RESUMEN
Pentachlorophenol (PCP), a persistent organic pollutant, has been banned in many countries, but it is still used in China as a wood preservative, molluscicide, or reagent for fish-pond cleaning, which may pose risks to the ecosystem and humans. However, data on the occurrence of PCP in the environment are scarce in the recent decade. The Yangtze River was regarded as a priority area of PCP pollution according to previous documents. This study aimed to examine the spatial distribution of PCP in the Yangtze River water, the differences in dry and wet seasons, the ecological risk for aquatic organisms, and its removal efficiency in tap water treatment plants. The river water samples (n = 144) were collected from the upper, middle, and lower reaches across ten provinces (or municipalities) in December 2020 and June 2021, respectively. PCP was detected in 88.9% of all the samples, ranging from Asunto(s)
Pentaclorofenol
, Contaminantes Químicos del Agua
, Humanos
, Animales
, Pentaclorofenol/análisis
, Ecosistema
, Contaminantes Químicos del Agua/análisis
, Monitoreo del Ambiente
, Ríos
, Ciudades
, China
, Medición de Riesgo
, Organismos Acuáticos
RESUMEN
Rapid industrial and agricultural developments in China have led to the wide use and discharge of chemical products and pesticides, resulting in extensive residues in environmental media. These residues can enter the human body through various pathways, leading to high exposure risks and health hazards. Because the human body is exposed to a variety of chemical pollutants, accurately quantifying the exposure levels of these pollutants in the human body and evaluating their health risks are of great importance. In this study, the serum concentrations of 97 typical chemical pollutants of 60 adults in central China were simultaneously determined using solid-phase extraction coupled with gas chromatography-tandem mass spectrometry (SPE-GC-MS/MS). In this method, 200 µL of a serum sample was mixed with 10 µL of an isotope-labeled internal standard solution. The sample was vortexed and refrigerated overnight at 4 â. Each sample was then deproteinized by the addition of 200 µL of 15% formic acid aqueous solution and vortexed. The serum sample was loaded into a preconditioned Oasis® PRiME HLB SPE cartridge and rinsed with 3 mL of methanol-water (6â¶1, v/v). The SPE cartridge was subsequently vacuumed. The analytes were eluted with 3 mL of dichloromethane followed by 3 mL of n-hexane. The eluent was concentrated to near dryness under a gentle nitrogen stream and reconstituted with 100 µL of acetone. The samples were determined by GC-MS/MS and separated on a DB-5MS capillary column (30 m×0.25 mm×0.25 µm) with temperature programming. The column temperature was maintained at 70 â for 2 min, increased at a rate of 25 â/min to 150 â, increased at a rate of 3 â/min to 200 â, and then held for 2 min. Finally, the column temperature was increased at a rate of 8 â/min to 300 â and maintained at this temperature for 8 min. The samples were detected in multiple-reaction monitoring (MRM) mode and quantitatively analyzed using the internal standard method. Multiple linear regression models were used to analyze the effects of demographic characteristics, lifestyle habits, and diet on the concentrations of the chemical pollutants in the serum samples, and known biomonitoring equivalents (BEs) and human biomonitoring (HBM) values were combined to compute hazard quotients (HQs) and hazard indices (HIs) and evaluate the health risks of single and cumulative exposures to the chemical pollutants. The results showed that the main pollutants detected in human serum were organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The detection rates of eight pollutants, including hexachlorobenzene (HCB) (100%), pentachlorophenol (PCP) (100%), p,p'-dichlorodiphenylene (p,p'-DDE) (100%), PCB-138 (100%), PCB-153 (98.3%), ß-hexachlorocyclohexane (ß-HCH) (91.7%), fluorene (Flu) (85.0%), and anthracene (Ant) (75.0%), were greater than 70%. The serum levels of ß-HCH were higher in females than in males, and age was positively correlated with exposure to p,p'-DDE, PCB-138, PCB-153, and ß-HCH. Increased exposure levels to p,p'-DDE and ß-HCH may be associated with a high frequency of meat intake, whereas increased exposure level to PCP may be associated with a high frequency of vegetable intake. The serum HQ of PCP was greater than 1 in 6.7% of the samples, and no risk was observed for HCB and p,p'-DDE exposure in the study population. Approximately 28.3% of the study subjects had HI values greater than 1. Overall, the general adult population in this region is widely exposed to a wide range of chemical pollutants, and gender, age, and diet are likely to be the main factors influencing the concentration of chemical pollutants. The health risk of single and compound exposures to chemical pollutants should not be ignored.
