Association between prenatal exposure to alkylphenols and intelligence quotient among preschool children: sex-specific effects.

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) (ß = -2.38; 95% CI: -4.59, -0.16) and working memory index (WMI) (ß = -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 (ß = 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.

Electrospun of functionalized mesoporous UiO-66 as the selective coating of solid phase microextraction Arrow for the determination of nine alkylphenols.

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.

Cetaceans as Bioindicators to Assess Alkylphenol Exposure and Hormone-Disrupting Effects in the South China Sea.

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

Emerging Contaminants and New POPs (PFAS and HBCDD) in Endangered Southern Resident and Bigg's (Transient) Killer Whales (Orcinus orca): In Utero Maternal Transfer and Pollution Management Implications.

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

Influence of mobile phase composition on the analytical sensitivity of LC-ESI-MS/MS for the concurrent analysis of bisphenols, parabens, chlorophenols, benzophenones, and alkylphenols.

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

Ginkgols and bilobols in Ginkgo biloba L. A review of their extraction and bioactivities.

Ginkgo biloba (GB) has enormous bioactives with anti-bacterial, anti-oxidant, anti-cancer, and immune-stimulating properties, with global sales exceeding $10 billion. The terpene trilactones (ginkgolides A, B, and C) and flavonoids (mostly quercetin, isorhamnetin, and kaempferol) have received the most significant focus in GB research to date, whereas other bioactive compounds such as ginkgols and bilobols with various bioactivities such as anti-viral, anti-oxidant, and anti-tumor actions have received less attention. Therefore, for the first time, this review focused on GB ginkgols, bilobols extraction, and bioactivities. This review showed that petroleum ether and acetone extraction had successfully extracted ginkgols and bilobols. Furthermore, bioactivities such as anti-tumor activity and so on have been demonstrated for ginkgols, and bilobols, providing theoretical justification for ginkgols and bilobol as raw material for nutraceuticals, functional foods, pharmaceuticals, and cosmeceuticals. Future research could look into other biological applications (such as anti-oxidant, antitoxins, anti-radiation, anti-microbial, and antiparasite) and their applications in the pharmaceutical, cosmetic, and nutraceutical industries. Besides, the primary research should be on developing green and effective methods for preparing ginkgols and bilobols and fully utilizing their pharmacological activity. This will also provide a new avenue for efficiently utilizing these bioactive compounds.

Monitoring ocean water quality by deployment of lumpfish (Cyclopterus lumpus) eggs: In situ bioaccumulation and toxicity in embryos.

Fish embryos can bioaccumulate and are particularly sensitive to a wide range of contaminants, which makes them suitable sentinels for environmental biomonitoring. However, fish embryos are very rarely utilized in environmental monitoring surveys, possibly due to their fragility and seasonality. In the present work, we assessed the applicability of caged lumpfish (Cyclopterus lumpus) eggs for in situ biomonitoring of exposure and effects of organic contaminants focusing on polyaromatic hydrocarbons and phenolic compounds. Fertilized eggs (1 dpf) were transplanted for 17-19 days at different locations that differed in terms of contaminant load, depths and weather conditions, namely at three stations close to the city of Trondheim (two harbour areas and a one in the Fjord) and three stations at a coastal aquaculture facility. High survival upon retrieval after deployment showed that lumpfish eggs are relatively robust and survive encaging in different environments. Bioaccumulation of organic contaminants (PAHs and phenolic compounds) was measured and potential effects on hatching, development, survival and larvae morphometry were determined. Chemical analyses showed that especially PAHs were effectively accumulated in eggs in contaminated sites, with concentrations of Æ©PAHs being 15 - 25 times higher in harbour areas compared to those at the aquaculture facility. A higher incidence of embryonic deformations was observed in the most polluted deployment location, but larvae morphometry revealed no evidence of toxicity related to pollutant body burden. In conclusion, the in-situ exposure method was proven to work well, making it attractive for implementations in environmental monitoring programs.

