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Bisphenols, parabens, alkylphenols and triclosan are anthropogenic substances with a phenolic group that have been introduced to the environment in recent decades. As they possess hormone-like effects, they have been termed endocrine disruptors (EDs), and can interfere with steroid pathways in organisms. To evaluate the potential impact of EDs on steroid biosynthesis and metabolism, sensitive and robust methods enabling the concurrent measurement of EDs and steroids in plasma are needed. Of crucial importance is the analysis of unconjugated EDs, which possess biological activity. The aim of the study was to develop and validate LC-MS/MS methods with and without a derivatization step for the analysis of unconjugated steroids (estrone-E1, estradiol-E2, estriol-E3, aldosterone-ALDO) and different groups of EDs (bisphenols, parabens, nonylphenol-NP and triclosan-TCS), and compare these methods on a set of 24 human plasma samples using Passing-Bablok regression analysis. Both methods were validated according to FDA and EMA guidelines. The method with dansyl chloride derivatization allowed 17 compounds to be measured: estrogens (E1, E2, E3), bisphenols (bisphenol A-BPA, BPS, BPF, BPAF, BPAP, BPZ, BPP), parabens (methylparaben-MP, ethylparaben-EP, propylparaben-PP, butylparaben-BP, benzylparaben-BenzylP), TCS and NP, with lower limits of quantification (LLOQs) between 4 and 125 pg/mL. The method without derivatization enabled 15 compounds to be analyzed: estrogens (E1, E2, E3), ALDO, bisphenols (BPA, BPS, BPF, BPAF, BPAP, BPZ), parabens (MP, EP, PP, BP, BenzylP) with LLOQs between 2 and 63 pg/mL, and NP and BPP in semiquantitative mode. Adding 6 mM ammonium fluoride post column into mobile phases in the method without derivatization achieved similar or even better LLOQs than the method with the derivatization step. The uniqueness of the methods lies in the simultaneous determination of different classes of unconjugated (bioactive) fraction of EDs together with selected steroids (estrogens + ALDO in the method without derivatization), which provides a useful tool for evaluating the relationships between EDs and steroid metabolism., 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.)

The Mediterranean is a region of substantial agriculture production that faces concurrent environmental stresses and freshwater pollution given the occurrence of emerging contaminants (ECs). Among these pollutants, the surface-active substances have been suggested to enhance the bioavailability of other ECs. This research evaluates a comparative uptake and translocation assessment of irrigation exposure to atenolol (ATN, 60 µg/L), carbamazepine (CBZ, 60 µg/L) and triclosan (TCS, 30 µg/L) alone vs. these combined with perfluorooctanesulfonic acid (PFOS, 10 µg/L) under semifield (i.e., soil experimental set) vs. hydroponics (i.e., soilless experimental set) growing conditions with lettuce, radish and tomato plants. Both experimental sets revealed efficient root uptake and translocation for the three ECs regardless of their co-existence with PFOS. The overall results of the uptake and translocation of the ECs in the lettuce and tomato plants suggested a simultaneous treatment-plant organ interaction, which was not affected by PFOS being present in both experimental sets. PFOS in irrigation water did not increase cellular perviousness to the other three ECs. These observations support the hypothesis of factors other than PFOS being responsible for the differential bioaccumulation and translocation potentials seen in both experimental sets. However, the radish plants co-irrigated with PFOS brought about increased movement of ECs from roots to aerial parts, more specifically ATN and CBZ in the soil experimental set, and ATN and TCS in the soilless set. These results support the notion that factors inherent to the physiological characteristics of this root vegetable contributed to ECs' increased tendency to move from roots to aerial parts. Despite the three ECs efficiently accumulating, the risk to humans from eating the edible parts of these plants grown under soil or soilless conditions was low., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Triclosan (TCS), an extensively used broad-spectrum antimicrobial agent, has raised significant environmental concerns regarding its widespread occurrence in waters. In this study, the removal of TCS in aqueous solution via peroxymonosulfate (PMS) activated by an extremely low-level Co 2+ (0.02 μM) was systematically investigated. During preliminary test, TCS (10 μM) was totally degraded in 30 min by using 0.1 μM Co 2+ and 40 μM PMS at pH 7.0 with a degradation rate constant of 0.1219 min -1 . A first-order apparent degradation rate of TCS was found with respect to the PMS concentrations. At extremely low dosage of Co 2+ (0.02 μM), the presence of NO 3 - , HCO 3 - , PLFA, and SRHA within test concentrations significantly inhibited TCS removal, while a dual effect of Cl - on the degradation rate of TCS was observed. The quenching experiments verified that SO 4 - was the dominant reactive oxygen species (ROS) rather than OH. Six major intermediates were identified using TOF-LC-MS, based on which we proposed three associated reaction pathways including hydroxylation, ether bond breakage, and dechlorination. Toxicity predictions by ECOSAR software exhibited aquatic toxicity reduction of TCS after Co 2+ /PMS treatment. We outlook these findings to advance the feasibility of organic