(2-ethylhexyl)phthalate had the highest frequency of detection (43% of the roadside samples). While BPA and octylphenols had relatively high frequencies of detection (50% for BPA and 81% for octylphenols), they were present in comparatively low concentrations (up to 0.2 μg/L BPA and 1.1 μg/L octylphenols). The control site displayed generally low concentrations of the pollutants studied, indicating that atmospheric deposition was not a significant source of the pollutants found in the roadside snow. Several of the pollutants in the roadside snow exceeded the applicable surface water and stormwater effluent guideline values. Thus, the transport of these pollutants with runoff posed risk of causing adverse effects in the receiving surface waters., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Alkylphenols are a type of endocrine disruptors, which are commonly found in personal care products, food, and water and are more harmful to the human body. To investigate the relationship between exposure of alkylphenols in serum of pregnant women during early pregnancy and adverse birth outcomes, a total of 2035 healthy pregnant women and their neonates were recruited in the birth cohort of Zhuang nationality in Guangxi from 2015 to 2018. The peripheral venous blood samples were collected from pregnant women in early pregnancy; the concentrations of nonylphenol (NP), 4-nonylphenol (4-N-NP), 4-tert-octylphenol (4-T-OP), and 4-n-octylphenol (4-N-OP) in serum were detected by ultra-performance liquid performance chromatography-tandem mass spectrometry (UPLC-MS). Binary logistic regression showed that NP [OR = 1.40 (95% CI: 1.00, 1.94)] was positively associated with preterm birth. Restricted cubic spline analyses showed that logNP and log4-T-OP had non-linearity associations with preterm birth (logNP: P overall = 0.006, P non-linear = 0.003; log4-T-OP: P overall = 0.004, P non-linear = 0.002). Multiple linear regression analysis showed that maternal serum concentration of NP was negatively associated with birth weight of perinatal infants (β = -14.68, 95% CI: -29.18, -0.19), which may be sensitive in male neonates (β = -26.18, 95% CI: -47.33, -5.02). The findings demonstrate that nonylphenol is a risk factor of preterm birth, and nonylphenol is negatively associated with the birth weight in male infants., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Aquatic biotests are important tools targeting various effects in ecotoxicology, including endocrine disruption. Unintentional exposure of bioassay organisms to endocrine disruptors during cultivation or testing may interfere with assessed endpoints. We illustrate this issue on the example of laboratory phytoplankton cultivation, where possible sources of estrogenic compounds have been revealed. Fifty-four blank samples (water and fresh or cultivated growth media) were assessed by in vitro biotests for their estrogenicity, and major known estrogens originating from plastic materials, bisphenol A and alkylphenols, were analyzed in selected samples. The samples of freshly prepared growth medium elicited weak estrogenic response in bioassays and some samples of the aerated media caused responses even above the 50% of maximum of the reference compound (17β-estradiol, E2), while the samples from diverse laboratory water sources did not show significant estrogenic activity. The results identified substances contained in the growth medium as minor but reproducible contributors to estrogenicity in the cultivations. Sporadic but significant effects (up to 4.9 ng E2 equivalent/L) can be ascribed to compounds released from the used plastic materials during aeration of the cultivations. The potential sources of unintentional exposure to estrogenic compounds need to be considered in aquatic cultivations and biotests, since they could impact their outcomes, especially in arrangements assessing reproduction or whole life cycle biotests, or production of bioactive compounds by phytoplankton. The findings emphasize the necessity to assess all relevant blanks, ideally by sensitive high throughput in vitro assays that reflect also unknown pollutants and minimize all potential sources of background contamination. In vitro assays show very good applicability for this purpose since they enable to screen for any background estrogenicity of the used media and materials without the need of analyzing individual compounds, which often might not be known., (Copyright © 2022. Published by Elsevier B.V.)

In this work, the analysis of alkylphenols, bisphenols and alkylphenol ethoxylates in bottled waters, kombuchas and water kefir was performed through a vortex-assisted dispersive liquid-liquid microextraction method based on a natural hydrophobic eutectic solvent. For this purpose, mixtures of monoterpenes and fatty acids were employed. Different factors affecting extraction were optimized and the method was validated in terms of matrix effect, linearity, limits of detection and recovery. Recovery values varied between 70.0 and 124.3% (except for 4-tert-butylphenol: 67.0% and 4-n-nonylphenol: 60.8% in water kefir) and limits of detection were in the range 0.10 ng/L - 2.99 µg/L. Finally, 8 bottled waters, 8 kombuchas and 4 water kefirs were analyzed and 4-tert-octylphenol monoethoxylate was detected in water (20.28 ± 0.99 - 62.08 ± 3.63 µg/L). This is the first application analyzing xenobiotic contaminants in kombucha and water kefir and the first time in which the three types of compounds are simultaneously extracted by dispersive liquid-liquid microextraction., (Copyright © 2021 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Phenolic root exudates (PREs) released from wetland plants are potentially effective for accelerating the biodegradation of alkylphenols, yet the inherent behavior is still unclear. In this study, two representative root exudates (REs), namely p-coumaric acid (PREs) and oxalic acid (non-PREs) were exogenously added as specific and non-specific co-metabolic substrates, respectively, to elucidate the quantification of each removal pathway and degradation mechanism of co-metabolism for alkylphenols (i.e. p-tert-butylphenol (PTBP)) from synthetic wastewater. The results showed that soil adsorption (31-37%), microbial degradation (27-37%), and plant uptake (16-41%) are the main removal pathways of PTBP by PREs in the Phragmites australis rhizosphere. Both REs enriched anaerobic functional community (anaerobic ammonium oxidation bacteria and denitrifying bacteria) and promoted the usage of PTBP as carbon source and/or electron donor. The activity of non-specific enzyme (polyphenol oxidase) was enhanced by RE which owning a