Asunto(s)
Contaminantes Ambientales , Hexaclorociclohexano , Hidrocarburos Clorados , Pentaclorofenol , Plaguicidas , Bifenilos Policlorados , Adulto , Masculino , Femenino , Humanos , Contaminantes Ambientales/análisis , Diclorodifenil Dicloroetileno/análisis , Diclorodifenil Dicloroetileno/metabolismo , Hexaclorobenceno/análisis , Espectrometría de Masas en Tándem , Monitoreo del Ambiente , Cromatografía de Gases y Espectrometría de Masas , Bifenilos Policlorados/análisis , Hidrocarburos Clorados/análisis , Plaguicidas/análisis , Pentaclorofenol/análisis , Medición de RiesgoRESUMEN
Pentachlorophenol (PCP) is a ubiquitous environmental contaminant commonly existing as its sodium salt (NaPCP), which enters the human body primarily through long term but low-level dietary exposure. PCP contributes to chemical carcinogenesis and teratogenesis. In this study, the probabilistic risk of dietary exposure to PCP in Guangzhou citizens was investigated. In total, 923 food samples in the categories of pork, livestock (beef and lamb), poultry, offal, eggs, and freshwater fish (considered to be relatively susceptible to PCP contamination) were collected from various markets in Guangzhou and tested for PCP. Probabilistic risk assessment model calculations for PCP dietary exposure and margin of exposure (MOE) values were performed using @RISK software, based on a Monte Carlo simulation with 10,000 iterations. The overall detection rate of PCP (above 1 µg kg-1, the detection limit) was 19.9% (184/923), with an average of 7.9 µg kg-1. The highest rate of PCP detection, 28.2%, was in livestock (beef and lamb). The MOE value for dietary PCP exposure in general Guangzhou residents averaged 400, which was far below 5,000 (the borderline for judging a health risk). The lowest MOE value, 190, was observed in the 3- to-6-year old population and indicates a significant risk. In conclusion, this study suggests that PCP exposure in Guangzhou residents is of considerable health risk, especially for the pre-school young children.
Asunto(s)
Pentaclorofenol , Niño , Bovinos , Preescolar , Humanos , Animales , Ovinos , Pentaclorofenol/análisis , Exposición Dietética/análisis , Medición de Riesgo , China , Modelos EstadísticosRESUMEN
Pentachlorophenol (PCP) has been widely used as an insecticide for killing oncomelania (the intermediate host of schistosome) in China and leads to severe environmental contamination. Poyang Lake, as the largest freshwater lake and bird habitat in China, was once a schistosomiasis epidemic area. In this study, the concentrations of PCP in water and aquatic products from Poyang Lake were determined and analyzed, and then the human health ambient water quality criteria (AWQC) was derived based on native parameters of Poyang Lake basin. Finally, a comprehensive analysis of the health risks of drinking water and different types of aquatic products consumption was carried out. The results showed that PCP concentrations were ranged from 0.01 to 0.43 µg/L in surface water and 3.90 to 85.95 µg/kg in aquatic products. Due to the carcinogenicity of PCP, the human health AWQC for PCP are 0.02 µg/L for consumption of water and organisms and 0.03 µg/L for consumption of organisms only. Deterministic and probabilistic risk analysis indicated that the non-carcinogenic risk of PCP were acceptable in Poyang Lake, while the carcinogenic risk cannot be ignored. The health risks of PCP caused by aquatic products consumption were higher than that by drinking water. The percentages of acceptable risk for the population in Poyang Lake Basin were 99.95% at acceptable level of 10-4. Based on the sensitivity analysis, the impact of PCP concentrations on health risk values ranged from 53 to 82%. The study provided valuable information for regional water quality criteria development and water quality assessment.
Asunto(s)
Agua Potable , Pentaclorofenol , Humanos , Calidad del Agua , Lagos/análisis , Pentaclorofenol/toxicidad , Pentaclorofenol/análisis , Agua Potable/análisis , Medición de Riesgo , China/epidemiología , Monitoreo del Ambiente/métodosRESUMEN
Environmental pollution has become a major human concern with the extensive exploitation of pesticides. Pentachlorophenol (PCP) is the most hazardous of all chlorophenols which are being used as pesticide, fungicide, and wood preservative. Thus, the fabrication of ultrasensitive electrochemical methods for the determination of pesticides is of great significance. In the present experiment, a simple, green, and sensitive electrochemical sensor was constructed for the determination of PCP by using a chemically modified nickel ferrite glassy carbon electrode (NiFe2O4/GCE). The fabricated nanoparticles were primarily characterized by several analytical tools to confirm the functionalities, surface texture, crystallinity, and elemental composition. For the investigation of conductive nature, the proposed NiFe2O4/GCE was exploited to the primary electrochemical characterization tools e.g. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The ultra-sensitive determination of PCP was carried out under the linear dynamic range from 0.01 to 90 µM at the pulse amplitude of 80 mV/s in BRB buffer pH of 4. The limit of detection of the developed methods for PCP was calculated to be 0.0016 µM. The analytical applicability of the fabricated sensor was tested in different water samples depicting the acceptable recovery values.
