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In recent decades, increasing attention has been directed toward the effects of alkylphenols and bisphenols due to their demonstrated endocrine-disruptive effects. This study investigated the occurrence and potential risk assessment of two alkylphenols and seven bisphenols in surface water collected from rivers (Cau River, Duong River, and Thai Binh River) flowing through Bac Ninh province, one of the pivotal economic regions in the North of Vietnam. The results demonstrated that these compounds were widely distributed in the rivers. The average concentrations were ranked as follows: 4-tert-octylphenol (4-t-OP) (91.2 ng/L) > 4-nonylphenol (4-NP) (78.9 ng/L) > bisphenol S (BPS) (72.4 ng/L) > bisphenol A (BPA) (5.6 ng/L) > bisphenol F (BPF) (below method detection limit) with detection frequencies of 100% (except for BPF of 23%). The presence of alkylphenols and bisphenols in aquatic environments closely correlates with anthropogenic activity. The environmental risk assessment was carried out based on the Risk Quotient (RQ) evaluation, indicating that 4-NP poses medium risk in all three rivers. In addition, 4-t-OP, which is more toxic than 4-NP, poses high risk to aquatic organisms in the Duong River (RQ = 1.1), while BPA and BPS show low risk to aquatic organisms in three rivers (RQ < 0). [ABSTRACT FROM AUTHOR]

The oxidation of a series of alkylphenols (alkyl is methyl and/or isobornyl) with chlorine dioxide using the VO(acac)2 as the catalyst was studied. In the presence of VO(acac)2, the selectivity to quinones increases and the yield of oxidative chlorination products decreases significantly. [ABSTRACT FROM AUTHOR]

A high-performance liquid chromatography with diode array detector (HPLC-DAD) analytical method was developed for the simultaneous detection of 17 phenolic compounds, including phenols, chlorophenols, alkylphenols, and nitrophenols, in two types of water matrices: wastewater and surface water. Prior to HPLC-DAD determination, a solid-phase extraction (SPE) procedure was optimized. The proposed method uses multiwavelength analysis, with the optimum detection wavelengths selected as 268 nm, 280 nm, 386 nm, 304 nm, and 316 nm. The highest resolution was achieved using a chromatographic column, Eclipse XDB-C18 (150 × 4.6 mm, 5 μm), which was kept at 20 °C. The mobile phase consisted of a gradient elution program, with mobile phase A being a 0.1% H3PO4 aqueous solution and mobile phase B being acetonitrile. The flow rate was set at 0.6 mL/min. The 17 target phenolic compounds were fully separated in less than 27 min. All compounds showed good linear regression, with correlation coefficients higher than 0.999. The method's quantitation limits ranged from 4.38 to 89.7 ng/L for surface water and 7.83 to 167 ng/L for wastewater. The recovery rates were in the range of 86.2–95.1% for surface water and 79.1–86.3% for wastewater. The SPE-HPLC-DAD method was proven to be fast, sensitive, accurate, and reproducible. The developed method was successfully applied for the analysis of the 17 phenolic compounds in real surface water and wastewater samples, with phenol, 2,4-DNP, and 2,4-DNP being determined at levels greater than the method's limits of quantitation (LOQs). The proposed analytical method represents an original technical resource for the simultaneous determination of 17 phenolic compounds in environmental water matrices. [ABSTRACT FROM AUTHOR]

In this study, the spatial distribution of alkylphenols in the sediments of the Marmara Sea was investigated for the first time. The targeted alkylphenol analysis was made by gas chromatography with triple quadrupole (GC-MS/MS) system. The 4-tert-octylphenol and 4-nonylphenol were detected in the studied sediments, while 4-n-octylphenol was not quantified. The measured concentrations of 4-tert-octylphenol and 4-nonylphenol were in the range of

