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The monitoring of organic compounds in aquatic matrices poses challenges due to its complexity and time-intensive nature. To address these challenges, we introduce a novel approach utilizing a dual-channel mono (1D) and comprehensive two-dimensional (2D) gas chromatography coupled with time-of-flight mass spectrometry (GC × GC-TOFMS) system, integrated with a robotic pretreatment platform, for online monitoring of both volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) in water matrices. Employing the robotic platform, we establish a suite of online liquid-liquid extraction (LLE) pretreatment processes for water samples, marking the first instance of such procedures. Leveraging the automatic headspace (HS) module, dual robotic preparations of HS and LLE are sequentially executed to extract VOCs and SVOCs from water matrices. The GC × GC-TOFMS system is distinguished by its dual-channel analytical column configuration, facilitating sequential analysis of VOCs in GC-TOFMS mode and SVOCs in GC × GC-TOFMS mode. Quantitative detection of 55 target VOCs and 104 SVOCs is achieved in a water sample using the instrument system. Our method demonstrates excellent correlation coefficients ranging from 0.990 to 1.000, method detection limits ranging from 0.08 to 4.78 µg L-1, relative standard deviations below 19.3 %, and recovery rates ranging from 50.0 % to 124.0 %. To validate the online monitoring capabilities of our system, we assess target SVOCs at three different concentration levels over a 3-day period. Most compounds exhibit recovery rates ranging from 70.0 % to 130.0 %. Furthermore, we apply our method to analyze a real water sample, successfully identifying over 100 target and nontarget VOCs/SVOCs, including alcohols, aldehydes, ketones, acids, esters, and phenols. These results highlight the efficacy of the proposed analysis system, capable of conducting two distinct analyses in automatic sequence, thereby enhancing the efficiency and accuracy of organic compound analysis in water matrices.
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Cromatografía de Gases y Espectrometría de Masas , Extracción Líquido-Líquido , Robótica , Compuestos Orgánicos Volátiles , Compuestos Orgánicos Volátiles/análisis , Compuestos Orgánicos Volátiles/aislamiento & purificación , Cromatografía de Gases y Espectrometría de Masas/métodos , Extracción Líquido-Líquido/métodos , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/aislamiento & purificación , Límite de DetecciónRESUMEN
Polyfluoroalkyl phosphate esters (PAPs) are a group of emerging alternatives to the legacy per- and polyfluoroalkyl substances (PFAS). To better understand the transport and risk of PAPs in the water cycle, 21 PFAS including 4 PAPs and 17 perfluoroalkyl acids were investigated in multiple waterbodies in an urban area, China. PFAS concentrations ranged from 85.8 to 206 ng/L, among which PAPs concentrations ranged from 35.0 to 71.8 ng/L, in river and lake water with major substances of perfluorooctanoic acid (PFOA), 6:2 fluorotelomer phosphate (6:2 monoPAP), and 8:2 fluorotelomer phosphate (8:2 monoPAP). As transport pathways, municipal wastewater and precipitation were investigated for PFAS mass loading estimation, and PAPs transported via precipitation more than municipal wastewater discharge. Concentrations of PFAS in tap water and raw source water were compared, and PAPs cannot be removed by drinking water treatment. In tap water, PFAS concentrations ranged from 132 to 271 ng/L and among them PAPs concentrations ranged from 41.6 to 61.9 ng/L. Human exposure and health risk to PFAS via drinking water were assessed, and relatively stronger health risks were induced from PFOS, PAPs, and PFOA. The environmental contamination and health risk of PAPs are of concern, and management implications regarding their sources, exposure, and hazards were raised.
