Phenolic Endocrine Disrupting Chemicals Research Articles

Preparation of ionic porous polymers for extraction of four phenolic endocrine disrupting chemicals from fish and water samples

In this paper, series of ionic polymers were synthesized by crosslinking alkyl quaternary ammonium salts with 1,4-bis(chloromethyl)benzene. Among them, hyper-crosslinked polymer fabricated with dodecyl dimethyl benzyl ammonium chloride (HCP-DD) as monomer delivered superior adsorption performance for endocrine disrupting chemicals (EDCs). The adsorption mechanism mainly includes π-π stacking, hydrophobic and electrostatic interaction. With HCP-DD as solid phase extraction sorbent, a high performance liquid chromatography-diode array detection method was developed for the detection of four phenolic EDCs in water and fish samples. The detection limits of the method were 0.005–0.02 ng mL−1 for water samples and 3–30 ng g−1 for fish samples. The recoveries of EDCs in water samples and fish samples were 80–119% and 81.3–117% (relative standard deviations <4.4%), respectively. The study not only provides a route for preparation ionic porous polymers, but also highlights the applications of ionic polymers as efficient adsorbent to enrich organic pollutants.

[Determination of four phenolic endocrine-disrupting chemicals in water by dispersive solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on metal-organic skeleton porous carbon materials].

Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4-tert-octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 μg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 μg/L and 0.03-0.42 μg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 μg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.

Efficient bisphenol A removal by a photocatalyst-enzyme hybrid system: Horseradish peroxidase integrated with carbon vacancy-modified carbon nitride nanosheets

Peroxidase-based treatment that uses H2O2 as the clean oxidant appears promising for the removal of aqueous phenolic endocrine disrupting chemicals (EDCs). However, oxidative degradation of active heme species at high H2O2 concentrations leads to irreversible enzyme inactivation. The method of combining photocatalysis and enzyme biocatalysis could alleviate the issue by photocatalytic in-situ H2O2 production. In this study, we constructed a photocatalyst-enzyme hybrid system that integrated the horseradish peroxidase with carbon vacancy-modified carbon nitride nanosheets (HRP@ACNNs). Attributed to the modified carbon nitride, the HRP@ACNNs exhibited higher substrate affinity and comparable catalytic efficiency compared to free HRP. This photocatalyst-enzyme hybrid system could offer H2O2 continuously to sustain enzymatic catalysis without enzyme inactivation as well as stabilize the enzyme. The bisphenol A (BPA) removal experiments further confirmed the effectiveness in treating phenolic EDCs of the prepared HRP@ACNNs.

The seasonality of the concentration of endocrine phenolic compounds in the matter attached to the surface of microplastics

Rapid biofilm formation on microplastic (MP) surfaces in marine environments and the tendency of hydrophobic pollutants to bioaccumulate may increase the exposure of organisms to ingested plastics and transport pollutants far from their sources. The role of the matter attached to MPs (MaM) in the interactions between MPs and other pollutants in marine environments is poorly understood. This paper studies pollutant sorption in MaM for three phenolic endocrine-disrupting chemicals (EDCs): bisphenol A (BPA), 4-tert-octylphenol (4-t-OP), and 4-nonylphenol (4-NP). Polypropylene (PP), expanded polystyrene (EPS), and polylactide (PLA) MPs were exposed to an environment conducive to biofouling (Vistula Lagoon, Baltic Sea) for four weeks in summer, spring, and winter. The concentrations of EDCs in MaM and the suspended particulate matter (SPM) were similar and were 2–3 orders of magnitude higher than those in water and sediment. The type and morphology of the polymers were less significant for determining the concentrations of EDCs in MaM than the season. The concentrations were higher in the growing season than in winter. EDCs increased linearly with the increase in particulate organic carbon. The relationships between organic carbon partition coefficients and octanol/water partition coefficients indicate that hydrophobic partitioning into organic matter was the dominant mechanism of 4-t-OP and 4-NP binding in MaM and in SPM. For BPA, additional sorption mechanisms seem to be significant. In addition to the direct sorption from ambient water, the binding of phytoplankton-derived particles, most probably via attachment to extracellular polymeric substances, appears to be a source of EDCs in MPs. Rough estimates showed that the largest load of particulate matter and EDCs was attached to expanded polystyrene. This study suggests that the potential negative impacts of MPs on the environment are seasonal and that low-density porous plastics can be particularly effective carriers of large EDC loads.