In this study, concentrations of alkylphenolic (AP) compounds were measured and quantified in sediments, soil and aerosols collected in the vicinity of Cortiou Creek in the coastal area of Marseilles directly downstream of wastewater treatment plants (WWTPs). The three isomers of the nonylphenols (NPs), i.e. NP1, NP2 and NP3, were detected in sediments throughout the plume with average concentrations at each station of 62.93 µg.kg−1, 28.09 µg.kg−1, and 117.58 µg.kg−1, respectively. The stations beyond the plume measured levels of 33.67 µg.kg−1, 11.11 µg.kg−1, and 23.89 µg.kg−1, respectively. These chemicals were also found principally in soil samples with average concentrations of each isomer distributed at 6 stations at amounts of 48.08 µg.kg−1, 19.49 µg.kg−1 and 339.13 µg.kg−1 exposed to the prevailing wind, while at stations protected from predominantly high winds, concentrations ranged from 5.8 µg.kg−1 to 41.41 µg.kg−1. The most wide-ranging measurement is for the occurrence of these APs in aerosol samples, which were detected at levels of 0.81 to 8.46 ng.m−1. In addition, 4 tert-OP and 4 n-OP were not detected in these samples. The most elevated isomers found in this study were NP1 (28.44%) and NP3 (57.54%) within the three different matrices. According to the predicted no-effect concentrations (PNECs), these concentrations in the sediments exceeded the PNEC value, which indicates that they are likely to exert an adverse effect on benthic organisms. Alkylphenols were found in three environmental matrices APs, which were detected in aerosol samples, ranged in concentration from 0.81 to 8.46 ng. m-2 The most elevated isomers found in this study were NP1 (28.44%) and NP3 (57.54%) APs were derived from the emission points of WWTPs and other sources Sedimentary APs exceeded the PNEC value, signifying a potentially adverse effect [ABSTRACT FROM AUTHOR]

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-NH2 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. [ABSTRACT FROM AUTHOR]

The widely used 4-octylphenol (OP) belongs to the group of endocrine disrupters (ED). However, it exerts potentially adverse effects on human health and the environment and has been detected in various environmental matrices. Adsorption is an effective treatment method for removing ED. This study analyzes the adsorption process of OP on graphene oxide (GO) on a bench scale and the central composite design was used for analyses of adsorption with four factors, namely, adsorbate concentration (100 to 120 mg.L-1 COP), adsorbent concentration (0.2 to 3.4 g.L-1 CGO), contact time (15 to 90 min Ct), and pH (2 to 10). The results helped investigate adsorption capacity, adsorption kinetics pseudo-first order, pseudo-second order, Elovich equation, and in- traparticle diffusion (IPD) and equilibrium conditions Langmuir, Freundlich, and Redlich-Peterson by mathematical models and showed 158.92 mg.g-1 (120 mg.L-1 COP, 0.2 g.L-1 CGO, 90 min Ct, and pH 2) maximum adsorption capacity. Regarding kinetics, Elovich equation best fitted the experimental data (R² = 0.9961) and IPD indicated the adsorption process took place in the intraparticle and in the boundary layer. Redlich-Peterson model showed the best fit to the data (R² = 0.9971) in the isotherms. The study demonstrated the adsorption of OP by GO in an aqueous solution can be used over a wide range of pH and contact times with no significant loss of efficiency. [ABSTRACT FROM AUTHOR]

Alkylphenols, which are industrial chemicals, are xenoestrogens; however, their sublethal effects on aquatic animals are poorly studied. The aim of this work is to study possible metabolic and reproductive disorders in amphipods using the example of Gmelinoides fasciatus from the Gulf of Finland (Baltic Sea) after experimental exposure to 4-tert-octylphenol (4t-OP) from the group of alkylphenols. The mortality of G. fasciatus amphipods in 4t-OP concentration ranges from 0.5 to 1000 μg/L after 96 h and 7 days increases with increasing concentration. At 4t-OP concentrations of 0.5 and 5 μg/L, the mortality of G. fasciatus has not been observed. At a concentration of 20 μg/L, after 7 days, the mortality of crustaceans is 20%; at a concentration of 100 μg/L, it is 60%. Exposure to sublethal concentrations of 4t-OP (0.5 μg/L) resulted in a decrease in sexual activity of these amphipods after 1 week: only 25% of amphipods retain precopulatory pairs versus 100% in control. Under chronic exposure (28 days) to the lowest concentration, males show signs of demasculinization (a decrease in the width of the gnatopods and an increase in the depth of the coxal plates); females show a decrease in the overall fecundity and irreversible disturbances in the state of embryos (a high proportion (>50%) of embryos stop their development at different stages of organogenesis). The study shows significant functional disorders of metabolic processes and reproduction in crustaceans even when exposed to nonlethal concentrations of octylphenol. These results confirm the high toxicity of this industrial pollutant, the presence of which in the aquatic environment can lead to irreversible changes in the biota. [ABSTRACT FROM AUTHOR]

