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The activity of crystalline contact insecticides relies on the extraction of surface molecules by insect tarsi upon contact. Most crystals are inherently anisotropic, and surface molecules on symmetry independent faces are expected to have different free energies. The facet-dependent bioavailability and associated efficacy of insect lethality have not been investigated, however. We discriminate the bioactivity of various facets of single crystals of DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane), a well-known contact insecticide. Our findings reveal facet-dependent lethality differences of nearly 75% among four crystallographically unique facets. Furthermore, computations reveal that the respective lethalities of the facets are strongly correlated with the detachment energies of molecules from the crystal surfaces. This facet-dependent lethality suggests a pathway to enhance the efficacy of known contact insecticides through crystal habit control.

Chlorinated pollutants may follow distinct degradation pathways in anaerobic environments compared to aerobic settings. However, the understanding of the behaviors and fate of dichlorodiphenyltrichloroethanes (DDTs) under anaerobic conditions remains limited. To address this knowledge gap, we conducted a study on flooded soil samples collected from three typical paddy fields in China using an integrated approach of enantiomer-specific analysis and compound-specific stable carbon isotope analysis. It is unexpected that the dichlorodiphenyldichloroethane /dichlorodiphenyldichloroethylene ratios (DDD/DDE=(o,p'-DDD+p,p'-DDD)/(o,p'-DDE+p,p'-DDE)) were below 1 in over 90 % of the samples. This might be attributed to the higher recalcitrance of p,p'-DDE, which concentrations were found to be 36 times higher than p,p'-DDD on average. There were 71.7 % of the samples showing enantiomeric fractions (EFs) of o,p'-DDT below 0.5, indicating a preferential accumulation of the (-)-enantiomer. The δ 13 C values of the anaerobic metabolite o,p'-DDD (-24.76 ± 1.35 ‰ to -34.39 ± 0.20 ‰) all deviated negatively from the initial product, while those of the aerobic metabolite o,p'-DDE (-23.61 ± 0.48 ‰ to -38.95 ± 0.81 ‰) displayed either negative or positive deviations. This demonstrates that o,p'-DDD is the primary metabolite of o,p'-DDT under anaerobic conditions. However, no clear correlations were observed between the δ 13 C and EF of o,p'-DDT. This study underscores the importance of such an integrated methodology in unraveling the fate and behaviors of DDTs in complex environmental systems., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The long-term and indiscriminate use of pesticides has resulted in serious health effects. Aside from that, developing countries do not have any monitoring systems in place to prevent the consumption of high levels of pesticides in foods. Therefore, this study aimed to determine pesticide residues and the effect of processing in commonly consumed vegetables in the southwestern part of Ethiopia. In total, 12 samples of 1 kg of each type of vegetable were collected from selected markets. Moreover, as a solution to pesticide residue problems in vegetables, the effect of different processing methods such as washing, peeling, boiling, and their cumulative effect was studied. In the analytical procedure, the modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction with florisil as a cleanup sorbent was used and the identification of pesticides was done by using gas chromatography with an electron capture detector (GC-ECD). The parent p,p' -DDT was detected at a concentration of 0.015 mg/kg in potato samples from the Serbo market and a concentration of 0.516, 0.232, 0.174, and 1.512 mg/kg in Merkato, Kochi, Serbo, and Shebe onion samples, respectively. P `p -DDT is detected at a high concentration compared to its metabolites (p,p' -DDE and p,p' -DDD), which is an indication of recent use. DDT and its metabolites, other organochlorines (lindane, γ -chlordane, dimethachlor, and heptachlor), and pyrethroids (cypermethrin and deltamethrin) exceeded the recommended limits by FAO and WHO in multiple samples of potato, onion, and cabbage. The processing result showed that washing, boiling, and the combination of the two revealed a 100% reduction in o,p' -DDT, and p,p' -DDT pesticides detected in cabbage. In conclusion, multiple residues were detected in the three vegetables studied, indicating that pesticides were applied intensively. Pesticide levels were reduced by home processing procedures, which is important for consumer safety., Competing Interests: The authors declare that there are no conflicts of interest., (Copyright © 2023 Amare Terfe et al.)

Honey is considered to be a health-promoting food product. Therefore, it is assumed that it should be free of contaminants. Although the use of organochlorine pesticides (OCPs) was banned a few decades ago in developed countries, persistent organic pollutants (POPs) are still detected in various environmental and biological matrices, including food. These contaminants exhibit toxic properties and bioaccumulate in some food chains. The validation of a modified QuEChERS extraction method was successfully performed for o,p' -DDT, o,p' -DDE, o,p' -DDD, p,p' -DDT, p,p' -DDE, p,p' -DDD, heptachlor and dieldrin. 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153) was used as an internal standard. The modification involved changing the solvent from acetonitrile to n-hexane after extraction. Quantitation was carried out using gas chromatography with an electron capture detector (µECD). The mean recovery values for o,p' -DDT, o,p' -DDE, o,p' -DDD, p,p' -DDT, p,p' -DDE, p,p' -DDD and dieldrin, spiked at 2.9 ng/g and 20 ng/g, ranged from 64.7% to 129.3%, and, for heptachlor spiked at 5.6 ng/g and 20 ng/g, ranged from 68.0% to 88.3%. The relative standard deviation (RSD) for these concentrations did not exceed 20%, and the within-laboratory reproducibility was below 20%, except o,p' -DDE and p,p' -DDT, which were 25.2% and 20.7%, respectively. This modified QuEChERS extraction method for selected organochlorine compounds was demonstrated as effective for routine testing in honey.

Emission of harmful pollutants from different sources into the environment is a major problem nowadays. Organochlorine pesticides such as DDT (C 14 H 9 Cl 5 ) are toxic, bio-accumulative, and regularly seen in water bodies, air, biota, and sediments. Various systems can be considered for minimizing the DDT (dichloro-diphenyl-trichloroethane) pollution. However, due to simplicity and acceptability, the adsorption method is the most popular method. Adsorption is gradually employed for the removal of both organic and inorganic pollutants found in soil and water. Thus, in this regard, efforts are being made to design inorganic nanoclusters (B 12 N 12 ) encapsulated with late transition metals (Zn, Cu, Ni, Co, and Fe) for effective adsorption of DDT. In this context, detailed thermodynamics and quantum chemical study of all the designed systems have been carried out with the aid of density functional theory. The adsorption energy of DDT on metals cocooned in a nanocluster is found to be higher, and better adsorption energy values as compared to that of the pristine B 12 N 12 -DDT nanocluster have been reported. Further, analysis of the dipole moment, frontier molecular orbitals, molecular electrostatic potential plots, energy band gap, Q NBO , and Fermi level suggested that the late-transition-metal-encapsulated inorganic B 12 N 12 nanoclusters are efficient candidates for effective DDT adsorption. Lastly, the study of global descriptors of reactivity confirmed that the designed quantum mechanical systems are quite stable in nature with a good electrophilic index. Therefore, the recommendation has been made for these novel kinds of systems to deal with the development of DDT sensors.

This chapter describes the complementary experimental techniques Electron Transmission Spectroscopy and Dissociative Electron Attachment Spectroscopy, two of the most suitable means for investigating interactions between electrons and gas-phase molecules, resonance formation of temporary molecular negative ions, and their possible decay through the dissociative electron attachment (DEA) mechanism. The latter can be seen as the gas-phase counterpart of the transfer of a solvated electron in solution, accompanied by dissociation of the molecular anion, referred to as dissociative electron transfer (DET). DET takes place in vivo under reductive conditions, for instance, in the intermembrane space of mitochondria under interaction of xenobiotic molecules possessing high electron affinity with electrons "leaked" from the mitochondrial respiratory chain. A likely mechanism of the toxic activity of dichlorodiphenyltrichloroethane based on its DEA properties is briefly outlined, and compared with the well-established harmful effects of the model toxicant carbon tetrachloride ascribed to reductive dechlorination in a cellular ambient. A possible mechanism of the antioxidant activity of polyphenolic compounds present near the main site of superoxide anion production in mitochondria is also briefly discussed.

