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1.
Chemosphere ; 243: 125392, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31995868

RESUMO

Long-term (2004-2018) persistent organic pollutants (POPs) data were collected for urban soils of China. The dataset included concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in soils, comprising a range of different compounds. Understanding the source of OCP and PCB pollution is an important step in controlling and reducing pollution levels in the environment. This study aimed to analyze the spatio-temporal distribution, pollution sources, and potential health risks of OCPs and PCBs in urban soils in different regions of China. It was found that the total OCP concentrations ranged from 7.6 to 37331 µg/kg with a mean value of 2861 µg/kg, and PCBs concentrations ranged from 0.3 to 123467 µg/kg with a mean value of 4984 µg/kg. The highest OCP concentrations were observed in Beijing and Hebei, whereas the highest PCB concentrations were found in the Zhejiang province. The geographical distribution showed that the total mean concentration of POPs of urban soil was much higher in East China than in West China. According to the isomer ratios, about 64% of provinces and cities showed new sources of dichlorodiphenyltrichloroethane (DDT) input and dicofol input was found in 30% of China. Hexachlorocyclohexane (HCH) in urban soils was mainly derived from fresh usage of lindane (γ-HCH) in most regions of China. Lifetime carcinogenic and non-carcinogenic risks of OCPs and PCBs through ingestion, inhalation, and dermal contact indicated that PCBs in urban soils of China often exceeded safe levels. The total lifetime carcinogenic risk values of PCBs were higher than the individual lifetime acceptable risk level (10-4) in 64% of the studied regions and the non-carcinogenic risk values exceeded the target risk level (10-1) in 53% of the regions. The improved knowledge of the distribution and main pollution sources of POPs in urban soil of China as a result of this study can contribute to better decision-making support for soil pollution control and monitoring.


Assuntos
Hidrocarbonetos Clorados/análise , Praguicidas/análise , Bifenilos Policlorados/análise , Poluentes do Solo/análise , Pequim , China , DDT/análise , Dicofol/análise , Monitoramento Ambiental , Hexaclorocicloexano , Análise Espaço-Temporal , Urbanização
2.
Chemosphere ; 235: 662-669, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31276879

RESUMO

Uptake and depuration kinetics of 4,4'-dichlorobenzophenone (main metabolite of dicofol) in the edible clam Meretrix meretrix were evaluated through a mesocosm experiment. M. meretrix was exposed to different dicofol concentrations (environmental concentration, D1 = 50 ng/L; supra-environmental concentration, D2 = 500 ng/L) for 15 days, followed by the same depuration period. To accomplish this goal, an analytical method was successfully optimized for 4,4'-DCBP using QuEChERS as extraction method with a range of concentrations 0.3-76.8 ng/g ww quantified by gas chromatography coupled to tandem mass spectrometry. Our results demonstrated different kinetics of accumulation depending on the two dicofol treatments. For D1, the uptake kinetic was best fitted using a plateau followed by one phase association kinetic model, while for D2 a one phase association kinetic model suited better. Similar bioconcentration factors were obtained for both concentrations but only animals exposed to D2, showed 4,4'-DCBP levels above the limits of quantification after 24 h exposure. These animals also showed lower uptake rate (ku) than organisms exposed to D1. During the depuration period, only organisms exposed to D1 successfully depurated after 24 h. On the other hand, although animals exposed to D2 presented higher elimination factor, they did not reach the original levels after depuration. Moreover, values detected in these clams were higher than the Maximum Residue Level (10 ng/g) established by the European legislation. This indicates that longer periods of depuration time than the ones used in this study, may be needed in order to reach safe levels for human consumption. This work also demonstrated that studies on metabolite kinetics during uptake/depuration experiments, could be a new alternative to understand the impact and metabolism of pesticides in the marine environment.


