Determination of Dicofol in Tea Using Surface-Enhanced Raman Spectroscopy Coupled Chemometrics.

Dicofol is a highly toxic residual pesticide in tea, which seriously endangers human health. A method for detecting dicofol in tea by combining stoichiometry with surface-enhanced Raman spectroscopy (SERS) technology was proposed in this study. AuNPs were prepared, and silver shells were grown on the surface of AuNPs to obtain core-shell Au@AgNPs. Then, the core-shell Au@AgNPs were attached to the surface of a PDMS membrane by physical deposition to obtain a Au@AgNPs/PDMS substrate. The limit of detection (LOD) of this substrate for 4-ATP is as low as 0.28 × 10-11 mol/L, and the LOD of dicofol in tea is 0.32 ng/kg, showing high sensitivity. By comparing the modeling effects of preprocessing and variable selection algorithms, it is concluded that the modeling effect of Savitzky-Golay combined with competitive adaptive reweighted sampling-partial least squares regression is the best (Rp = 0.9964, RPD = 10.6145). SERS technology combined with stoichiometry is expected to rapidly detect dicofol in tea without labels.

Immunological quantitative detection of dicofol in medicinal materials.

In this study, a highly specific and sensitive monoclonal antibody against dicofol (DIC) was prepared and used to create a colloidal gold immunochromatographic strip (ICS) for the quantitative analysis of DIC in liquorice and Angelica sinensis samples. We found that for both the liquorice and Angelica sinensis samples, the cut-off value for the ICS was 500 ng g-1, respectively, and using a colloidal gold test strip reader, the half-maximal inhibitory concentrations (IC50) were found to be 35 ng g-1 and 88 ng g-1, the limits of detection were 2 ng g-1 and 3 ng g-1, and the linear detection scopes (IC20-IC80) were from 6 to 201 ng g-1 and from 10 to 819 ng g-1, respectively. In the recovery test, we found that recoveries were within the range of 90.6% to 97.2% and the coefficients of variation were less than 8.6% in the intra-assay and inter-assay for the liquorice samples and the recoveries ranged from 90.8% to 97.3% and the coefficients of variation were less than 9.1% in the intra-assay and inter-assay for the Angelica sinensis samples. The established ICS assay could be used for the rapid quantitative screening of chemicals in Chinese traditional medicinal materials.

Application of the QuEChERS method for the determination of pesticides, PAHs and PCBs in fish in Senegal.

Pollution of water by persistent organic pollutants is well described; however, little is known about the accumulation of these pollutants by aquatic organisms. For this reason, a method based on QuEChERS extraction and gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) was developed for the determination of pesticides, polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in the muscles of five fish species from the bay of Soumbedioune (Dakar, Senegal). This method shows good recoveries of extraction (68.2-98.1% for pesticides, 83.87-98.10% for PAHs and 81.30-98.15% for PCBs), precision (% RSD ≤ 1%), sensitivity (LODs between 0.001 and 0.079 ng g-1), linearity (R2 ≥ 0.99) and repeatability and reproducibility, evaluated for three concentration levels (10 ng g-1, 200 ng g-1 and 500 ng g-1), ≤ 15% for the majority of pollutants under study except for alachlor, atrazine, acetochlor, dicofol, deltamethrin and dichlorvos where a RSD ≥ 20% was determined for the 10 ng g-1 concentration. Organic pollutants have been detected in fish from the Soumbedioune coast demonstrating the necessity of a regular survey of water and fish in order to protect the populations.

Development of immunochromatographic strips for the detection of dicofol.

In this study, a monoclonal antibody (mAb) against dicofol was developed to prepare immunochromatographic strips (ICAs) for the detection of dicofol residues in fruit and vegetables. The mAb exhibited high affinity and high sensitivity, with an affinity constant of 2.96 × 1010 and a limit of detection of 3.142 ng mL-1. A cross reactivity test revealed that the mAb also had good specificity for dicofol. This ICA method gave a visible limit of detection of 50 ng g-1, and a cut-off value of 500 ng g-1 for the detection of dicofol in both apple and cucumber with the naked eye. Importantly, the results here are consistent with results obtained using liquid chromatography mass spectrometry and ic-ELISAs indicating that this ICA method is reliable and practical when used for the detection of dicofol in fruit and vegetables.

A method for the minimally invasive drug monitoring of mitotane by means of volumetric absorptive microsampling for a home-based therapeutic drug monitoring.