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Ácidos Alcanesulfónicos , Agua Potable , Fluorocarburos , Contaminantes Químicos del Agua , Humanos , Aguas Residuales , Ciclo Hidrológico , Contaminantes Químicos del Agua/análisis , Fosfatos , Fluorocarburos/análisis , ChinaRESUMEN
The increasing applications of emerging per- and polyfluoroalkyl substances (PFAS) have raised global concern. However, the release of emerging PFAS from the fluorochemical industry remains unclear. Herein, the occurrence of 48 emerging and legacy PFAS in wastewater from 10 fluorochemical manufacturers and mass flows of PFAS in a centralized wastewater treatment plant were investigated. Their distribution and ecological risk in neighboring riverine water were also evaluated. In wastewater from fluorochemical manufacturers, PFAS concentrations were in the range of 14,700-5200,000 ng/L and 2 H,2 H-perfluorooctanoic acid (6:2 FTCA), perfluorooctanoic acid (PFOA), N-ethyl perfluorooctane sulfonamide (N-EtFOSA), and 1 H,1 H,2 H,2 H-perfluorodecanesulfonate (8:2 FTS) were the major PFAS detected. Several PFAS displayed increased mass flows after wastewater treatment, especially PFOA and 6:2 FTCA. The mass flows of PFAS increased from - 20% to 233% after the activated sludge system but decreased by only 0-13% after the activated carbon filtration. In riverine water, PFAS concentrations were in the range of 5900-39,100 ng/L and 6:2 FTCA, 1 H,1 H,2 H,2 H-perfluorodecyl phosphate monoester (8:2 monoPAP), 1 H,1 H,2 H,2 H-perfluorooctyl phosphate monoester (6:2 monoPAP), PFOA, and perfluorohexanoic acid (PFHxA) were the major PFAS detected. PFOA and 6:2 FTCA exhibited comparable hazard quotients for ecological risk. Current wastewater treatment processes cannot fully remove various PFAS discharged by fluorochemical manufacturers, and further investigations on their risk are needed for better chemical management.
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In this study, a new methodology for evaluating full-scale landfill leachate treatment processes by non-targeted analysis using comprehensive two-dimensional gas chromatography quadrupole time-of-flight mass spectrometry (GC × GC-QTOF-MS) was proposed. The method revealed the chemical complexity of organic compounds in landfill leachate samples at the molecular level and evaluated the removal efficiency of the anaerobic-anoxic-oxic (A2O) - membrane bioreactor (MBR) - nanofiltration (NF) treatment process in conjunction with multi-level classification of organic compounds. Results showed that the results of non-targeted analysis combined with multi-level classification of organic compounds had a significant correlation with the conventional water quality parameters and can be used to evaluate the treatment process. A total of 2508 organic compounds were detected in 6 samples. 17 emerging contaminants (ECs) with known potentially hazards were detected, including Diisobutyl Phthalate (DIBP), which is toxic to male reproduction and development, and 4-Tert-Butylphenol, which causes endocrine disruption in animals. The removal rate of organic compounds by this full-scale landfill leachate treatment processes reached 79.14%. The anaerobic tank played a crucial role with 64.98% contribution. For compounds, the removal rate of heterocyclics was as high as 94.67%, and the removal rate of aliphatics was poor, only 63.49%. This treatment process had almost perfect removal effect on the steroids in alicyclics and phenols in aromatics, but poor treatment effect on saturated alkanes in aliphatics and naphthenes in alicyclics. This study provides a methodology for accurate assessment of the molecular level of treatment processes, new insights for process optimization in waste treatment plants, and data support for the detection of emerging contaminants. The environmental hazards of landfill leachate can be further evaluated in the future in conjunction with ecotoxicity assessment studies.