Synthesis of cyano and ionic dual-functional hypercrosslinked porous polymer for effective adsorption and detection of endocrine disrupting chemicals in milk matrix

Endocrine disrupting chemicals (EDCs) can interfere with the normal function of endocrine system, posing serious risk to human health. The monitoring of EDCs in foods is of great importance to ensure food security. Herein, a cyano and ionic dual-functionalized hypercrosslinked porous polymer (CN-iHCP) was designed and prepared for the first time through hyper-crosslink of 1-(4-cyanophenyl)imidazole and 1,4-bis(chloromethyl)benzene. The adsorption mechanism mainly involves electrostatic interaction, hydrogen bonding and π-π stacking interaction. A sensitive analytical method for simultaneous detection of the four phenolic EDCs was established by coupled CN-iHCP based solid-phase extraction with high performance liquid chromatography. Under optimal conditions, the target EDCs exhibited good linearity with coefficient r > 0.993 and high enrichment factors of 164–243. The detection limits (S/N = 3) of EDCs were 0.20–0.50 ng mL−1 for milk sample. The extraction recoveries for the spiked milk samples were in the range of 85.5%− 116.0%. This work not only highlights the CN-iHCP as a promising adsorbent to efficiently enrich EDCs and other pollutants, but also provides a new strategy for the functionalization of HCP for wide applications.

Hydroxyl and carboxyl group functionalized conjugated microporous nanomaterial as adsorbent for the solid-phase extraction of phenolic endocrine disrupting chemicals from freshwater fish samples

Endocrine disruption chemicals (EDCs) in food can seriously harm human health. In this study, a hydroxyl and carboxyl group functionalized conjugated microporous nanomaterial (CMP) was prepared by Friedel-Crafts reaction and used as solid-phase extraction (SPE) adsorbent. A functionalized CMP based SPE combined with high performance liquid chromatography-diode array detection was built for the determination of phenolic EDCs from nine fish samples. The extraction conditions were optimized by both single factor and response surface methodology (Box-Behnken Design). The established method performed well in terms of the response linearity (in the range of 0.50–100 ng g−1 with coefficient of determination larger than 0.9942), limits of detection (0.15–0.30 ng g−1, S/N of 3), limits of quantification (0.50–1.00 ng g−1, S/N = 10), method recoveries (78.4–121 %) and repeatability (relative standard deviation < 11 %). It can be used as an efficient method to detect trace phenolic EDCs in real fish samples.

Magnetic covalent organic frameworks for extraction and determination of endocrine-disrupting chemicals in beverage and water samples.

Phenolic endocrine-disrupting chemicals (EDCs) are widespread and easily ingested through the food chain. They pose a serious threat to human health. Magnetic solid-phase extraction (MSPE) is an effective sample pre-treatment technology to determine traces of phenolic EDCs. Magnetic covalent organic framework (COF) (Fe3 O4 @COF) nanospheres were prepared and characterized. The efficient and selective extraction of phenolic EDCs relies on a large specific surface and the inherent porosity of COFs and hydrogen bonding, π-π, and hydrophobic interactions between COF shells and phenolic EDCs. Under optimal conditions, the proposed magnetic solid-phase extraction-high-performance liquid chromatography-ultra violet (MSPE-HPLC-UV) based on the metallic covalent organic framework method for phenolic EDCs shows good linearities (0.002-6 μg mL-1 ), with R2 of 0.995 or higher, and low limits of detection (6-1.200 ng mL-1 ). Magnetic covalent organic frameworks (Fe3 O4 @COFs) with good MSPE performance for phenolic EDCs were synthesized by the solvothermal method. The magnetic covalent organic framework-based MSPE-HPLC-UV method was applied successfully to determine phenolic EDCs in beverage and water samples with satisfactory recoveries (90.200%-123%) and relative standard deviations (2.100%-12.100%). © 2023 Society of Chemical Industry.