Carbonic anhydrase (CA, EC 4.2.1.1) plays crucial physiological roles in many different organisms, such as in pH regulation, ion transport, and metabolic processes. CA was isolated from the European bee Apis mellifera (AmCA) spermatheca and inhibitory effects of pesticides belonging to various classes, such as carbamates, thiophosphates, and pyrethroids, were investigated herein. The inhibitory effects of methomyl, oxamyl, deltamethrin, cypermethrin, dichlorodiphenyltrichloroethane (DDT) and diazinon on AmCA were analysed. These pesticides showed effective in vitro inhibition of the enzyme, at sub-micromolar levels. The IC 50 values for these pesticides ranged between of 0.0023 and 0.0385 μM. The CA inhibition mechanism with these compounds is unknown at the moment, but most of them contain ester functionalities which may be hydrolysed by the enzyme with the formation of intermediates that can either react with amino acid residues or bid to the zinc ion from the active site.

Phytoremediation and advanced oxidation processes are among the most promising techniques for removing organic pollutants from soils. A field trial was performed for six months to evaluate the effect of nano-Fe 3 O 4 on the degradation of organochlorine pesticide residues including Lindane, p,p'-dichlorodiphenyltrichloroethane (DDT), p,p'-dichlorodiphenyldichloroethylene (DDE), and p,p'-dichlorodiphenyldichloroethane (DDD) in pesticide-contaminated soils in the presence of vetiver in Bac Giang province, Vietnam. Vetiver was planted in three zones with different nano-Fe 3 O 4 concentrations. Soil samples from each zone were periodically collected to determine the remaining concentrations of selected organochlorine pesticides via gas chromatography-electron capture detector. Results indicated that the total DDT concentrations in the examined soil were 1.9-13 times higher than the permissible threshold level (10 µg g -1 ) established by the national technical regulation on pesticide residues in soil. The (p,p'-DDE + p,p'-DDD)/p,p'-DDT ratios ranged from 13.5 to 114, indicating the absence of recent inputs of technical DDTs at the study area. DDT dechlorination mainly occurred under aerobic pathways to form DDE. Furthermore, DDE degradation in soil was adequately described by the pseudo-first-order kinetics model (R 2  > 0.892). In the presence of vetiver, the rate constants of DDE degradation were 0.264, 0.350, and 0.434 month -1 with 0, 25, and 100 mg kg -1 of added nano-Fe 3 O 4 , respectively, indicating that the degradation of DDE correlated positively with Fe 3 O 4 concentration in the soil. Additionally, the presence of vetiver and nano-Fe 3 O 4 in the soil increased DDT removal rates, which might be linked to the involvement of Fenton/Fenton-like reactions.

Dechlorination of dichlorodiphenyltrichloroethane (DDT) as a model compound was performed with zero-valent iron (micro-ZVI and nano-ZVI) as reductant and carbonaceous adsorbents as sink and catalyst in water. DDT is rapidly converted to dichlorodiphenyldichloroethane (DDD) in direct contact with ZVI. However, up to 90% of the DDD is transformed into non-identified, most likely oligomeric products. There is no indication of dechlorination at the aromatic rings. DDT is still rapidly dechlorinated when it is adsorbed on carbonaceous adsorbents, even though ZVI particles have no direct access to the adsorbed DDT. The carbonaceous materials function as adsorbent and catalyst for the dechlorination reaction at once. From electrochemical experiments, we deduced that direct physical contact between ZVI particles and the adsorbent is essential for enabling a chemical reaction. Electron conduction alone does not effect any dechlorination reaction. We hypothesize hydrogen species (H∗) which spill from the ZVI surface to the carbon surface and initiate reductive transformations there. The role of carbonaceous adsorbents is different for different degradation pathways: in contrast to hydrodechlorination (reduction), adsorption protects DDT from dehydrochlorination (hydrolysis)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier Ltd.)

This study was the first to evaluate the occurrence, residue levels, spatial distribution and sources of DDT and other Persistence Organic Pollutants (POPs), which can be found in the Nyabarongo lower catchment (NLC) in Rwanda. These include Aldrin, Dieldrin, Endosulfan, Endrin, Hexachlorocyclohexane (HCH), Heptachlor, Heptachlorepoxide, Hexachlorobenzene (HCB), Isodrin, Methoxychlor, Mirex and Polychlorinated biphenyls (PCBs). A total of 108 soil samples were collected in the wetland area, both extracted and eluted with cyclohexane and analysed by GC-MS. The results indicated that DDT isomers and degradation products were major POPs and were detected in 44 samples (40%). Their detection frequency followed the order of 4,4'-DDE > 4,4' -DDT > 4,4' -DDD > 2,4' -DDT > 2,4' -DDD and 2,4' -DDE. Residues varied from non-detected (nd) to 120 μg kg -1 dry weight (dw), with a mean value of 3.93 μg kg -1 dw and a high variation (SD = 10.17 μg kg -1 dw). The degradation ratios confirmed both the historical and recent application of DDT and Dieldrin (0.53-18 μg kg -1 dw). Other detected POPs included PCBs in Kigali city which ranged from 0.1 to 0.21 μg kg -1 dw, confirming that the old contamination drifted from electric transformers. Aldrin (0.38-0.59 μg kg -1 dw); Heptachlor (0.14-0.19 μg kg -1 dw) residues probably reached the catchment through rain-washout. This study confirms that even though Rwanda banned the use of DDT and other POPs including pesticides (Aldrine, Chlordane, DDT, Dieldrine, Endrine, Heptachlor, Hexachlorobenzene, Mirex, and Toxaphene); Industrial products (Hexachlorobenzene and Polychlorobiphenyl PCBS) and unintentional sub-products, since 2002, some of above products are still used in random areas (e.g: DDT, Dieldrin). The highest residues were detected close to Lake Muhazi and areas surrounding Kigali city. This study recommends full evaluation of human health and ecological risks from exposure to DDT. Additionally, the National Implementation Plan (NIP) for the Stockholm Convention to eliminate POPs should be reinforcement through strengthening the market control and educational programs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The present work reports microwave-assisted synthesis of SnO 2 nanoparticles via green route using Psidium Guajava extract. For the enhancement of catalytic activity, nanohybrids of SnO 2 were formulated using different ratios of polyaniline (PANI) via ultrasound-assisted chemical polymerization. Formation of nanohybrids was confirmed via IR and XPS studies. The UV-vis DRS spectra of PANI/SnO 2 revealed significant reduction in the optical band gap upon nanohybrid formation. Microwave-assisted catalytic efficiency of pure SnO 2 , PANI, PANI/SnO 2 nanohybrids was investigated using DDT as a model persistent organic pollutant. The degradation efficiency of PANI/SnO 2 was found to increase with the increase in the loading of PANI. Around 87% of DDT degradation was achieved within a very short period of 12 min under microwave irradiation using PANI/SnO 2 -50/50 as catalyst. The effect of DDT concentration was explored and the degradation efficiency of PANI/SnO 2 -50/50 catalyst was noticed to be as high as 82% in presence of 100 mg/L of DDT. The effect of microwave power on the degradation efficiency revealed 79% degradation using the same nanohybrid when exposed to microwave irradiation for 5 min under 1110 W microwave power. Scavenging studies confirmed the generation of OH, O 2 - radicals. The fragments with m/z values as low as 86 and 70 were confirmed by LCMS analysis. Recyclability tests showed that PANI/SnO 2 -50/50 nanohybrid exhibited 81% degradation of DDT (500 mg/L) even after the third cycle, which reflected high catalytic efficiency as well as remarkable stability of the catalyst. This green nanohybrid could therefore be effectively utilized for the rapid degradation of persistent organic pollutants., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Several Glutathione S-transferases (GSTs) enzymes, in insects, have previously been implicated in resistance developed against DDT and other insecticides. The GST enzyme particularly sigma class have important physiological role in detoxification of lipid peroxidation by-products in insects. Phlebotomus argentipes has been intensely exposed to DDT over years due to Indoor Residual Spray (IRS) programme for Kala-azar elimination in Bihar, India. However, in P. argentipes, role of GSTs in DDT resistance have not been elucidated. Here, sigma class GST of P. argentipes (Parg-GSTσ) was successfully cloned, expressed and purified by affinity chromatography. The recombinant Parg-GSTσ was found to be highly active towards cumene hydroperoxide and 4-HNE having specific activity 92.47 & 203.92 µM/min/mg of protein, respectively and exhibited low activity towards universal substrate CDNB i.e., 8.75 µM/min/mg of protein. RT-PCR and immunoblot analysis showed at least 2 and 1.8 fold overexpression of Parg-GSTσ in the single exposed and non exposed DDT resistant P. argentipes as compared to susceptible, implicating Parg-GSTσ also involved in DDT resistance probably by imparting enhanced stress tolerance. The DDT, H 2 O 2 and temperature induction assays demonstrated stress-dependent induction of Parg-GSTσ expression indicating its important role in oxidative stress redressal.