Bioaccumulation of phenolic endocrine disruptors in the clam Rangia cuneata: Storage in shells and influence of size and sex.

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

The Agonist Action of Alkylphenols on TRPA1 Relates to Their Effects on Membrane Lipid Order: Implications for TRPA1-Mediated Chemosensation.

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

Comparison of three explorative methods for identifying building surface materials contributing pollutants to stormwater.

Runoff from building and structure surfaces may contribute to the pollution of urban stormwater and, thereby, to the degradation of the receiving water quality. Various micropollutants have been found in surface runoff from buildings in the urban environment, including metals and organic micropollutants. Effective methods for identification of such pollutants and their sources are the prerequisites for the development of control measures. In this paper, three different methods for the identification of building surface materials acting as sources of metals (Cd, Cr, Cu, Ni, Pb and Zn), nonylphenols and phthalates are presented: (i) screening of the material composition, (ii) laboratory leaching experiments with synthetic rainwater, and (iii) open-air pilot testing of material panels exposed to actual rainfall and runoff. These three methods cover a wide span of experimental aspects, including, e.g., size of material samples, resource demands, and control of influential factors. Nine materials commonly used on building and structure surfaces in the urban environment were tested: metal sheets of zinc, copper, galvanised steel, coated corrugated steel and stainless steel; and, four different roofing membranes of bitumen as well as polyvinyl chloride (PVC). The experimental results indicated that all three methods were meritorious in providing some information contributing to the identification of pollutant sources. The screening of material composition for targeted pollutants is relatively quick and inexpensive, but may fail to identify minor sources of pollutants, or may identify the substances present in the material, but not released in contact with water. Laboratory leaching was generally effective in identifying sources of substances present in surface runoff, but was unsuitable for estimating the magnitude of actual concentrations in building runoff. Open-air pilot studies of material samples (exposed area = 2 m2) were thought to provide the results corresponding well to concentrations in runoff from actual building surfaces, but required relatively large financial and labour resources. Thus, the choice of the method for pollutant identification should be based on study objectives, and some benefits may be achieved using more than one method in an integrated manner; e.g., composition screening and lab or open-air leaching of targeted materials.

Impact of endocrine disrupting compounds in sewage impacted coastal area on seabream.

The pollution of coastal regions worldwide has been of a great concern due to the presence of endocrine disrupting chemicals (EDCs). These chemicals find their way to the marine environment via the sewage treatment plants (STPs). Hence, this study was designed to investigate the status and sources of EDCs and their effect on fish in Kuwait's coastal areas, from the chemical and biological perspectives. The assessment of three STPs indicated the presence of significant levels of phthalates (19 and 31µg/l), alkylphenols (85 and 159ng/l), and estrogens (30 and 368ng/l) in both inflow and outflow samples. The analysis of samples from field exposure sites revealed significant levels of EDCs in seawater (phthalates: 2.1-4.6µg/l; alkylphenols: 1.2-16.4ng/l; estrogens: 0-36.2ng/l) and sediment (phthalates: 2.1-15.7mg/kg dry wt; alkyphenols: 2.5-15.1µg/kg dry wt.; estrogens: 4.1-214.2µg/kg dry wt.) samples. The biological perspective investigated through the exposure of fish to sewage outlets at five sites. The hepatosomatic index (HSI) revealed a higher level in winter samples 0.48-0.79%) in comparison to summer samples 1-1.5%). Histological observation of hepatic tissue of fish exposed during winter months in all sites, showed much less necrotic changes and hepatic vacuolation in the hepatic tissue of summer exposed fish. Imunnohistochemistry evidences revealed a significant level of positive signals and Vtg localization in the hepatic tissue as the results support the histopathological alterations observed. Results of enzyme-linked immunosorbent assay (ELISA) showed no significant difference between the plasma protein content of winter and summer samples. Overall, the study suggest that there is possible local source or a chronic input of untreated and/or partially treated water due to the significant levels of phthalates, alkyphenols, and estrogens detected in the Kuwait Bay. These levels were enough to initiate alteration in the hepatic tissue of fish exposed to the sewage outlets in Kuwait for two weeks.