Synthesis of amine-functionalized magnetic porous organic polymers for effective extraction of phenolic endocrine disrupting chemicals

Amine-functionalized porous organic polymers (EDA-POP-PC and EDA-POP-BT) were prepared by post-modification of POP-PC and POP-BT with ethylenediamine (EDA) for the first time. The POP-PC and POP-BT were obtained through Friedel-Crafts acylation reaction of potassium tetraphenylborate with p-phthaloyl chloride (PC) and 1,3,5-benzenetricarbonyl trichloride (BT), respectively. The EDA-POPs exhibited superior adsorption capacity for phenolic endocrine disrupting chemicals (EDCs). After magnetically functionalization, the obtained M-EDA-POP-PC was employed as a magnetic adsorbent for enrichment of phenolic EDCs from real samples prior to high performance liquid chromatography-ultraviolet detection. The current strategy showed low detection limits (S/N = 3) of 0.02–0.07, 0.04–0.08 and 0.04–0.10 ng mL−1 for river water, white peach juice and lychee juice, respectively. The method recoveries were 81.7%–115% with relative standard deviations below 8.6%. The proposed strategy showed good practicality for sensitive determination of phenolic EDCs in real samples.

Synthesis of MRGO@ZIF-7-Based Molecular Imprinted Polymer by Surface Polymerization for the Fast and Selective Removal of Phenolic Endocrine-Disrupting Chemicals from Aqueous Environments

In this study, Zn(NO3)2·6H2O was selected as the metal source, and ZIF-7-modified magnetic graphene-based matrix materials (MRGO@ZIF-7) were prepared by in situ growth. ZIF-7 modified magnetic graphene-based molecular imprinting complexes (MRGO@ZIF7-MIP) were successfully synthesized by a surface molecular imprinting technique using bisphenol A (BPA) as the template molecule. The obtained experimental materials were characterized by X-ray diffraction (XRD), Brunner–Emmet–Teller (BET) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), and X-ray photoelectron spectroscopy (XPS). The proper adsorption and selective recognition ability of the MRGO@ZIF7-MIP were studied by an equilibrium adsorption method. The obtained MRGO@ZIF7-MIP showed significant molecular recognition of bisphenol A (BPA) and good selectivity and reproducibility for BPA in different aqueous environments such as drinking water, river water, and lake water. These properties make this material potentially applicable for the efficient removal of phenolic endocrine disruptors in real water environments.

The assembly of polysaccharide ZIF-8-based foam for efficient adsorptive removal of PEDCs from environmental water

ZIF-8 is a type of porous coordination metal-organic frameworks (MOFs) material with excellent adsorption properties. However, the inevitable acid-base sensitivity and low plasticity of ZIF-8 impede its application to the field of compound adsorption and separation. Here, a novel reusable monolithic MOFs foam material, polysaccharides (CMC & chitin) gels zeolitic imidazolate frameworks (PC-ZIF-8), has been developed to effectively adsorb five Phenolic Endocrine Disrupting Chemicals (PEDCs) from environmental water. In this study, the forming strategy of a continuous phase change sol-gel MOFs material was designed. The carboxymethyl cellulose and chitin hydrosol were used as the self-assembly medium for in-situ synthesizing sol-type MOFs by a one-step method. Several favorable characteristics of PC-ZIF-8 have been confirmed, including large surface area (619.47 m2/g), low density (<0.085 g/cm3), high ZIF-8 loading rate (>80%, wt%), high structural strength, high acid, and alkali tolerance, and easy recyclability. The adsorption efficiency of PC-ZIF-8 for 5 BPs in water is 92.97%− 99.12%, and the maximum adsorption capacity is 120.1–172.9 mg/g. After simple regeneration treatment, PC-ZIF-8 has been recycled 5 times, and the overall recovery rate still remains above 80.0%. The results of this study indicate that PC-ZIF-8 is a reliable adsorbent for BPs in environmental water purification.