Asunto(s)
Contaminantes Ambientales , Nanopartículas , Pentaclorofenol , Carbono/química , Técnicas Electroquímicas/métodos , Electrodos , Contaminantes Ambientales/análisis , Compuestos Férricos , Humanos , Límite de Detección , Níquel , Pentaclorofenol/análisis , Extractos VegetalesRESUMEN
Thyroid cancer (TC) has inflicted huge threats to the health of mankind. Chlorophenols (CPs) were persistent organic pollutant and can lead to adverse effects in human health, especially in thyroid. However, epidemiological studies have revealed a rare and inconsistent relationship between internal exposure to CPs and TC risk. The purpose of this study was to investigate the correlation between urinary CPs and TC risk in Chinese population. From June 2017 to September 2019, a total of 297 histologically confirmed TC cases were recruited. Age- and gender-matched controls were enrolled at the same time. Gas chromatography-mass spectrometry (GC-MS) was used to determine the levels of three CPs in urine. Conditional logistic regression models were adopted to assess the potential association. Restricted cubic spline function was used to explore the non-liner association. After adjusting for confounding factors, multivariate analysis showed that, compared with the first quartile, the fourth quartile concentrations of 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) were associated with TC risk (odds ratio (OR)2,4-DCP =2.28, 95% confidence interval (CI): 1.24-4.18; OR2,4,6-TCP =3.09, 95% CI: 1.66-5.77; ORPCP =3.30, 95% CI: 1.71-6.36, respectively), when CPs were included in the multivariate model and restricted cubic spline function as continuous variables, presenting significant dose-response relationships. Meanwhile, whether in the TC group with tumor diameter > 1 cm or metastatic TC, the changes of 2,4,6 TCP and PCP concentrations were positively correlated with the risk of TC. Our study suggests that higher concentrations of urinary CPs are associated with increased TC risks. Moreover, 2,4,6-TCP and PCP have certain effects on the invasiveness of thyroid cancer. Targeted public health policies should be formulated to reduce the CP pollution. These findings need further in-depth studies to confirm and relevant mechanism also needed to be clarified.
Asunto(s)
Clorofenoles , Pentaclorofenol , Neoplasias de la Tiroides , Estudios de Casos y Controles , China , Clorofenoles/análisis , Humanos , Pentaclorofenol/análisisRESUMEN
As a persistent organic pollutant, pentachlorophenol (PCP) has serious impacts on human health. However, its presence in animal source food products sold in the Guangdong Province (GD) of China, and the resultant dietary exposure have not been elucidated. To address this gap, 3,100 samples from seven food categories, including beef, pork, mutton, offals, broilers, hen eggs, and farmed freshwater fish, marketed throughout four geographical regions of GD, were collected from 2015 to 2018. Gas chromatography coupled with mass spectrometry was employed to detect PCP levels in these food matrices. PCP was found in all food categories, but the average contamination levels were low, ranging from 0.40 µg/kg wet weight (ww) (hen eggs) to 5.85 µg/kg ww (offals). However, higher concentrations of PCP were detected (P < 0.05) in animal source food from the North region. Additionally, a temporal declining trend was observed in this four-year consecutive survey. The estimated human dietary exposure of PCP to population groups, including the general population and subgroups (male and female, children, and adults), was found to be far below the permissible daily intake (3 µg/kg body weight). Therefore, the health impacts of PCP should be correspondingly low for local residents, based on current toxicological knowledge. Regional exposure patterns varied due to different extents of contamination in the four areas, and pork, broilers, and freshwater fish were the major sources of dietary PCP exposure. PRACTICAL APPLICATION: As a persistent organic pollutant, pentachlorophenol (PCP) has serious impacts on human health. However, its presence in animal source food products sold in Guangdong Province of China, and the resultant dietary exposure have not been elucidated. In this study, we conducted an in-depth investigation on the occurrence of PCP in major foodstuff categories, including beef, pork, mutton, broilers, offals, hen eggs, and farmed freshwater fish, marketed in all 21 prefecture-level divisions of Guangdong Province, in order to provide integral insights for regulatory authorities.