Job-exposure matrix for the assessment of alkylphenolic compounds.

OBJECTIVES: Our aim was to develop a job-exposure matrix (JEM) to assess occupational exposure to alkylphenolic compounds in epidemiological research, considering changes in their use over time, and including exposure probabilities in the assessments. METHODS: We consulted multiple sources of information, and performed interviews with 9 key people from industry and academia. 3 hygienists coded frequency (minority or majority of workers involved) and intensity of exposure (including dispersive processes, with shaking, or aerosol generation, or otherwise) to alkylphenolic compounds for all the 390 International Standard Classification of Occupations (ISCO)-88 job titles by period of time. Intensity and frequency of exposure were combined in a single score as follows: unlikely=0, occasionally+low intensity=1, occasionally+high intensity=2, frequent+low intensity=2, and frequent+high intensity=3. RESULTS: We identified 54 (13.8%) of the 390 ISCO-88 job titles with potential exposure to alkylphenolic compounds. In 6 of jobs deemed as exposed, exposure depended on the economic sector of the occupation. Nonylphenol ethoxylates were the compounds most commonly involved (30 job titles, 55.6% of the exposed). Variations in alkylphenolic compounds use varied greatly over time; while they are still used in the plastic and rubber industry, in domestic cleaning agents their use began to decline before 1995. CONCLUSIONS: We built a JEM to assess exposure to alkylphenolic compounds, taking into account changes in use over time, different types of alkylphenolic compounds and different scenarios of exposure, which can be a valuable tool for exposure assessment in epidemiological research on the health effects of these chemicals.

Melatonin abrogates nonylphenol-induced testicular dysfunction in Wistar rats.

Endocrine-disrupting chemicals present in the environment can bring about hormonal imbalance and be potentially harmful to the human health. Alkylphenols are omnipresent in the environment as they are constituents of several products. The aim of this study was to evaluate the effect of exogenous melatonin treatment on nonylphenol (NP)-induced oxidative stress and testicular toxicity in Wistar rats using biochemical and histopathological parameters. The oxidative stress biomarkers, activities of enzymatic and non-enzymatic antioxidants and histopathological evaluation were performed in testicular tissues. NP caused elevated TBARS levels and marked alteration of both nonenzymatic and enzymatic biomarkers. Furthermore, severe histopathological alterations were observed in the testis of NP-exposed animals as compared with that of the control rats. Melatonin supplementation ameliorated the alterations in these biochemical and histopathological variables in rats. In conclusion, our results demonstrated that melatonin through its antioxidant activity effectively protected against the NP-induced testicular toxicity.

Fully automated on-line solid phase extraction coupled to liquid chromatography-tandem mass spectrometry for the simultaneous analysis of alkylphenol polyethoxylates and their carboxylic and phenolic metabolites in wastewater samples.