The strategy for estrogen receptor mediated-risk assessment in environmental water: A combination of species sensitivity distributions and in silico approaches

Risk assessment for molecular toxicity endpoints of environmental matrices may be a pressing issue. Here, we combined chemical analysis with species sensitivity distributions (SSD) and in silico docking for multi-species estrogen receptor mediated-risk assessment in water from Dongjiang River, China. The water contains high levels of phenolic endocrine-disrupting chemicals (PEDCs) and phthalic acid esters (PAEs). The concentration of ∑4PEDCs and ∑6PAEs ranged from 2202 to 3404 ng/L and 834–4368 ng/L, with an average of 3241 and 2215 ng/L, respectively. The SSD approach showed that 4-NP, BPA, E2 of PEDCs, and DBP, DOP, and DEHP could severely threaten the aquatic ecosystems, while most other target compounds posed low-to-medium risks. Moreover, binding affinities from molecular docking among PEDCs, PAEs, and estrogen receptors (ERα, Erβ, and GPER) were applied as toxic equivalency factors. Estrogen receptor-mediated risk suggested that PEDCs were the main contributors, containing 53.37–69.79% of total risk. They potentially pose more severe estrogen-receptor toxicity to zebrafish, turtles, and frogs. ERβ was the major contributor, followed by ERα and GPER. This study is the first attempt to assess the estrogen receptor-mediated risk of river water in multiple aquatic organisms. The in silico simulation approach could complement toxic effect evaluations in molecular endpoints.

Spatiotemporal distribution, source apportionment and risk assessment of typical hormones and phenolic endocrine disrupting chemicals in environmental and biological samples from the mariculture areas in the Pearl River Delta, China

The present work studied the levels, distribution, potential sources, ecological and human health risks of typical hormones and phenolic endocrine disrupting chemicals (EDCs) in the mariculture areas of the Pearl River Delta (PRD), China. The environmental levels of 11 hormones (6 estrogens, 4 progestogens, and 1 androgen) and 2 phenolic EDCs were quantified in various matrices including water, sediment, cultured fish and shellfish. Ultrahigh performance liquid chromatography-triple quadrupole tandem mass spectrometry analyses showed that all the 13 target compounds were detected in biotic samples, whereas 10 were detected in water and sediment, respectively. The total concentrations ranged from 35.06–364.53 ng/L in water and 6.31–29.30 ng/g in sediment, respectively. The average contaminant levels in shellfish (Ostrea gigas, Mytilus edulis and Mimachlamys nobilis) were significantly higher than those in fish (Culter alburnus, Ephippus orbis and Ephippus orbis). Source apportionment revealed that the pollution of hormones and phenolic EDCs in PRD mariculture areas was resulted from the combination of coastal anthropogenic discharges and mariculture activities. The hazard quotient values of the contaminants were all less than 1, implying no immediate human health risk. Overall, the present study is of great significance for scientific mariculture management, land-based pollution control, ecosystem protection, and safeguarding human health.

Adsorption of phenol and bisphenol A on river sediments: Effects of particle size, humic acid, pH and temperature