Alkylphenols are widely applied in the field of industry and agriculture, but their endocrine disrupting properties harm to human health. Moreover, alkylphenols often exhibit the low content in complex samples. Thus, we proposed magnetic covalent organic framework composites (Fe3O4@TatTpa) for efficient magnetic solid phase extraction (MSPE) of alkylphenols via hydrogen bonding, π-π and hydrophobic interactions. In combination with HPLC detection, good linearity (0.006–10 µg mL−1) with R2 (≥0.997) and low limit of detections (1.8–6 × 10−3 µg mL−1) were realized for alkylphenols. The proposed method was successfully employed to determine alkylphenols in soft drink, black oolong tea, and watermelon samples with satisfactory recoveries (86.1–118.5 %) and relative standard deviations (6.3–14.8 %).

Abstract 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

Phthalates (PAEs) and alkylphenols (APs), known as endocrine-disrupting compounds (EDCs), are ubiquitous in aquatic environments worldwide and may be harmful to aquatic ecosystems. This study is the first to comprehensively assess the occurrence and potential ecological risks of 12 EDCs in the surface sediments of seven major harbors in Taiwan. In addition, a correlation model was established between the concentration levels of individual PAEs and APs in the sediments and their production. The total PAEs concentrations in the sediments ranged between 129–1894 ng/g dw (mean: 558 ± 479 ng/g dw). Total APs concentrations ranged between<0.2–913 ng/g dw with a mean of 52 ± 178 ng/g dw. Among the 12 EDCs, bis(2-ethylhexyl) phthalate (55.1%) and diisononyl phthalate (31.6%) were the predominant PAEs, while 4-nonylphenol (93.2%) was the main AP. The occurrence and concentrations of PAEs and APs in the sediments were significantly correlated with their production (r = 0.989, p <.01), reflecting the status and degree of anthropogenic pollution. The concentrations of PAEs and APs in the sediments of Taiwanese harbors showed a potential decreasing trend over time, which should be related to strengthened regulations and changes in the industrial market. The estimated total risk quotient (TRQ) of algae exposed to the concentrations of 12 EDCs in sediments suggests moderate to high potential risks (TRQ = 0.74–2.18), while crustaceans (TRQ = 0.02–0.27) and fish (TRQ = 0.03–0.10) may have low to moderate potential risks. The main compounds responsible for these risks are dibutyl phthalate, dioctyl phthalate, and 4-nonylphenols. The results show that the pollution degree of surface sediments in the harbor could reflect anthropogenic pollution. Therefore, it is necessary to monitor the pollution of surface sediments in harbors, grasp the pollution situation, and evaluate the regulatory effect. [ABSTRACT FROM AUTHOR]

A competitive chemiluminescent immunoenzyme assay (CL-EIA) technique is proposed for the sensitive determination of one of the environmentally significant toxicants of anthropogenic origin-nonylphenol—in natural waters. The chosen chemiluminescent detection is characterized by a higher sensitivity compared to the colorimetric. The limit of nonylphenol detection was 9 ng/mL compared to 55 ng/mL for colorimetric one in optimal conditions. The developed analysis can be used for two purposes; it is highly sensitive for the possibility of toxicological analysis and dilution of complex matrices with raw buffer solution, as well as for the analysis of water samples without pretreatment and dilution. The method has a working range from 28 to 1800 ng/mL. The degree of nonylphenol revealing in the spiked samples of river, spring, and waterfall water was 82–119%. [ABSTRACT FROM AUTHOR]

Results are presented from gravimetric anti-corrosion studies of pyridine salts 1-(4-isohexylphenoxy-)-3-propylpyridinium bromide (I) and 1-(4-isohexylphenoxy-2-diethylaminostil-)-3-pyridinium bromide (II) on St. 3 steel in 0.5 N Н2SO4. The effect the temperature (298, 303, 313, 323, 333 K) and concentrations of compounds (0.025, 0.05, and 0.1 g/L) have on the rate of corrosion and protective effect is studied (duration of test, 3 h). It is established that compounds I and (especially) II are strong inhibitors: the degree of protection against corrosion for St.3 steel at concentrations of 0.1 g/L is 96% on average. The thermodynamic parameters of the process (ΔG, ΔH, and ΔS) are calculated, and the blocking mechanism for protecting the metal surface from corrosion is considered. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 [ABSTRACT FROM AUTHOR]

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.