Assuntos
Benzofenonas/metabolismo , Bivalves/metabolismo , Poluentes Químicos da Água/metabolismo , Animais , Dicofol , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Cinética , Praguicidas/metabolismo , Alimentos Marinhos , Espectrometria de Massas em Tandem
3.
Environ Pollut ; 252(Pt A): 573-579, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31185345

RESUMO

Current-use pesticides (CUPs) are widely applied in agriculture; however, little is known about their environmental behaviors, especially in the freshwater-seawater transitional zone. Water and sediment samples were collected in an intensively human impacted river (Xiaoqing River) from the headwaters to Laizhou Bay to investigate the distributions and environmental fates of four CUPs: trifluralin, chlorothalonil, chlorpyrifos, and dicofol. These CUPs were frequently detected in water and sediment samples. ∑CUPs in water and sediment samples ranged from 1.20 to 100.2 ng L-1 and 6.6-2972.5 ng g-1 dry weight (dw), respectively. Chlorpyrifos and chlorothalonil were the most abundant CUPs in water and sediment samples, respectively. Spatial distribution of CUPs in the Xiaoqing River aquatic ecosystem was mainly influenced by point sources, agricultural activities, the dilution effect by seawater, and environmental parameters. Field-based sediment water partitioning coefficients, normalized by organic carbon (log Koc), were calculated. Interestingly, temperature and salinity exhibited significant impacts on the distribution of log Koc of the four CUPs. The effect of temperature on the distribution of log Koc of the four CUPs varied between the CUPs. In most water samples, the levels of chlorpyrifos exceed the freshwater screening benchmarks. Hence, urgent control measures need to be devised and implemented.


Assuntos
Baías/química , Monitoramento Ambiental , Sedimentos Geológicos/química , Praguicidas/análise , Rios/química , Poluentes Químicos da Água/análise , Agricultura , China , Clorpirifos/análise , Dicofol/análise , Ecologia , Ecossistema , Humanos , Nitrilos/análise , Água do Mar/química , Trifluralina/análise
4.
Anal Bioanal Chem ; 411(17): 3951-3962, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31093700

RESUMO

Mitotane is the only currently approved treatment for adrenocortical carcinoma (ACC), a rare endocrine malignancy. Plasma levels within the range of 14 to 20 mg L-1 are correlated with higher clinical efficacy and manageable toxicity. Because of this narrow therapeutic index and slow pharmacokinetics, therapeutic drug monitoring is an essential element of mitotane therapy. A small step towards the therapeutic drug monitoring (TDM) by volumetric absorptive microsampling (VAMS) was made with this work. A simple method enabling the patient to collect capillary blood at home for the control of mitotane blood concentration was developed and characterized using MITRA™ VAMS 20 µL microsampler. Dried blood samples were extracted prior to HPLC-UV analysis. Mitotane and the internal standard dicofol (DIC) were detected at 230 nm by ultra-violet detection after separation on a C8 reversed phase column. The assay was validated in the range of 1 to 50 mg L-1. Dried samples were stable at room temperature and at 2-8 °C for 1 week. At 37 °C, a substantial amount of the analyte was lost probably due to evaporation. Hematocrit bias, a common problem of conventional dried blood techniques, was acceptable in the tested range. However, a significant difference in recovery from spiked and authentic patient blood was detected. Comparison of mitotane concentration in dried blood samples (CDBS) by VAMS with venous plasma in patients on mitotane therapy demonstrated poor correlation of CDBS with the concentration in plasma (CP). In conclusion, application of VAMS in clinical routine for mitotane TDM appears to be of limited value in the absence of a method-specific target range.


Assuntos
Antineoplásicos Hormonais/sangue , Monitoramento de Medicamentos/métodos , Mitotano/sangue , Cromatografia Líquida de Alta Pressão/métodos , Dicofol/sangue , Humanos , Padrões de Referência , Reprodutibilidade dos Testes , Espectrofotometria Ultravioleta/métodos
5.
Ultrason Sonochem ; 51: 526-532, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30224289

RESUMO

Dicofol, a recommended Stockholm convention persistent organic pollutants (POPs) candidate is well known for its endocrine disruptive properties and has been extensively used as an organochlorine pesticide worldwide. The hydrodynamic cavitation (HC) treatment of Dicofol in aqueous media induced by a liquid whistle hydrodynamic cavitaion reactor (LWHCR) has been investigated while considering important parameters such as inlet pressure, initial concentration of Dicofol, solution temperature, pH, addition of H2O2 and radical scavenger for the extent of degradation. The pseudo-first-order degradation rate constant (k) was determined to be 0.073 min-1 with a cavitational yield of 1.26 × 10-5 mg/J at optimum operating conditions and a complete removal of Dicofol was achieved within 1 h of treatment. Considering the removal rate and energy efficiency, the optimal inlet pressure was found to be 7 bar, resulting in a cavitation number of 0.17. High performance liquid chromatography (HPLC) and Gas chromatography mass spectroscopy (GC-MS) analyses indicated a sharp decline in the concentration of Dicofol with treatment time and indicated the presence of degraded products. An 85% total organic carbon (TOC) removal was achieved within 1 h of treatment time, demonstrating successful mineralization of Dicofol. The obtained results suggest that the degradation of Dicofol followed thermal decomposition and successive recombination reactions at bubble-vapor interface. Overall, the attempted hydrodynamic cavitation demonstrated successful and rapid removal of endocrine disruptive chemicals such as Dicofol and is expected to provide efficient solution for wastewater treatment.