Phenolic Endocrine Disrupting Chemicals (EDCs) have drawn more and more interest due to their prevalence and persistence in aquatic environment. To study the adsorption of various phenolic EDCs on river sediments under natural conditions, we first sought to analyze the distribution characteristics of phenol and bisphenol A (BPA) in sediment from the Bahe River. The static adsorption experiments contained either single- or dual-contaminant of phenol and/or BPA in the system; they were conducted to characterize the adsorption of these two pollutants in the surface sediments and the main factors affecting the adsorption processes of the dual-contaminant system, including particle size, humic acid (HA) concentration, pH, and temperature. Results showed that in certain seasons, there was a significant correlation between the levels of phenol and BPA in Bahe sediments. When comparing the adsorption behaviors of phenol and BPA on sediments in single- and dual-contaminant systems, we found that the phenol adsorption behavior varied, while that of BPA remained consistent across the different systems. Moreover, different effects were observed with regards to a single factor and the interaction of multiple factors on the adsorption of pollutants. Of the four single factors, only HA concentration had a significant effect on the phenol adsorption in sediment. When considering the interaction of multiple factors, the interaction between HA concentration and temperature significantly promoted the adsorption of phenol. The influence of factors on the adsorption of BPA was in the following order: particle size > HA concentration > pH > temperature. Particle size significantly inhibited BPA adsorption in the sediment, while the interaction between particle size and pH increased BPA adsorption.

Association of placental concentrations of phenolic endocrine disrupting chemicals with cognitive functioning in preschool children from the Environment and Childhood (INMA) Project.

Developmental exposure to bisphenol A (BPA) and other phenolic endocrine disrupting chemicals (EDCs) may affect child neurodevelopment, but data on the effects of prenatal exposure to phenols on cognitive function remain sparse. Our aim was to examine the association of placental concentrations of several phenolic EDCs, including BPA, parabens (PBs), and benzophenones (BzPs), with cognitive development in preschool children from the Environment and Childhood (INMA) Project in Spain. Concentrations of BPA, four PBs (methylparaben [MePB], ethylparaben [EtPB], propylparaben [PrPB], and butylparaben [BuPB]), and six BzPs (BzP-1, BzP-2, BzP-3, BzP-6, BzP-8, and 4-hydroxybenzophenone [4-OH-BzP]) were measured in 490 placenta samples randomly selected from five INMA cohorts collected between 2000 and 2008. Neuropsychological assessment of cognitive and motor function was performed with the McCarthy Scales of Children's Abilities (MSCA) at the age of 4-5 years. Associations were assessed in a sub-sample of 191 mother-child pairs using linear and logistic regression models adjusted for confounding factors. PB compounds were detected in more than 71% of placentas, BPA in 62%, 4-OH-BzP in 50%, and the remaining BzPs in <9% of the samples. Because of the low detection frequency of BzP compounds, only 4-OH-BzP was included in the exposure-outcome analyses. After adjustment for confounders, BPA was associated with greater odds of scoring lower (below the 20th percentile) in the verbal (third vs. first exposure tertile: odds ratio [OR]=2.78, 95% confidence interval [CI]=1.00; 5.81, p-trend=0.05) and gross motor (detected vs. undetected: OR=1.75, 95%CI=1.06; 9.29) areas, and these associations were only significant for boys. Regarding PB compounds, PrPB was associated with lower scores in memory (detected vs. undetected: β=-4.96, 95%CI=-9.54; -0.31), span memory (OR=2.50, 95%CI=0.95; 6.92 and 2.71, 95%CI=0.97; 6.64, respectively for second and third tertiles, p-trend=0.03), and motor function (β=-5.15, 95%CI=-9.26; -0.01 for third vs. first exposure tertile, p-trend=0.04). EtPB and total PBs concentrations in the second tertile were also associated with poorer visual function of posterior cortex and worse quantitative performance, respectively, but linear trends were not statistically significant. The associations of BPA and PrPB with poorer verbal, memory, and motor skills are novel observations that warrant further attention. Larger prospective studies are required to confirm whether prenatal exposure to BPA and other phenolic EDCs is associated with impaired cognitive development.