Asunto(s)
Exposición Dietética/análisis , Contaminación de Alimentos/análisis , Carne/análisis , Pentaclorofenol/análisis , Medición de Riesgo/métodos , Adulto , Animales , Niño , China , Exposición Dietética/efectos adversos , Femenino , Peces/metabolismo , Análisis de los Alimentos , Humanos , Ganado/metabolismo , Masculino , Pentaclorofenol/efectos adversos , Aves de Corral/metabolismoRESUMEN
An enzyme-free, metal-free, and preconcentration-free electrochemical sensor for pentachlorophenol assay has been fabricated. The interface of the sensor is based on a hollow zeolitic imidazolate framework-derived mesoporous carbon material (denoted as HZC/SPCE). The sensor exhibits linear amperometric response upon pentachlorophenol at 0.82 V (vs. Ag/AgCl) in the concentration range 0.001 to 26.8 mg L-1 (3.75 × 10-8~1.006 × 10-4 M) (R2 = 0.997). The sensitivity of HZC/SPCE is 3.53 × 102 µA mM-1 cm-2 with a detection limit of 2.05 × 10-9 M (S/N = 3) for pentachlorophenol. The method has been applied to the determination of pentachlorophenol in spiked food packaging samples with recoveries in the range 92.0 to 107.0%. Graphical abstract Schematic representation of the synthesis of hollow ZIFs-derived hollow carbon material. Free protons derived from tannic acid penetrated into ZIF-8 to destroy its solid framework and the outer parts covered by tannic acid were protected from further etching. After pyrolysis, the morphology of HZC remained similar to that of HZIF-8. Abbreviation: CTAB: hexadecyl trimethyl ammonium bromide; Melm: 2-methylimidazole; ZIF-8: zeolitic imidazolate framework-8; TA: tannic acid; HZIF-8: hollow zeolitic imidazolate framework-8; HZC: hollow zeolitic imidazolate frameworks (ZIFs)-derived mesoporous carbon material.
Asunto(s)
Técnicas Biosensibles , Carbono/química , Técnicas Electroquímicas , Contaminación de Alimentos/análisis , Pentaclorofenol/análisis , Zeolitas/química , Electrodos , Embalaje de Alimentos , Tamaño de la Partícula , Porosidad , Propiedades de SuperficieRESUMEN
Understanding the spatial distribution of organic and/or inorganic contaminants is crucial to facilitate decision-making of rehabilitation strategies in order to ensure the most appropriate management of contaminated sites in terms of contaminant removals efficiencies and operating costs. For these reasons, various interpolation methods [Thiessen Polygon (TP) method, inverse of distance (IDW) method, ordinary kriging (OK), as well as sequential Gaussian simulations (SGS)] were used to better understand the spatial distribution of As, Cr, Cu, pentachlorophenol (PCP) and dioxins and furans (PCDD/F) found onto a specific industrial site. These methods do not only vary in complexity and efficiency but also lead to different results when using values coming from the same characterization campaign. Therefore, it is often necessary to evaluate their relevance by performing a comparative analysis. The results showed that ordinary kriging (OK) was a better estimator of the mean and more advanced compared to the two other methods of interpolation (TP and IDW). However, it appeared that SGS has the same power than OK but it also permitted to calculate a reliable value of the probabilities of exceeding regulatory cut-offs of contamination.
Asunto(s)
Monitoreo del Ambiente/métodos , Distribución Normal , Contaminantes del Suelo/análisis , Suelo/química , Análisis Espacial , Arsénico/análisis , Dioxinas/análisis , Monitoreo del Ambiente/estadística & datos numéricos , Furanos/análisis , Metales Pesados/análisis , Pentaclorofenol/análisisRESUMEN
Methanogenesis is commonly mass-produced under anaerobic conditions and serves as a major terminal electron accepting process driving the degradation of organic biomass. In this study, a cofactor of methanogenesis (coenzyme M, CoM) and a classic methanogensis inhibitor (2-bromoethanesulfonate, BES) were added at different concentrations to investigate how methanogenesis would affect PCP degradation in flooded soil. Strikingly, the processes of methanogenesis and PCP degradation were simultaneously promoted with CoM, or inhibited with BES, significantly (p < 0.05). High-throughput sequencing for soil bacterial and archaeal community structures revealed that members of Desulfitobacterium, Dethiobacter, Sedimentibacter, Bacillus and Methanosarcina might act as the core functional groups jointly perform PCP degradation in flooded soil, possibly through assisting microbial mediated dechlorination in direct organohalide-respiration, and/or indirect co-metabolization in complex anaerobic soil conditions. This study implied an underlying synergistic coupling between methanogenesis and dechlorination, and provided insights into a novel consideration with respect to coordinating methanogenesis while promoting anaerobic degradation of PCP for complex polluted soil environment, which is necessary for the improved all-win remediation.