significant positive correlation with bacterial abundance, whereas only PREs strengthened the activity of specific enzyme (monophenol oxidase) catalyzing the phenolic ring hydroxylation of PTBP followed by a dehydrogenation route. Moreover, exogenous PREs significantly improved the growth of degrading-related bacteria (Sphingomonas and Gemmatimonas), especially in unplanted soils with high activity of dioxygenase catalyzing the cleavage pathway of PTBP, instead of plant presence., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Alkylphenols are industrial pollutants commonly present in wastewater. They are difficult to eliminate by conventional treatment processes, ending up in the sludge of wastewater treatment plants. In this study, we propose to use cross-linked cyclodextrin-based polymers (ECP) as sorbents to treat three alkylphenols, namely, one nonylphenol (4-n-NP) and two octylphenols (4-n-OP and 4-tert-OP), present in aqueous solution by a batch method. The experiments were carried out with five cyclodextrin polymers (α-ECP, β-ECP, γ-ECP, α,β,γ-ECP, and HP-β-ECP). Sorption results showed that all polymers, with the exception of α-ECP, had high sorption capacities between 60 and 100% of the alkylphenols in the concentration range studied (between 25 and 100 μg/L). In all cases, HP-β-ECP has shown the highest removals, regardless of the structure of the molecule. The order obtained was HP-β-ECP >> β-ECP ~ α,β,γ-ECP >> γ-ECP > α-ECP. The 4-tert-OP compound was the best adsorbed, regardless the material and the solution studied. Sorption results also indicated that (i) the sorption efficiency decreased with the increasing of alkylphenol concentration; (ii) sodium chloride had a strong negative effect on the sorption process; and (iii) the performance remained unchanged after five sorption-regeneration cycles. The main sorption mechanism of alkylphenols occurring in ECP was the inclusion within the cyclodextrin cavities. The obtained results proved that cyclodextrin polymers could serve as efficient sorbents for the removal of alkylphenols from real effluents., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Runoff from building and structure surfaces may contribute to the pollution of urban stormwater and, thereby, to the degradation of the receiving water quality. Various micropollutants have been found in surface runoff from buildings in the urban environment, including metals and organic micropollutants. Effective methods for identification of such pollutants and their sources are the prerequisites for the development of control measures. In this paper, three different methods for the identification of building surface materials acting as sources of metals (Cd, Cr, Cu, Ni, Pb and Zn), nonylphenols and phthalates are presented: (i) screening of the material composition, (ii) laboratory leaching experiments with synthetic rainwater, and (iii) open-air pilot testing of material panels exposed to actual rainfall and runoff. These three methods cover a wide span of experimental aspects, including, e.g., size of material samples, resource demands, and control of influential factors. Nine materials commonly used on building and structure surfaces in the urban environment were tested: metal sheets of zinc, copper, galvanised steel, coated corrugated steel and stainless steel; and, four different roofing membranes of bitumen as well as polyvinyl chloride (PVC). The experimental results indicated that all three methods were meritorious in providing some information contributing to the identification of pollutant sources. The screening of material composition for targeted pollutants is relatively quick and inexpensive, but may fail to identify minor sources of pollutants, or may identify the substances present in the material, but not released in contact with water. Laboratory leaching was generally effective in identifying sources of substances present in surface runoff, but was unsuitable for estimating the magnitude of actual concentrations in building runoff. Open-air pilot studies of material samples (exposed area = 2 m 2 ) were thought to provide the results corresponding well to concentrations in runoff from actual building surfaces, but required relatively large financial and labour resources. Thus, the choice of the method for pollutant identification should be based on study objectives, and some benefits may be achieved using more than one method in an integrated manner; e.g., composition screening and lab or open-air leaching of targeted materials., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The influence of alkylphenols to environment cannot be ignored, as they are common product from chemical industries and potential threat to human health. Some alkylphenols are listed as persistent toxic substances (PTS) by the United Nations Environment Programme (UNEP). In this study, the optimized magnetic reduced graphene oxide (MrGO) was synthesized by a facile solvothermal method, and investigated for adsorption of three typical alkylphenols. In neutral condition, MrGO showed extremely high adsorption capacity of three typical alkylphenols, 4-heptylphenol (4-HP), 4-tert-octylphenol (4-OP), and 4-nonylphenol (4-NP), which could reach 938.9 mg g -1 (40 °C), 987.8 mg g -1 (40 °C), and 989.7 mg g -1 (20 °C), respectively. This study revealed that the adsorption process was a heterogeneous multi-layer physical adsorption, and the adsorption rates were related to the number of unoccupied vacancies on the adsorbent surface. From batch experiments and density functional theory (DFT) calculations, the main adsorption interactions between MrGO and alkylphenols were deduced to be π-π, hydrogen-bond, and hydrophobic interactions. What's more, the different affinities of MrGO towards different targets were further distinguished and explained in detail. The wonderful stability and recyclability of MrGO made it a promising cost-effective remediation candidate., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Nonylphenol (NP) is an endocrine disrupting and ecotoxic substance that has been detected in a variety of environmental matrices. It is utilized for the production of non-ionic nonylphenol ethoxylate (NPEO) detergents and other high production volume chemicals. Human biomonitoring data are scarce and mostly limited to the non-oxidized NP, which is ubiquitous in the (laboratory) environment and susceptible to external contamination. Here, we describe a sensitive, precise, accurate and rugged analytical method for the determination of OH-NP and oxo-NP, two potential alkyl-chain-oxidized metabolites of NP in human urine. We used single isomer standards, obtained