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Contaminantes Químicos del Agua , Animales , Contaminantes Químicos del Agua/análisis , Cromatografía de Gases y Espectrometría de Masas , Compuestos Orgánicos , Reactores BiológicosRESUMEN
Nowadays, the prevalence of metabolic syndromes (MSs) has attracted increasing concerns as it is closely related to overweight and obesity, physical inactivity and overconsumption of energy, making the diagnosis and real-time monitoring of the physiological range essential and necessary for avoiding illness due to defects in the human body such as higher risk of cardiovascular disease, diabetes, stroke and diseases related to artery walls. However, the current sensing techniques are inconvenient and do not continuously monitor the health status of humans. Alternatively, the use of recent wearable device technology is a preferable method for the prevention of these diseases. This can enable the monitoring of the health status of humans in different health domains, including environment and structure. The use wearable devices with the purpose of facilitating rapid treatment and real-time monitoring can decrease the prevalence of MS and long-time monitor the health status of patients. This review highlights the recent advances in wearable sensors toward continuous monitoring of blood pressure and blood glucose, and further details the monitoring of abnormal obesity, triglycerides and HDL. We also discuss the challenges and future prospective of monitoring MS in humans.
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Enfermedades Metabólicas , Humanos , Arterias , Glucemia , Presión Sanguínea , Obesidad/diagnósticoRESUMEN
Accelerated urbanization and industrialization have led to an alarming increase in the generation of wastewater with complex chemical contents. Industrial wastewaters are often a primary source of water contamination. The chemical characterization of different industrial wastewater types is an essential task to interpret the chemical fingerprints of wastewater to identify pollution sources and develop efficient water treatment strategies. In this study, we conduct a non-target chemical analysis for the source characterization of different industrial wastewater samples collected from a chemical industrial park (CIP) located in southeast China. The chemical screening identified volatile and semi-volatile organic compounds that included dibutyl phthalate at a maximum concentration of 13.4 µg/L and phthalic anhydride at 35.9 µg/L. Persistent, mobile, and toxic (PMT) substances among the detected organic compounds were identified and prioritized as high-concern contaminants given their impact on drinking water resources. Moreover, a source analysis of the wastewater collected from the wastewater outlet station indicated that the dye production industry contributed the largest quantities of toxic contaminates (62.6%), and this result was consistent with the ordinary least squares and heatmap results. Thus, our study utilized a combined approach of a non-target chemical analysis, a pollution source identification method, and a PMT assessment of different industrial wastewater samples collected from the CIP. The results of the chemical fingerprints of different industrial wastewater types as well as the results of the PMT assessment benefit risk-based wastewater management and source reduction strategies.
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Contaminantes Ambientales , Compuestos Orgánicos Volátiles , Contaminantes Químicos del Agua , Contaminantes Ambientales/análisis , Aguas Residuales , Contaminantes Químicos del Agua/análisis , ChinaRESUMEN
Currently, the pharmaceutical and personal care products (PPCPs) have posed great challenge to advanced oxidation techniques (AOTs). In this study, we decorated sponge iron (s-Fe0) with Cu and Pd (s-Fe0-Cu-Pd) and further optimized the synthesis parameters with a response surface method (RSM) to rapidly degrade diclofenac sodium (DCF). Under the RSM-optimized conditions of Fe: Cu: Pd = 100: 4.23: 0.10, initial solution pH of 5.13, and input dosage of 38.8 g/L, 99% removal of DCF could be obtained after 60 min of reaction. Moreover, the morphological structure of trimetal was characterized with high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS). Electron spin resonance (ESR) signals have also been applied to capture reactive hydrogen atoms (H*), superoxygen anions, hydroxyl radicals, and single state oxygen (1O2). Furthermore, the variations of DCF and its selective degradation products over a series of s-Fe0-based bi(tri)metals have been compared. Additionally, the degradation mechanism of DCF has also been explored. To our best knowledge, this is the first report revealing the selective dechlorination of DCF with low toxicity over Pd-Cu co-doped s-Fe0 trimetal.