Because of its hydrophobicity and persistence, dichlorodiphenyltrichloroethane (DDT) is ubiquitous in sediments and poses significant risk to benthic organisms. Therefore, it is imperative to evaluate the long-term toxicity of DDT. However, limited information is available on its chronic toxicity to benthic invertebrates. Full-life cycle toxicity of sediment-bound DDT to Chironomus dilutus was assessed. Median lethal concentrations (with 95% confidence limits) of DDT and its degradation products (DDX) to C. dilutus were 334 (165-568), 21.4 (11.2-34.3), and 7.50 (4.61-10.6) nmol/g organic carbon after 10-, 20-, and 63-d exposure, respectively. In addition, median effect concentrations of DDX were 20.0 (15.0-25.3), 7.13 (4.10-10.5), and 8.92 (3.32-15.1) nmol/g organic carbon for growth, emergence, and reproduction, respectively. A toxicity spectrum was established to visually summarize chronic effects of DDX to midges. In addition, DDT degraded to dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethylene (DDE) during sediment aging, and their toxicity differed from that of the parent compound. Predicted toxic units of DDX in porewater were utilized to distinguish between toxicity from DDT and that of DDD and DDE. The results showed that DDD was the main contributor to the toxicity in C. dilutus. To improve the accuracy of sediment risk assessment of DDT, the composition of DDX should be considered. Environ Toxicol Chem 2019;38:2698-2707. © 2019 SETAC., (© 2019 SETAC.)

Although persistent organic pollutants (POPs) are currently banned or strictly controlled under the Stockholm Convention on Persistent Organic Pollutants, POPs are still distributed worldwide due to their environmental persistence, atmospheric transport, and bioaccumulation. Herein we investigated the current concentrations of POPs in the sediments from Seto Inland Sea, Japan and sought to clarify the factors currently controlling the POPs concentration of the surface sediments from Seto Inland Sea. The concentrations of hexachlorocyclohexane isomers (HCHs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), and chlordane isomers (CHLs) in sediments from Seto Inland Sea were <0.002-1.20 ng g -1 , 0.01-2.51 ng g -1 , and 0.01-0.48 ng g -1 , respectively. Resuspension increased the concentrations of HCHs, HCB, and DDTs in the surface sediment with the release of historically contaminated pollutants accumulated in a lower layer. We speculate that CHLs in air that were removed by atmospheric deposition affects the concentration of CHLs in surface sediments., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Dichlorodiphenyltrichloroethane (DDT) is an organochlorine insecticide that has been used for indoor residual spraying for the control of mosquito-borne diseases including malaria. However, due to its toxicity and environmental persistence, there are concerns about its potential deleterious effects in humans and wildlife. Therefore, the current study aimed to monitor and estimate the level of DDTs in human communities. The accumulation of DDT and its metabolites was evaluated in house rat (as sentinel) livers collected in an area where DDT was sprayed. DDTs were measured using a gas chromatography / Electron Capture Detector. The results revealed high concentrations of DDTs in the rat livers and the levels of DDTs were similar to findings reported from the same area in 2014.

Polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT), and dichlorodiphenyldichloroethylene (DDE) are suspected to be associated with breast cancer risk, but the results are controversial. This study was performed to evaluate the associations between adipose tissue PCB, DDT, and DDE concentrations and breast cancer risk. Two hundred and nine pathologically diagnosed breast cancer cases and 165 controls were recruited from three local hospitals in Shantou city, China, from 2014 to 2016. Concentrations of 7 PCB congeners, p,p'-DDT, and p,p'-DDE were measured in adipose tissues obtained from the breast for cases and the breast/abdomen for controls during surgery. Clinicopathologic information and demographic characteristics were collected from medical records. PCBs, p,p'-DDT, and p,p'-DDE concentrations in adipose tissues were compared between cases and controls. Multivariate logistic regression model was used to analyze the risk of breast cancer by PCBs, p,p'-DDT, and p,p'-DDE concentrations in adipose tissues. Breast cancer cases have relatively higher menarche age, higher breastfeeding and postmenopausal proportion than controls. Levels of PCB-52, PCB-101, PCB-118, PCB-138, PCB-153, PCB-180, total PCBs (∑PCBs), and p,p'-DDE were relatively higher in breast cancer cases than controls. Breast cancer risk was increased in the third tertile of PCB-101, PCB-118, PCB-138, PCB-153, PCB-180, ∑PCBs, and p,p'-DDE as compared with the first tertile in both adjusted and unadjusted logistic regression models (odds ratios [ORs] were from 1.58 to 7.88); and increased linearly across categories of PCB-118 and p,p'-DDE in unadjusted model, and PCB-118 and PCB-153 in the adjusted model with trend (all P < 0.01). While breast cancer risk was declined in the second tertile of PCB-28, PCB-52, and PCB-101 in both unadjusted and adjusted models, also second tertile of p,p'-DDT and third tertile of PCB-28 in the adjusted models. This study suggests associations between the exposure of PCBs, p,p'-DDT, and p,p'-DDE and breast cancer risk. Based on adjusted models, PCB-118, PCB-138, PCB-153, PCB-180, ∑PCBs, and p,p'-DDE exposures increase breast cancer risk at current exposure levels, despite existing inconsistent even inverse results in PCB-28, PCB-52, PCB-101, and p,p'-DDT. More epidemiological studies are still needed to verify these findings in different populations.

Perfluoroalkyl substances (PFAS) and organochlorine pesticides (OCPs) in surface sediments were investigated from the Bering Sea, the Chukchi Sea and adjacent Arctic Ocean in 2010. Total concentrations (dry weight) of Σ 14 PFAS in surface sediments (0.85 ± 0.22 ng g -1 ) of the Bering Sea were lower than that in the Chukchi Sea and adjacent Arctic Ocean (1.27 ± 0.53 ng g -1 ). Perfluoro-butanoic acid (PFBS) and perfluoro-octanoic acid (PFOA) were the dominant PFAS in these areas. The concentrations of Σ 15 OCPs in the sediment of the Bering Sea (13.00 ± 6.17 ng g -1 ) was slightly higher than that in the Chukchi and Arctic Ocean (12.05 ± 2.27 ng g -1 ). The most abundant OCPs were hexachlorocyclohexane isomers (HCHs) and dichlorodiphenyltrichloroethane (DDT) and its metabolites. The composition patterns of HCHs and DDTs indicated that they were mainly derived from the early residues via river runoff. Increasing trends of PFAS, HCHs and DDTs in surface sediments from the Bering Sea to the Arctic Ocean were found, indicating oceanic transport. In summary, the concentrations of OCPs were orders of magnitude greater than the observed PFAS concentrations, and the concentrations of PFAS and OCPs in surface sediments from the Bering Sea to the Chukchi Sea and adjacent Arctic Ocean are at the low to moderate levels by comparing with other coastal and marine sediments worldwide., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Malaria control is under threat by the development of vector resistance to pyrethroids in long-lasting insecticidal nets, which has prompted calls for a return to the notorious crystalline contact insecticide DDT. A faster acting difluoro congener, DFDT, was developed in Germany during World War II, but in 1945 Allied inspectors dismissed its superior performance and reduced toxicity to mammals. It vanished from public health considerations. Herein, we report the discovery of amorphous and crystalline forms of DFDT and a mono-fluorinated chiral congener, MFDT. These solid forms were evaluated against Drosophila as well as Anopheles and Aedes mosquitoes, the former identified as disease vectors for malaria and the latter for Zika, yellow fever, dengue, and chikungunya. Contact insecticides are transmitted to the insect when its feet contact the solid surface of the insecticide, resulting in absorption of the active agent. Crystalline DFDT and MFDT were much faster killers than DDT, and their amorphous forms were even faster. The speed of action (a.k.a. knockdown time), which is critical to mitigating vector resistance, depends inversely on the thermodynamic stability of the solid form. Furthermore, one enantiomer of the chiral MFDT exhibits faster knockdown speeds than the other, demonstrating chiral discrimination during the uptake of the insecticide or when binding at the sodium channel, the presumed destination of the neurotoxin. These observations demonstrate an unambiguous link between thermodynamic stability and knockdown time for important disease vectors, suggesting that manipulation of the solid-state chemistry of contact insecticides, demonstrated here for DFDT and MFDT, is a viable strategy for mitigating insect-borne diseases, with an accompanying benefit of reducing environmental impact.

