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1.
Environ Sci Technol ; 2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-39016874

RESUMO

Emerging aryl organophosphate esters (aryl-OPEs) have been employed as substitutes for organohalogen flame retardants in recent years; however, their environmental occurrence and associated impacts in urban estuarine sediments have not been adequately investigated, impeding regulatory decision-making. Herein, field-based investigations and modeling based on surface sediment and sediment core analysis were employed to uncover the historical pollution and current environmental impacts of aryl-OPEs in the Pearl River Estuary, South China. Our results revealed a substantial increase in aryl-OPE emission, particularly emerging aryl-OPEs, through sediment transport to the estuary since the 2000s. The emerging aryl-OPEs comprised 83% of the total annual input in the past decade, with an average annual input of 155,000 g. Additionally, the emerging-to-traditional aryl-OPE concentration ratios increased with decreasing distance from the shore, peaking in the highly urbanized riverine outlets. These findings indicate that inventories of emerging aryl-OPEs are likely increasing in estuarine sediments and their emissions are surpassing those of traditional aryl-OPEs. Our risk-based priority screening approach indicates that some emerging aryl-OPEs, particularly bisphenol A bis(diphenyl phosphate), can pose a higher environmental risk than traditional aryl-OPEs in estuarine sediments. Overall, our study highlights the importance of recognizing the environmental impacts of emerging aryl-OPEs.

2.
Environ Sci Technol ; 58(15): 6814-6824, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38581381

RESUMO

Identifying persistent, mobile, and toxic (PMT) substances from synthetic chemicals is critical for chemical management and ecological risk assessment. Inspired by the triazine analogues (e.g., atrazine and melamine) in the original European Union's list of PMT substances, the occurrence and compositions of alkylamine triazines (AATs) in the estuarine sediments of main rivers along the eastern coast of China were comprehensively explored by an integrated strategy of target, suspect, and nontarget screening analysis. A total of 44 AATs were identified, of which 23 were confirmed by comparison with authentic standards. Among the remaining tentatively identified analogues, 18 were emerging pollutants not previously reported in the environment. Tri- and di-AATs were the dominant analogues, and varied geographic distributions of AATs were apparent in the investigated regions. Toxic unit calculations indicated that there were acute and chronic risks to algae from AATs on a large geographical scale, with the antifouling biocide cybutryne as a key driver. The assessment of physicochemical properties further revealed that more than half of the AATs could be categorized as potential PMT and very persistent and very mobile substances at the screening level. These results highlight that AATs are a class of PMT substances posing high ecological impacts on the aquatic environment and therefore require more attention.


Assuntos
Atrazina , Poluentes Químicos da Água , Poluentes Químicos da Água/análise , Rios/química , Triazinas/análise , Atrazina/análise , China , Monitoramento Ambiental
3.
Environ Sci Technol ; 58(17): 7529-7542, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38644662

RESUMO

We investigated the fluorescent dissolved organic matter (FDOM) composition in two watersheds with variable land cover and wastewater infrastructure, including sanitary sewers and septic systems. A four-component parallel factor analysis model was constructed from 295 excitation-emission matrices recorded for stream samples to examine relationships between FDOM and geospatial parameters. The contributions of humic acid- and fulvic acid-like fluorescence components (e.g., C1, C2, C3) were fairly consistent across a 12 month period for the 27 sampling sites. In contrast, the protein-like fluorescence component (C4) and a related ratiometric wastewater indicator (C4/C3) exhibited high variability in urban tributaries, suggesting that some sites were impacted by leaking sewer infrastructure. Principal component analysis indicated that urban areas clustered with impervious surfaces and sanitary sewer density, and cross-covariance analysis identified strong positive correlations between C4, impervious surfaces, and sanitary sewer density at short lag distances. The presence of wastewater was confirmed by detection of sucralose (up to 1,660 ng L-1) and caffeine (up to 1,740 ng L-1). Our findings not only highlight the potential for C4 to serve as an indicator of nearby, compromised sanitary sewer infrastructure, but also suggest that geospatial data can be used to predict areas vulnerable to wastewater contamination.