by custom synthesis, for the quantification of the sum of the respective isomers. After enzymatic hydrolysis of potential urinary phase II conjugates, urine samples were analyzed by online turbulent flow chromatography for analyte enrichment and matrix depletion coupled to reversed phase liquid chromatography with negative electrospray-ionization triple quadrupole tandem mass spectrometry detection (online-SPE-LC-MS/MS). Quantification was performed by stable isotope dilution analysis. Limits of quantification in urinary matrix were 0.5 µg/L for OH-NP and 0.25 µg/L for oxo-NP. Mean relative recoveries were 101-105% (OH-NP) and 112-117% (oxo-NP) and the method imprecision (CV) in matrix was below 5%. In spite of extensive use restrictions in the EU since 2003, we could quantify OH-NP and oxo-NP in 94% and 47% of spot urine samples from the general German population (n = 32) collected in 2014. Thus, both metabolites seem suitable as sensitive and specific urinary biomarkers of NP exposure for future human biomonitoring population studies. Currently this method is used to quantitatively investigate human NP metabolism and to derive urinary metabolite excretion fractions that can be used to calculate external doses based on urinary biomarker concentrations., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A new matrix solid-phase dispersion (MSPD) extraction methodology, combined with high-performance liquid chromatography equipped with a diode-array detector, was developed and validated for the simultaneous determination of 10 compounds in mussels from Galician Rias (Spain). These pollutants are compounds commonly used for plastic production as additives, as well as common plastic contaminants. The compounds selected were bisphenol-A, bisphenol-F, bisphenol-S, nonylphenol-9, nonylphenol, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dichlorodiphenyltrichloroethane, dichlorodiphenyldichloroethane, and dichlorodiphenyldichloroethylene. The parameters affecting the MSPD extraction efficiency such as the type of sorbent, mass sample-sorbent ratio, and extraction solvent were optimised. The proposed method provided satisfactory quantitative recoveries (80-100%), with relative standard deviations lower than 7%. In all cases, the matrix-matched calibration curves were linear in the concentration range of 0.32-120.00 µg/kg, with quantification limits of 0.25-16.20 µg/kg. The novel developed MSPD-high-performance liquid chromatography methodology provided good sensitivity, accuracy, and repeatability for quality control analysis in mussels., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This study aimed to investigate the sequestration of phenolic endocrine disrupting compounds (EDCs) such as bisphenol A (BPA), 4-t-octylphenol (4-t-OP), and 4-nonylphenol (4-NP) in the shells of the mature clam Rangia cuneata from the Vistula Lagoon (southern Baltic Sea) and to determine the influence of sex and shell length on bioaccumulation of these contaminants. Even though there is broad interest in EDCs influences on aquatic organisms, these basic parameters are poorly understood, yet necessary for assessing environmental risks for clams. Average proportions of the total body burden (ng/individual) deposited in shells of R. cuneata were more than 70% for BPA and 4-NP and up to 32% for 4-t-OP. These results indicate that shell storage can be an important route for elimination of specific EDCs. Relationships between EDCs concentrations and the size and sex of R. cuneata indicate that females and large individuals experience greater exposures to the adverse effects of these pollutants than males and smaller clams. This effect could have significant impacts on population ecology and ultimately affect the entire ecosystem, in which bivalves play an important role. In the context of using clams to assess water pollution, the co-variation of EDCs concentrations with the size and sex of bivalves could influence the quality of monitoring data, unless accounted for in sampling design and data analysis., (Copyright © 2021 Elsevier Inc. All rights reserved.)

In this research, an efficient (94.9-99.4%) and fast (5 min) method has been developed and validated for simultaneous identification and quantification of phenolic endocrine disrupting compounds with an emphasis on bisphenol A (BPA) and 4-cumylphenol (4-CP) in food stuffs using a dual-template magnetic, molecularly-imprinted polymer (dt-MMIP). The dt-MMIP was synthesized by a sol-gel method using Fe 3 O 4 @SiO 2 (as the core) and BPA and 4-CP (as templates). The dt-MMIP was coupled with magnetic solid phase extraction to simultaneously detect BPA and 4-CP in food samples. BPA was measured from bottled water and fruit juice samples samples at 0.36 and 0.24 ng mL -1 , respectively, while 4-CP in those samples was 0.33 and 0.16 ng mL -1 , respectively. Their detection limits were estimated as 0.04 and 0.05 ng mL -1 , respectively. The developed dt-MMIP method was highly reproducible, while maintaining a good cyclability up to 20 cycles., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The Transient Receptor Potential Ankyrin 1 cation channel (TRPA1) is a broadly-tuned chemosensor expressed in nociceptive neurons. Multiple TRPA1 agonists are chemically unrelated non-electrophilic compounds, for which the mechanisms of channel activation remain unknown. Here, we assess the hypothesis that such chemicals activate TRPA1 by inducing mechanical perturbations in the plasma membrane. We characterized the activation of mouse TRPA1 by non-electrophilic alkylphenols (APs) of different carbon chain lengths in the para position of the aromatic ring. Having discarded oxidative stress and the action of electrophilic mediators as activation mechanisms, we determined whether APs induce mechanical perturbations in the plasma membrane using dyes whose fluorescence properties change upon alteration of the lipid environment. APs activated TRPA1, with potency increasing with their lipophilicity. APs increased the generalized polarization of Laurdan fluorescence and the anisotropy of the fluorescence of 1,6-diphenyl-1,3,5-hexatriene (DPH), also according to their lipophilicity. Thus, the potency of APs for TRPA1 activation is an increasing function of their ability to induce lipid order and membrane rigidity. These results support the hypothesis that TRPA1 senses non-electrophilic compounds by detecting the mechanical alterations they produce in the plasma membrane. This may explain how structurally unrelated non-reactive compounds induce TRPA1 activation and support the role of TRPA1 as an unspecific sensor of potentially noxious compounds.