A competitive chemiluminescent immunoenzyme assay (CL-EIA) technique is proposed for the sensitive determination of one of the environmentally significant toxicants of anthropogenic origin-nonylphenol—in natural waters. The chosen chemiluminescent detection is characterized by a higher sensitivity compared to the colorimetric. The limit of nonylphenol detection was 9 ng/mL compared to 55 ng/mL for colorimetric one in optimal conditions. The developed analysis can be used for two purposes; it is highly sensitive for the possibility of toxicological analysis and dilution of complex matrices with raw buffer solution, as well as for the analysis of water samples without pretreatment and dilution. The method has a working range from 28 to 1800 ng/mL. The degree of nonylphenol revealing in the spiked samples of river, spring, and waterfall water was 82–119%.

[Display omitted] • CO 2 assisted fast pyrolysis of palm kernel shells. • Ni-Ce/CN50 catalyst enhanced oxygen removal efficiency. • High potential use of NiCe/CN50 catalyst for phenol production. • The presence of Ce reduced coke formation. Catalytic fast pyrolysis is one of the most promising techniques for the production of bio-oils. Generally, pyrolysis is carried out in an inert atmosphere; however, reactive catalytic pyrolysis has emerged as an alternative technique for achieving high catalytic efficiency. Herein, NiCe/CN catalysts with different Ni:Ce ratios were developed, and their catalytic efficiency in the catalytic fast pyrolysis of palm kernel shells in a CO 2 atmosphere was evaluated. The effects of reaction conditions, including the reaction temperature (400–600 °C) and ratio of Ni:Ce (10:0, 10:1, 10:3, 10:5, and 10:10), on the product yields were studied using in situ and ex situ analyses. NiCe/CN50 exhibited enhanced oxygen removal efficiency owing to the presence of oxygen vacancies in CeO x. In addition, the acidic site of the catalyst promoted the highly selective demethoxylation of alkylphenols. The presence of Ce promoted the Boudouard reaction (C + CO 2 → 2CO), which reduced coke deposition on the spent catalyst. Our results indicate that the NiCe/CN50 catalyst exhibited good catalytic efficiency, achieving the highly selective production of alkylphenols and acetic acid and low deactivation. Therefore, NiCe/CN50 can be used as an alternative catalyst for phenol production from biomass via catalytic fast pyrolysis. [ABSTRACT FROM AUTHOR]

In this study, the effect of metal-loaded biochar as a catalyst on the catalytic pyrolysis of lignin was investigated. The metal active sites (Ni, Fe) were introduced into the pine sawdust-derived biochar by an incipient-wetness impregnation method, and then the prepared catalysts were tested in catalytic pyrolysis of lignin in a fixed-bed reactor. The results showed that the relative content of phenolic compounds increased to 79.69%–90.46% during the pyrolysis of lignin under the function of biochar-based catalysts. The biochar introduced with bimetallic Fe/Ni enhanced the dissociation of side chains of alkylphenols in the pyrolysis process. The selectivity to phenol increased from 14.52% to 49.02%, which simplified the composition of bio-oil. Bio-oil rich in hydrocarbons and phenols can be used as a substitute for petroleum fuel or as an industrial-grade chemical. Thus, low-cost and readily available Fe/Ni biochar-based catalysts provide an effective research basis for production of aromatic compounds in catalytic pyrolysis of biomass. • Fe/Ni-loaded biochar shows high performance on bio-oil upgrading. • Synergistic effect of Fe and Ni promoted dealkylation and deoxygenation. • High selectivity to phenol is achieved during the catalytic pyrolysis of lignin. [ABSTRACT FROM AUTHOR]