Assuntos
Águas Residuárias , Águas Residuárias/química , Monitoramento Ambiental/métodos , Poluentes Químicos da Água/análise , Fluorescência
4.
Environ Res ; 249: 118344, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38311200

RESUMO

More and more previously designed wastewater treatment plants (WWTPs) are upgraded to tertiary treatment to meet the higher effluent discharge standards of conventional pollutants. Contaminants of emerging concern (CECs) can cause adverse effects on organisms and usually flow into WWTPs along with urban sewage. How the retrofitted WWTPs targeting conventional pollutants will influence the treatment efficiency of CECs is seldom discussed. This study investigates the removal of CECs in two full-scale newly retrofitted WWTPs (CD and JM WWTPs), containing high-efficiency sedimentation tank and denitrification deep bed filter for enhancing total nitrogen removal. The overall CEC removal efficiencies in the CD and JM WWTPs were 73.79 % and 93.63 %, respectively. Mass balance results indicated that CD WWTP and JM WWTP release a total of 36.89 and 88.58 g/d of CECs into the environment through effluent and excess sludge, respectively. Analysis of the concentration of CECs along the treatment process revealed most CECs were removed in the biological treatment units. The incorporation of newly constructed tertiary treatment proved beneficial for CEC removal and removed 2.93 % and 2.36 % CECs, corresponding to CEC removal of 2.92 and 27.49 g/d in the CD and JM WWTPs, respectively. The data of this study were further used to evaluate the suitability of the SimpleTreat model for simulating the fate of CECs in WWTPs. The predicted fraction of CECs discharged through the biological treatment effluent were generally within ten-fold difference from the measured results, highlighting its potential for estimating CEC removal in WWTPs.


Assuntos
Nitrogênio , Eliminação de Resíduos Líquidos , Águas Residuárias , Poluentes Químicos da Água , Poluentes Químicos da Água/análise , Nitrogênio/análise , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias/química , Águas Residuárias/análise
5.
Ecotoxicol Environ Saf ; 280: 116513, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38820820

RESUMO

In Canada, every day, contaminants of emerging concern (CEC) are discharged from waste treatment facilities into freshwaters. CECs such as pharmaceutical active compounds (PhACs), personal care products (PCPs), per- and polyfluoroalkyl substances (PFAS), and microplastics are legally discharged from sewage treatment plants (STPs), water reclamation plants (WRPs), hospital wastewater treatment plants (HWWTPs), or other forms of wastewater treatment facilities (WWTFs). In 2006, the Government of Canada established the Chemicals Management Plan (CMP) to classify chemicals based on a risk-priority assessment, which ranked many CECs such as PhACs as being of low urgency, therefore permitting these substances to continue being released into the environment at unmonitored rates. The problem with ranking PhACs as a low priority is that CMP's risk management assessment overlooks the long-term environmental and synergistic effects of PhAC accumulation, such as the long-term risk of antibiotic CEC accumulation in the spread of antibiotic resistance genes. The goal of this review is to specifically investigate antibiotic CEC accumulation and associated environmental risks to human and environmental health, as well as to determine whether appropriate legislative strategies are in place within Canada's governance framework. In this research, secondary data on antibiotic CEC levels in Canadian and international wastewaters, their potential to promote antibiotic-resistant residues, associated environmental short- and long-term risks, and synergistic effects were all considered. Unlike similar past reviews, this review employed an interdisciplinary approach to propose new strategies from the perspectives of science, engineering, and law.


Assuntos
Antibacterianos , Poluentes Químicos da Água , Antibacterianos/análise , Canadá , Humanos , Poluentes Químicos da Água/análise , Monitoramento Ambiental/métodos , Medição de Risco , Saúde Ambiental , Águas Residuárias/química , Eliminação de Resíduos Líquidos/métodos
6.
Photochem Photobiol Sci ; 22(3): 603-613, 2023 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-36374373

RESUMO

Photo-Fenton processes activated by biodegradable Fe(III)-EDDS complexes have attracted huge attention from the scientific community, but the operative mechanism of the photo-activation of H2O2 in the presence of Fe(III)-EDDS has not been fully clarified yet. The application of the Fe(III)-EDDS complex in Fenton and photo-Fenton (mainly under UV-B light) processes, using 4-chlorophenol (4-CP) as a model pollutant was explored to give insights into the operative mechanism. Furthermore, the potential synergistic contribution of soybean peroxidase (SBP) was investigated, since it has been reported that upon irradiation of Fe(III)-EDDS the production of H2O2 can occur. SBP did not boost the 4-CP degradation, suggesting that the possibly produced H2O2 reacts immediately with the Fe(II) ion with a quick kinetics that does not allow the diffusion of H2O2 into the bulk of the solution (i.e., outside the solvent cage of the complex). So, a concerted mechanism in which the photochemically produced H2O2 and Fe(II) react inside the hydration sphere of the Fe(III)-EDDS complex is proposed.