Although the levels of micropollutants in landfill leachate and municipal wastewater are well-established, the individual removal mechanisms and the fate of micropollutants throughout a landfill leachate treatment plant (LTP) were seldom investigated. Therefore, the determination of the removal efficiencies and the fates of micropollutants in a full-scale leachate treatment plant located in the largest city of Turkey were aimed in this study. Some important processes, such as equalization pond, bioreactor, ultrafiltration (UF) and nanofiltration (NF), are being operated in the treatment plant. Landfill leachate was characterized as an intense pollution source of macro and micropollutants compared to other water types. Chemical oxygen demand (COD), NH 3 , suspended solids (SS) and electrical conductivity (EC) values of the landfill leachate (and their removal efficiencies in the treatment plant) were determined as 18,656 ± 12,098 mg/L (98%), 3090 ± 845 mg/L (99%), 4175 ± 1832 mg/L (95%) and 31 ± 2 mS/cm (51%), respectively. Within the scope of the study, the most frequently and abundantly detected micropollutants in the treatment plant were found as heavy metals (8 ± 1.7 mg/L), VOCs (38 ± 2 μg/L), alkylphenols (9 ± 3 μg/L) and phthalates (8 ± 3 μg/L) and the overall removal efficiencies of these micropollutants ranged from -11% to 100% in the treatment processes. The main removal mechanism of VOCs in the aerobic treatment process has been found as the volatilization due to Henry constants greater than 100 Pa·m 3 /mol. However, the molecular weight cut off restriction of UF membrane has caused to less or negative removal efficiencies for some VOCs. The biological treatment unit which consists of sequential anoxic and oxic units (A/O) was found effective on the removal of PAHs (62%) and alkylphenols (87%). It was inferred that both NO 3 accumulation in anoxic reactor, high hydraulic retention time (HRT) and sludge retention time (SRT) in aerobic reactor provide higher biodegradation and volatilization efficiencies as compared to the literature. Membrane processes were more effective on the removal of alkylphenols (60-80%) and pesticides (59-74%) in terms of influent and effluent loads of each unit. Removal efficiencies for Cu, Ni and Cr, which were the dominant heavy metals, were determined as 92, 91 and 51%, respectively and the main removal mechanism for heavy metals has thought to be coprecipitation of suspended solids by microbial biopolymers in the bioreactor and the separation of colloids during membrane filtration. Total effluent loads of the LTP for VOCs, semi volatiles and heavy metals were 1.0 g/day, 5.2 g/day and 1.5 kg/day, respectively. It has been concluded that the LTP was effectively removing both conventional pollutants and micropollutants with the specific operation costs of 0.27 $/(kg of removed COD), 0.13 $/(g of removed VOCs), 0.35 $/(g of removed SVOCs) and 2.6 $/(kg of removed metals)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The distribution of per- and polyfluoroalkyl substances (PFAS), alkylphenols, organotin compounds, phthalates, alkylated polycyclic aromatic hydrocarbons, current-use pesticides (CUPs) and personal care products (PCPs) was characterized in 29 surface sediments from two Spanish Iberian continental shelf areas (14 on the Atlantic and 15 on the Mediterranean coasts). Concretely, 115 organic contaminants were determined and a specific methodology was used for each contaminant group, including contaminants of emerging concern (CECs) and traditional ones, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs). PAHs, alkylated PAHs, alkylphenols and phthalates were found in all samples, showing mean concentrations per group higher than 20 ng/g (16-4974 ng/g d.w.) in the subregions under consideration (Galician, Cantabrian, Levantine-Balearic and Strait-Alboran). CUPs and PCPs were found in the majority of samples at very low concentrations of ng/g (1.4-46.8 ng/g d.w.), whereas organotins and PFAS were found principally in sediments from the Mediterranean subregions (2.5-3.9 ng/g d.w.). Different distribution patterns were observed for the contaminant groups and subregions under consideration as a consequence of the diverse predominant sources (industrial, urban, transport and agricultural activities) and environmental behavior (mainly hydrophobicity and persistence). Risk assessment confirmed the impact of phthalates, alkylphenols, PAHs and PCBs on Atlantic ecosystems and of alkylphenols, chlorpyrifos, phthalates, TBT, PAHs, OCPs and PCBs on the Mediterranean ones. Furthermore, the presence of CUPs, PCPs and PFAS in sediments from the Spanish continental shelf located between 2 and 31 km from the coast suggested that those contaminants may also provoke adverse effects on coastal marine ecosystems between their sources and their depositional areas. CAPSULE: Alkylphenols, phthalates and organotins may provoke adverse effects on Spanish coastal marine ecosystems from their sources to the sediment depositional areas., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Contamination status of traditional and emerging persistent toxic substances (PTSs) in sediments and their major sources were investigated in