Assuntos
Dicofol/química , Disruptores Endócrinos/química , Hidrodinâmica , Resíduos de Praguicidas/química , Acústica , Depuradores de Radicais Livres/química , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Pressão , Temperatura
6.
Chemosphere ; 219: 645-654, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30557720

RESUMO

As an effective organochlorine pesticide, Dicofol has been extensively applied in more than 30 countries for protecting over 60 different crops. Considering its large consumption and potential adverse effect on human health (endocrine disrupting and carcinogenicity), the fate of Dicofol sprayed into the air is of public concern. In this study, we conducted a comprehensive study on the reaction mechanisms of p,p'-Dicofol with OH and NO3 radicals using DFT method. Comparing the abstrations by OH and NO3 radical, OH and NO3 radical addition reactions are predominant due to the lower potential barriers and stronger heat release. The phenolic substances (P1P5), epoxides (P11 and P15), dialdehyde (P13) and other species (P8, P9, P10 and P14) are generated by OH additions and their subsequent reactions while OH abstraction reactions produce DCBP, P7 and chlorphenyl radical. Particularly, NO3 additions and their subsequent reactions yield dialdehydes (P16 and P17) and 2,8-DCDD, which is the first report of the generation of dioxin from atmospheric oxidation of p,p'-Dicofol. Additionally, based on the structure optimization and energy calculation, rate constants and Arrhenius formulas of the elementary reactions of p,p'-Dicofol with OH and NO3 radicals were obtained over the temperature range of 280-380 K and at 1 atm. The rate constants for the reactions of p,p'-Dicofol with OH and NO3 radicals are 1.51 × 10-12 and 8.88 × 10-14 cm3 molecule-1 s-1, respectively. The lifetime (τTotal) of p,p'-Dicofol determined by the reactions of OH and NO3 radical is 5.86 h, indicating a potential long-range transport in the atmosphere.


Assuntos
Poluentes Atmosféricos/química , Atmosfera/química , Dicofol/química , Radicais Livres/química , Radical Hidroxila/química , Inseticidas/química , Cinética , Nitratos/química , Oxirredução , Temperatura
7.
Chemosphere ; 204: 101-108, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29655102

RESUMO

Dicofol, an extensively used organochlorine pesticide and a recommended Stockholm convention persistent organic pollutant (POP) candidate is well known for its endocrine disruptive properties. The sonochemical degradation of Dicofol in aqueous media has been investigated using a 20-kHz probe type sonicator with power inputs from 150 to 450 W. The degradation rate was determined as a function of concentration of Dicofol, solution pH, bulk phase temperature, ultrasonic power density and H2O2 addition. At optimum operating conditions, the pseudo-first-order degradation rate constant (k) was determined to be 0.032 min-1 and the extent of degradation was found to be 86% within 60 min of ultrasound treatment. High performance liquid chromatography (HPLC) and Gas chromatography coupled with mass spectroscopy (GC-MS) analysis indicated the presence of degraded products. The obtained results of Dicofol degradation and control experiments in the presence of H2O2 and radical scavenger test suggest thermal decomposition along with radical attack at bubble-vapor interface to be the dominant degradation pathway. Sonochemical treatment is effective and promising for successful removal of harmful pesticides such as Dicofol and superior removal efficiency for other POPs is expected in the near future with the successful implementation of ultrasound-based wastewater treatment.