The liver toxicity of alkylphenols (APs) has been demonstrated in animal studies. However, relevant epidemiological evidence is still lacking in humans, especially during pregnancy. We obtained the levels of biochemical indicators of liver function in early (<13 weeks, mean gestation=9.80±1.96 weeks) and late (≥32 weeks, mean gestation = 37.23±2.45 weeks) pregnancies from 219 pregnant women in the Guangxi Zhuang birth cohort from 2015–2017. We also examined the serum levels of APs in these pregnant women in early pregnancy. The present study aimed to investigate the correlations between the exposure of pregnant women to APs and their serum liver function indices. The results of the generalized linear model (GLM) in this study revealed that nonylphenol (NP) was positively correlated with total bilirubin (TBIL) (P=0.04) in early pregnancy, and 4-n-nonylphenol (4-N-NP) was negatively correlated with glutamyl transferase (GGT) (P=0.012). In late pregnancy, NP was positively associated with TBIL (P=0.002), and 4-tert-octylphenol (4-T-OP) was positively correlated with alanine aminotransferase (ALT) (P=0.02). Restricted cubic spline (RCS) results revealed dose response relationships between NP and TBIL (Poverall=0.011) and between 4-N-NP and GGT (Poverall=0.007) in early pregnancy. In late pregnancy, there were dose response relationships between NP and TBIL (Poverall=0.001) and between 4-T-OP and ALT (Poverall=0.033). There was also a dose response relationship between NP volume and GGT with an inverted 'U' shape (Poverall=0.041, Pnonlinear=0.012). Bayesian kernel machine regression modeling (BKMR) revealed that TBIL increased significantly (P<0.05) with increasing levels of coexposure to APs in both early and late pregnancy. Overall, exposure to APs during pregnancy affects maternal liver function to varying degrees. The present study provides new epidemiological evidence that exposure to alkylphenols in pregnant women interferes with liver function. • The first study to link APs exposure during pregnancy to maternal liver function. • Different APs affect liver function variably during early and late pregnancy. • BKMR analysis shows significant TBIL increase with APs coexposure in pregnancy. [ABSTRACT FROM AUTHOR]

The study explored the catalytic hydrodeoxygenation (HDO) of guaiacol using nickel-loaded cerium oxide (Ni/Ce) and molybdenum-promoted Ni/Ce (Mo-Ni/Ce) catalysts in supercritical ethanol. The use of Mo-Ni/Ce at 300 °C maximized H 2 production, guaiacol conversion (84.1%), and deoxygenation compared to Ni/Ce. Mo-Ni/Ce also achieved the highest efficiency for producing desired products, resulting in 7.8% phenol and 29.0% alkylphenols selectivities. Mo-Ni/Ce's better efficiency stemmed from enhanced ethanol dehydrogenation, H 2 dissociation and spillover, and accelerated HDO reactions owing to improved Ni dispersion and catalyst oxygen vacancies. Testing different Ni and Mo loading amounts revealed the optimum catalyst efficiency when using 20% Ni and 5% Mo (5Mo-20Ni/Ce). Temperature optimization with 5Mo-20Ni/Ce increased guaiacol conversion (up to 95.6% at 340 °C) and yielded more phenol (27.4%) and alkylphenols (66.1%). DFT calculations revealed that adding molybdena clusters notably reduced the energy required for creating oxygen vacancies, indicating enhanced catalytic properties for oxygen vacancy generation in 5Mo-20Ni/Ce. [Display omitted] • Catalytic guaiacol HDO was performed in supercritical ethanol without external H 2. • The use of Mo-Ni/Ce obtained the highest guaiacol conversion and deoxygenation. • A higher selectivity toward alkylphenols was achieved over Mo-Ni/Ce than Ni/Ce. • Catechol was proposed as the main intermediate produced by guaiacol demethylation. • The DFT calculations were employed to identify the optimal oxygen vacancy sites. [ABSTRACT FROM AUTHOR]

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.)

[Display omitted] • An acid–induced dispersive liquid–liquid microextraction is developed. • Analytes are extracted by in situ formation of deep eutectic solvents with formed fatty acids. • The method is successfully used for detection of bisphenol A and alkylphenols. • The method is simple, rapid, sensitive, low cost, and environmentally friendly. • The new method expands the application pathway and scope of deep eutectic solvents. 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. [ABSTRACT FROM AUTHOR]

The majority of the phenolic compounds in coal tar are alkyl-substituted phenols. To overcome the difficulty of separation, zeolites catalyzed dealkylation of alkylphenols was studied in a slurry-bed reactor. ZSM-5 displayed higher catalytic performance than other zeolites within a group of acidic zeolites with various topologies (including SAPO-34, ZSM-23, MCM-22, USY, and Mordenite). The yield of phenol gradually increased together with the zeolite acidity, but the types and yields of byproducts also increased in step with it. The pore size of the zeolites was a significant influence at similar acidity. The micropore of ZSM-5 inhibited some bimolecular processes, decreasing disproportionation/transalkylation as a result of transition state shape selection. In this study, the reaction paths of alkylphenols were investigated, based on the composition of products catalyzed by different zeolites, the distribution of products under different conditions, and the reaction process of various alkylphenols. Reaction process of alkylphenols included dealkylation, isomerization, disproportionation, transalkylation, and C-C cracking. Dealkylation took the place of isomerization as the primary reaction when the reaction temperature exceeded 350 °C. Disproportionation, transalkylation, and C-C cracking were exacerbated by excessive temperature. In addition, excessive reaction time and pressure can exacerbate side reactions, alkylphenols yields and coke deposition. [Display omitted] • The orientation reaction of alkylphenol dealkylation by zeolite in a slurry-bed. • The dealkylation is facilitated by comparable pore size and molecular diameter. • Dealkylation and isomerization were prone to occur at low temperatures. • The disproportionation reaction produced more cresol than the C-C cracking. [ABSTRACT FROM AUTHOR]