Ulsan Bay, Korea. A total of 47 PTSs, including 15 traditional PAHs, ten styrene oligomers (SOs), six alkylphenols (APs), and 16 emerging PAHs (E-PAHs) were analyzed. Concentrations of traditional PAHs, SOs, and APs ranged from 35 to 1300 ng g -1 dry weight (dw), 30 to 3800 ng g -1 dw, and 30 to 430 ng g -1 dw, respectively. For the last 20 years, PTSs contamination in the bay area has been improved. However, 12 E-PAHs were widely detected in sediments, with a maximum of 240 ng g -1 dw (for benzo[e]pyrene) at the creek site. These E-PAHs seemed to originate from surrounding activities, such as biomass combustion, mobile sources, and diesel combustion. Due to environmental concerns for E-PAHs, further research on the potential toxicity, distribution, and behavior of these compounds should be implemented., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Alkylphenols (AP) are widespread environmental compounds belonging to the large family of substances known as Endocrine Disrupting Chemicals (EDCs). The present study was carried out to assess the effects of Octylphenol (OP) alone and in combination with Nonylphenol (NP) on the hypothalamus-pituitary-adrenal gland (HPA) axis of the lizard Podarcis sicula. Lizards are good bioindicators due to their features such as wide distribution, large population and good sensitivity to contaminants. Results obtained showed a time and dose-dependent stimulation of the HPA together with a high variation of both catecholamine plasma levels and greater vascularization and hypertrophy of steroidogenic cord of adrenal gland after both OP and OP + NP treatments. Interestingly, the OP + NP mixture treatment has provoked a state of stress of the adrenal gland which in fact appeared to be characterized by the presence of a marked macrophage infiltration which can be seen especially close to the connective capsule surrounding the gland. This macrophage infiltration could be an evidence of a particularly pronounced inflammatory state to indicate, probably, an animal's response to a non-physiological situation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Forage fish are primary prey for seabirds, fish and marine mammals. Contaminant transfer and biomagnification of the toxic compounds measured in this study likely contribute to elevated levels in Puget Sound, Washington, salmon and killer whale tissues that could be sufficiently high to elicit adverse effects and hamper population recovery efforts. Polychlorinated biphenyls, polybrominated diphenyl ethers, chlorinated pesticides, polycyclic aromatic hydrocarbons, alkylphenols, and chlorinated paraffins were detected in all Pacific sand lance tissue samples generally below available health effect levels. Residual polycyclic aromatic hydrocarbon tissue concentrations near a former creosote site suggest ongoing contaminant exposure. Biomagnification calculations suggest that concentrations of polychlorinated biphenyls in some forage fish could result in predator tissue concentrations exceeding effect levels. The emerging contaminants alkylphenols and chlorinated paraffins are first reported here in Puget Sound forage fish, and their frequent detection, high production volumes and endocrine-disrupting properties highlight the need for further study., (Published by Elsevier Ltd.)

A new permanently positively charged stable isotope labeling (SIL) agent pair, 4-(((2,5-dioxopyrrolidin-1-yl)oxy)carbonyl)- N , N , N -trimethylbenzenaminium iodide(DPTBA) and its deuterated counterpart d -DPTBA, was designed and synthesized. The SIL agents were applied to the liquid chromatography-tandem mass spectrometry analysis of alkylphenols. Light labeled standards and heavy labeled samples were mixed and analyzed simultaneously. Matrix effect which mainly occurred during the ionization process was minimized because of the identical ionization processes between samples and standards. Meanwhile, derivatization made alkylphenols be positively charged, and thus the sensitivity was enhanced. The limits of detection were in the range of 1.5-1.8 ng/L, and the limits of quantitation were in the range of 4.8-6.1 ng/L. The developed method was applied to analyze alkylphenols migrated from plastics to edible oils. The recoveries for all analytes were in the range of 88.6-95.3%, while the matrix effects for all analytes were in the range of 96.2-99.6%.3 -DPTBA, was designed and synthesized. The SIL agents were applied to the liquid chromatography-tandem mass spectrometry analysis of alkylphenols. Light labeled standards and heavy labeled samples were mixed and analyzed simultaneously. Matrix effect which mainly occurred during the ionization process was minimized because of the identical ionization processes between samples and standards. Meanwhile, derivatization made alkylphenols be positively charged, and thus the sensitivity was enhanced. The limits of detection were in the range of 1.5-1.8 ng/L, and the limits of quantitation were in the range of 4.8-6.1 ng/L. The developed method was applied to analyze alkylphenols migrated from plastics to edible oils. The recoveries for all analytes were in the range of 88.6-95.3%, while the matrix effects for all analytes were in the range of 96.2-99.6%.