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.

Using Isomeric and Metabolic Ratios of DDT To Identify the Sources and Fate of DDT in Chinese Agricultural Topsoil.

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.

Deciphering the toxic effects of organochlorine pesticide, dicofol on human RBCs and lymphocytes.

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.

HCHs and DDTs in Yellow River of Henan section-a typical agricultural area in China: levels, distributions and risks.

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.

Global inventory, long-range transport and environmental distribution of dicofol.

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.

DDT Vertical Migration and Formation of Accumulation Layer in Pesticide-Producing Sites.

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.

Reaction mechanism of dicofol removal by cellulase.

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.

Effects of metal ions on the catalytic degradation of dicofol by cellulase.

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.

A novel mutation in the thyroglobulin gene that causes goiter and dwarfism in Wistar Hannover GALAS rats.

Outbred stocks of rats have been used extensively in biomedical, pharmaceutical and/or toxicological studies as a model of genetically heterogeneous human populations. One of such stocks is the Wistar Hannover GALAS rat. However, the colony of Wistar Hannover GALAS rat has been suspected of keeping a problematic mutation that manifests two distinct spontaneous abnormalities, goiter and dwarfism, which often confuses study results. We have successfully identified the responsible mutation, a guanine to thymine transversion at the acceptor site (3' end) of intron 6 in the thyroglobulin (Tg) gene (Tgc.749-1G>T), that induces a complete missing of exon 7 from the whole Tg transcript by mating experiments and subsequent molecular analyses. The following observations confirmed that Tgc.749-1G>T/Tgc.749-1G>T homozygotes manifested both dwarfism and goiter, while Tgc.749-1G>T/+ heterozygotes had only a goiter with normal appearance, suggesting that the mutant phenotypes inherit as an autosomal semi-dominant trait. The mutant phenotypes, goiter and dwarfism, mimicked those caused by typical endocrine disrupters attacking the thyroid. Hence a simple and reliable diagnostic methodology has been developed for genomic DNA-based genotyping of animals. The diagnostic methodology reported here would allow users of Wistar Hannover GALAS rats to evaluate their study results precisely by carefully interpreting the data obtained from Tgc.749-1G>T/+ heterozygotes having externally undetectable thyroidal lesions.

Effects of DDT and dicofol on population growth of Brachionus calyciflorus under different algal (Scenedesmus obliquus) densities.

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.

Selected pesticidal POPs and metabolites in the soil of five Vietnamese cities: Sources, fate, and health risk implications.

Large quantities of organochlorine pesticides (OCPs) have been used in tropical regions. The fate processes and risks of these legacy contaminants in the tropics are poorly understood. Herein, we investigated the occurrence of three classes of widely used OCPs and their metabolites in surface and core soil from five cities across Vietnam with a prevalent tropical monsoon climate and a long history of OCP application. We aimed to elucidate migration potentials, degradation conditions, and transformation pathways and assess current health risks of these contaminants. Generally, the concentrations of OCPs and metabolites in the soil core were slightly lower than those in surface soil except for hexachlorocyclohexane (HCH) isomers. 2,2-bis(4-chlorophenyl)-1,1,1-trichloroethane (p,p'-DDT), 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (p,p'-DDE), the sum of dicofol and 4,4'-dichlorobenzophenone (p,p'-DBP), and 2,2-bis(4-chlorophenyl)-1,1-dichloroethane (p,p'-DDD) were the most abundant compounds in both surface and core soils. A uniform distribution of HCHs (the sum of α-, ß-, γ-, and δ-HCH) at trace levels was found in almost all soils, serving as evidence of the lack of recent use of HCH pesticides. Higher concentrations of DDTs (the sum of DDT, DDD, and DDE) were observed in north-central Vietnamese soil, whereas appreciable concentrations of ENDs (the sum of α- and ß-endosulfan and endosulfan sulfate) were only found in southern Vietnamese soils. Empirical diagnostic ratios indicated residuals of DDTs were mainly from technical DDT rather than dicofol, whereas aged HCHs could be explained by the mixture of lindane and technical HCH. Both historical applications and recent input explain DDTs and ENDs in Vietnamese soil. Total organic carbon performs well in preventing vertical migration of more hydrophobic DDTs and ENDs. The dominant transformation pathway of DDT in surface soil followed p,p'-DDE→2,2-bis(4-chlorophenyl)-1-chloroethylene or p,p'-DDMU→1,1-bis(4-chlorophenyl)ethylene or p,p'-DDNU→p,p'-DBP, whereas the amount of p,p'-DDMU converted from p,p'-DDD and p,p'-DDE is similar in soil core. Non-cancer risks of OCPs and metabolites in all soils and cancer risks of those chemicals in core soils were below the safety threshold, whereas a small proportion of surface soil exhibited potential cancer risk after considering the exposure pathway of vegetable intake. This study implied that organic matter in non-rainforest tropical deep soils still could hinder the leaching of hydrophobic organic contaminants as in subtropical and temperate soils. When lands with a history of OCP application are used for agricultural purposes, dietary-related risks need to be carefully assessed.