contaminants removal via Co 2+ /PMS system with Co 2+ at extremely low levels., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Water scarcity is a natural condition in the Mediterranean rim countries. In this region, reuse of reclaimed water (RW) from wastewater treatment plants (WWTPs) is becoming a potential source for highly water-demanding activities such as agriculture. However, the removal capacity of contaminants in regular WWTPs has been found to be limited. Considering a Mediterranean scenario, this research investigated the plant uptake and translocation of three representative pharmaceuticals and personal care products (PPCPs) typically present in RW samples from a WWTP located in an urban area in Spain, and assessed the potential risk to humans from plant consumption. The RW samples were collected and analyzed for three representative PPCPs (atenolol -ATN-, carbamazepine -CBZ- and triclosan -TCS-). The target contaminants were also spiked at two levels in the RW samples to consider two worst-case scenarios. Three plant models (lettuce, maize and radish) were grown outdoors and irrigated with four treatments: tap water; RW samples, and the two spiked RW samples. Generally speaking, results revealed an efficient root uptake for the three PPCPs regardless of plant species and fortification level, and suggested an interaction effect of treatment and plant organ. Different bioaccumulation and translocation potentials of the three PPCPs were seen into the aerial organs of the plants. Overall, these observations support the idea that factors including the physico-chemical properties of the PPCPs and physiological plant variables, could be responsible for the differential accumulation and translocation potentials observed. These variables could be critical for crops irrigated with RW in regions with extended dry seasons, high solar incidence and low annual rainfall such as those in the Mediterranean rim where plants are subjected to high transpiration rates. However, the results obtained from this experimental approach suggested a negligible risk to humans from consumption of edible plants irrigated with RW samples with presence of PPCPs, despite the fact that the three representative PPCPs under study accumulated efficiently in the plants., Competing Interests: Declaration of competing interest The authors declare they have no conflict of interest to disclose., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Reclaimed wastewater (RW) is increasingly used to irrigate agricultural land and to alleviate agricultural water shortages worldwide. This usage has resulted in concerns about soil contamination by pharmaceuticals and personal care products (PPCPs) and the human health risks associated with dietary crop intake. In this study, we systematically analysed the occurrence and accumulation of 11 PPCPs and one active metabolite in soils and various crops (cucumber, eggplant, long bean and wheat) from realistic RW irrigation fields with different irrigation histories (20, 30 and 40 years) in Beijing and evaluated the human health risks associated with the consumption of these crops. The 11 PPCPs and one active metabolite were detected at concentrations ranging from 0.67 to 22.92 ng L -1 in RW, 0.029-28.13 μg kg -1 in irrigated soil, and <0.01-28.01 μg kg -1 in crops. The concentrations of N4-acetyl-sulfamethoxazole and triclosan were higher than those of other PPCPs, with respective concentrations of 14.39-31.44 ng L -1 and 15.93-26.23 ng L -1 in RW, 10.92-23.29 μg kg -1 and 20.22-28.13 μg kg -1 in irrigated soil and 17.92-28.01 μg kg -1 and 8.92-14.91 μg kg -1 in crops. However, the estimated threshold of toxicological concern (TTC) and hazard quotient (HQ) values revealed that the concentrations of N4-acetyl-sulfamethoxazole and triclosan in crops irrigated with RW should be considered a de minimis risk to human health. The concentrations of 11 PPCPs and one active metabolite in soils and crops and the calculated fruit bioconcentration factors (BCFs) did not display obvious increases associated with the duration of RW irrigation in real agricultural systems (P > 0.05). The concentrations of the studied PPCPs in the RW used for irrigation followed different patterns from the concentrations detected in the irrigated soils and crops. Although the concentrations of sulfamethoxazole, sulfisoxazole, sulfamethazine and trimethoprim in RW were higher than those of many other studied PPCPs, their respective values in the irrigated soils and crops did not display a similar tendency. The uptake and accumulation of PPCPs varied among the crop species (P < 0.05). Although PPCPs were detected in eggplant, long bean and wheat (BCFs: not applicable-1.67, 0.03-1.35 and 0.01-5.01, respectively), PPCPs accumulated at increased levels in cucumber (BCFs 0.03-18.98). The estimated TTC and HQ values showed that the consumption of crops irrigated long-term with RW presents a de minimis risk to human health. However, further studies with more PPCPs and additional crop species need to be conducted, the synergistic effects of chemical mixtures of multiple PPCPs and the toxic effects of PPCP metabolites should be elucidated to obtain more reliable information on the safety of wastewater reuse for irrigation., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Due to the abundant binding sites and high stability, a synthesized meso-MIL-53(Al) was selected as the backbone and used for immobilizing laccase (Lac-MIL-53(Al)) to catalytically degrade of TCS. XRD, BET and