Although 1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane (DDT) was banned in the United States in 1972, it is still often detected in sediments where pyrogenic carbonaceous matter (PCM) and sulfate-reducing bacteria (SRB) co-exist. In this study, we found that 70.2 ± 0.2% of DDT disappeared in the presence of SRB and graphite powder, a model PCM, after 21 days at pH 7. Our results suggest that the observed DDT decay was due to the reaction between graphite powder and the reduced sulfur species that were produced by SRB. No biofilm formation was observed on the surface of graphite powder. Rather, the activity of SRB was inhibited by the presence of graphite powder. To understand the involvement of PCM in DDT decay, electrochemical cells and batch reactor experiments with sulfur-pretreated PCM as well as direct electrochemical reduction by a potentiostat were employed. Our results suggest that polysulfide, sulfide, sulfite, and thiosulfate could all react with PCM, forming surface-bound intermediates that subsequently led to DDT decay. The reactivity of reduced sulfur species was the highest for polysulfide, followed by sulfide, sulfite, and thiosulfate., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

As persistent organic pollutants, dichlorodiphenyltrichloroethanes (DDTs) and their metabolites pose considerable risks to human health and the environment. Therefore, monitoring DDTs in the environment is essential. Here, we developed a green, simple, and effective magnetic solid-phase extraction (MSPE) method coupled with gas chromatography tandem triple-quadrupole mass spectrometry to determine the DDT content of environmental water samples. A magnetic ionic liquid (IL) adsorbent was developed based on a modified magnetic multiwalled carbon nanotube/zeolitic imidazolate framework-8 (MM/ZIF-8/IL), synthesized by immobilizing the IL on the surface of MM/ZIF-8. We confirmed successful synthesis of MM/ZIF-8/IL by material characterization, and our results suggested that the MM/ZIF-8/IL had a high Brunauer-Emmett-Teller surface area (159.9 m 2 g -1 ), good thermostability (<800 °C), and a high degree of superparamagnetism (52.9 emu g -1 ). Several experimental conditions affecting the MSPE efficiency were optimized. Under the best conditions, good detection linearity was achieved (0.5-500 µg L -1 ) with determination coefficients ranging from 0.9927 to 0.9971. The lower limits of detection (0.0016-0.0072 µg L -1 ) also had good precision, having an intraday relative standard deviation (RSD) ≤ 6.5% and an interday RSD ≤ 8.9%. Finally, we used the as-developed method to determine DDT levels in environmental water samples., Competing Interests: The authors declare no conflict of interest.

Herein, we report the comparison of two different mixing methods for reductive dechlorination of gamma-hexachlorocyclohexane (γ-HCH), aldrin, and p, p'-dichlorodiphenyl-trichloroethane (p, p'-DDT), using iron/palladium (Fe/Pd) bimetallic nanoparticles. A noticeable enhancement of the reaction rate was found when the reductive dechlorination reaction was carried out in an ultrasound bath as compared with a platform shaker. These enhancements could be attributed to (a) the continuous cleaning and chemical activation of the surfaces of nanoscale Fe/Pd bimetallic nanoparticles by the combined chemical and physical effects of acoustic cavitation; and (b) the accelerated mass transport rates of target POPs to the surfaces of the Fe/Pd nanoparticles. Finally, the degradation intermediates and final products were determined by gas chromatography/mass spectrometry (GC/MS) analysis and the plausible degradation pathways for γ-HCH, aldrin, and p, p'-DDT by Fe/Pd bimetallic nanoparticles were proposed. PRACTITIONER POINTS: Exposure to POPs is a resilient global environmental and health issue. Fe/Pd bimetallic nanoparticles demonstrated > 90 % removal of POPs in the first 30 minutes of the reaction via ultrasonic mixing. GC-MS analyses provided verification of POPs degradation intermediates and final products., (© 2018 Water Environment Federation.)

DDT transformation to DDD in soil is the most commonly reported pathway under anaerobic conditions. A few instances of DDT conversion to products other than DDD/DDE have been reported under aerobic conditions and hardly any under anaerobic conditions. In particular, few reports exist on the anaerobic degradation of DDT in African tropical soils, despite DDT contamination arising from obsolete pesticide stockpiles in the continent as well as new contamination from DDT use for mosquito and tsetse fly control. Moreover, the development of possible remediation strategies for contaminated sites demands adequate understanding of different soil processes and their effect on DDT persistence, hence necessitating the study. The aim of this work was to study the effect of simulated anaerobic conditions and slow-release carbon sources (compost) on the dissipation of DDT in two tropical clay soils (paddy soil and field soil) amenable to periodic flooding. The results showed faster DDT dissipation in the field soil but higher metabolite formation in the paddy soil. To explain this paradox, the levels of dissolved organic carbon and carbon mineralization (CH 4 and CO 2 ) were correlated with p,p-DDT and p,p-DDD concentrations. It was concluded that DDT underwent reductive degradation (DDD pathway) in the paddy soil and both reductive (DDD pathway) and oxidative degradation (non-DDD pathway) in the field soil.

Even though the application of dichlorodiphenyltrichloroethanes (DDTs) has been restricted for over 30 years, their ubiquitous existence still poses profound adverse impacts on ecosystem and human health. In this study, simultaneous soil and air sampling campaigns at different functional areas were conducted in warm and cold seasons. Based on the residue levels and enantiomeric signatures of DDT and its metabolites in soils and air, the parameters influencing ecological and human health risks were explored. ΣDDT concentrations in soils correlated positively with organic matter (OM) and negatively with pH, whereas atmospheric DDT levels were primarily facilitated by increased temperature. High temperature and low soil pH were also favorable for the transformation of DDT into its metabolites. The inhabitants living in agricultural regions or in areas with higher soil OM or pH < 7 were exposed to higher existing and potential health risks of soil DDTs. In addition, at lower temperatures, the existing and potential carcinogenic risks of DDTs from soil exposure were higher, whereas risks from air inhalation were lower. Health risks would be increased when considering the enantioselective toxicity of o,p'-DDT and o,p'-DDD. The results from this study could provide baseline support for risk control and avoidance of DDTs., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Attention has been paid to the environmental distribution and fate of nanomedicines. However, their effects on the toxicity of environmental pollutants are lack of knowledge. In this study, the negatively charged poly (ethylene glycol)-b-poly (L-lactide-co-glycolide) (mPEG-PLA) and positively charged polyethyleneimine-palmitate (PEI-PA) nanomicelles were synthesized and served as model drug carriers to study the interaction and combined toxicity with dichlorodiphenyltrichloroethane (DDT). DDT exerted limited effect on the biointerfacial behavior of mPEG-PLA nanomicelles, whereas it significantly mitigated the attachment of PEI-PA nanomicelles on the model cell membrane as monitored by quartz crystal microbalance with dissipation (QCM-D). The cytotoxicity of DDT towards NIH 3T3 cells was greatly decreased by either co-treatment or pre-treatment with the nanomicelles according to the results of real-time cell analysis (RTCA). The cell viability of NIH 3T3 exposed to DDT was increased up to 90% by the co-treatment with mPEG-PLA nanomicelles. Three possible reasons were proposed: (1) decreased amount of free DDT in the cell culture medium due to the partitioning of DDT into nanomicelles; (2) mitigated cellular uptake of nanomicelle-DDT complexes due to the complex agglomeration or electrostatic repulsion between complexes and cell membrane; (3) detoxification effect in the lysosome upon endocytosis of nanomicelle-DDT complexes., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Among the methods used in the literature for the synthesizing of nano zero valent iron (nZVI), borohydride is the most commonly used method; it is seen that different variables are used together. In this study, optimum nano zero valent iron (nZVI) synthesizing method using borohydride method has been modified by using multiple optimization method in terms of both particle size and zeta potential. Selected independent variables are selected as iron sulfate concentration, ethanol ratio, and flow rate of borohydride solution. With the optimum synthesis method determined, the lowest particle size was obtained as 70 nm only when the particle size was taken into consideration, whereas 88.2 nm nZVI could be produced when both the particle size and the zeta potential were taken into consideration. In addition, the removal of DDT, which is the most commonly used persistent organic pollutant pesticides in the world, was investigated by nZVI synthesized. Different initial DDT concentration was investigated by expressing oxidation reduction potential (ORP) difference, removal rates, and oxidation byproducts. When DDD and DDE concentrations are considered, it is found that DDT is more likely to oxidize in DDD in all studied initial DDT concentrations. Removal rate was higher than 80% with initial concentrations lower than 125 μg/L, which is a high concentration that could be found in surface waters.