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Hierro , Contaminantes Químicos del Agua , Hierro/química , Diclofenaco/química , Aniones , Oxidación-Reducción , Contaminantes Químicos del Agua/análisisRESUMEN
A variety of chemicals discharged into the aquatic environment by the wastewater treatment plant (WWTP), which is a potential source of hazard to the ecological environment and human health. This study established a novel analytical method for all compounds using non-targeted screening to comprehensively explore the fate and transport of organic compounds from WWTP to aquatic environment. 3967 and 3636 features were detected in WWTP samples and river samples, respectively. Multi-level classification was applied to all identified compounds, and results showed that aliphatics were dominant in both abundance and response, accounting for an average of 35.49 % and 74.10 %, respectively. A total of 88 Emerging Contaminants (ECs), including 22 endocrine disrupting chemicals (EDCs), 12 pharmaceuticals and personal care products (PPCPs), 12 pesticides, 10 volatile organic compounds (VOCs), 5 persistent organic pollutants (POPs) and 27 chemicals with other uses, were identified from all compounds, and their traceability analysis was performed. Furthermore, the contribution rate of organic compounds from WWTP effluent to river was calculated to be 33.60 % by the analysis of source-sink relationship. An in-depth and comprehensive exploration of the fate and transport of all organic compounds will help to provide guidelines for the treatment technologies and achieve the traceability of pollutants.
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Contaminantes Químicos del Agua , Purificación del Agua , Humanos , Eliminación de Residuos Líquidos/métodos , Contaminantes Químicos del Agua/análisis , Compuestos Orgánicos , Purificación del Agua/métodos , Aguas Residuales , Monitoreo del Ambiente/métodos , Preparaciones FarmacéuticasRESUMEN
Sulfate radical (SO4â-) based advanced oxidation is considered as a promising pretreatment strategy to degrade organic pollutants and thereby mitigate the membrane fouling in the membrane process. In this study, heat-activated persulfate (PS) activation was integrated with the membrane distillation (MD) process for the alleviation of membrane fouling in treatment of wastewater treatment plant (WWTP) secondary effluent and surface water. In-depth understanding of the molecular fate during membrane fouling control process was performed by using a non-targeted screening method of two-dimensional gas chromatography-time-of-flight mass spectrometry (GC × GC-TOF-MS) coupling with multiple characterizations. It was found that the heat-activated PS activation pretreatment could effectively degrade the dissolved organic matter (DOM) and change its molecular conformation, wherein the relative abundance of oxygen-containing substances was remarkably increased through oxygenation reactions. Moreover, the refractory organics with higher molecular weight (MW) and unsaturation degree were more inclined to be destroyed, following by partial mineralization during pretreatment process. It was also identified that oxygen-deficient compounds and the molecular formulas featuring higher double bond equivalent (DBE) values and lower MW tended to be deposited on the membrane surface to cause the membrane fouling. In particular, the aliphatic substances were the predominant components irrespective of membrane foulant samples from secondary effluent or surface water. Meanwhile, the complexation between organic compounds and high valence cations as well as the precipitation of inorganics were restrained owing to the reduction of DOM concentration and the transformation of molecular structure, consequently leading to reduced membrane fouling. This study is believed to further provide new insight into the membrane fouling control mechanism at molecular level.
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Destilación , Purificación del Agua , Calor , Ultrafiltración/métodos , Membranas Artificiales , Purificación del Agua/métodos , Oxígeno , AguaRESUMEN
Robots replacing humans as the executioners is crucial work for intelligent multi-pesticide residue analysis to maximize reproducibility and throughput while minimizing the expertise required to perform the entire process. Traditional analysis methods are predicated on manual execution, so we configured our robot experimenter, automated the analytical workflow, and achieved the goal of robotics execution. Our robot experimenter with an X-Y-Z axis robotic arm was interfaced with seven modules and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for automated standard solution preparation, sample pre-treatment, and UPLC-MS/MS detection. An algorithm was established to make the prepared matrix-matched standard solutions meet the monitoring requirements. The strategy was demonstrated and validated for the detection of 325 pesticides in 4 typical food matrices, suggesting that the developed method is applicable for the analysis of pesticide residues in vegetables and tea as part of regulatory monitoring programs and other purposes.