Assuntos
Poluentes Ambientais , Poluentes Químicos da Água , Compostos Ferrosos , Peróxido de Hidrogênio/química , Ferro/química , Oxirredução , Peroxidase , Peroxidases , Glycine max
7.
Microb Ecol ; 85(4): 1448-1462, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-35507048

RESUMO

The practice of using recycled wastewater (RWW) has been successfully adopted to address the growing demand for clean water. However, chemicals of emerging concern (CECs) including pharmaceutical products remain in the RWW even after additional cleaning. When RWW is used to irrigate crops or landscapes, these chemicals can enter these and adjacent environments. Unfortunately, the overall composition and concentrations of CECs found in different RWW sources vary, and even the same source can vary over time. Therefore, we selected one compound that is found frequently and in high concentrations in many RWW sources, acetaminophen (APAP), to use for our study. Using greenhouse grown eggplants treated with APAP concentrations within the ranges found in RWW effluents, we investigated the short-term impacts of APAP on the soil bacterial population under agricultural settings. Using Illumina sequencing-based approaches, we showed that APAP has the potential to cause shifts in the microbial community most likely by positively selecting for bacteria that are capable of metabolizing the breakdown products of APAP such as glycosides and carboxylic acids. Community-level physiological profiles of carbon metabolism were evaluated using Biolog EcoPlate as a proxy for community functions. The Biolog plates indicated that the metabolism of amines, amino acids, carbohydrates, carboxylic acids, and polymers was significantly higher in the presence of APAP. Abundance of microorganisms of importance to plant health and productivity was altered by APAP. Our results indicate that the soil microbial community and functions could be altered by APAP at concentrations found in RWW. Our findings contribute to the knowledge base needed to guide policies regulating RWW reuse in agriculture and also highlight the need to further investigate the effects of CECs found in RWW on soil microbiomes.


Assuntos
Microbiota , Águas Residuárias , Solo/química , Acetaminofen/metabolismo , Irrigação Agrícola/métodos , Bactérias/genética , Produtos Agrícolas , Ácidos Carboxílicos/metabolismo , Microbiologia do Solo
8.
Environ Sci Technol ; 57(36): 13408-13418, 2023 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-37651547

RESUMO

Characterization of gestational exposure to complex contaminants of emerging concern (CECs) is critical to the identification of environmental risk factors for pregnancy complications. However, determination of various CECs with diverse physicochemical properties in biological fluids is technically challenging. In the present study, we developed a target exposome protocol, consisting of simple liquid-liquid extraction-based sample preparation and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, to determine 325 CECs covering 11 subclasses, including poly- and perfluoroalkyl substances, organophosphate esters, ultraviolet (UV) stabilizers, synthetic antioxidants, phthalate esters, and several others. The protocol exhibits exceptional advantages over traditional approaches in the coverage of chemicals, sample volume demand, and time and financial cost. The protocol was applied in a prospective nested gestational diabetes mellitus (GDM) study including 120 cases and 240 matched healthy controls. Thirty-three CECs were detected in >70% of the samples, with a combined concentration of 17.0-484.7 ng/mL. Bayesian kernel machine regression analysis showed that exposure to the CEC mixture was significantly associated with a higher GDM risk. For example, when increasing all CECs in the mixture from 50th percentile to 75th percentile, the estimated probit of GDM incidence had an increase of 92% (95% CI: 56%, 127%). Meanwhile, perfluorohexanesulfonic acid, 1,3-diphenylguanidine, and dibutyl fumarate were identified as the key CECs driving the joint effect. This work demonstrates great potential of our target exposome protocol for environmental risk factor identification in large-scale epidemiology or biomonitoring studies.