Asunto(s)
Anaerobiosis , Biodegradación Ambiental , Cloro/análisis , Metano/química , Pentaclorofenol/análisis , Contaminantes del Suelo/análisis , Suelo/química , Ácidos Alcanesulfónicos/metabolismo , Archaea/metabolismo , Bacillus , Clostridiales , Desulfitobacterium , Firmicutes , Inundaciones , Concentración de Iones de Hidrógeno , Mesna/metabolismo , Methanosarcina , Microbiología del Suelo , Factores de TiempoRESUMEN
Chlorophenols (CPs), including pentachlorophenol (PCP), are chemicals of concern due to their toxicity and persistence. Here we describe a successful reactor-based remediation of CP-contaminated soil and assess changes in the toxicity patterns and bacterial communities during the remediation. The remediation consisted of separating half of the contaminated soil to be ground (samples M) in order to test whether the grinding expedited the remediation, the other half was left unground (samples P). Both soils were mixed with wastewater treatment sludge to increase their bacterial diversity and facilitate the degradation of CPs, and the resultant mixtures were placed in 2 bioreactors, M and P, operated for 16 months under anaerobic conditions to favor dehalogenation and for an additional 16 months under aerobic conditions to achieve complete mineralization. Samples were taken every 4 months for toxicity and microbial analyses. The results showed a 64% removal of total CPs (ΣCPs) in reactor P after just 18 months of remediation, whereas similar depletion in reactor M occurred after â¼25 months, indicating that the grinding decelerated the remediation. By the end of the experiment, both reactors achieved 93.5-95% removal. The toxicity tests showed a decrease in toxicity as the remediation progressed. The succession of bacterial communities over time was significantly associated with pH, anaerobic/aerobic phase and the concentration of the majority of CP congeners. Our data indicate that the supplementation of contaminated soil with sludge and further incubation in pilot-scale bioreactors under consecutive anaerobic-aerobic conditions proved to be effective at the remediation of CP-contaminated soil.
Asunto(s)
Reactores Biológicos/microbiología , Clorofenoles/análisis , Microbiología del Suelo , Contaminantes del Suelo/análisis , Suelo/química , Aerobiosis , Anaerobiosis , Biodegradación Ambiental , Pentaclorofenol/análisis , Proyectos Piloto , Aguas del Alcantarillado/microbiologíaRESUMEN
Hematite nanoparticles (NPs) exist naturally and ubiquitously in soil, and they are always associated with soil organic matter by forming organic-inorganic complexes. In this work, hematite NPs coated with peat humic acid (HApeat) and soil humic acid (HAsoil) were chosen as sorbents for hydrophobic organic contaminants (HOCs) to simulate the sorption processes in soil. Ionizable pentachlorophenol (PCP) and non-ionizable phenanthrene (PHE) were selected as representative HOCs. Compared with sorption isotherms of uncoated hematite NPs, the coating of HA onto the surface of hematite NPs substantially increased its sorption affinity for PCP and PHE by about 1-2 orders of magnitude, and the increasing degree was positively correlated to the HA content. These phenomena emphasized the dominant role of HA in the sorption process. The reduced polarity and the introduction of functional groups contributed to the enhanced sorption of HOCs on HA-coated hematite NPs. Furthermore, HApeat-hematite NPs showed higher sorption affinity for both PCP and PHE than HAsoil-hematite NPs, which was mainly due to the lower polarity and higher hydrophobicity of HApeat-hematite NPs. The sorption of PCP and PHE on HA-coated hematite NPs was inhibited obviously with increasing pH values and the pH effect on PCP sorption was more significant than that of PHE, due to the deprotonation of functional groups within adsorbed HA, the loose structure of adsorbed HA and the dissociation of PCP. Our findings elucidated the mechanisms involved in HOCs sorption processes by HA-hematite NPs and provided a theoretical basis for environmental remediation with natural NPs (e.g., hematite NPs).