A year-long passive sampling of phenolic endocrine disrupting chemicals in the East River, South China

The occurrence of endocrine disrupting chemicals (EDCs) in the aquatic environment is a global concern. In this study, we employed two different passive samplers Diffusive Gradients in Thin-films (DGT) and Chemcatcher for in situ measurement of 8 phenolic EDCs in the East River of the Pearl River system over one-year. These data were assessed alongside results from traditional grab sampling. Six chemicals (4tOP, 4NP, BPA, E1, EE2 and DES) were regularly detected in the water samples, of which the three phenols (i.e. 4tOP, 4NP and BPA) were in all samples and at high concentrations (0.4–1040 ng/L for 4tOP, 2.6–58500 ng/L for NP and 11.4–123300 ng/L for BPA). Fewer target chemicals were detected in both passive samplers, with only 4tOP, 4NP and BPA found in most samplers; E1 and DES were occasionally measurable above detection limits. The higher (by about a factor of 2–3) measurements provided by DGT compared to Chemcatcher could be attributed to the effect of the diffusive boundary layer on Chemcatcher uptake or the strong adsorption of target chemicals on the Chemcatcher PES filter. The temporal trends of EDC monthly loadings indicated that they were from different sources and that WWTPs were not effective in EDC removal and/or there was still some untreated wastewater discharged into the rivers.

Oxidative Oligomerization of Phenolic Endocrine Disrupting Chemicals Mediated by Mn(III)-L Complexes and the Role of Phenoxyl Radicals in the Enhanced Removal: Experimental and Theoretical Studies.

Soluble manganese(III), stabilized by ligands as Mn(III)-L complexes, are ubiquitous in natural waters and wastewaters and can potentially serve as both the oxidant and reductant in one-electron transfer reactions with organic contaminants. In this study, the oxidative transformations of 14 phenolic endocrine disrupting chemicals (EDCs) by in situ-formed Mn(III)-L complexes, generated from irradiated water containing Mn(II) and humic acid, were investigated. The pseudo-first-order rate constants (kobs, h-1) of these phenols varied from 1.0 × 10-4 to 5.9 × 10-2. A quantitative structure-activity relationship model was developed, which suggests that the electron-donating ability (EHOMO) of phenolic chemicals was the most important molecular characteristic for the Mn(III)-L-mediated oxidative transformation. Phenol transformation was initiated by the generation of a phenoxyl radical through electron transfer to Mn(III)-L. Subsequent self-coupling reactions between phenoxyl radicals resulted in the formation of self-coupling dimers and trimers. With the addition of simple phenol as a cosubstrate, enhanced transformations of these phenolic EDCs were clearly observed, and cross-coupling products of simple phenol and the substrates were also detected. In addition, a reaction activation energy calculation based on the transition-state theory indicated that the cross-coupling reaction was more likely than the self-coupling reaction to occur in the presence of phenol. This work provides new insights into the environmental fate of phenolic compounds.

Novel PEP-PAN@PSF rods extraction of EDCs in environmental water, sediment, and fish homogenate followed by pre-column derivatization and UHPLC-MS/MS detection

In the study, novel polysulfone hollow fiber membrane (PSF) supported polar enhanced phase (PEP) particles-polyacrylonitrile (PAN) polymer thin-film rods (PEP-PAN@PSF rods) were developed for the extraction of five steroidal endocrine disrupting chemicals (EDCs) (estrone (E1), estradiol (E2), estriol (E3), ethinyloestradiol (EE2), 2-methoxyestradiol (2ME2)) and four phenolic EDCs (bisphenol A (BPA), hexestrol (HEX), diethylstilbestrol (DES), dienestrol (DE)) in environmental water, sediment, and fish muscle homogenates, followed by pre-column derivatization and ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The traditional preparation method for thin-film rods was improved by introducing a supporting membrane PSF between the external thin-film coating and the internal bare rod, avoiding the conventional pre-corrosion by strong acid/base. The commercial PEP prepared rods showed competitive capacity for both polar and nonpolar EDCs. In addition, pre-column derivatization with dansyl chloride (DNS-Cl) was adopted for the phenolic analytes prior to UHPLC-MS/MS detection, leading to a significant enhancement of sensitivity via analyzing the dansylated derivatives under positive electrospray ionization (ESI) mode instead of the analytes under negative ESI mode. The protocol was validated in four matrices including environmental water, sediment and two fish species. No matrix effects were observed in four matrices. The limits of detection (LODs) for the analytes were in the range of 0.002–0.072 μg L−1 for environmental water, 0.032–0.734 ng g−1 for sediment, and 0.011–0.435 ng g−1 for two fish species, respectively. Appropriate linearity was observed for all the analytes with correlation coefficients (R2) above 0.997. The intra-day trueness of the approach at low, medium and high levels was in the range of 86.6–116.1% with relative standard deviations (RSDs) lower than 15.4%. And the inter-day trueness was in the range of 84.6–114.8% with RSDs lower than 16.3%. The proposed method was successfully applied for the analysis of nine EDCs in environmental water, sediment, and fish muscle homogenates.