The delivery of nano-zerovalent iron (nZVI) as a remediation agent to targeted areas in soil was studied using different carriers. Among water, surfactant solution, and surfactant foam, the nZVI transport and carrying abilities followed the order of surfactant foam > surfactant solution > water. The nZVI migration was also facilitated by increased soil particle size and high surfactant concentration. Batch experiments probed the remediation of dichlorodiphenyltrichloroethane (DDT)-contaminated sand under different conditions. Compared to surfactant solution, the use of foam as a carrier achieved much higher DDT removal efficiencies for both coarse (foam/solution: 99/69%) and fine (foam/solution: 60/26%) sands. Additionally, the DDT removal efficiency was strongly influenced by surfactant concentration: foams generated using 1 and 5 g L -1 sodium lauryl ether sulfate (SLES) solutions reached the respective efficiencies of 44% and 75% under identical experimental conditions. However, the nature of the surfactant did not significantly affect the total removal efficiency of DDT. Solubilization, increased sweep efficiency, and reduction by nZVI were identified as factors affecting the DDT removal efficiency, and all three of them were involved when foam-nZVI was used as the flushing fluid., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Laboratory and field studies were used to evaluate the performance of low-density polyethylene (PE) passive samplers for assessing the freely dissolved concentrations of DDT and its degradates (DDD and DDE, together referred to as DDx) in an Italian lake environment. We tested commercially available 25 μm thick PE sheets as well as specially synthesized, 10 μm thick PE films which equilibrated with their surroundings more quickly. We measured PE-water partitioning coefficients (K pew ) of the 10 μm thick PE films, finding good correspondence with previously reported values for thicker PE. Use of the 10 μm PE for ex situ sampling of a lake sediment containing DDx in laboratory tumbling experiments showed repeatability of ±15% (= standard deviation/mean). Next, we deployed replicate 10 μm and 25 μm PE samplers (N = 4 for 10 d and for 30 d) in the water and sediment of a lake located in northern Italy; the results showed dissolved DDx concentrations in the picogram/L range in porewater and the bottom water. Values deduced from 10 μm thick PE films compared well (95% of all comparison pairs matched within a factor of 5) with those obtained using PE films of 25 μm thickness when dissolved DDx concentrations were estimated using performance reference compound (PRC) corrections, whether left at the bed-water interface for 10 or 30 days. These results demonstrated the potential of this sampling method to provide estimation of the truly dissolved DDx concentrations, and thereby the mobile and bio-available fractions in both surface waters and sediment beds., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Voltage gated sodium channels (VGSC) of mosquito vectors are the primary targets of dichlorodiphenyltrichloroethane (DDT) and other synthetic pyrethroids used in public health programmes. The knockdown resistant (kdr) mutations in VGSC are associated with the insecticide resistance especially in Anophelines. The present study is aimed to emphasize and demarcate the impact of three kdr-mutations such as L1014S, L1014F and L1014H on insecticide resistance. The membrane model of sodium transport domain of VGSC (STD-VGSC) was constructed using de novo approach based on domain and trans-membrane predictions. The comparative molecular modelling studies of wild type and mutant models of STD-VGSC revealed that L1014F mutant was observed to be near native to the wild type model in all the respects, but, L1014S and L1014H mutations showed drastic variations in the energy levels, root mean square fluctuations (RMSF) that resulted in conformational variations. The predicted binding sites also showed variable cavity volumes and RMSF in L1014S and L1014H mutants. Further, DDT also found be bound in near native manner to wild type in L1014F mutant and with variable orientation and affinities in L1014S and L1014H mutants. The variations and fluctuations observed in mutant structures explained that each mutation has its specific impact on the conformation of VGSC and its binding with DDT. The study provides new insights into the structure-function-correlations of mutant STD-VGSC structures and demonstrates the role and effects of kdr mutations on insecticide resistance in mosquito vectors.

Huge numbers of chemicals are released uncontrolled into the environment and some of these chemicals induce unwanted biological effects, both on wildlife and humans. One class of these chemicals are endocrine-disrupting chemicals (EDCs), which are released even though EDCs can affect not only the functions of steroid hormones but also of various signaling molecules, including any ligand-mediated signal transduction pathways. Dichlorodiphenyltrichloroethane (DDT), a pesticide that is already banned, is one of the best-publicized EDCs and its metabolites have been considered to cause adverse effects on wildlife, even though the exact molecular mechanisms of the abnormalities it causes still remain obscure. Recently, an industrial raw material, bisphenol A (BPA), has attracted worldwide attention as an EDC because it induces developmental abnormalities even at low-dose exposures. DDT and BPA derivatives have structural similarities in their chemical features. In this short review, unclear points on the molecular mechanisms of adverse effects of DDT found on alligators are summarized from data in the literature, and recent experimental and molecular research on BPA derivatives is investigated to introduce novel perspectives on BPA derivatives. Especially, a recently developed BPA derivative, bisphenol C (BPC), is structurally similar to a DDT derivative called dichlorodiphenyldichloroethylene (DDE).

Background: Environmental contaminants ranging from legacy chemicals like p,p'-dichlorodiphenyltrichloroethane (DDT) to emerging chemicals like phthalates are ubiquitous. Research aims/questions: This research aims to examine the presence and co-occurrence of contaminants in human milk and effects of pasteurization on human milk chemical contaminants., Methods: We analyzed human milk donated by 21 women to a milk bank for 23 chemicals, including the persistent organic pollutants (POPs) polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), dichlorodiphenyltrichloroethane (DDT), and dichlorodiphenyldichloroethylene (DDE) isomers that are known to sequester in adipose tissue, along with the current-use and nonpersistent pesticides chlorpyrifos and permethrin, phthalates, and bisphenol A (BPA). Human milk was analyzed raw and pasteurized for these chemicals using gas chromatography-tandem mass spectrometry for the POPs and high-performance liquid chromatography-tandem mass spectrometry for non-POPs., Results: Within the different chemical classes, PBDE47, PCB153, ppDDE, and MEHHP (phthalate metabolite) had the highest median concentrations and were observed in all samples. We also observed chlorpyrifos and BPA in all samples and permethrin in 90% of the samples tested. Only two chemicals, chlorpyrifos and permethrin, were susceptible to substantial degradation from pasteurization, a standard method for processing donated human milk., Conclusion: We detected 19 of 23 chemicals in all of our prepasteurized milk and 18 of 23 chemicals in all of our pasteurized milk. Pasteurization did not affect the presence of most of the chemicals. Future research should continue to explore human milk for potential chemical contamination and as a means to surveil exposures among women and children.