[Display omitted] • Fast miniaturized extraction for analysis of 3 classes of pollutants in sediment. • US extraction with non-chlorinated solvent and extract clean-up performed in one step. • Cost-effective sample preparation and LC–FLD-DAD analysis. • Method meets the maximum permissible concentrations set by the Dutch RIVM. The study presents a simple and non-laborious method for the determination of 16 polycyclic aromatic hydrocarbons (PAHs), 2 phthalate esters (PEs), 2 alkylphenols (APs) and 4 alkylphenol ethoxylates (APEOs) in sediment. The method employs sample preparation combining focused ultrasound solid–liquid extraction (FUSLE) and in situ clean-up followed by liquid chromatography with fluorescence and ultraviolet detection. Extraction of 0.5 g sediment samples with 7 mL acetone in the presence of activated silica (0.5 g) and powdered copper (0.2 g) using an ultrasonic probe for 1 min resulted in recoveries of target analytes ≥ 78 %. The analytical method was classified as "acceptable green analysis" by the analytical Eco-Scale assessment (AESA) and scored 0.54 in the AGREEprep greenness assessment for sample preparation. Matrix-matched calibration was used to quantify analytes with a linear range for PAHs 2–1000 ng g–1, for PEs 100–5000 ng g–1 and for APs and APEOs 40–2000 ng g–1 dry weight. The reached limits of quantification (LOQ) for PAHs ranged from 1.1 to 3.1 ng g−1, for PEs from 122 to 124 ng g−1, for APs from 40 to 51 ng g−1 and for APEOs from 36 to 53 ng g−1. The applicability of the method was demonstrated by the analysis of real sediment samples and natural matrix certified reference material. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • Nonionic surfactants are widespread present in indoor environments. • Di-NPE was found to be the most prevalent isomer among the APs and APEs. • Levels of APs and APEs are influenced by house characteristics and human lifestyle. • Home repairs and polished floor were associated with high levels of 4-n-NP and di-NPE. • Ingestion was the primary exposure route for both adults and children. [ABSTRACT FROM AUTHOR]

H-ZSM-5 and H-Beta zeolites ion-exchanged with alkali (Na+ and K+) and alkaline-earth (Mg2+) metals have been explored for the catalytic fast pyrolysis of lignin. Incorporating these metals led to a significant change in the acidic properties of the parent zeolites turning into mostly Lewis-type acidity. Catalytic fast pyrolysis experiments of lignin were performed in a fixed bed reactor with ex-situ configuration operating at 550 °C (thermal zone) and 450 °C (catalytic zone), atmospheric pressure and under a nitrogen flow. Moreover, two catalysts to lignin mass ratios (C/L = 0.2 and 0.4) were studied. Compared with non-catalytic tests, the use of parent zeolites caused a decrease in the bio-oil* (water-free basis) yield due to enhanced production of gases, water, and the coke deposition on the catalyst. In addition, the quality of bio-oil* was improved since it presents a lower oxygen content regarding the thermal test. H-Beta zeolite showed a higher deoxygenation degree than H-ZSM-5, but the latter exhibited a higher share of light components in the bio-oil* that can be detected by GC-MS analyses. Both catalysts promoted the production of light oxygenates, aromatics, and oxygenated aromatics. Regarding the effect of the incorporation of metals, oxygenated aromatic compounds were the predominant family in the bio-oil* obtained with all ion-exchanged zeolites. Likewise, significant differences were observed among the catalysts regarding the main components of this family (alkylphenols, guaiacols, syringols, catechols, and methoxybenzenes), achieving guaiacols concentrations in bio-oil* near to 24 wt.% for NaH-ZSM-5 and KH-ZSM-5 catalysts, and alkylphenols concentrations close to 16 wt.% for MgH-Beta and KH-Beta zeolites. [Display omitted] • Compared to thermal test, bio-oil* quality is improved by using H-Beta and H-ZSM-5. • CFP increases the concentration of GC-MS detected bio-oil* compounds. • The main family in bio-oil* is oxygenated aromatics for all the ion-exchanged zeolites. • NaH-ZSM-5 and KH-ZSM-5 catalysts favoured the formation of guaiacols. • MgH-Beta and KH-Beta zeolites promote guaiacols and alkylphenols production. [ABSTRACT FROM AUTHOR]