The occurrence and risk assessment of phenolic endocrine-disrupting chemicals in Egypt's drinking and source water.

This is the first nationwide survey of bisphenol A (BPA), methylparaben, ethylparaben, propylparaben, butylparaben, and o-phenylphenol, in Egypt's water. Five hundred fifty-five water samples were collected from source water (SW, 109 samples) and drinking water (DW, 446 samples) of twenty-three Egyptian governorates. These chemicals were determined by direct ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) analysis of a filtered aliquot of samples. The impacts of the measured concentrations on the aquatic organisms and human health were evaluated as well. BPA, methylparaben, propylparaben, and butylparaben were frequently detected in SW and DW, while ethylparaben and o-phenylphenol were not detected whatsoever. The most frequently detected endocrine-disrupting chemical (EDC) was BPA in SW and methylparaben in DW. The recorded highest concentrations of BPA and methylparaben in SW and BPA and methylparaben, propylparaben, and butylparaben in DW were the highest worldwide. Of the investigated twenty-three governorates, the SW and DW of Aswan, Red Sea, Cairo, Sharqia, and Damietta were free of the studied EDCs. Contrarily, BPA, MeP, PrP, and BuP were detected in Sohag's SW and DW. A detection ratio > 70% was recorded in SW of Faiyum, Dakahlia, and Ismailia, and > 90% in DW of Sohag, Port Said, Dakahlia, and Faiyum. The environmental risk assessment results excluded any human health risk even in the worst-case scenario and showed that BPA represents the highest risk to the aquatic organisms.

Distribution and ecological risk assessment of PEDCs in the water, sediment and Carex cinerascens of Poyang Lake wetland, China

Phenolic endocrine disrupting chemicals (PEDCs), such as 4-nonylphenol (NP), 4-t-octylphenol (OP), bisphenol A (BPA), and nonylphenol-di-ethoxylate (NP2EO), can cause feminization and carcinogenesis. This study assessed the distributions of NP, OP, BPA, and NP2EO in the water, sediment, and Carex cinerascens of Poyang Lake wetland. The four PEDCs were ubiquitous. The concentrations of NP and OP in the water and sediment of the wetland were significantly lower than those in other regions of China. Average BPA concentrations in the water, sediment, and Carex cinerascens samples were 40.49 ± 18.42 ng/L, 9.840 ± 3.149 ng/g, and 3.25 ± 1.40 ng/g, respectively; the BPA concentration in the water was similar to that of other rivers in China. Average NP2EO concentrations in the wetland were 3125.9 ± 478.1 ng/L, 650.0 ± 209.9 ng/g, and 275.8 ± 59.0 ng/g in the water, sediment, and Carex cinerascens samples, respectively. The predicted no-effect concentrations in sediment for NP, OP, BPA, and NP2EO were estimated to be 75.41, 45.25, 8.22, and 237.5 ng/g, respectively. The risk quotient (RQ) method was used to characterise the ecological risk from these PEDCs. A high ecological risk (RQ ≥ 1) from BPA was observed for 0%, 57.69%, and 5.00% of water, sediment, and C. cinerascens samples, respectively, while a high risk from NP2EO was observed for 71.43%, 96.15%, and 55.00% of samples. Ecological risk varied spatially. The high ecological risk from NP2EO in Poyang Lake wetland may be a result of non-point pollution from rural areas and sewage from Poyang Lake basin.

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

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