Assuntos
Diabetes Gestacional , Expossoma , Feminino , Gravidez , Humanos , Diabetes Gestacional/epidemiologia , Teorema de Bayes , Cromatografia Líquida , Estudos Prospectivos , Espectrometria de Massas em Tandem , Ésteres
9.
Environ Sci Technol ; 57(1): 360-374, 2023 01 10.
Artigo em Inglês | MEDLINE | ID: mdl-36512803

RESUMO

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.


Assuntos
Poluentes Ambientais , Fluorocarbonos , Orca , Animais , Monitoramento Ambiental/métodos , Ecossistema , Cromatografia Líquida , Espectrometria de Massas em Tandem
10.
Environ Sci Technol ; 57(15): 6063-6071, 2023 04 18.
Artigo em Inglês | MEDLINE | ID: mdl-36988440

RESUMO

Pharmaceuticals have been detected at high concentrations in municipal solid waste (MSW) landfill leachates, which are recognized as an underestimated source of pharmaceutical residues in the environment. However, limited efforts have been made to characterize pharmaceuticals in MSW landfill refuse, which is also of significant concern given the potential long-term environmental impact. Herein, we excavated landfill refuse from six cells with landfill ages of 7-27 years in the largest MSW landfill in Shanghai (in each cell, landfill refuse was collected from different depths of 2-8 m) and analyzed samples for the presence of 55 pharmaceuticals, including antibiotics and non-antibiotics. The results reveal the presence of 42 pharmaceuticals in landfill refuse, with median concentrations ranging from 0.30 to 116 µg/kg. Antibiotic and non-antibiotic pharmaceuticals exhibited diverse concentration trends with age, related to changes in policy intervention and consumption over time. Different concentration variations of individual pharmaceuticals were observed in refuse samples excavated at different depths and positively correlated to their sorption ability. The mass of pharmaceuticals in the investigated landfill was estimated from the obtained concentrations to be 80-220 tons with 95% probability, based on Monte Carlo analysis. To the best of our knowledge, this study provides the first estimate of pharmaceutical mass in an MSW landfill. The results will be helpful for understanding the potential long-term environmental impact of pharmaceuticals in landfills.


Assuntos
Eliminação de Resíduos , Resíduos Sólidos , Eliminação de Resíduos/métodos , China , Antibacterianos , Instalações de Eliminação de Resíduos , Preparações Farmacêuticas
11.
Environ Sci Technol ; 57(2): 1049-1059, 2023 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-36580485

RESUMO

The antidiabetic drug Metformin (MET), one of the most prevalent pharmaceuticals in the environment, is currently detected in surface waters in the range of ng/L to low µg/L. As current knowledge regarding the long-term effects of environmentally relevant concentrations of MET in nontarget organisms is limited, the present study aimed at investigating the generational effects of MET, in concentrations ranging from 390 to 14 423 ng/L in the model organism Danio rerio (up to 9 mpf), including the effects on its nonexposed offspring (until 60 dpf). We integrate several apical end points, i.e., embryonic development, survival, growth, and reproduction, with qRT-PCR and RNA-seq analyses to provide additional insights into the mode of action of MET. Reproductive-related parameters in the first generation were particularly sensitive to MET. MET parental exposure impacted critical molecular processes involved in the metabolism of zebrafish males, which in turn affected steroid hormone biosynthesis and upregulated male vtg1 expression by 99.78- to 155.47-fold at 390 and 14 432 MET treatment, respectively, pointing to an estrogenic effect. These findings can potentially explain the significant decrease in the fertilization rate and the increase of unactivated eggs. Nonexposed offspring was also affected by parental MET exposure, impacting its survival and growth. Altogether, these results suggest that MET, at environmentally relevant concentrations, severely affects several biological processes in zebrafish, supporting the urgent need to revise the proposed Predicted No-Effect Concentration (PNEC) and the Environmental Quality Standard (EQS) for MET.