Organochlorine pesticides (OCPs) were banned by the Stockholm Convention many years ago; however, they are still detected in the environment due to their high persistence, their current illegal use, and their import from countries where they have not been banned. We evaluated the serum concentrations of selected OCPs (hexachlorobenzene (HCB), β-hexachlorocyclohexanes (β-HCH), p,p'-dichlorodiphenyltrichloroethane (DDT) and its metabolite p,p'-dichlorodiphenyldichloroethylene (DDE) in a sample of Lebanese adults using gas chromatography coupled to an ion trap mass spectrometer detector. The mean concentrations of HCB, β-HCH, DDT, and DDE were 7.1, 8.6, 2.1, and 18.9 ng/g of lipids, respectively, and the major contributor among the four OCPs was DDE. The OCP levels in the present study were in general lower than the values observed in several countries worldwide and their concentrations at the 95th percentile were lower than the biomonitoring equivalents (BEs) excluding any appreciable health risk. We observed an inverse association between HCB concentrations and body mass index (BMI) as well as HCB, β-HCH, and DDE levels, and smoking habits. Milk consumption however was positively associated with an increased serum level of β-HCH. This study, which was the first to investigate OCP serum levels in a Lebanese population, provides a baseline to which future measurements can be compared.

Enantio-selective molecular dynamics of (±)-o,p-DDT uptake and degradation in water-sediment system is described. Both uptake and degradation processes of (-)-o,p-DDT were slightly higher than (+)-o,p-DDT enantiomer. The optimized parameters for uptake were 7.0μgL -1 concentration of o,p-DDT, 60min contact time, 5.0pH, 6.0gL -1 amount of reverine sediment and 25°C temperature. The maximum degradation of both (-)- and (+)-o,p-DDT was obtained with 16 days, 0.4μgL -1 concentration of o,p-DDT, pH 7 and 35°C temperature. Both uptake and degraded process followed first order rate reaction. Thermodynamic parameters indicated exothermic nature of uptake and degradation processes. Both uptake and degradation were slightly higher for (-)-enantiomer in comparison to (+)-enantiomer of o,p-DDT. It was concluded that both uptake and degradation processes are responsible for the removal of o,p-DDT from nature but uptake plays a crucial role. The percentage degradations of (-)- and (+)-o,p-DDT were 30.1 and 29.5, respectively. This study may be useful to manage o,p-DDT contamination of our earth's ecosystem., (Copyright © 2017. Published by Elsevier Inc.)

The insecticide DDT is an omnipresent environmental contaminant and an ongoing toxicological concern. The recent discovery that methylenetetrahydrofolate (MTHF) models are capable of reducing a range of halocarbons to hydrocarbons under biomimetic conditions has prompted us to investigate the possible role of MTHF in the metabolism of DDT. We now report that the reaction of MTHF models with DDT produces no less than five known in vivo metabolites of DDT, namely DDD, DDE, DDMU, DBP, and DDM. The capability of the MTHF models to produce the full spectrum of known DDT dehalogenation products is strong evidence that the mechanistically obscure metabolism of DDT may involve MTHF. The findings also suggest that DDT should be capable of disrupting folate-dependent pathways., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The cationic dimethyldioctadecylammonium/trehalose 6,6,9-dibehenate (DDA/TDB) liposome is as a strong adjuvant system for vaccines, with remarkable immunostimulatory activity. The mucosal administration of vaccines is a potential strategy for inducing earlier and stronger mucosal immune responses to infectious diseases. In this study, we assessed whether the intranasal administration of cationic DDA/TDB liposomes combined with influenza antigen A (H3N2) can be used as a highly efficacious vaccine to induce mucosal and systemic antibody responses. Confocal laser scanning microscopy and a flow-cytometric analysis showed that the uptake of the cationic DDA/TDB liposome carrier was significantly higher than that of neutral 1,2-distearoyl-sn-glycero-3-phosphocholine/cholesterol (DSPC/Chol) or cationic 1,2-dioleoyl-3-trimethylammonium-propane/3β-(N-[N',N'-dimethylaminoethane]-carbamoyl (DOTAP/DC-Chol) liposomes. Our results indicate that the cationic DDA/TDB liposome is more effective in facilitating its uptake by dendritic cells (DCs) in vitro than the DSPC/Chol or DOTAP/DC-Chol liposome. DCs treated with DDA/TDB liposomes strongly expressed CD80, CD86, and MHC II molecules, whereas those treated with DSPC/Chol or DOTAP/DC-Chol liposomes did not. C57BL/6 mice intranasally immunized with H3N2-encapsulating cationic DDA/TDB liposomes had significantly higher H3N2-specific s-IgA levels in their nasal wash fluid than those treated with other formulations. The DDA/TDB liposomes also simultaneously enhanced the serum IgG IgG2a, IgG1, and IgG2b antibody responses. In summary, DDA/TDB liposomes effectively facilitated their uptake by DCs and DCs maturation in vitro, and induced significantly higher mucosal IgA, systemic IgG, IgG1, and IgG2b antibody titres than other formulations after their intranasal administration in vivo. These results indicate that DDA/TDB liposomes are a promising antigen delivery carrier for clinical antiviral applications.

The Palos Verdes Shelf (PVS) and the continental slope off the Palos Verdes Peninsula are highly contaminated by degradation products of the pesticide DDT (1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene). Sediment samples from two box cores were analyzed to obtain further information about the fate of DDT and its degradation products within the environment. After solvent extraction, an alkaline hydrolysis procedure was applied. A comprehensive screening for 26 DDT compounds revealed that DDT and its degradates contaminate not only the extractable fraction but also the fraction released by alkaline hydrolysis. A comparison of the quantitative distribution of DDT degradation products in the extractable fraction and released by alkaline hydrolysis showed a distinct difference. DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene), DDD (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethyl]benzene), DDMS (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethyl]benzene), and DDMU (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene) were predominant in the sediment extracts but minor components of the hydrolyzable fraction. The most abundant compounds released by the alkaline hydrolysis were DBP (bis(4-chlorophenyl)methanone), DDNU (1-chloro-4-[1-(4-chlorophenyl)ethenyl]benzene), DDM (1-chloro-4-[(4-chlorophenyl)methyl]benzene) and the water-soluble DDA (2,2-bis(4-chlorophenyl)acetic acid). The release of DDA may point to the presence of an important degradation pathway in marine environments. Concentration levels of DDT-related compounds showed corresponding vertical profiles in both fractions, but were significantly lower in the fraction released by alkaline hydrolysis. In contrast to fluvial sediments contaminated by DDT and its degradates the alkaline hydrolysis products represented a minor portion of the total sedimentary burden in the analyzed marine sediments. These findings show the necessity of a comprehensive screening for all DDT isomers and breakdown products in the extractable and non-extractable fraction to assess the total contamination abundance and potential environmental risks., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Fake news?? The contact insecticide DDT has been reappraised as a safe, life-saving compound by special interest groups committed to repealing environmental regulations. It is shown in this essay how some specific toxicological data has been misused by those aiming to disingenuously influence public policy. Graphic: Pestroy, a DDT-laced coating marketed in 1946 by Sherwin-Williams Research Laboratories., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hexachlorocyclohexane (HCH) isomers and dichlorodiphenyltrichloroethane (DDT) metabolites were analyzed in sediments of three different depths (0-10, 10-20 and 20-30 cm) collected from Kabul River, Pakistan, in February 2014. The occurrence levels, enantiomer fractions and potential ecological risk of these organochlorine pesticides (OCPs) were evaluated. The total concentrations of ∑HCHs and ∑DDTs in surface sediments ranged from 4.9-23.9 ng g -1 and from 6.4-18.8 ng g -1 (dry weight basis), respectively. The vertical contamination profile of DDTs was found in order of 20-30 cm >10-20 cm >0-10 cm, indicated that the residue levels of DDTs gradually decreased after it was banned. The ratios of β-HCH/HCHs ranged from 0.04 to 0.73 (69 % of samples below 0.5) suggesting the fresh input of HCHs, while isomeric ratios of α-HCH/γ-HCH (ranged from 0.02 to 7.94), with 76 % of samples less than 3, indicating the cocktail use of technical grade HCH and lindane in the study area. The ratio of (DDE + DDD)/DDTs (ranged from 0.42 to 0.90) indicated long-term biodegradation of parent DDT. The enantiomer of α-HCH was generally racemic or close to racemic for most of the samples, with enantiomeric fraction (EF) value <0.5 for some of the samples indicated the preferential biodegradation of (+)-α-HCH enantiomer, while for o,p'-DDT the EF values >0.5 indicated the depletion of (-)-o,p'-DDT enantiomer in most of the samples. According to sediment quality guidelines (SQGs), HCH contamination is the main concern for ecotoxicological risk in Kabul River.