Assuntos
Dicofol/química , Disruptores Endócrinos/química , Cromatografia Gasosa-Espectrometria de Massas , Halogenação , Peróxido de Hidrogênio/química , Praguicidas/química , Temperatura , Ultrassom
8.
Environ Sci Technol ; 52(4): 1990-1996, 2018 02 20.
Artigo em Inglês | MEDLINE | ID: mdl-29345919

RESUMO

The metabolic ratio of (p,p'-DDE + p,p'-DDD)/p,p'-DDT or p,p'-DDE/p,p'-DDT has been used previously to estimate the approximate half-life of p,p'-DDT, with a relatively unclear concept of "old" and "new" sources of p,p'-DDT and without paying attention to the influence by dicofol-type DDT contributed from the more recent usage of dicofol. Based on the isomeric ratio of o,p'-DDT/p,p'-DDT to distinguish the sources of DDT, this study used the corrected metabolic ratio of (p,p'-DDE + p,p'-DDD)/p,p'-DDT to estimate a more accurate half-life of p,p'-DDT using a model-based approach. This indicates the average half-life of p,p'-DDT in Chinese topsoils was 14.2 ± 0.9 years with dicofol-type DDT input considered. In deeper soil, the half-life was >30 years and the metabolic pathway of p,p'-DDT was significantly different with topsoil's. Further analysis on the fraction of DDT from technical DDT suggested that a region that had been sprayed with technical DDT was likely to have been sprayed with dicofol as well, but the monitoring residues of DDT in topsoil mainly derive from historical use of technical DDT.


Assuntos
DDT , Monitoramento Ambiental , Agricultura , China , Dicofol , Solo
9.
Pestic Biochem Physiol ; 143: 127-134, 2017 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-29183581

RESUMO

Organochlorine pesticides have generated growing concern owing to their diverse toxicities. In this connection, we have evaluated toxic potential of an acaricide, dicofol (DCF) and its harmful effects on human RBCs and lymphocytes. DCF caused hemolysis and rupture of human erythrocytes as confirmed by scanning electron microscopy (SEM). Significant increase in protein oxidation, lipid peroxidation, ROS production, methemoglobin formation with enhanced activities of superoxide dismutase and catalase but decreased level of reduced glutathione were observed as a result of DCF exposure to human erythrocytes. SEM showed significant DCF induced alterations in RBCs from normal discoid shape to echinocytes. Similarly, lymphocytes showed membrane damage, formation of membrane blebs and distorted cell morphology. In vitro comet assay indicated a significant DNA fragmentation in human lymphocytes upon DCF exposure. These results strongly suggest that DCF induces oxidative stress in RBCs via generation of ROS and alters the cellular architecture directly and indirectly.


Assuntos
Dicofol/toxicidade , Eritrócitos/efeitos dos fármacos , Inseticidas/toxicidade , Linfócitos/efeitos dos fármacos , Adulto , Catalase/metabolismo , Células Cultivadas , Ensaio Cometa , Dano ao DNA , Eritrócitos/metabolismo , Eritrócitos/patologia , Eritrócitos/ultraestrutura , Glutationa/metabolismo , Hemólise/efeitos dos fármacos , Humanos , Linfócitos/metabolismo , Linfócitos/patologia , Linfócitos/ultraestrutura , Malondialdeído/metabolismo , Metemoglobina/metabolismo , Microscopia Eletrônica de Varredura , Superóxido Dismutase/metabolismo
10.
Environ Sci Pollut Res Int ; 24(15): 13307-13314, 2017 May.
Artigo em Inglês | MEDLINE | ID: mdl-28386885

RESUMO

The acaricide, dicofol, is a well-known pesticide and partly a substitute for dichlorodiphenyltrichloroethane (DDT). Only few reports on environmental occurrence and concentrations have been reported calling for improvements. Hence, an analytical method was further developed for dicofol and dichlorobenzophenone (DCBP) to enable assessments of their environmental occurrence. Concentrated sulfuric acid was used to remove lipids and to separate dicofol from DCBP. On-column injection was used as an alternative to splitless injection to protect dicofol from thermal decomposition. By the method presented herein, it is possible to quantify dicofol and DCBP in the same samples. Arctic cod (Gadus morhua) were spiked at two dose levels and the recoveries were determined. The mean recovery for dicofol was 65% at the low dose (1 ng) and 77% at the high dose (10 ng). The mean recovery for DCBP was 99% at the low dose (9.2 ng) and 146% at the high dose (46 ng). The method may be further improved by use of another lipid removal method, e.g., gel permeation chromatography. The method implies a step forward in dicofol environmental assessments.