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Residuos de Plaguicidas , Robótica , Humanos , Residuos de Plaguicidas/análisis , Cromatografía Liquida/métodos , Reproducibilidad de los Resultados , Cromatografía Líquida de Alta Presión/métodos , Espectrometría de Masas en Tándem/métodos , Contaminación de Alimentos/análisisRESUMEN
This work presents the temporal and spatial characteristics of the major air pollutants and their associated health risks in China from 2019 to 2020, by using the monitoring data from 367 cities. The annual average PM2.5, PM10, NO2, SO2, CO, and O3 concentrations decreased by 10.9%, 13.2%, 9.3%, 10.1%, 9.4%, and 5.5% from 2019 to 2020. National average PM2.5 concentration in 2020 met the standard of 35 µg/m3, and that of O3 decreased from 2019. COVID-19 lockdown affected NO2 level dramatically, yet influences on PM2.5 and O3 were less clear-cut. Positive correlations between PM2.5 and O3 were found, even in winter in all five key regions, e.g., Jing-Jin-Ji (JJJ), FenWei Plain (FWP), Yangtze River Delta (YRD), Pearl River Delta (PRD) and Chengdu-Chongqing Region (CCR), indicating importance of secondary production for both PM2.5 and O3. Large seasonal variability of PM2.5-SO2 correlation indicates a varying role of SO2 to PM2.5 pollution in different seasons; and generally weak correlations in winter between PM2.5 and NO2 or SO2 reveal the complexity of secondary formation processes to PM2.5 pollution in winter. Multilinear regression analysis between PM2.5 and SO2, NO2 and CO demonstrates that PM2.5 is more sensitive to the change of NO2 than SO2 in JJJ, FWP, PRD and CCR, suggesting a priority of NOx emission control for future PM2.5 reduction. Furthermore, the new World Health Organization Air Quality Guidelines (WHO AQG2021) were adopted to calculate the excess health risks (ER) as well as the health-risk based air quality index (HAQIWHO) of the pollutants. Such assessment points out the severity of air pollution associated health risks under strict standards: 40.0% of days had HAQIWHO>100, while only 14.4% days had AQI>100. PM2.5 ER was generally larger than O3 ER, but O3 ER in low PM2.5 region (PRD) and during summer became more serious. Notably, NO2 ER became even more important than PM2.5 due to its strict limit of WHO AQG2021. Overall, our results highlight the increasing importance of O3 in both air quality evaluation and health risk assessment, and the importance of coordinated mitigation of multiple pollutants (mainly PM2.5, O3 and NO2) in protecting the public health.
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Contaminantes Atmosféricos , Contaminación del Aire , COVID-19 , Contaminantes Atmosféricos/análisis , Contaminación del Aire/análisis , China , Ciudades , Control de Enfermedades Transmisibles , Monitoreo del Ambiente , Humanos , Dióxido de Nitrógeno/análisis , Material Particulado/análisisRESUMEN
In this work, Caenorhabditis elegans was employed as an in vivo model to determine the toxic effects of atrazine at different concentrations. After the exposure period from the larval stage L1 to adulthood day 1, atrazine (10 mg/L) significantly decreased the body length and lifespan of nematodes. In addition, exposure to ≥0.01 mg/L atrazine remarkably increased the intestinal reactive oxygen species (ROS) levels and reduced locomotion behavior of nematodes, while exposure to ≥ 1 mg/L atrazine decreased the brood size of nematodes. Moreover, atrazine (0.001-0.1 mg/L) upregulated the expression levels of hsp-6::GFP and hsp-6/60 in nematodes, indicating the activation of mitochondrial unfolded protein response (mtUPR). On the contrary, atrazine (1-10 mg/L) downregulated the expression levels of hsp-6::GFP and hsp-6/60 in nematodes. Furthermore, mtUPR induction governed by the RNAi knockdown of atfs-1 could increase the vulnerability of nematodes against atrazine toxicity. Overall, our findings highlighted the dynamic responses of nematodes toward different concentrations of atrazine, which could be monitored using different sublethal endpoints as bioindicators.