Asunto(s)
Compuestos Férricos/química , Sustancias Húmicas/análisis , Nanopartículas/química , Pentaclorofenol/análisis , Fenantrenos/análisis , Contaminantes del Suelo/análisis , Adsorción , Restauración y Remediación Ambiental , Interacciones Hidrofóbicas e Hidrofílicas , Suelo/química , Propiedades de SuperficieRESUMEN
Environmentally persistent free radicals (EPFRs) in atmospheric fine particulate matters (PM2.5) possess high bioactivity and result in severe health problems. The facile transformation of aromatic pollutants into EPFRs on montmorillonite (MMT), an important solid component in PM2.5, is an activation of air pollutants into more toxic chemical species and also attributes to the secondary source of EPFRs in PM2.5. In this study, the interfacial reactions of pentachlorophenol (PCP), a typical EPFR precursor in air pollution, on the Fe(III)-, Ca- and Na-MMT surfaces have been explored by the density functional theory (DFT) calculations using the periodic slab models. The PCP molecule is found to be exothermically adsorbed on the three MMT surfaces. Moreover, significant charge transfer from PCP to Fe takes place and finally leads to the surface-bound phenoxyl radical formation on the Fe(III)-MMT surface since the half-filled 3d orbital of Fe3+ in Fe(III)-MMT could act as electron acceptor allowing the electron transferring from the 2p orbital of the phenolic O in PCP to Fe ion. However, similar charge transfer is not found in the Ca- and Na-MMTs, and the PCP transformation reaction is hindered on the Ca- and Na-MMT surfaces. Namely, the PCP activation to the corresponding EPFRs is impossible on the Ca-MMT and Na-MMT surfaces, while the catalytically active Fe(III)-MMT in PM2.5 can transform the chlorinated phenols into more toxic phenoxy-type EPFRs at ambient temperatures. Accordingly, more attention should be paid on the effect of MMT with catalytical capacity on the toxicity of PM2.5.
Asunto(s)
Contaminantes Atmosféricos/análisis , Bentonita/química , Compuestos Férricos/química , Radicales Libres/análisis , Material Particulado/química , Pentaclorofenol/análisis , Adsorción , Oxidación-Reducción , Tamaño de la Partícula , Propiedades de SuperficieRESUMEN
A new cationic gemini surfactant-resorcinol/formaldehyde resin was designed and synthesized. Cationic gemini surfactant was introduced into the resorcinol/formaldehyde resin for the first time and led to the retention of negatively charged endocrine disrupting compounds (EDCs) through electrostatic interactions, hydrogen bonding and π-π interactions. The synthesized material showed good performance in the dispersive micro-solid phase extraction (D-µ-SPE) of EDCs such as alkylphenol and phenoxy acid herbicides from food packaging migrants. Extraction parameters such as pH, adsorbent dose, extraction time and salting out effect were optimized. The limits of detections were in the range of 0.5-0.8â¯ng/mL, and the recoveries were in the range of 90-100%. The developed method was applied to the analysis of EDCs from food contacting materials migrants with pentachlorophenol, 2,4-dichlorophenoxyacetic acid and bisphenol A detected in the concentration range of 0.2-1.2â¯mg/kg. It also showed great potential in the D-µ-SPE of other compounds with negative charge or high hydrophobicity.
Asunto(s)
Disruptores Endocrinos/análisis , Contaminación de Alimentos/análisis , Formaldehído/química , Resorcinoles/química , Tensoactivos/química , Ácido 2,4-Diclorofenoxiacético/análisis , Compuestos de Bencidrilo/análisis , Embalaje de Alimentos , Pentaclorofenol/análisis , Fenoles/análisis , Reproducibilidad de los Resultados , Microextracción en Fase SólidaRESUMEN
An anaerobic incubation was launched with varying nitrate (1, 5, 10 and 20â¯mM exogenous NaNO3) and molybdate (20â¯mM Na2MoO4, a sulfate-reducing inhibitor) additions to investigate the characteristics of PCP dechlorination, as well as the reduction of natural co-occurring electron acceptors, including NO3-, Fe(III) and SO42-, and the responses of microbial community structures under a unique reductive mangrove soil. Regardless of exogenous addition, nitrate was rapidly eliminated in the first 12 days. The reduction process of Fe(III) was inhibited, while that of SO42- reduction depended on addition concentration as compared to the control. PCP was mainly degraded from orth-position, forming the only intermediate 2,3,4,5-TeCP by anaerobic microbes, with the highest PCP removal rate of average 21.9% achieved in 1 and 5â¯mM NaNO3 as well as 20â¯mM Na2MoO4 treatments and the lowest of 7.5% in 20â¯mM NaNO3 treatment. The effects of nitrate on PCP dechlorination depended on addition concentration, while molybdate promoted PCP attenuation significantly. Analyses of the Illumina sequencing data and the relative abundance of dominant microorganisms indicated that the core functional groups regulated PCP removal at genera level likely included Bacillus, Pesudomonas, Dethiobacter, Desulfoporosinus and Desulfovbrio in the nitrate treatments; while that was likely Sedimentibacter and Geosporobacter_Thermotalea in the molybdate treatment. Nitrate supplement but not over supplement, or addition of molybdate are suggested as alternative strategies for better remediation in the nitrate-deficient and sulfur-accumulated soil ecosystem contaminated by PCP, through regulating the growth of core functional groups and thereby coordinating the interaction between dechlorination and its coupled soil redox processes due to shifts of more available electrons to dechlorination. Our results broadened the knowledge regarding microbial PCP degradation and their interactions with natural soil redox processes under anaerobic soil ecosystems.