Assuntos
Dicofol , Inseticidas , Animais , Benzofenonas , DDT
11.
Chemosphere ; 176: 32-38, 2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-28254712

RESUMO

Dicofol application may be an important source to elevate the dichlorodiphenyltrichloroethane (DDT) residues to soils in Fujian, Southeast China, after the technical DDT was banned, which left DDT residues from the historical application. The DDT residues varied geographically, corresponding to the varied potential sources of DDT. In this study, a novel approach based on the Bayesian method (BM) was developed to identify the source contributions of DDT to soils, composed with both historical DDT and dicofol. The Naive Bayesian classifier was used basing on the subset of the samples, which were determined by chemical analysis independent of the Bayesian approach. The results show that BM (95%) was higher than that using the ratio of o, p'-/p, p'-DDT (84%) to identify DDT source contributions. High detection rate (97%) of dicofol (p, p'-OH-DDT) was observed in the subset, showing dicofol application influenced the DDX levels in soils in Fujian. However, the contribution from historical technical DDT source was greater than that from dicofol in Fujian, indicating historical technical DDT was still an important pollution source to soils. In addition, both the DDX (DDT isomers and derivatives) level and dicofol contribution in non-agricultural soils were higher than other agricultural land uses, especially in hilly regions, the potential cause may be the atmospheric transport of dicofol type DDT, after spraying during daytime, or regional difference on production and application.


Assuntos
DDT/análise , Dicofol/análise , Monitoramento Ambiental/métodos , Poluentes do Solo/análise , Solo/química , Agricultura , Teorema de Bayes , China , DDT/química , Dicofol/química , Monitoramento Ambiental/estatística & dados numéricos , Isomerismo , Poluentes do Solo/química
12.
Environ Geochem Health ; 38(6): 1241-1253, 2016 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26694483

RESUMO

The levels, potential sources and ecological risks of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) in Yellow River of Henan section, a typical agricultural area in China, were investigated. Surface water samples and suspended particulate matters (SPMs) were collected from 23 sites during two seasons. In wet season, the residues of ∑HCHs (α-HCH, ß-HCH, γ-HCH and δ-HCH) and ∑DDTs (p,p'-DDT, o,p'-DDT, p,p'-DDE, p,p'-DDD) ranged from 41.7 to 290 and 4.42 to 269 ng/L in surface water, while those varied from 0.86 to 157 and 1.79 to 96.1 ng/g dw in SPM, respectively. Moreover, in surface water, the levels of HCHs and DDTs in wet season were much higher than those in dry season. The reverse was true for residues of HCHs and DDTs in SPM. Compared with the large rivers in other regions, the levels of HCHs and DDTs in the studied area ranked at high levels and the residual concentrations might cause adverse biological risk, especially for ∑HCHs during wet season. Distributions of HCHs and DDTs delineated that the input of tributaries made a significant effect on the residue of HCHs and DDTs in the mainstream. ∑HCHs in surface water were consist of 26.7 % α-HCH, 30.0 % ß-HCH, 37.9 % γ-HCH and 5.45 % δ-HCH and those in SPM contained 5.16 % α-HCH, 22.1 % ß-HCH, 60.5 % γ-HCH and 12.2 % δ-HCH on average. Combined with ratios of α-HCH/γ-HCH in surface water (0.70) and in SPM (0.09), the results strongly indicated that lindane was recently used or discharged in the studied area. The mean percentage of DDTs' isomers were 28.7 % p,p'-DDT, 29.8 % o,p'-DDT, 28.1 % p,p'-DDE and 13.4 % p,p'-DDD in surface water, while those were 12.5 % p,p'-DDT, 31.8 % o,p'-DDT, 30.5 % p,p'-DDE and 25.1 % p,p'-DDD in SPM. The ratios of (DDE + DDD)/∑DDTs and o,p'-DDT/p,p'-DDT revealed that the DDTs in the studied area mainly derived from long-term weathering of technical DDTs residue and the input of dicofol.