FTIR analyses proved that the carboxyl groups on PTA of meso-MIL-53(Al) could provide sufficient adsorption sites for physically immobilizing laccase through hydrogen bonds and electrostatic interactions. Although the catalytic efficiency of V max /K m slightly decreased from 785 to 607 min -1 due to the mass transfer limitation upon immobilized, Lac-MIL-53(Al) showed high activity recovery (93.8%) and stability. The conformational analysis indicated the laccase could partially enter into the MOF by conformational changes without impairing laccase, although the laccase molecular (6.5 nm × 5.5 nm × 4.5 nm) was larger than the mesopore sizes of the MOF (4 nm). The kinetics indicated that Lac-MIL-53(Al) could remove 99.24% of TCS within 120 min due to the synergy effect of the adsorption of meso-MIL-53(Al) and catalytic degradation of laccase. Meanwhile, Lac-MIL-53(Al) could remain approximately 60% of activity for up to 8 times reuse without desorption. The GC/MS and LC/MS/MS analyses further confirmed that TCS could be transformed to 2, 4-DCP by laccase via the breakage of the ether bond, or to passivated dimers, trimers and tetramers by the self-coupling and oxidization of the phenoxyl radicals, and finally removed by precipitation. In summary, enzyme-MOF composite might be a potential strategy to control the micropollutants in the wastewater., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Synthetic antimicrobials known as parabens, triclosan (TCS), and triclocarban (TCC) are emerging environmental contaminants. Limited studies on these contaminants have been conducted in coastal environments. In our study, parabens, their metabolites, TCS, and TCC were measured in sediment collected along the Korean coast, to investigate contamination status, spatial distribution, and potential health risks to coastal environments. Methyl paraben and 4-hydroxybenzoic acid were detected in all sediment samples, suggesting widespread contamination. Total concentrations of parent parabens, their metabolites, TCS, and TCC ranged from 0.19 to 11.2 (mean: 2.40) ng/g dry weight, 9.65 to 480 (mean: 120) ng/g dry weight, and < limit of quantification (LOQ)-6.10 (mean: 0.41) ng/g dry weight, and from < LOQ-41.0 (mean: 2.78) ng/g dry weight, respectively. The overall contamination of parabens and antimicrobials in sediment was different from that reported for persistent organic pollutants due to different contamination sources among chemical groups. Significant correlation was found among target contaminants in sediment, suggesting the existence of a common source. Total organic carbon (TOC) was significantly correlated with the concentrations of target contaminants, implying a major factor for coastal distribution of parabens and antimicrobials. The concentrations of parabens and TCS measured in sediment did not exceed a hazard quotient (HQ), implying low potential health risks associated with exposure to these contaminants. This is the first study to report the nationwide distribution of parabens, their metabolites, and antimicrobials in the coastal environments of Korea., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The occurrence of antimicrobial agent triclosan (TCS) in the global aquatic and terrestrial environment is an emerging concern. While risk assessment for TCS is available in certain countries, no studies have attempted to assess the risk of TCS worldwide. This could be due to lack of method to characterize the global exposure. The present study therefore proposed a probabilistic-based approach to approximate the percent-ranked measured environmental concentrations (MECs) by estimating exposure concentration distribution (ECD) for different environmental compartments on a global scale, incorporating approximate 1200 single MECs. Hazard of TCS was assessed from species sensitivity distribution as well as predicted no effect concentrations (PNECs) derived from ecotoxicological and toxicological endpoints. We draw on experiences from previous risk assessment exercises and present a holistic approach for characterizing the risk of TCS to microorganism in sewage treatment plant, aquatic and soil organisms, avian and mammalian species, and humans. Using the approach, we estimated risk of TCS to organisms dwelling in sediment and living in surface waters, and the risk quotients (MEC/PNEC) were within the range of 0.95 - 33.3 and 0.49 - 9.5, respectively. While the risk quotients for other environmental compartments were below a value of 1, there are large uncertainties likely due to an insufficient dataset of exposure and hazard of TCS., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Triclosan, an antimicrobial compound found in consumer products, may be introduced into the aquatic environment via residual concentrations in municipal wastewater treatment effluent. We conducted an aquatic risk assessment that incorporated the available measured triclosan data from Minnesota lakes and rivers. Although only data reported from Minnesota were considered in the risk assessment, the developed toxicity benchmarks can be applied to other environments. The data were evaluated using a series of environmental fate models to ensure the data were internally consistent and to fill any data gaps. Triclosan was not detected in over 75% of the 567 surface water and sediment samples. Measured environmental data were used to model the predicted environmental exposures to triclosan in surface water, surface sediment, and biota tissues. Toxicity benchmarks based on fatty