Asunto(s)
Bacterias/metabolismo , Biodegradación Ambiental , Pentaclorofenol/análisis , Pentaclorofenol/metabolismo , Contaminantes del Suelo/análisis , Contaminantes del Suelo/metabolismo , Anaerobiosis , Compuestos Férricos/química , Inundaciones , Halogenación , Molibdeno/química , Nitratos/química , Óxidos de Nitrógeno/química , Oxidación-Reducción , Suelo/química , Microbiología del Suelo , Sulfatos/químicaRESUMEN
Process-based models have been widely used for predicting environmental fate of contaminants. Nevertheless, accurate modeling of pentachlorophenol (PCP) dissipation in soils at the millimeter-scale remains a challenge due to the scarcity of observation data and uncertainty associated with model assumptions and estimation of the model parameters. To provide quantitative analysis of PCP-dissipation at the anaerobic/aerobic interface of a rhizobox experiment, this study implemented Bayesian parameter estimation for a process-based reactive chemical transport model. The model considered the main transport and transformation processes of chemicals including diffusion, sorption and degradation. The contributions of the processes to PCP dissipation were apportioned both in space and time. Using the maximum-a-posteriori (MAP) estimation of parameters, our model fitted the experimental data better compared with the previous work. Our results indicated that the most reactive zone for PCP dissipation occurred in the layer of 0-2.4â¯mm where degradation in solid phase dominated the PCP dissipation, while upward diffusion was the main mechanism for the reduction of PCP concentration in deeper layer (2.4-4.8â¯mm). By considering the coupled reactive transport of PCP and Cl-, the average degrees of PCP dechlorination in each layer were estimated from corresponding total concentrations of PCP and Cl-. The degrees of PCP dechlorination in the ponding water and the top layer of soil profile were highest, while 2,3,4,5- TeCP and 3,4,5- TCP were identified as the main dechlorination products in the soil. This study demonstrated that combining Bayesian estimation with process-based reactive chemical transport model can provide more insights of PCP dissipation at the millimeter-scale. This approach can help to understand complex dissipation mechanisms for other contaminants.
Asunto(s)
Modelos Químicos , Pentaclorofenol/análisis , Contaminantes del Suelo/análisis , Suelo/química , Teorema de Bayes , Inundaciones , Agua Dulce/análisis , Halogenación , Microbiología del SueloRESUMEN
A method was developed for the determination of trace pentachlorophenol and its sodium salt in animal-origin foods by modified QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Sodium pentachlorophenolate in samples was converted to pentachlorophenol under acidic condition. The pentachlorophenol was extracted twice with acetonitrile containing 1% (v/v) acetic acid by ultrasonic extraction. The extracts were purified by dispersive solid-phase extraction. The usages of dispersive sorbents were optimized based on the recoveries and matrix effects. Chromatographic analysis was conducted on a Waters Acquity UPLC HSS T3 column with gradient elution. The pentachlorophenol was further analyzed by negative electrospray ionization under the multiple reaction monitoring mode. The recoveries at fortification levels of 1.0, 2.0 and 10.0 µg/kg in six matrices (pork, pork liver, chicken, fish, milk and egg) ranged from 73.2% to 108.4% with the relative standard deviations of 4.0%-14.8%. The limits of quantification (S/N>10) were 1.0 µg/kg. The method is simple, sensitive, accurate, economical and environmentally safe, and is suitable for the determination of the trace pentachlorophenol and its sodium salt in animal-origin foods.