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Atrazina , Proteínas de Caenorhabditis elegans , Animales , Atrazina/toxicidad , Caenorhabditis elegans/genética , Caenorhabditis elegans/metabolismo , Proteínas de Caenorhabditis elegans/genética , Proteínas de Caenorhabditis elegans/metabolismo , Locomoción , Estrés Oxidativo , Especies Reactivas de OxígenoRESUMEN
Tetrabromobisphenol A (TBBPA) is a kind of brominated flame retardant that is usually added to products to reduce their flame retardancy. However, its extensive use has resulted in their residues being found in the environment, which is very harmful. Herein, an indirect competitive immunosensor has been established for TBBPA detection based on the signal amplification system. Pd nanospheres in situ reduced on the surface of MnO2 nanosheet hybrid (MnO2/Pd) was used as the label for the secondary antibody through the Pd-N bond, and gold-toluidine blue composite was loaded onto MWCNTs (MWCNTs/Au-TB), which functioned as the platform for the immunosensor. The spherical structure of Pd had abundant catalytic active sites, which enhanced the catalytic activity of MnO2/Pd as the label, hence amplifying the signal response. Besides, MWCNTs/Au-TB improved electron transfer and produced a strong signaling pathway for immobilizing antigens through the Au-NH2 bond, which can specifically recognize primary antibodies to improve sensitivity. The immunosensor had a linear concentration range of 0-81 ng/mL, a low detection limit of 0.17 ng/mL (S/N = 3), with good stability, selectivity, and reproducibility based on the above advantages. Additionally, the acceptable accuracy and recoveries (recoveries, 92-124%; CV, 3.3-8.8%) in the real water sample analysis indicated that this strategy is promising for emerging pollutant analysis.
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Cetrimonio/química , Técnicas Electroquímicas/métodos , Compuestos de Manganeso/química , Óxidos/química , Bifenilos Polibrominados/análisis , Contaminantes Químicos del Agua/análisis , Anticuerpos Inmovilizados/química , Técnicas Biosensibles/métodos , Inmunoensayo/métodos , Límite de Detección , Nanoestructuras/químicaRESUMEN
In the original publication of the article, there was an error in the name of institution. The incorrect name of institution "Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection, 8, Jiangwangmiao Road, XuanWu District, 210042 Nanjing, People's Republic of China" should be revised to "Nanjing Institute of Environmental Sciences, Ministry of Ecology and Environmental, 8, Jiangwangmiao Road, XuanWu District, 210042 Nanjing, People's Republic of China". The institution was still the same, but the name of the institution was changed.
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Indoor dust is an important route of exposure for organophosphate esters (OPEs), which are associated with adverse health effects. In the present study, the pollution occurrence and potential health risks of 13 OPEs in indoor dust from urban homes, college dormitories, and rural homes in Nanjing were investigated. Most OPEs were detected in the tested samples. College dormitories dust samples showed significantly higher OPEs concentrations (132.31-1.61 × 103 ng/g), followed by that in urban homes (31.42-49.84 ng/g) and rural homes (51.19-309.75 ng/g). The Mann-Whitney U test found no significant difference in the total concentrations of OPEs except for some individual OPEs between urban and rural homes. Tris (2-chloroisopropyl) phosphate (TCPP) was the most abundant compound in all tested areas. Spearman correlation coefficients and principal component analysis indicated that OPEs might originate from different sources in three microenvironments. Estimated exposures for adults and children in all indoor dust were below the relevant reference doses. Additionally, TCPP was the primary contributors to the non-carcinogenic risk, ranging from 1.07 × 10-6 to 2.20 × 10-5. Tris (2,3-dibromopropyl) phosphate was the dominant carcinogenic risk contributor in indoor dust, with a range of 1.33 × 10-11 to 8.74 × 10-10. These results suggested that the health risk of OPEs was within acceptable limits in the tested areas.