Assuntos
DDT/análise , Hexaclorocicloexano/análise , Poluentes Químicos da Água/análise , Agricultura , China , Dicofol , Monitoramento Ambiental , Sedimentos Geológicos/análise , Inseticidas , Resíduos de Praguicidas , Rios , Estações do Ano
13.
J Environ Sci (China) ; 36: 22-8, 2015 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-26456602

RESUMO

It remains unclear whether dicofol should be defined as a persistent organic pollutant. Its environmental persistence has gained attention. This study focused on its degradation by cellulase. Cellulase was separated using a gel chromatogram, and its degradation activity towards dicofol involved its endoglucanase activity. By analyzing the kinetic parameters of cellulase reacting with mixed substrates, it was shown that cellulase reacted on dicofol and carboxyl methyl cellulose through two different active centers. Thus, the degradation of dicofol was shown to be an oxidative process by cellulase. Next, by comparing the impacts of tert-butyl alcohol (a typical OH free-radical inhibitor) on the removal efficiencies of dicofol under both cellulase and Fenton reagent systems, it was shown that the removal of dicofol was initiated by OH free radicals produced by cellulase. Finally, 4,4'-dichloro-dibenzophenone and chloride were detected using gas chromatography mass spectrometry and ion chromatography analysis, which supported our hypothesis. The reaction mechanism was analyzed and involved an attack by OH free radicals at the orthocarbon of dicofol, resulting in the degradation product 4,4'-dichloro-dibenzophenone.


Assuntos
Celulase/metabolismo , Dicofol/metabolismo , Inseticidas/metabolismo , Poluentes Químicos da Água/metabolismo , Cromatografia por Troca Iônica , Dicofol/química , Cromatografia Gasosa-Espectrometria de Massas , Peróxido de Hidrogênio/química , Inseticidas/química , Ferro/química , Cinética , Poluentes Químicos da Água/química
14.
Mar Pollut Bull ; 100(1): 516-522, 2015 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-26362455

RESUMO

The environmental occurrence, sources and risk factors of organochlorine pesticides (HCHs and DDTs) and their isomers or metabolites were studied using comprehensive surveys (including soil, surface water, groundwater and sediment sampling) conducted in the Yellow River Delta (YRD). HCHs and DDTs were all detected in multi environmental media. Compared with reported organochlorine pesticide values in China and abroad and with related environmental quality standards, the concentrations of HCHs and DDTs were generally at low levels in the YRD. Composition of OCPs (DDT metabolites and HCH isomers) showed that DDTs in the multiple environments of the YRD not only came from residues of dicofol but also from atmospheric deposition, while HCH pollution results from the historical usage of a mixture of technical HCH and lindane. Furthermore, the sum of Excess Lifetime Cancer Risk (∑ELCR) exposure to HCHs exceeded the generally acceptable risk level of 1.0E-06 recommended by the USEPA for carcinogenic chemicals.


Assuntos
Sedimentos Geológicos/análise , Hidrocarbonetos Clorados/análise , Praguicidas/análise , Poluentes do Solo/análise , Poluentes Químicos da Água/análise , China , DDT/análise , Dicofol/análise , Monitoramento Ambiental/métodos , Estuários , Água Subterrânea , Hexaclorocicloexano/análise , Humanos , Fatores de Risco , Rios/química
15.
Environ Sci Technol ; 49(15): 9084-91, 2015 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-26131590

RESUMO

Soil samples were collected at various depths (0.5-21.5 m) from ten boreholes that were drilled with a SH-30 Model Rig, four of which were at a dicofol production site while six were at a dichlorodiphenyltrichloroethane (DDT) production site. In industrial sites, the shallow soils at depths of 0-2 m were mostly backfill soils, which cannot represent the contamination situation of the sites. The contaminated levels in the deep original soil can represent the situation in contaminated sites. All the soil samples investigated at the DDT and dicofol production sites were found to be seriously polluted. The contents of both DDT (0.6-6071 mg/kg) and dicofol (0.5-1440 mg/kg) were much higher at the dicofol production site than at the DDT production site (DDTs, 0.01-664.6 mg/kg; dicofol, <0.1 mg/kg), even in the deep soil. DDTs had a different distribution in the soil of the pesticide production site from that in the soil outside the sites and that in agricultural soils. The results of the investigation revealed that DDTs were easily enriched in cohesive soil and in the bottom zone of aquifers, where the concentration was higher than in above the layers. DDTs were found to be hard to degrade, and their degradation speed was slower than their vertical migration, despite the fact that hydrophobic DDTs did not migrate easily in soils. In the dicofol production site, the value of DDE/DDD cannot indicate the degradation condition of DDTs, nor can the value of (DDE + DDD)/DDT identify how long DDTs have remained in the soil. It is debatable that the half-life of DDT inputted to soils is about 20-30 years, maybe longer than the generally recognized time.