Assuntos
Metformina , Poluentes Químicos da Água , Animais , Masculino , Estrogênios , Metformina/toxicidade , Reprodução , Fatores de Risco , Poluentes Químicos da Água/toxicidade , Peixe-Zebra
12.
J Sep Sci ; 46(1): e2200282, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36337037

RESUMO

In toxicological analysis, the analytical validation method is important to assess the exact risk of contaminants of emerging concern in the environment. Syringe filters are mainly used to remove impurities from sample solutions. However, the loss of analyte to the syringe filter could be considerable, causing an underestimate of the analyte concentrations. The current study develops and validates simultaneous liquid chromatography-mass spectrometry analysis using a direct filtration method to detect four groups of contaminants of emerging concern. The adsorption of the analyte onto three different matrices and six types of syringe filters is reported. The lowest adsorption of analytes was observed in methanol (16.72%), followed by deionized water (48.19%) and filtered surface lake water (48.94%). Irrespective of the type of the matrices, the lowest average adsorption by the syringe filter was observed in the 0.45 µm polypropylene membrane (15.15%), followed by the 0.20 µm polypropylene membrane (16.10%), the 0.20 µm regenerated cellulose (16.15%), the 0.20 µm polytetrafluoroethylene membrane (47.38%), the 0.45 µm nylon membrane (64.87%) and the 0.20 µm nylon membrane (71.30%). In conclusion, the recommended syringe filter membranes for contaminants of emerging concern analysis are polypropylene membranes and regenerated cellulose, regardless of the matrix used.


Assuntos
Nylons , Polipropilenos , Nylons/análise , Cromatografia Líquida , Filtração , Espectrometria de Massas , Água/análise
13.
J Environ Manage ; 330: 117153, 2023 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-36603246

RESUMO

Estimating the emissions of chemical pollutants to water is a fundamental step for the development and application of effective and sustainable management strategies of water resources, but methods applied so far to build chemicals inventories at the European or national scale show several limitations when applied at the local scale. The issue is particularly relevant when considering contaminants of emerging concern (CECs), whose environmental releases and occurrence are still poorly studied and understood. In this work, an approach to estimate water emissions of nine active pharmaceutical ingredients (APIs) and ten most applied plant protection products (PPPs) is presented, considering proxy indicators (e.g., sales data and census information). The application area is the lagoon of Venice (Italy), a complex transitional environment highly influenced by anthropic pressures (e.g., agricultural and industrial activities, animal breeding, and wastewater discharge). The presented approach can be tailored to the information available for any local scale case study. Data on annual regional sales of PPPs and APIs were integrated with georeferenced demographic and economic statistics (such as census and land-use information) to estimate chemicals emissions to surface water and groundwater. A sensitivity and uncertainty analysis identified the main factors affecting emissions estimates, and those contributing more significantly to results uncertainty. Results showed the highest estimated emissions of APIs for antibiotics (i.e., amoxicillin, clarithromycin, azithromycin, and ciprofloxacin) used for humans and animals, while most of hormones' emission (i.e., 17- α-ethinylestradiol and 17-ß-estradiol) derived from animal breeding. Regarding PPPs, glyphosate and imidacloprid emissions were one to two orders of magnitude higher compared to the other chemicals. Uncertainty and sensitivity analysis showed that the variability of each parameter used to estimate emissions depends greatly both on the target chemical and the specific emission source considered. Excretion rates and removal during wastewater treatment were major key parameters for all the target pharmaceutical compounds, while for PPPs the key parameter was their loss into the natural waters after application.


Assuntos
Poluentes Químicos da Água , Humanos , Animais , Poluentes Químicos da Água/química , Monitoramento Ambiental/métodos , Águas Residuárias , Água/análise , Preparações Farmacêuticas
14.
Molecules ; 28(23)2023 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-38067644

RESUMO

Contaminants of Emerging Concern (CECs), a new category of contaminants currently in the limelight, are a major issue of global concern. The pervasive nature of CECs and their harmful effects, such as cancer, reproductive disorders, neurotoxicity, etc., make the situation alarming. The perilous nature of CECs lies in the fact that even very small concentrations of CECs can cause great impacts on living beings. They also have a nature of bioaccumulation. Thus, there is a great need to have efficient sensors for the detection of CECs to ensure a safe living environment. Electrochemical sensors are an efficient platform for CEC detection as they are highly selective, sensitive, stable, reproducible, and prompt, and can detect very low concentrations of the analyte. Major classes of CECs are pharmaceuticals, illicit drugs, personal care products, endocrine disruptors, newly registered pesticides, and disinfection by-products. This review focusses on CECs, including their sources and pathways, health effects caused by them, and electrochemical sensors as reported in the literature under each category for the detection of major CECs.