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Contaminación del Aire Interior/análisis , Retardadores de Llama/análisis , Niño , China , Polvo/análisis , Monitoreo del Ambiente , Ésteres/análisis , Humanos , Organofosfatos/análisis , Medición de RiesgoRESUMEN
OBJECTIVE: To develop a simple, fast and sensitive analytical method based on isotope dilution-headspace gas chromatography-mass spectrometry for the determination of 1, 4-dioxane residue in the aerosol cosmetics. METHODS: Sample was successive weighed and dissolved in 1, 3-dimehyl-2-imidazolidinone(DMI)solvent and isotope internal standard was added. Then transfered to a 20 mL headspace vial. The headspace vial was sealed and extracted 15 min by ultrasonic-assisted extraction. After separated by HP-5 MS fused silica capillary column(30 m×25 mm, 0. 25 µm), the compound was analyzed by gas chromatography-mass spectrometry in selected ion monitoring mode(GC-MS-SIM) and quantified by internal standard method. RESULTS: There were good linear correlations with R~2 no less than 0. 999 in the range of 1. 0-100 mg/kg. The limit of detection(LOD) of this method was 0. 3 mg/kg. At 0. 3, 1. 0, 5. 0 and 30 mg/kg four added concentration, recovery for five kinds of aerosol cosmetic were all between 91. 4% and 104. 2%. The relative standard deviations(RSDs) were 1. 5%-6. 3% and 1. 7%-6. 4%(n=6), respectively. CONCLUSION: The developed method has proved convenient, time-saving, accurate and sensitive and suited for determination 1, 4-dioxane in aerosol cosmetic.
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Cosméticos/análisis , Aerosoles , Dioxanos , Cromatografía de Gases y Espectrometría de Masas , Espectrometría de MasasRESUMEN
A method based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) with a small homemade mixed column was developed for the simultaneous determination of seven metabolites of organophosphate esters (OPEs) and 8-hydroxy-2'-deoxyguanosine (8-OHdG), an DNA oxidative damage marker, in urine. The urine samples were extracted by acetonitrile and enriched by the self-made column. All the samples were separated by gradient elution with acetonitrile-0.2% (v/v) ammonia solution, and then analyzed by an electrospray ionization source in negative ion multiple reaction monitoring mode. The results showed that the eight targets had good linearities in the range of 0.1-200 µg/L. The recoveries of the seven metabolites of OPEs and 8-OHdG in urine samples were in the ranges of 52.36% to 114.56% and 88.63% to 97.72%, respectively. The established method was successfully applied for the determination of the abovementioned eight target compounds in real urine samples, with the mass concentrations of the seven metabolites of OPEs and 8-OHdG being 6.24-46.07 µg/L and 5.90-16.71 µg/L, respectively. In addition, significant correlations were found between 8-OHdG and the total content of the seven metabolites of OPEs. The established method is simple, sensitive, accurate, and reproducible, and it provides reliable technical support for a more comprehensive evaluation of the level of human exposure to OPEs and the resulting health hazards.