Assuntos
DDT/análise , Praguicidas/análise , Poluentes do Solo/análise , China , DDT/química , DDT/metabolismo , Dicofol/química , Geografia , Isomerismo , Solo/química
16.
J Environ Sci (China) ; 33: 163-8, 2015 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-26141889

RESUMO

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, Km, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, Vmax, was 0.40 mg/L/min, while that of free cellulase was Km=8.18 mg/L, and Vmax=0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn2+, reversible competition with Cd2+, and irreversible inhibition by Pb2+. Ca2+ promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment.


Assuntos
Celulase/metabolismo , Dicofol/metabolismo , Metais/farmacologia , Praguicidas/metabolismo , Celulase/química , Dicofol/química , Poluentes Ambientais/química , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Cinética , Praguicidas/química
17.
Environ Sci Technol ; 49(1): 212-22, 2015 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-25442667

RESUMO

The uncertainties on whether dicofol can be identified as a persistent organic pollutant (POP) in terms of its long-range transport (LRT) potential and global distribution, are always a controversial topic during international regulation deliberations. The lack of monitoring data in remote background regions necessitates a model-based evaluation approach for assessing the global distribution of dicofol. However, few model simulations are available at present, as there is no inventory available for global historical usage of dicofol that has sufficiently high spatial and temporal resolution. To describe the current status of global emission, we first developed an inventory of global dicofol usage for the period of 2000-2012 at 1° × 1° latitude/longitude resolution. We then assessed the LRT potential of dicofol by calculating its Arctic Contamination Potential using the Globo-POP model. In addition, we simulated the global mass distribution and the fate of dicofol in the environment using the BETR-Global model at 15° × 15° latitude/longitude resolution. Our estimated inventory established that over the period of 13 years, a total of 28.2 kilo tonnes (kt) of dicofol was applied and released into the environment. East and Southeast Asia, the Mediterranean Coast, and Northern and Central America were identified as hotspots of usage and release. Dicofol exhibited a higher Arctic Contamination Potential than several confirmed Arctic contaminants, and a larger current volume of consumption than most existing POPs. The results of our BETR-Global simulation suggest that (i) dicofol can indeed be transported northward, most likely driven by both atmospheric and oceanic advections from source regions at midlatitudes, and (ii) dicofol will be enriched in remote background regions. Continuous use of dicofol in source regions will result in exposure both locally and in remote regions, and the examination of the potential for adverse effects is therefore of paramount importance. Proactive restrictions at the international level may be warranted.


Assuntos
Dicofol/análise , Poluentes Ambientais/análise , Agricultura/estatística & dados numéricos , Regiões Árticas , Ásia Sudeste , América Central , Monitoramento Ambiental , Inseticidas/análise , Região do Mediterrâneo , Modelos Teóricos , América do Norte
18.
J Food Prot ; 77(12): 2081-7, 2014 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-25474054

RESUMO

This study investigated the feasibility of detecting pesticides using terahertz (THz) spectroscopy in high-density polyethylene and/or wheat flour mixtures. The absorption spectra of seven pesticides (dicofol, chlorpyrifos, chlorpyrifos-methyl, daminozide, imidacloprid, diethyldithiocarbamate, and dimethyldithiocarbamate) were measured in the frequency range 0.1 to 3 THz at room temperature. Five of the seven pesticides exhibited specific absorption peaks in the low-energy THz range. The two remaining pesticides had no specific absorption peaks in this frequency range, but they exhibited different frequency-dependent refractive indices. The absorption coefficients of imidacloprid increased with its increasing weight ratio in high-density polyethylene, and the fitted power absorptions and refractive indices using a Maxwell-Garnett effective medium model were comparable to the measured data. Imidacloprid was also identified from its characteristic absorption peaks in wheat flour mixtures, and a linear relationship between the absorption coefficient and the weight ratio was observed. Our results show the potential of detection of selected pesticides in foods, such as wheat flour, using THz spectroscopy.