Assuntos
Praguicidas , Poluentes Químicos da Água , Poluentes Químicos da Água/análise , Praguicidas/análise , Monitoramento Ambiental
15.
Molecules ; 28(3)2023 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-36770833

RESUMO

Diverse reducing mediators have often been used to increase the degradation of emerging pollutants (EPs) and dyes through the Fenton reaction (Fe2+ + H2O2 → Fe3+ + HO● + HO-). Adding reductants can minimize the accumulation of Fe3+ in a solution, leading to accelerated Fe2+ regeneration and the enhanced generation of reactive oxygen species, such as the HO● radical. The present study consisted in reviewing the effects of gallic acid (GA), a plant-extracted reductant, on the Fenton-based oxidation of several EPs and dyes. It was verified that the pro-oxidant effect of GA was not only reported for soluble iron salts as a catalyst (homogeneous Fenton), but also iron-containing solid materials (heterogeneous Fenton). The most common molar proportion verified in the studies was catalyst:oxidant:GA equal to 1:10-20:1. This shows that the required amount of both catalyst and GA is quite low in comparison with the oxidant, which is generally H2O2. Interestingly, GA has proven to be an effective mediator at pH values well above the ideal range of 2.5-3.0 for Fenton processes. This allows treatments to be carried out at the natural pH of the wastewater. The use of plant extracts or wood barks containing GA and other reductants is suggested to make GA-mediated Fenton processes easier to apply for treating real wastewater.

16.
Molecules ; 28(16)2023 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-37630246

RESUMO

Endocrine-disrupting compounds (EDCs) constitute a wide variety of chemistries with diverse properties that may/can pose risks to both humans and the environment. Herein, a total of 26 compounds, including steroids, flame retardants, and plasticizers, were monitored in three major and heavily urbanized river catchments: the R. Liffey (Ireland), the R. Thames (UK), and the R. Ter (Spain), by using a single solid-phase extraction liquid chromatography-mass spectrometry (SPE-LC-MS/MS) method. Occurrence and frequency rates were investigated across all locations over a 10-week period, with the highest concentration obtained for the flame retardant tris(2-chloroethyl) phosphate (TCEP) at 4767 ng∙L-1 in the R. Thames in Central London. Geographical variations were observed between sites and were partially explained using principal component analysis (PCA) and hierarchical cluster analysis (HCA). In particular, discrimination between the R. Ter and the R. Thames was observed based on the presence and concentration of flame retardants, benzotriazole, and steroids. Environmental risk assessment (ERA) across sites showed that caffeine, a chemical marker, and bisphenol A (BPA), a plasticizer, were classified as high-risk for the R. Liffey and R. Thames, based on relative risk quotients (rRQs), and that caffeine was classified as high-risk for the R. Ter, based on RQs. The total risks at each location, namely ΣRQriver, and ΣrRQriver, were: 361, 455, and 723 for the rivers Liffey, Thames, and Ter, respectively. Caffeine, as expected, was ubiquitous in all 3 urban areas, though with the highest RQ observed in the R. Ter. High contributions of BPA were also observed across the three matrices. Therefore, these two compounds should be prioritized independently of location. This study represents a comprehensive EDC monitoring comparison between different European cities based on a single analytical method, which allowed for a geographically independent ERA prioritization to be performed.


Assuntos
Disruptores Endócrinos , Retardadores de Chama , Humanos , Irlanda , Espanha , Cafeína , Cromatografia Líquida , Rios , Espectrometria de Massas em Tandem , Medição de Risco , Plastificantes , Reino Unido
17.
Molecules ; 28(6)2023 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-36985414

RESUMO

Although heterogeneous photocatalysis has shown promising results in degradation of contaminants of emerging concern (CECs), the mechanistic implications related to structural diversity of chemicals, affecting oxidative (by HO•) or reductive (by O2•-) degradation pathways are still scarce. In this study, the degradation extents and rates of selected organics in the absence and presence of common scavengers for reactive oxygen species (ROS) generated during photocatalytic treatment were determined. The obtained values were then brought into correlation as K coefficients (MHO•/MO2•-), denoting the ratio of organics degraded by two occurring mechanisms: oxidation and reduction via HO• and O2•-. The compounds possessing K >> 1 favor oxidative degradation over HO•, and vice versa for reductive degradation (i.e., if K << 1 compounds undergo reductive reactions driven by O2•-). Such empirical values were brought into correlation with structural features of CECs, represented by molecular descriptors, employing a quantitative structure activity/property relationship (QSA/PR) modeling. The functional stability and predictive power of the resulting QSA/PR model was confirmed by internal and external cross-validation. The most influential descriptors were found to be the size of the molecule and presence/absence of particular molecular fragments such as C - O and C - Cl bonds; the latter favors HO•-driven reaction, while the former the reductive pathway. The developed QSA/PR models can be considered robust predictive tools for evaluating distribution between degradation mechanisms occurring in photocatalytic treatment.