Removal of pesticides from secondary treated urban wastewater by reverse osmosis.

The residues of pesticides that reach water resources from agricultural activities in several ways contaminate drinking water resources and threaten aquatic life. This study aimed to investigate the performance of three reverse osmosis (RO) membranes (BW30-LE, SW30-XLE, and GE-AD) in rejecting four different pesticides (tributyl phosphate, flutriafol, dicofol, and irgarol) from secondary treated urban wastewater and also to elucidate the mechanisms underlying the rejection of these pesticides. RO experiments were conducted using pesticide-spiked wastewater samples under 10 and 20 bar transmembrane pressures (TMP) and membrane performances were evaluated. Overall, all the membranes tested exhibited over 95% rejection performances for all pesticides at both TMPs. The highest rejections for tributyl phosphate (99.0%) and irgarol (98.3%) were obtained with the BW30-LE membrane, while for flutriafol (99.9%) and dicofol (99.1%) with the GE-AD membrane. The increase in TMP from 10 to 20 bar did not significantly affect the rejections of all pesticides. The rejection performances of RO membranes were found to be governed by projection area as well as molecular weight and hydrophobicity/hydrophilicity of pesticides. Among the membranes tested, the SW30-XLE membrane was the most prone to fouling due to the higher roughness.

A glutamate-gated chloride channel as the mite-specific target-site of dicofol and other diphenylcarbinol acaricides.

Dicofol has been widely used to control phytophagous mites. Although dicofol is chemically related to DDT, its mode of action has remained elusive. Here, we mapped dicofol resistance in the spider mite Tetranychus urticae to two genomic regions. Each region harbored a glutamate-gated chloride channel (GluCl) gene that contained a mutation-G314D or G326E-known to confer resistance against the unrelated acaricide abamectin. Using electrophysiology assays we showed that dicofol and other diphenylcarbinol acaricides-bromopropylate and chlorobenzilate-induce persistent currents in Xenopus oocytes expressing wild-type T. urticae GluCl3 receptors and potentiate glutamate responses. In contrast, the G326E substitution abolished the agonistic activity of all three compounds. Assays with the wild-type Drosophila GluClα revealed that this receptor was unresponsive to dicofol. Homology modeling combined with ligand-docking confirmed the specificity of electrophysiology assays. Altogether, this work elucidates the mode of action of diphenylcarbinols as mite-specific agonists of GluCl.

Multiomics analyses reveal dose-dependent effects of dicofol exposure on host metabolic homeostasis and the gut microbiota in mice.

BACKGROUND: Environmental exposure to dicofol (DCF), one of common organochlorine pesticides (OCPs) widely used for controlling agricultural pests, elicits a potential risk for human health due to its toxicity. However, potential physiological hazards of oral DCF exposure remain largely unknown. METHODS: Mice were exposed to relatively chronic and subacute DCF at different doses (5, 20 and 100 mg/kg) by gavage for 2 weeks. 1H NMR-based metabolomics was used to explore alterations of metabolic profiling induced by DCF exposure. Targeted metabolomics was subsequently employed to investigate the dose-dependent effects of oral DCF exposure on lipid metabolism and the gut microbiota-derived metabolites of mice. 16S rRNA gene sequencing was further employed to evaluate the changes of gut community of mice exposed to DCF. RESULTS: Oral exposure to DCF dose-dependently induced liver injury, manifested by hepatic lipogenesis, inflammation and liver dysfunction of mice. Typically, DCF exposure disrupted host fatty acids metabolism that were confirmed by marked alteration in the levels of related genes. DCF exposure also dose-dependently caused dysbiosis of the gut bacteria and its metabolites including altered microbial composition accompanied by inhibition of bacterial fermentation. CONCLUSION: These results provide metabolic evidence that DCF exposure dose-dependently induces liver lipidosis and disruption of the gut microbiota in mice, which enrich our views of molecular mechanism of DCF hepatoxicity.