Assuntos
Farinha/análise , Praguicidas/análise , Espectroscopia Terahertz , Triticum/química , Carbamatos/análise , Clorpirifos/análogos & derivados , Clorpirifos/análise , Dicofol/análise , Dimetilditiocarbamato/análise , Ditiocarb/análise , Estudos de Viabilidade , Imidazóis/análise , Análise dos Mínimos Quadrados , Neonicotinoides , Nitrocompostos/análise , Polietileno , Sementes/química , Succinatos/análise
19.
J Environ Biol ; 35(5): 907-16, 2014 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-25204066

RESUMO

A number of organochlorine pesticides, including DDT and dicofol, used to be important in crop protection and management. Their residues may reach water bodies and eventually affect the non-target organisms such as rotifers. In the present study, we evaluated the effects of DDT (0.05, 0.1, 0.2 and 0.4 mg l(-1)) and dicofol (0.1, 0.2, 0.4 and 0.8 mg l(-1)) on the population growth of rotifer Brachionus calyciflorus under two levels of Scenedesmus obliquus (1.0 x 10(6) and 3.0 x 10(6) cell ml(-1)). Regardless of the food level, DDT was more toxic than dicofol to B. calyciflorus. Under low food level, DDT at 0.1 and 0.2 mg l(-1) decreased the population growth rate (r), and DDT at 0.05-0.4 mg l(-1) decreased the maximum population density (K). Dicofol at 0.4 and 0.8 mg l(-1) decreased r and K, but dicofol at 0.2 mg l(-1) increased K. Under high food level, DDT at 0.05-0.2 mg l(-1) increased K, whereas DDT at 0.4 mg l(-1) as well as dicofol at 0.4 and 0.8 mg l(-1) decreased r and K. Increase in food level increased r exposed to DDT at 0.05-0.2 mg l(-1) as well as dicofol at 0.8 mg l(-1), and Kexposed to DDTat 0.05-0.2 mg l(-1) as well as dicofol at 0.1 and 0.2 mg l(-1). DDT concentration, algal density and their interaction affected r and K of B. calyciflorus. Both dicofol concentration and algal density affected r. Dicofol concentration, algal density and their interaction affected K. Both r and K were suitable endpoints for assessing the effects of DDT and dicofol on the rotifers population dynamics under two algal densities, and the latter was more sensitive.


Assuntos
DDT/toxicidade , Dicofol/toxicidade , Rotíferos/efeitos dos fármacos , Scenedesmus , Animais , Cadeia Alimentar , Dinâmica Populacional
20.
J Chromatogr A ; 1361: 53-9, 2014 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-25152489

RESUMO

A new type of ionic liquid molecularly imprinted polymers (IL-MIPs) synthesized by precipitation polymerization using 1-allyl-3-methylimidazolium bromide as an auxiliary solvent and α-chloro-dichlorodiphenyltrichloroethane (α-chloro-DDT) as the template was applied as a selective sorbent of minimized pipette tip-solid-phase extraction (PT-SPE) for rapid isolation and extraction of dicofol (DCF) from celery samples. The pretreatment procedure of celery samples involved only 2.0mg of IL-MIPs, 0.8 mL of acetonitrile-water (ACN-H2O; 1:1, v/v) (washing solvent), and 1.0 mL of acetone-10% acetic acid (HOAc) (elution solvent). Compared with molecularly imprinted polymers (MIPs), ionic liquid-non-imprinted polymers (IL-NIPs) and conventional sorbents such as C18, Si, NH2, and Al2O3-N, IL-MIPs showed higher adsorption and purification capacity to DCF in aqueous solution. Good linearity for DCF was observed in the range from 2.3 to 232.5 ng g(-1) (r(2)=0.9995). The average recoveries at three spiking levels ranged from 86.6% to 101.9% with relative standard deviations (RSDs) of ≤ 6.5% (n=3). The presented IL-MIPs-PT-SPE-GC/ECD method combines the advantages of MIPs, IL, and PT-SPE, and can be used in aqueous conditions with high affinity and selectivity to analytes of complex samples.


Assuntos
Apium/química , Cromatografia Gasosa/métodos , Dicofol/análise , Líquidos Iônicos/química , Impressão Molecular/métodos , Polímeros/química , Extração em Fase Sólida/métodos , Adsorção
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