Contaminants of emerging concern (CECs) have recently been detected in bottled water and have brought about discussions on possible risks for human health. However, a systematic review of CECs in bottled water is currently lacking due to the relatively new introduction and/or detection of these pollutants. Hence, this paper reviews the existing studies on the presence of six major groups of emerging contaminants including microplastics (MPs), pharmaceuticals and personal care products (PPCPs), bisphenol A (BPA), phthalates, alkylphenols (APs), and perfluoroalkyl and polyfluoroalkyl substances (PFASs) in bottled water from different countries. Also, the findings related to CECs' levels, their possible sources, and their risks are summarized. The gathered data indicate that MPs within the size range of 1-5 μm are the most predominant and potentially toxic classes of MPs in bottled water. In addition, PPCPs, PFASs, APs, and BPA occur in concentration levels of ng/L, while phthalates occur in the μg/L level in bottled water. The bottle type plays an important role in the contamination level. As expected, water in plastic bottles with plastic caps is more polluted than in glass bottles. However, other sources of contamination such as contact materials during cleaning, bottling, and storage are not negligible. Based on the gathered data in this review, the CEC levels except for MPs (no threshold values) in bottled water of most countries do not raise a safety concern for the human. However, the occurrence of individual CECs and their association in bottled water need more accurate data to understand their own/synergistic effects on human health., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The Yellow and Bohai seas comprise one of the most rapidly developing regions in the world, but efforts to assess coastal pollution by persistent toxic substances (PTSs) on wide spatial scale are lacking. The present study aimed to (1) measure the concentrations of PTSs, such as polycyclic aromatic hydrocarbons (PAHs), alkylphenols (APs), and styrene oligomers (SOs) via large-scale sediment monitoring (total of 125 locations), (2) assess potential ecological risk of PTSs in sediments to coastal ecosystems, (3) estimate various sources and fresh inputs of PTSs, (4) determine distribution patterns of PTSs by human activities and land-use type, and (5) address decadal (2008-2018) changes in distributions of PTSs. The high concentrations of PAHs [> 7000 ng g -1 dry weight (dw)] in sediments were detected in Nantong in the Yellow Sea of China (YSC) and Huludao and Qinhuangdao in the Bohai Sea (BS), whereas lesser concentrations (< 200 ng g -1 dw) were detected in the Yellow Sea of Korea (YSK). We found relatively high concentrations of sedimentary APs and SOs in Nantong, Huludao, and Qinhuangdao from the YSC and BS regions, but corresponding concentrations were generally below < 100 ng g -1 dw in other locations. Concentrations of PAHs at 38 locations (30% of YSC and BS) posed a potential risk to aquatic ecosystems, whereas relatively low risk concentrations occurred in all locations of YSK. The main source of PAHs (concentrated in YSC and BS) were by-products of diesel and gasoline combustion (42% of total concentration), whereas biomass combustion (24%) dominated in YSK. Fresh inputs of PTSs indicated that the generation and use of PTSs continue across all regions and locations. Among PTSs, concentrations of PAHs were significantly associated with location (p < 0.05) relative to land-use within a given region, whereas concentrations of APs and SOs showed no significant relationships (p > 0.05) among or within regions. Over time, concentrations of PAHs have generally declined, but sediment contamination has increased at some locations in China, with sources shifting from a mixture of PAHs types to those linked to diesel and gasoline combustion. Additional studies are needed on the fate and potential ecological risk posed by certain PTSs in hotspots. This is one of the first efforts providing backgrounds on PTS pollution in the large marine ecosystem of the Yellow and Bohai seas., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Hexadecyl trimethylammonium bromide (CTAB) micelles were applied in the synthesis of covalent organic frameworks (COFs) for the first time to achieve the synthesis of 3D COF from 2D materials. Benzidine, one raw material for COF, was enclosed in the CTAB micelles because of the hydrophobic effect, and thus the target COF, which can be formed immediately with the aid of p-toluenesulfonic acid, grew in a micelle guided 3D form. The synthesized 3D COF showed a flower-like structure, whereas the COF synthesized without CTAB showed a smooth structure. The diameter of the 3D COFs showed direct correlations with CTAB concentrations. Moreover, the CTAB modified COF also showed a dramatically improved fluorescence property in comparison with that of normal COFs. The synthesized 3D COF showed good adsorption performance for UV filters and alkylphenols with recoveries ranged from 90.2% to 99.8%, and it also showed good fluorescence response for Pb 2+ . The utility of CTAB modified COF was verified in the enrichment of UV filters and alkylphenols from food packaging material migrants.

Endocrine disrupting chemicals (EDCs) are common pollutants in coastal waters. To investigate the estrogen risk of EDCs in the coastal areas of Japan, the Japanese common goby, which is a commonly observed species in these waters, was used as the target fish. Plasma 17β-estradiol (E 2 ) and vitellogenin (VTG) levels were analyzed and the gonads of fish collected from the Taira River (northern Nagasaki, reference site), Nagasaki Port, and two sites in Tokyo Bay were observed. Abnormal levels (>150 ng/mL, p < 0.05) of plasma VTG and high levels of plasma E 2 were detected in the fish from Nagasaki Port and Tokyo Bay, whereas the levels of both were low in the fish from the Taira River. The target EDCs, including natural estrogen [estrone (E 1 ), and E 2 ] and alkylphenols [4-t-octylphenol (4-t-OP), 4-nonylphenol (4-NP), and bisphenol-A (BPA)] in water samples were quantified using gas chromatography tandem mass spectrometry (GC/MS/MS), respectively. It was observed that the E 2 -equivalent (EEQ) in Nagasaki Port and Tokyo Bay, which was calculated from the actual EDC measurement value, were almost 20- and 150-fold higher, respectively, than that at the reference site (Taira River, 0.021 ng/L). The EEQs mostly comprised natural estrogen in the sampling sites, although there was some influence of alkylphenols. There was an association between the EEQ and the E 2 in environmental water, suggesting a high estrogen risk in Japan coastal waters. Moreover, the results indicated that abnormal VTG synthesis was induced by environmental estrogen (EE) pollution in Nagasaki Port and Tokyo Bay., Competing Interests: Declaration of competing interest This manuscript has not been published or presented elsewhere in part or in entirety and is not under consideration by another journal. The study design was approved by the appropriate ethics review board. We have read and understood your journal’s policies, and we believe that neither the manuscript nor the study violates any of these. There are no conflicts of interest to declare. All the authors listed have approved the manuscript that is enclosed., (Copyright © 2019. Published by Elsevier Ltd.)