Background: Although indoor residual spraying (IRS) is an effective tool for malaria control, its use contributes to high insecticide exposure in sprayed communities and raises concerns about possible unintended health effects., Objective: The Venda Health Examination of Mothers, Babies and their Environment (VHEMBE) is a birth cohort study initiated in 2012 to characterize prenatal exposure to IRS insecticides and exposures' impacts on child health and development in rural South Africa., Methods: In this report, we describe the VHEMBE cohort and dichlorodiphenyltrichloroethane (DDT) and dichlorodiphenyldichloroethylene (DDE) serum concentrations measured in VHEMBE mothers when they presented for delivery. In addition, we applied a causal inference framework to estimate the potential reduction in population-level p , p' -DDT and p , p' -DDE serum concentrations under five hypothetical interventions. A total of 751 mothers were enrolled., Results: Serum concentrations of p , p' isomers of DDT and DDE were above the limit of detection (LOD) in ≥98% of the samples, whereas the o , p' isomers were above the LOD in at least 80% of the samples. Median (interquartile range) p , p' -DDT and p , p' -DDE serum concentrations for VHEMBE cohort participants were 55.3 (19.0-259.3) and 242.2 (91.8-878.7) ng/g-lipid, respectively. Mothers reporting to have lived in a home sprayed with DDT for malaria control had ~5-7 times higher p , p' -DDT and p , p' -DDE serum concentrations than those who never lived in a home sprayed with DDT. Of the five potential interventions tested, we found increasing access to water significantly reduced p , p' -DDT exposure and increasing the frequency of household wet mopping significantly reduced p , p' -DDT and p , p' -DDE exposure., Conclusion: Our findings suggest that several intervention approaches may reduce DDT/DDE exposure in pregnant women living in IRS communities. https://doi.org/10.1289/EHP353.

Several lines of evidence suggest that exposures to Endocrine Disrupting Chemicals (EDCs) such as pesticides increase the risks of neuropsychiatric disorders. Despite extended residual persistence of dichlorodiphenyltrichloroethane (DDT) in the environment, the mechanisms of perinatal actions of DDT that could account for adult-onset of depression are largely unknown. This study demonstrated the isomer-specific induction of depressive-like behavior and impairment of Htr1a/serotonin signaling in one-month-old mice that were prenatally exposed to DDT. The effects were reversed by the antidepressant citalopram as evidenced in the forced swimming (FST) and tail suspension (TST) tests in the male and female mice. Prenatally administered DDT accumulated in mouse brain as determined with gas chromatography and tandem mass spectrometry, led to global DNA hypomethylation, and altered the levels of methylated DNA in specific genes. The induction of depressive-like behavior and impairment of Htr1a/serotonin signaling were accompanied by p,p'-DDT-specific decrease in the levels of estrogen receptors i.e. ESR1 and/or GPER1 depending on sex. In contrast, o,p'-DDT did not induce depressive-like effects and exhibited quite distinct pattern of biochemical alterations that was related to aryl hydrocarbon receptor (AHR), its nuclear translocator ARNT, and ESR2. Exposure to o,p'-DDT increased AHR expression in male and female brains, and reduced expression levels of ARNT and ESR2 in the female brains. The evolution of p,p'-DDT-induced depressive-like behavior was preceded by attenuation of Htr1a and Gper1/GPER1 expression as observed in the 7-day-old mouse pups. Because p,p'-DDT caused sex- and age-independent attenuation of GPER1, we suggest that impairment of GPER1 signaling plays a key role in the propagation of DDT-induced depressive-like symptoms., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

DDT and pyrethroid insecticides were among the earliest neurotoxins identified to act on voltage-gated sodium channels. In the 1960s, equipped with, at the time, new voltage-clamp techniques, Professor Narahashi and associates provided the initial evidence that DDT and allethrin (the first commercial pyrethroid insecticide) caused prolonged flow of sodium currents in lobster and squid giant axons. Over the next several decades, continued efforts by Prof. Narahashi's group as well as other laboratories led to a comprehensive understanding of the mechanism of action of DDT and pyrethroids on sodium channels. Fast forward to the 1990s, genetic, pharmacological and toxicological data all further confirmed voltage-gated sodium channels as the primary targets of DDT and pyrethroid insecticides. Modifications of the gating kinetics of sodium channels by these insecticides result in repetitive firing and/or membrane depolarization in the nervous system. This mini-review focuses on studies from Prof. Narahashi's pioneer work and more recent mutational and computational modeling analyses which collectively elucidated the elusive pyrethroid receptor sites as well as the molecular basis of differential sensitivities of insect and mammalian sodium channels to pyrethroids., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Organochlorine pesticides (OCPs) in sediments could be released into water, posing great threats to human health and organisms. In this study, the treatment effectiveness of in situ sequestration of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethane (DDTs) in sediments was explored using multiwalled carbon nanotubes (MWCNTs) as adsorbents. Physicochemical tests (aqueous equilibrium concentrations, semipermeable membrane device (SPMD) uptake, and quiescent flux to overlying water) were conducted to evaluate the sequestration effectiveness of MWCNTs. Compared to the control, the MWCNT-treated sediments showed great reductions of HCHs and DDTs in aqueous equilibrium concentrations, SPMD uptake, and quiescent flux to overlying water. And the effects of dose of MWCNTs, diameter of MWCNTs, and contact time between MWCNTs and sediments on sequestration effectiveness were studied. Increased dose, decreased MWCNT diameter, and prolonged contact time resulted in a better sequestration effectiveness. The results indicated that the addition of MWCNTs to sediment could reduce the content of HCHs and DDTs released from sediments, reducing bioavailability of HCHs and DDTs and minimizing risks to ecosystem and human. MWCNTs have potential applications as adsorbents for in situ treatment of OCP-contaminated sediments.

Concentrations of persistent organic pollutants (POPs) were measured for an entire year in the region of Tuscany, Italy. Passive air samplers consisting of polyurethane foam (PUF) disks were deployed over four sampling periods of 3-5 months from April 2008 to July 2009 in urban (n = 6) and rural (n = 4) sites. The aim of the study was to characterize the spatial and seasonal variations in selected POPs. The POP concentrations (pg m -3 ) in the air were dominated by dichlorodiphenyltrichloroethane and metabolites (DDTs) and polychlorinated biphenyls (∑ 7 PCBs). DDTs, and ∑ 7 PCBs showed a clear decreasing urban > rural gradient. The concentrations of DDTs and PCBs were up to 10 and 6 times higher, respectively, in urban sites than in rural sites. ∑ 7 PCBs showed a significant correlation with the urbanized areas located <5 km around the sampling sites. For hexachlorocyclohexanes (HCHs), α-HCH concentrations were similar at both sampling sites and were found to be quite uniform during the four sampling periods. Seasonal fluctuations were observed for DDTs, and ∑ 7 PCBs, with the highest concentrations observed during period 4 (summer-spring); this is most likely due to a temperature-driven re-emission from local sources. These findings were also supported by an air back trajectory analysis in the study area. This study contributes new information about POP levels in the Italian atmosphere and demonstrates the feasibility of using PUF disks to simultaneously assess seasonal concentrations at different sampling sites., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

In this study, the bioavailability of DDTr (sum of DDT, DDD and DDE isomers) in pesticide-contaminated soil was assessed using an in vivo mouse model. DDTr relative bioavailability (RBA) ranged from 18.7±0.9 (As35) to 60.8±7.8% (As36) indicating that a significant portion of soil-bound DDTr was not available for absorption following ingestion. When DDTr bioaccessibility was assessed using the organic Physiologically Based Extraction Test (org-PBET), the inclusion of a sorption sink (silicone cord) enhanced DDTr desorption by up to 20-fold (1.6-3.8% versus 18.9-56.3%) compared to DDTr partitioning into gastrointestinal fluid alone. Enhanced desorption occurred as a result of the silicone cord acting as a reservoir for solubilized DDTr to partition into, thereby creating a flux for further desorption until equilibrium was achieved. When the relationship between in vivo and in vitro data was assessed, a strong correlation was observed between the mouse bioassay and the org-PBET+silicone cord (slope=0.94, y-intercept=3.5, r(2)=0.72) suggesting that the in vitro approach may provide a robust surrogate measure for the prediction of DDTr RBA in contaminated soil., (Copyright © 2016 Elsevier Inc. All rights reserved.)