acid synthesis inhibition and narcosis were determined for aquatic organisms based, in part, on a species sensitivity distribution of chronic toxicity thresholds from the available literature. Predicted and measured environmental concentrations for surface water, sediment, and tissue were below the effects benchmarks, indicating that exposure to triclosan in Minnesota lakes and rivers would not pose an unacceptable risk to aquatic organisms., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Triclosan, an antimicrobial compound found in consumer products, has been detected in low concentrations in Minnesota municipal wastewater treatment plant (WWTP) effluent. This assessment evaluates potential health risks for exposure of adults and children to triclosan in Minnesota surface water, sediments, and fish. Potential exposures via fish consumption are considered for recreational or subsistence-level consumers. This assessment uses two chronic oral toxicity benchmarks, which bracket other available toxicity values. The first benchmark is a lower bound on a benchmark dose associated with a 10% risk (BMDL 10 ) of 47mg per kilogram per day (mg/kg-day) for kidney effects in hamsters. This value was identified as the most sensitive endpoint and species in a review by Rodricks et al. (2010) and is used herein to derive an estimated reference dose (RfD (Rodricks) ) of 0.47mg/kg-day. The second benchmark is a reference dose (RfD) of 0.047mg/kg-day derived from a no observed adverse effect level (NOAEL) of 10mg/kg-day for hepatic and hematopoietic effects in mice (Minnesota Department of Health [MDH] 2014). Based on conservative assumptions regarding human exposures to triclosan, calculated risk estimates are far below levels of concern. These estimates are likely to overestimate risks for potential receptors, particularly because sample locations were generally biased towards known discharges (i.e., WWTP effluent)., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The reuse of treated municipal sewage ('biosolids') on land is an effective method to divert waste away from landfill and to use an alternative, low cost method of fertilisation. While legislation has mainly focused on the control of nutrient and metal application rates to land, other potentially harmful emerging contaminants (ECs) may be present in biosolids. Up to 80% of municipal sewage sludge is reused in agriculture in Ireland, which is currently the highest rate of reuse in Europe. However, unlike other countries, no study has been conducted on the presence of ECs across a range of wastewater treatment plants (WWTPs) in this country. This study evaluated the concentrations of two ECs in sewage sludge, the antimicrobials triclosan (TCS) and triclocarban (TCC), and their presence in surface runoff following land application in controlled rainfall simulation studies. In 16 WWTPs, concentrations of TCS and TCC were 0.61 and 0.08µgg -1 , which is at the lower end of concentrations measured in other countries. The concentrations in runoff post land application were also mainly below the limits of detection (90ngL -1 for TCS, 6ngL -1 for TCC), indicating that runoff is not a significant pathway of entry into the environment., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Home and personal care products (HPCPs) including biocides, benzotriazoles (BTs) and ultraviolet (UV) filters are widely used in our daily life. After use, they are discharged with domestic wastewater into the receiving environment. This study investigated the occurrence of 29 representative HPCPs, including biocides, BTs and UV filters, in the riverine environment of a rural region of South China where no wastewater treatment plants were present, and assessed their potential ecological risks to aquatic organisms. The results showed the detection of 11 biocides and 4 BTs in surface water, and 9 biocides, 3 BTs and 4 UV filters in sediment. In surface water, methylparaben (MeP), triclocarban (TCC), and triclosan (TCS) were detected at all sites with median concentrations of 9.23 ng/L, 2.64 ng/L and 5.39 ng/L, respectively. However, the highest median concentrations were found for clotrimazole (CLOT), 5-methyl-1H-benzotriazole (MBT) and carbendazim (CARB) at 55.6 ng/L, 33.7 ng/L and 13.8 ng/L, respectively. In sediment, TCC, TCS, and UV-326 were detected with their maximum concentrations up to 353 ng/g, 155 ng/g, and 133 ng/g, respectively. The concentrations for those detected HPCPs in surface water and sediment were generally lower in the upper reach (rural area) of Sha River than in the lower reach of Sha River with close proximity to Dongjiang River (Pt-test<0.05), indicating other input sources of HPCPs in the lower reach. Biocides showed significantly higher levels in surface water in the wet season than in the dry and intermediate seasons. Preliminary risk assessment demonstrated that the majority of HPCPs monitored represented low risk in surface waters. There are potentially greater risks to aquatic organisms from the use of TCS and TCC in the wet season than in dry and intermediate seasons in surface waters. This preliminary assessment also indicates potential concerns associated with TCC, TCS, DEET, CARB, and CLOT in sediments, although additional data should be generated to assess this fully. Thus future research is needed to investigate ecological effects of these HPCPs on benthic organisms in sediment of rural rivers receiving untreated wastewater discharge., (Copyright © 2015 Elsevier Inc. All rights reserved.)