The validation of a procedure for the determination of six alkylphenols (APs), 4-tert-butylphenol, 4-pentylphenol, 4-tert-octylphenol, 4-hexylphenol, 4-octylphenol and 4-nonylphenol, and three bisphenols (BPs), bisphenol A, bisphenol F and bisphenol Z, in seven human organs and tissues (kidney, liver, heart, lung, spleen, brain and abdominal fat) obtained from eight autopsies is presented. Previously ground samples were treated by salt-assisted liquid-liquid extraction (SALLE) for isolation of the analytes and then pre-concentrated using dual stir bar sorptive extraction (SBSE), allowing two different extraction conditions for the same sample. Finally, thermal desorption was used as the injector system in combination with gas chromatography coupled to mass spectrometry (GC-MS). To determine BPs, derivatization using acetic anhydride was required, although this step was not necessary for the APs. Two parallel extractions of the contaminants with the stir bars were performed, followed by thermal desorption and chromatographic analysis. The procedure provided quantification limits between 0.050 and 4.0 ng g -1 for APs and from 0.26 to 2.6 ng g -1 for BPs. Repeatability and reproducibility values were lower than 15% in all cases. The accuracy of the procedure was established by a recovery study, which provided values in the 85.8-115% range for APs and 83.6-120% for BPs. Samples were analyzed with the proposed methodology and data were processed by ANOVA tests to study the behaviour and bioaccumulation of these compounds in human tissues or organs. In addition, discriminant analysis detected age- and sex-dependent differences in bioaccumulation., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This study presents an accurate method for the determination of alkyl phenols and bisphenol A at trace levels using gas chromatography mass spectrometry after preconcentration with switchable liquid-liquid microextraction. In order to achieve high extraction output, the environmentally friendly switchable liquid-liquid microextraction method was optimized by varying parameters such as amount of switchable solvent, sodium hydroxide concentration/amount and the mixing period in a Box-Behnken experimental design. Under optimum extraction conditions, the limits of detection calculated for the analytes were between 0.13 and 0.54 ng/mL. The analytes showed good linearity over broad calibration ranges, and low percent relative standard deviations established good precision. Spiked recovery studies were performed on municipal wastewater and tap water to determine the method's suitability and accuracy, and the results (87-106%) obtained were satisfactory. Bisphenol A was detected (4.0-14 ng/mL) in four plastic samples investigated under high temperature conditions., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

North Abu Ali Island is contaminated by crude oil from exogenous sources with a variety of persistent toxic substances (PTSs) being input into intertidal sediments. We detected an array of PTSs in sediments and benthic biota off north Abu Ali Island (Arabian Gulf), including 35 polycyclic aromatic hydrocarbons (PAHs), 6 alkylphenols (APEOs), 10 styrene oligomers (SOs), and tributyltin. The PTS concentrations were generally greater than those reported in other areas of Arabian Gulf. PAHs mainly originated from petrogenic sources, and APEOs and SOs seem to be of recent origin. Field-based biota-sediment accumulation factors (BSAF) varied by taxa and compounds, but clearly depended on the log K ow values of individual compounds. Some PTSs exceeded the established guidelines for sediments and biota; we found particularly great BSAFs for alkyl-naphthalenes (C1- and C2-), nonylphenol monoethoxylates, and 2,4,6-triphenyl-1-hexene. Remediation will require on-site clean-up of toxic chemicals together with immediate efforts on preventing input of current pollution sources in the given area., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Sources of organic matter in a polluted coastal embayment (Lake Sihwa) indicated that δ 13 C and δ 15 N of suspended particulate matter (SPM) and sediments could be distinguished by land-use type and surrounding activities. Specifically, low δ 15 N occurred in inland creeks near industrial complex, where severe contamination by persistent toxic substances (PTSs) is evidenced. To identify the sources of 15 N-depleted organic matter and PTSs, the SPM and/or sediments were collected along ~8 km of the Singil Creek and in stormwater drainage pipes that carried pollutants to the creeks from upland areas. Results indicated that stormwater originating in industrial areas was the main source of low δ 15 N and elevated PTSs, which appeared to flow into stormwater drains with rainwater and eventually into the creeks at stormwater outfalls. To improve the water quality of inland creeks, it will be necessary to reduce the amount of untreated stormwater entering stormwater drainage system from industrial complex., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Intake of endocrine-disrupting chemicals (EDCs) by humans could disturb the metabolism of hormones, induce cancer, and damage the liver and other organs. Phthalate acid esters (PAEs) and alkylphenols (APs) are important EDCs and environmental contaminants. With the increasing use of plastics and nonionic surfactants worldwide, PAEs and APs have entered environmental water and accumulated in edible fish, which are finally consumed by humans. In this study, a coated direct inlet probe (CDIP) based on an atmospheric solid analysis probe, which can rapidly and simultaneously extract both PAEs and APs in fish, was developed. Twelve PAEs and APs were quantified by using a stable-isotope-labeled internal standard. Standard curves of the PAEs and APs having correlation coefficients of R 2 ≥ 0.9837 were obtained. The limit of detection of the PAEs and APs was distributed from 0.01 to 40 ng g -1 . The relative recovery of the method was 78-120% between low, medium, and high spiked levels. Combined with principal component analysis, PAE- and AP-contaminated Carassius auratus from different habitats could be identified. Multiple sample analysis mode allowed the extraction of up to 12 samples at once, and the total analysis time (including sample pretreatment, extraction, and analysis time) was less than 10 min per sample, which indicates that CDIP is useful for rapid quantitative analysis.