Three different sorbents (i.e. endcapped octadecylsilane, octasilane and styrene-N-vinylpiperidinone co-polymer) were investigated in order to develop an on-line solid phase extraction-liquid chromatographic tandem mass spectrometric method (on-line SPE-LC-MS/MS) for the simultaneous analysis of alkylphenols polyethoxylate (AP(n)EOs, n = 1-8) and corresponding monocarboxylate (AP1ECs) and phenolic (APs) metabolites. The endcapped octadecylsilane was selected due to its full compatibility with a chromatographic approach, which allowed the elution of positively and negatively ionisable compounds in two distinct retention time windows, using a water-acetonitrile-tetrahydrofuran ternary gradient and a pellicular pentafluorophenyl column. On this SPE sorbent, the composition of the loading/clean-up solution was then optimized in order to achieve the best recoveries of target analytes. Under the best experimental conditions, the total analysis time per sample was 25 min and method detection limits (MDLs) were in the sub-nanograms per litre to nanograms per litre range (0.0081-1.0 ng L(-1)) for AP(n)EOs with n = 2-8, AP1ECs and APs, whereas for AP1EOs, an MDL of about 50 ng L(-1) was found. Using the mass-labelled compound spiking technique, the method performance was tested on inlet and outlet wastewater samples from three activated sludge treatment plants managing domestic and industrial sewages of the urban areas and the textile district of Prato and Bisenzio valley (Tuscany, Italy); in most cases, apparent recovery percentages approximately in the ranges of 50-110% and 80-120% were found for inlet and outlet samples, respectively. The on-line SPE-LC-MS/MS analysis of wastewater samples highlighted the presence of target analytes at concentrations ranging from few nanograms per litre to thousands nanograms per litre, depending on the compound and matrix analysed. AP2ECs were also tentatively identified in outlet samples.

Isotope dilution gas chromatography with mass spectrometry for the analysis of 4-octyl phenol, 4-nonylphenol, and bisphenol A in vegetable oils.

By the combination of solid-phase extraction as well as isotope dilution gas chromatography with mass spectrometry, a sensitive and reliable method for the determination of endocrine-disrupting chemicals including bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils was established. The application of a silica/N-(n-propyl)ethylenediamine mixed solid-phase extraction cartridge achieved relatively low matrix effects for bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils. Experiments were designed to evaluate the effects of derivatization, and the extraction parameters were optimized. The estimated limits of detection and quantification for bisphenol A, 4-octylphenol, and 4-nonylphenol were 0.83 and 2.5 µg/kg, respectively. In a spiked experiment in vegetable oils, the recovery of the added bisphenol A was 97.5-110.3%, recovery of the added 4-octylphenol was 64.4-87.4%, and that of 4-nonylphenol was 68.2-89.3%. This sensitive method was then applied to real vegetable oil samples from Zhejiang Province of China, and none of the target compounds were detected.

Pollution by endocrine disruptors in a southwest European temperate coastal lagoon (Ria de Aveiro, Portugal).

Ria de Aveiro is a Portuguese lagoon renowned for its ecological and economic importance. Nonetheless, in literature, few data exist about its organic pollution. Accordingly, this study chemically monitored for the first time a series of 17 endocrine disruptor compounds (EDCs). The target EDCs include natural (17ß-oestradiol, oestrone) and pharmaceutical (17α-ethynylestradiol) oestrogens, industrial/household xenoestrogenic pollutants (octylphenols, nonylphenols and their mono and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, genistein) and the phytosterol sitosterol (SITO). For the investigation of these EDCs, water samples were taken from eight sampling sites widely spread along the lagoon, at three different occasions in 2011, and analysed by gas chromatography-mass spectrometry. Results not only proved the ubiquitous distribution of all analysed EDCs but revealed that their amounts were extremely high at all sampling sites. The annual average concentrations were ≈ 46 ng/L for oestrogens, ≈ 3962 ng/L for industrial/household chemicals, ≈ 1740 ng/L for phytoestrogens and ≈ 908 ng/L for SITO. Normalising these values in ethynylestradiol equivalents (EE2eq), the oestrogenic load in this lagoon attained ≈ 50 ng/L EE2eq, which is a value well above that known to produce oestrogenic-induced disorders in aquatic fauna. Additionally, phosphate concentrations were also above the legal limits (>1 mg/L). Overall, data show EDCs at toxic relevant levels in the Ria de Aveiro and stress the need to enforce depollution measures in this habitat.

Pollution by oestrogenic endocrine disruptors and ß-sitosterol in a south-western European river (Mira, Portugal).