Asunto(s)
Huevos/análisis , Carne/análisis , Leche/química , Pentaclorofenol/análisis , Alimentos Marinos/análisis , Animales , Pollos , Cromatografía Líquida de Alta Presión , Extracción en Fase Sólida , Espectrometría de Masas en TándemRESUMEN
OBJECTIVE: A method was developed for the determination of pentachlorophenol( PCP) in food by ultrafast liquid chromatography-tandem mass spectrometry after solid phase extraction. METHODS: The sample was extracted in 8%triethylamine/acetonitrile( 70/30, V/V) and purified on a MAX-SPE cartridge. The UFLC separation was performed on a Shim-pack XR-ODS â ¢ column( 150 mm × 2. 0 mm, 2. 2µm) with a linear gradient elution program of acetonitrile and 5 mmol/L ammonium acetate( 0. 1% formic acid) as the mobile phase. Electrospray ionization was applied and operated in the negative ion mode. RESULTS: The limit of quantitation( LOQ) and limit of detection( LOD) for PCP were 0. 4-0. 5 µg/kg and 0. 12-0. 15 µg/kg. The calibration curve showed good linearity between 0. 5-50. 0 µg/L, and the correlative coefficients( r) were more than 0. 999. The recovery was between 82. 0%-108. 0%, and the RSD was between 1. 89%-5. 09%( n = 6). CONCLUSION: The method is sensitive, reproducible, and adapts to determination of PCP in variety of foods.
Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Cromatografía Liquida/métodos , Contaminación de Alimentos , Pentaclorofenol/análisis , Espectrometría de Masas en Tándem/métodos , Humanos , Extracción en Fase SólidaRESUMEN
Composite surface soil samples were collected at 0, 25, and 50 cm from the base of 12 utility poles on the Kenai National Wildlife Refuge in Alaska, to assess the extent to which pentachlorophenol, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo furans may have leached from pentachlorophenol-treated poles. Six pairs of utility poles were included, consisting of an "old" pole manufactured in 1959 or 1963, a "new" pole manufactured within the past 20 years, and a suitable background soil sample from the same vicinity. Old poles had greater concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) near the pole base and at 25 cm than "new" poles did. For all 12 poles combined, the mean pentachlorophenol levels in soil were 1810, 157, and 17.8 ppm dry weight (d.w.) near the pole bases, at 25 and 50 cm from the poles, respectively, while the mean total TEQ levels in soil were 15,200, 5170, and 1510 parts per trillion d.w. at those distances. Surface soil levels of pentachlorophenol and TCDD-TEQs exceeded both human health and ecological risk-based screening levels. The design and results of this study were similar to another project in Montreal, Quebec in Canada. Together the results are cause for concern, indicating that millions of similarly treated utility poles in North America may be point sources of pentachlorophenol and dioxins/furans to soil.
Asunto(s)
Dibenzofuranos/química , Dioxinas/análisis , Pentaclorofenol/análisis , Dibenzodioxinas Policloradas/análisis , Suelo/química , Alaska , Canadá , Dioxinas/química , Furanos , Humanos , América del Norte , Pentaclorofenol/química , Dibenzodioxinas Policloradas/química , QuebecRESUMEN
Various properties of soil affect the partition of organic contaminants within, and conversely, the properties of the organic contaminants also directly affect their partition behavior in soil. Therefore, understanding the effects of various properties of soil on the partition of organic contaminants favors subsequent assessment and provides soil remediation methods for policymakers. This study selected pentachlorophenol (PCP), a common hydrophobic ionizable organic compound in contaminated sites worldwide, as the target contaminant. The effects of pH, organic matter, and the combination of both, on PCP adsorption/desorption behavior in soil were investigated. Phosphoric acid and potassium hydroxide were used as buffer solutions to modify the soil pH by the batch and column extraction methods. A common retail organic fertilizer and fulvic acid were selected as additives to manipulate the soil organic content. Modifying the pH of the soil samples revealed that acidic soil exhibited a greater PCP adsorption rate than alkaline soil. The amount of PCP desorption increased regardless of pH of the in situ contaminated soil. The adsorption of PCP increased with increasing amount of organic additive. However, addition of fulvic acid yielded different results compared to the addition of organic fertilizer. Specifically, the organic fertilizer could not compete with the in situ contaminated soil in PCP adsorption, whereas fulvic acids increased the PCP dissolution to facilitate adsorbing contaminant adsorption. The combined effect of pH modification and organic matter addition provides additional PCP adsorption sites; therefore, adding the organic fertilizer to decrease the soil pH elevated the PCP adsorption rates of the laterite, alluvial, and in situ contaminated soil samples. The study results revealed that both pH and organic matter content are crucial to PCP adsorption/desorption in soil. Therefore, the effects of soil pH and organic matter should be considered in facilitating PCP treatment for soil remediation.