The spatial and temporal distribution of selected endocrine disrupting compounds (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol, and bisphenol A) in two coastal areas of the Iberian Peninsula (Ria de Vigo and Mar Menor lagoon) were evaluated for the first time. Seawater and sediment samples collected during spring and autumn of 2015 were analysed using greener extraction techniques and liquid chromatography-tandem mass spectrometry. The presence of branched isomers (4-tert-octylphenol and nonylphenol) and bisphenol A in almost all seawater and sediment samples demonstrated their importance as pollutants in the frame of water policy, while no concentrations of linear isomers (4-n-octylphenol and 4-n-nonylphenol) were found. Higher seawater levels were observed in Mar Menor lagoon, especially in spring, associated with wastewater treatment plant effluents and nautical, agricultural and industrial activities. Similar sediment concentrations were measured in both studied areas, being nonylphenol levels five times higher than those measured for the other EDCs. Experimental sediment-water partition coefficients showed a moderate sorption of target compounds to sediments. Risk quotients for water compartment evidenced a moderate risk posed by nonylphenol, considering the worst-case scenario. For sediments, moderate risk related to 4-tert-octylphenol and high risk to nonylphenol were estimated., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Removal of linear and branched alkylphenols with different alkyl chain lengths or different branchings (normal, secondary, and tertiary), some of which are suspected as endocrine disrupting chemicals, from an aqueous medium were investigated through quinone oxidation by polyphenol oxidase (PPO) and subsequent quinone adsorption on chitosan beads or powders at pH 7.0 and 40 °C. PPO-catalyzed quinone oxidation increased with an increase in alkyl chain length of the alkylphenols used. Although a higher PPO dose was required for quinone oxidation of branched alkylphenols, they were completely or mostly removed by quinone adsorption on chitosan beads or powders. The apparent activity of PPO increased by a decrease in quinone concentration. On the other hand, in the homogeneous systems with solutions of chitosan and PPO at pH 6.0, longer reaction times were required to generate insoluble aggregates, and a small amount of quinone derivatives were left in the solution even under optimum conditions. These results support that the two-step reaction, that is, PPO-catalyzed quinone oxidation and subsequent quinone adsorption on chitosan beads or powders, in the heterogeneous system is a good procedure for removing linear and branched alkylphenols from aqueous medium., Competing Interests: The authors declare no conflict of interest.

Plasticizers and other plastics additives have been extensively used as ingredients of plastics and are as a result thereof easily released in the aquatic environment, due to different physical diffusion processes. In this context, a dedicated method was developed for the simultaneous quantification of 27 known and a virtually unlimited number of unknown alkylphenols, Bisphenol A and phthalates in 2 aquatic matrices, i.e. sea- and freshwater. To this extent, a novel instrumental HESI-UHPLC-HRMS (heated electro-spray ionization ultra-high performance liquid chromatographic high resolution mass spectrometric) method was devised for the simultaneous analysis of 7 phenols (i.e. 6 alkylphenols and Bisphenol A) and 20 phthalates within 10 min. Thereafter, a solid-phase extraction protocol was statistically (95% confidence interval, p > 0.05) optimized based on experimental designs. The method was proven fit-for-purpose through a successful validation at environmentally relevant nanomolar concentrations. Analytical precautions were taken for minimizing false-positive results to suppress in-house contamination. The method demonstrated an excellent analytical performance across all known plasticizers and plastics additives for sea- and freshwater, revealing good linearity (R 2  > 0.99, n = 39), stable recoveries (98.5-105.8%), satisfactory repeatability (RSD < 8%, n = 54) and reproducibility (RSD < 10%, n = 36). Subsequently, a novel analytical strategy was devised for the tentative identification of unknown plasticizers and plastics additives using specific in-house determined fragments incorporated in a Python code. The applicability of the analytical platform was demonstrated by measuring 24 seawater samples. Interestingly, 16 out of 27 known plasticizers, plastics additives and primary metabolites could be quantified while the untargeted analysis uncovered 1042 compounds, whereof 5% (n = 46) could be assigned a plasticizer-plastics additive chemical identity, providing evidence for the severe plastic contamination status of our marine environment., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The quality and availability of water has become a pressing issue worldwide, being particularly important in semi-arid regions, where climate change has aggravated the problem. The use of anthropogenic chemicals, classified as emerging pollutants, adds to the problem representing a treat, since they are not regulated and have a potential impact on human and environmental health. This pressing problem has not been studied widely in complex environments like the one we present here. Distribution and seasonal variability of fecal sterols, alkylphenols, pesticides (emerging pollutants) and nutrients were determined in 35 wells used for agriculture and human consumption in the Valley of Maneadero, located in the semi-arid region of Baja California, Mexico. The presence of the tested pollutants in the saline aquifer was heterogeneous, showing important differences in concentration and distribution. Wells destined for household use showed the highest variability. In these wells, anthropogenic fecal sterols were detected and, alkylphenols, such as octyphenol and nonylphenol had maximum concentrations (2.7 ng/mL). In agriculture and urban wells, we identified DDT and organochlorine pesticides, as well as myclobutanil, which is considered a modern pesticide. Nitrates were identified in concentrations above international standards, mainly during the dry season, in both the agricultural and urban areas. As emerging pollutants represent a negative effect on environmental and human health, this is the first paper showing the importance of measuring this type of pollutant in agricultural/semi-urban areas, especially in aquifers that have been overexploited and communities that have relied on the use of septic tanks for decades., (Copyright © 2018 Elsevier Ltd. All rights reserved.)