Profiles and determinants of dicofol, endosulfans, mirex, and toxaphenes in breast milk samples from 10 prefectures in Japan.

Human exposure to persistent organic pollutants (POPs) is reflected by POP concentrations in breast milk. Many studies of POPs in breast milk have been performed in Japan, but insufficient information is available about some legacy POPs (e.g., mirex and toxaphenes, included in the Stockholm Convention in 2001) and novel POPs (e.g., dicofol and endosulfans, included in the Stockholm Convention in 2019 and 2011, respectively). In this study, dicofol, endosulfan, mirex, and toxaphene concentrations in breast milk from 10 prefectures in Japan were determined. The samples were collected between 2005 and 2010, before Stockholm Convention restrictions on endosulfans and mirex were implemented. Common POPs (e.g., polychlorinated biphenyls) were also analyzed to allow the contamination statuses to be compared. The α-endosulfan and ß-endosulfan concentrations were 0.26-13 and 0.012-0.82 ng/g lipid, respectively. The toxaphene #26 and #50 concentrations were <0.08-5.6 and < 0.1-8.5 ng/g lipid, respectively. The dicofol concentrations were <0.01-4.8 ng/g lipid. The mirex concentrations were <0.2-3.5 ng/g lipid. The α- and ß-endosulfan concentrations on a lipid weight basis negatively correlated with the lipid contents of the milk samples (ρ = -0.65, p < 0.01 for α-endosulfan; ρ = -0.58, p < 0.01 for ß-endosulfan). The toxaphene concentrations positively correlated with the lipid contents. The mirex concentrations positively correlated with the maternal age but negatively correlated with the maternal body mass index. No correlations between the dicofol concentrations and the factors were found. Principal component analysis divided the data into four groups, (1) chlordanes, dichlorodiphenyltrichloroethanes and related compounds, hexachlorobenzene, hexachlorocyclohexanes, hexachloroethane, and polychlorinated biphenyls, (2) endosulfans, (3) dicofol, dieldrin, and toxaphenes, and (4) bromodiphenyl ether 47. This indicated that bromodiphenyl ether 47, dicofol, endosulfans, and toxaphenes have different exposure routes or different kinetics to the other legacy POPs.

Outdoor Atmospheric Micro-/Nanomineral-Mediated Organochlorine Pesticides in Sichuan Basin, China: Adsorption, Occurrence, and Risk Assessment.

Atmospheric micro-/nanominerals play an important role in the adsorption, enrichment, and migration of organochlorine pesticides (OCPs). In the present study, the correlations between OCPs and minerals in outdoor atmospheric dustfall were investigated, and the correlations were used to speculate the source of p,p'-(dicofol+dichlorobenzophenone [DBP]), which is the sum of p,p'-dicofol and p,p'-DBP. Atmospheric dustfall samples were collected from 53 sites in the Chengdu-Deyang-Mianyang economic region in the Sichuan basin. In this region, 24 OCPs were analyzed by gas chromatography-tandem mass spectrometry. The average concentration of 24 OCPs was 51.2 ± 27.4 ng/g. The results showed that the concentration of Σ24 OCPs in urban areas was higher than that in suburban areas (p < 0.05). Minerals in atmospheric dustfall were semiquantitatively analyzed by X-ray diffraction. The primary minerals were quartz, calcite, and gypsum. A Spearman correlation analysis of OCPs and minerals showed that low-volatility OCPs could be adsorbed by minerals in atmospheric dustfall. A density functional theory simulation verified that p,p'-(dicofol+DBP) in atmospheric dustfall was primarily derived from the p,p'-dicofol adsorbed by gypsum. Isomeric ratio results suggested that the samples had weathered lindane and chlordane profiles and confirmed that residents in the Sichuan basin used technical dichlorodiphenyltrichloroethane. Finally, the OCPs were evaluated to determine the potential risk of cancer in adults and children from OCP exposure. Exposure to OCPs via atmospheric dustfall was safe for adults. The cancer risk for children exposed to OCPs was slightly lower than the threshold value (10-6 ) under a high dust ingestion rate, which poses a concern. Environ Toxicol Chem 2023;42:594-604. © 2022 SETAC.