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8-Hidroxi-2'-Desoxicoguanosina/orina , Ésteres/orina , Organofosfatos/orina , Cromatografía Líquida de Alta Presión , Humanos , Espectrometría de Masas en TándemRESUMEN
We explored the pollution characteristics, spatial and temporal distribution, ecological risk, and human health risk of organophosphate esters (OPEs) in the source water of the Nanjing section of the Yangtze River. Thirteen OPEs were determined by solid phase extraction-high performance liquid chromatography-tandem mass spectrometry. The results showed that twelve OPEs were detected to different extents with total concentrations ranging from 85.21 to 1557.96 ng·L-1[excluding tris (2,3-dibromopropyl) phosphate]. Chloroalkyl phosphate was the main compound and tris(2-chloroethyl) phosphate (TCEP) was the most abundant of the thirteen OPEs, which reached up to 447.08 ng·L-1. Seasonal variation of OPEs showed that the concentrations of OPEs in summer ranged from 220-1557.96 ng·L-1, with the average concentration of 493.78 ng·L-1 being 1.7-2.6 times higher than of that in spring and autumn. An ecological risk assessment showed that tricresyl phosphate and 2-ethylhexyl diphenyl phosphate were associated with moderate or high risks to organisms (algae, crustaceans, and fish). At a high exposure concentration, the total non-carcinogenic risk of OPEs in source water ranged from 4.41×10-3-2.91×10-2, with the highest risk being associated with children aged 0-3 months. The total cancer risk value was 5.88×10-7-3.89×10-6, among which TCEP and Tris(1,3-dichloro-2-propyl) phosphate was associated with a potential risk for children. We conclude that the long-term exposure risk for children of OPEs in the source water of the Nanjing section of the Yangtze River deserve more attention.
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Monitoreo del Ambiente , Retardadores de Llama/análisis , Organofosfatos/análisis , Ríos/química , Contaminantes Químicos del Agua/análisis , Animales , China , Ésteres/análisis , Humanos , Lactante , Recién Nacido , Medición de Riesgo , Estaciones del AñoRESUMEN
Occurrence characteristics of antibiotics in the source water of the Nanjing section of the Yangtze River were analyzed preliminarily by solid-phase extraction and high-performance liquid chromatography-tandem mass spectrometry (SPE-HPLC-MS/MS). The results showed that the cumulative concentration of 16 sampling points ranged from 13.37 ng·L-1 to 780.5 ng·L-1, with an average concentration of 92.95 ng·L-1. Four sulfonamides, three fluoroquinolones, one tetracycline, five macrolides, and one chloramphenicol antibiotic were detected with average concentration ranging from 0.14 ng·L-1 to 49.91 ng·L-1,including enrofloxacin (ERX) and clarithromycin (CLR) with the highest detection rate of 100%, and clindamycin (CLI) with the highest concentration of 739.44 ng·L-1. Overall, the concentration levels of antibiotics in the Nanjing section of the Yangtze River were low compared with other rivers and lakes in China. The risk assessment results showed that the largest cumulative risk of S2 was 0.31, and the environmental risk of sulfamethoxazole (SMX), doxycycline (DOX), and roxithromycin (ROX) had lower risk levels;the health risk indexes of nine antibiotics for different age groups were between 2.22×10-6and 4.86×10-3, while CLI and DOX are the main potential health risk factors for humans.
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Antibacterianos , Medición de Riesgo , Ríos , Contaminantes Químicos del Agua , China , Monitoreo del Ambiente , Humanos , Espectrometría de Masas en Tándem , AguaRESUMEN
A method was developed for the determination of five categories of 40 antibiotics in surface water by using solid-phase extraction-high performance liquid chromatography-tandem mass spectrometry (SPE-HPLC-MS/MS). The water samples were enriched and cleaned-up by filtration and with SPE cartridges. All antibiotics were separated by gradient elution with the mobile phase of 0.2% (v/v) formic acid aqueous solution and acetonitrile, and then analyzed with an electrospray ionization source in the positive ion and multiple reaction monitoring (MRM) modes. The results showed that the 40 antibiotics achieved great linearity in the range of 1-200 µg/L, and the average recoveries ranged from 41.3% to 112.6%. Using the developed method, thirteen antibiotics were identified in surface water from Nanjing section of the Yangtze River. The total antibiotic contents in the real samples ranged from 13.4 ng/L to 780.5 ng/L. The established method is efficient, sensitive and reliable, and is suitable for the determination of different antibiotics in real water samples.