Preventing asphaltene aggregation is one of the most severe technical challenges facing the oil industry in all stages, from extraction to transportation and refining. Alkylphenols are known as one of the most effective inhibitors of asphaltene aggregation, but the self-association through H-bonding, as well as the lack of proper interaction with asphaltene molecules (with low heteroatom), are the main disadvantages that limit their use. Using molecular dynamics (MD) simulations in a mixture of different asphaltene structures, the performance of 2,6-di-tert-butylnaphthalene in improving the inhibitory effect of octylphenol (as a non-ionic surfactant) is investigated. The proposed compound without heteroatoms can control the aggregation behavior of asphaltene molecules in the stacking phase and this structure is offered as an addition to alkylphenols. According to our results, based on quantum mechanical calculations, the affinity to interact and cover the aromatic cores of asphaltene molecules controls and inhibits the interactions between asphaltene molecules. Furthermore, di-tert-butylnaphthalene's side interactions with the formed nanoaggregates may intervene in the clustering phase. [Display omitted] • Asphaltene stacking inhibitors can be effective against a wider range of asphaltenes. • Two-ring structures with bulky side chains can reduce aggregation by blocking the active surface of asphaltene aromatic cores. • Based on MD simulations, the proposed structure reduces aggregation behavior in various asphaltenes without self-assembly. • The inhibitor compounds based on controlling the π-π interactions can be suitable supplements for alkylphenols. • Quantum mechanics energy decomposition analysis reveals the nature of inhibitor-asphaltene interactions and the range of energies. [ABSTRACT FROM AUTHOR]

[Display omitted] • Abundant metabolites of cross-coupling reaction of alkylphenols and estrogens were identified. • The coupling reactions were catalyzed by CYP3A4 and verified in general populations. • Alkylphenols disrupt estrogen homeostasis via cross-coupling reactions. • Spin-trapping screening and DFT calculations revealed the diradical mechanism of cross-coupling reactions. Estrogen, being an essential class of sex hormone, is an important target of endocrine disruption chemicals. It is well known that environmental disruptors could activate or inhibit estrogen receptors, acting as agonists or antagonists, and thus affect the circulating estrogen concentrations. Here, we report enzyme-mediated diradical cross-coupling reactions between alkylphenols (e.g., 2,4-di- tert -butylphenol [DBP], 4-nonylphenol [4-NP], and 4- tert -octylphenol [4-t-OP]) and estrogens (e.g., estradiol [E2]) that generate coupling metabolites and disrupt estrogen homeostasis. Among the phenolic xenobiotics, the screening of metabolic products revealed that alkylphenols had the highest reaction activities and generated coupling metabolites with high abundances (DBP-O-E2, 4-t-OP-O-E2, and 4-NP-O-E2). The coupling reactions were catalyzed by cytochrome P450 3A4 (CYP3A4) and verified by the detection of the coupling products in general populations. In vitro and in vivo exposures together with CYP3A4 inhibition demonstrated that cross-coupling reactions of phenols and E2 significantly reduced the normal levels of E2. We further established a unique spin-trapping-based high-throughput screening method to show the existence of diradicals in the coupling reaction. Density functional theory calculations revealed that spin aromatic delocalization was the fundamental cause of the high rebound barrier and sufficient lifetime of phenoxy radicals that enabled phenolic cross-coupling triggered by cytochrome P450. The identified mechanistic details for diradical cross-coupling reactions provide a novel pathway for phenolic chemicals to disrupt estrogen homeostasis. [ABSTRACT FROM AUTHOR]

• Exposure to phenols is ubiquitous in Japanese pregnant women during early pregnancy. • Bisphenol A and para -nitrophenol were determined in more than 60% of urine samples. • The hazard quotient of bisphenol A was 0.070, indicating a very low risk of exposure. 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. [ABSTRACT FROM AUTHOR]