18.
Molecules ; 28(6)2023 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-36985622

RESUMO

The removal of four Contaminants of Emerging Concern, namely bisphenol A, sulfamethoxazole, diclofenac and benzotriazole; two odorous compounds, geosmin and 2-methylisoborneol, frequently detected in recirculating aquaculture systems; and Hg(II) was investigated using ZnO-based materials doped or co-doped with Ce and Cu under simulated solar radiation. Photocatalysts were synthetized via a hydrothermal route and their efficiency was assessed by changing some operational parameters in different water matrices of increasing complexity. The mixture of contaminants was successfully degraded in just 1 h, while the complete mineralization was achieved in a few hours; experiments performed in an actual aquaculture water confirmed the efficiency and broad versatility of the synthesized materials.

19.
Molecules ; 28(20)2023 Oct 13.
Artigo em Inglês | MEDLINE | ID: mdl-37894551

RESUMO

In temperate environments, climate change could affect water pH by inducing enhanced dissolution of CaSO4 followed by biological sulphate reduction, with the potential to basify water due to H+ consumption. At the same time, increased atmospheric CO2 could enhance weathering of carbonate rocks (e.g., dolomite) and increase the total concentration of dissolved carbonate species. Both processes enhance phototransformation by the carbonate radical (CO3•-), as shown for the non-steroidal anti-inflammatory drug paracetamol, provided that the dissolved organic carbon of water does not undergo important fluctuations. Climate change could also affect hydrology, and prolonged drought periods might considerably decrease flow rates in rivers. This is a substantial problem because wastewater pollutants become less diluted and, as a result, can exert more harmful effects due to increased concentrations. At the same time, in low-flow conditions, water is also shallower and its flow velocity is decreased. Photochemical reactions become faster because shallow water is efficiently illuminated by sunlight, and they also have more time to occur because water takes longer to cover the same river stretch. As a result, photodegradation of contaminants is enhanced, which offsets lower dilution but only at a sufficient distance from the wastewater outlet; this is because photoreactions need time (which translates into space for a flowing river) to attenuate pollution.

20.
Environ Sci Technol ; 56(14): 10131-10140, 2022 07 19.
Artigo em Inglês | MEDLINE | ID: mdl-35786931

RESUMO

Fluorescent brighteners (FBs) are extensively used as important chemical additives in multiple industrial fields worldwide. The history of the use of global FBs spans over 60 years, but knowledge on their environmental occurrence and risks remains largely unknown. Here, we screened indoor dust and hand wipes from South China for a broad suite of 17 emerging FBs using a new comprehensive analytical method. All 17 FBs were detected in the indoor environment for the first time, most of them having been rarely investigated or never reported in prior environmental studies. Ionic FBs were found to be more abundant than nonionic ones. The median total concentrations of the 17 detectable FBs reached 11,000 ng/g in indoor dust and 2640 ng/m2 in hand wipes, comparable to or higher than those of well-known indoor pollutants. Human exposure assessment indicated that hand-to-mouth contact is a significant pathway for exposure to FBs, with a comparable contribution to that of dust ingestion. Most of the newly identified FBs are predicted to have persistent, bioaccumulative, or toxic properties. Our work demonstrates that FBs are another class of highly abundant, hazardous, and ubiquitous indoor pollutants that have been overlooked for decades and points to an emerging concern.


Assuntos
Poluição do Ar em Ambientes Fechados , Poluentes Ambientais , Retardadores de Chama , Poluição do Ar em Ambientes Fechados/análise , China , Poeira/análise , Exposição Ambiental/análise , Monitoramento Ambiental/métodos , Retardadores de Chama/análise , Humanos
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