The Mira River is a Portuguese water body widely known for its wilderness and is advertised as one of the less polluted European rivers. On this presumption, the levels of endocrine-disrupting compounds (EDCs) in Mira waters were never measured. However, because environmentalists have claimed that the Mira could be moderately polluted, a range of 17 EDCs were measured not only at the estuary but also along the river. The targeted EDCs included natural and pharmaceutical oestrogens (17ß-oestradiol, oestrone and 17α-ethynylestradiol), industrial/household pollutants (octylphenols, nonylphenols and their monoethoxylates and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, genistein) and the phytosterol sitosterol (SITO). For this propose, waters from six sampling sites were taken every 2 months, over a 1-year period (2011), and analysed by gas chromatography-mass spectrometry. Unexpectedly high levels of oestrogens and of industrial/household pollutants were measured at all sampling sites, including those located inside natural protected areas. Indeed, the annual average sum of EDCs was ≈57 ng/L for oestrogens and ≈1.3 µg/L for industrial/household chemicals. In contrast, the global average levels of phytoestrogens (≈140 ng/L) and of SITO (≈295 ng/L) were lower than those reported worldwide. The EDC concentrations were normalised for ethynylestradiol equivalents (EE2eq). In view of these, the oestrogenic load of the Mira River attained ≈47 ng/L EE2eq. In addition, phosphates were above legal limits at both spring and summer (>1 mg/L). Overall, data show EDCs at toxicant relevant levels in the Mira and stress the need to monitor rivers that are allegedly less polluted.

Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters.

In this study, a polymer, prepared by crosslinking cyclodextrin (CD) by means of a polycarboxylic acid, was used for the removal of pollutants from spiked solutions and discharge waters from the surface treatment industry. In spiked solutions containing five metals, sixteen polycyclic aromatic hydrocarbons (PAH) and three alkylphenols (AP), the material exhibited high adsorption capacities: >99% of Co2+, Ni2+ and Zn2+ were removed, between 65 and 82% of the PAHs, as well as 69 to 90% of the APs. Due to the structure of the polymer and its specific characteristics, such as the presence of carboxylic groups and CD cavities, the adsorption mechanism involves four main interactions: ion exchange, electrostatic interactions and precipitation for metal removal, and inclusion complexes for organics removal. In industrial discharge waters, competition effects appeared, especially because of the presence of calcium at high concentrations, which competed with other pollutants for the adsorption sites of the adsorbent.

Evaluation of low-cost materials for sorption of hydrophobic organic pollutants in stormwater.

Conventional stormwater treatment techniques such as sedimentation and filtration are inefficient for removing the dissolved and colloidal phases of hydrophobic organic compounds (HOCs) present in stormwater. Adsorption could be a promising technique for removing colloidal and dissolved pollutants. Five low-cost sorbent materials were investigated in this project, including two minerals ­ vermiculite and perlite ­ and three waste products ­ two pine barks and a sawdust ­ as potential adsorbents for removal of polycyclic aromatic hydrocarbons (PAHs), alkylphenols and phthalates; HOCs commonly found in stormwater. Adsorption capacity and kinetics were studied through batch adsorption tests using synthetic stormwater spiked with a mixture of HOCs. Vermiculite and perlite exhibited insignificant removal of the organic contaminants. The three wood-based materials retained >80% of the initial HOC concentration (10-300 µg/L). The two barks exhibited slightly higher adsorption capacities of HOCs than the sawdust. For all compounds tested, maximum adsorption onto the wood-based media was reached in <10 min. The highest adsorption capacity was found for PAHs (up to 45 µg/g), followed by alkylphenols and phthalates. No correlation was found between adsorption capacity and physical-chemical parameters such as solubility and partition coefficients (log K(ow)). Agreement between empirical data and the pseudo-second order kinetic model suggest chemisorption of HOCs onto a monolayer on wood-based media. This could lead to early saturation of the materials and should be investigated in future studies through repeated adsorption of HOCs, for example in column studies.

Levels, distribution, sources and human exposure pathways of alkylphenol and alkylphenol ethoxylates in indoor dust in Turkiye.

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.