In this work, the toxicity of lake sediments contaminated with DDT and its metabolites DDD and DDE (collectively, DDX) was evaluated with widely used toxicity tests (i.e., Vibrio fischeri, Daphnia magna, Pseudokirchneriella subcapitata, and Lumbriculus variegatus) and with the social amoeba Dictyostelium discoideum, a model organism that is also suitable for studying pollutant-induced alterations at the molecular and cellular levels. Although the DDX concentration in the sediments was high (732.5 ppb), the results suggested a minimal environmental risk; in fact, no evidence of harmful effects was found using the different bioassays or when we considered the results of more sensitive sublethal biomarkers in D. discoideum amoebae. In line with the biological results, the chemical data showed that the concentration of DDX in the pore water (in general a highly bioavailable phase) showed a minimal value (0.0071ppb). To confirm the importance of the bioavailability of the toxic chemicals in determining their biological effects and to investigate the mechanisms of DDX toxicity, we exposed D. discoideum amoebae to 732.5ppb DDX in water solution. DDX had no effect on cell viability; however, a strong reduction in amoebae replication rate was observed, which depended mainly on a reduction in endocytosis rate and on lysosomal and mitochondrial alterations. In the presence of a moderate and transient increase in reactive oxygen species, the glutathione level in DDX-exposed amoebae drastically decreased. These results highlight that studies of the bioavailability of pollutants in environmental matrices and their biological effects are essential for site-specific ecological risk assessment. Moreover, glutathione depletion in DDX-exposed organisms is a new finding that could open the possibility of developing new pesticide mixtures that are more effective against DDT-resistant malaria vectors., (Copyright © 2016 Elsevier Inc. All rights reserved.)

DDT (1,1,1-trichloro-2.2-bis(p-chlorophenyl)ethane), one of the most abused insecticides, is a highly hazardous component for both human health and environmental applications. The biodegradation of DDT into non-toxic, environmentally benign components is strongly limited by the poor bioavailability of DDT. In this work, we combined experiments and molecular simulations to examine the effect of three cyclodextrins (α-, β-, and γ-CD) on their structure-specific interactions with DDT, specifically in relation to DDT solubility and biodegradability. It was found that all three CDs were able to bind to DDT with their inner hydrophobic cavity and different binding affinities and orientations, demonstrating their ability to improve DDT solubility. Different from the strong binding between DDT and β-/γ-CDs via a fully DDT bury mode, α-CD had a relatively weak binding with DDT via a partial DDT bury mode, which allowed DDT to be readily disassociated from α-CD at the lipid membrane interface, followed by DDT permeation into and across the cell membrane. The different binding modes between DDT and CDs explain why only α-CD can promote the bioavailability and biodegradation of DDT by simultaneously increasing its aqueous solubility and membrane interaction. This work provides structural-based binding information for the further modification and optimization of these three CDs to enhance their solubility and biodegradability of DDT.

Significant knowledge gaps exist regarding the fate and transport of persistent organic pollutants like dichlorodiphenyltrichloroethane (DDT) in tropical environments. In Brazil, indoor residual spraying with DDT to combat malaria and leishmaniasis began in the 1950s and was banned in 1998. Nonetheless, high concentrations of DDT and its metabolites were recently detected in human breast milk in the community of Lake Puruzinho in the Brazilian Amazon. In this work, we couple analysis of soils and sediments from 2005 to 2014 at Puruzinho with a novel dynamic floodplain model to investigate the movement and distribution of DDT and its transformation products (dichlorodiphenyldichloroethylene (DDE) and dichlorodiphenyldichloroethane (DDD)) and implications for human exposure. The model results are in good agreement with the accumulation pattern observed in the measurements, in which DDT, DDE, and DDD (collectively, DDX) accumulate primarily in upland soils and sediments. However, a significant increase was observed in DDX concentrations in soil samples from 2005 to 2014, coupled with a decrease of DDT/DDE ratios, which do not agree with model results assuming a post-ban regime. These observations strongly suggest recent use. We used the model to investigate possible re-emissions after the ban through two scenarios: one assuming DDT use for IRS and the other assuming use against termites and leishmaniasis. Median DDX concentrations and p,p'-DDT/p,p'-DDE ratios from both of these scenarios agreed with measurements in soils, suggesting that the soil parameterization in our model was appropriate. Measured DDX concentrations in sediments were between the two re-emission scenarios. Therefore, both soil and sediment comparisons suggest re-emissions indeed occurred between 2005 and 2014, but additional measurements would be needed to better understand the actual re-emission patterns. Monte Carlo analysis revealed model predictions for sediments were very sensitive to highly uncertain parameters associated with DDT degradation and partitioning. With this model as a tool for understanding inter-media cycling, additional research to refine these parameters would improve our understanding of DDX fate and transport in tropical sediments.

Activated carbon (AC) sediment amendment for hydrophobic organic contaminants (HOCs) is attracting increasing regulatory and industrial interest. However, mechanistic and well-vetted models are needed. Here, we conduct an 18 month field mesocosm trial at a site containing dichlorodiphenyltrichloroethane (DDT) and chlordane. Different AC applications were applied and, for the first time, a recently published mass transfer model was field tested under varying experimental conditions. AC treatment was effective in reducing DDT and chlordane concentration in polyethylene (PE) samplers, and contaminant extractability by Arenicola brasiliensis digestive fluids. A substantial AC particle size effect was observed. For example, chlordane concentration in PE was reduced by 93% 6 months post-treatment in the powdered AC (PAC) mesocosm, compared with 71% in the granular AC (GAC) mesocosm. Extractability of sediment-associated DDT and chlordane by A. brasiliensis digestive fluids was reduced by at least a factor of 10 in all AC treatments. The model reproduced the relative effects of varying experimental conditions (particle size, dose, mixing time) on concentrations in polyethylene passive samplers well, in most cases within 25% of experimental observations. Although uncertainties such as the effect of long-term AC fouling by organic matter remain, the study findings support the use of the model to assess long-term implications of AC amendment.

Antifouling paint applied to fishing vessels is the primary source of dichloro-diphenyl-trichloroethane (DDT) to the coastal marine environments of China. With the aim to provide science-based support of potential regulations on DDT use in antifouling paint, we utilized a fugacity-based model to evaluate the fate and impact of p,p'-DDT, the dominant component of DDT mixture, in Daya Bay and Hailing Bay, two typical estuarine bays in South China. The emissions of p,p'-DDT from fishing vessels to the aquatic environments of Hailing Bay and Daya Bay were estimated as 9.3 and 7.7 kg yr(-1), respectively. Uncertainty analysis indicated that the temporal variability of p,p'-DDT was well described by the model if fishing vessels were considered as the only direct source, i.e., fishing vessels should be the dominant source of p,p'-DDT in coastal bay areas of China. Estimated hazard quotients indicated that sediment in Hailing Bay posed high risk to the aquatic system, and it would take at least 21 years to reduce the hazards to a safe level. Moreover, p,p'-DDT tends to migrate from water to sediment in the entire Hailing Bay and Daya Bay. On the other hand, our previous research indicated that p,p'-DDT was more likely to migrate from sediment to water in the maricultured zones located in shallow waters of these two bays, where fishing vessels frequently remain. These findings suggest that relocating mariculture zones to deeper waters would reduce the likelihood of farmed fish contamination by p,p'-DDT., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Recently, sulfate radical ( [Formula: see text] ) based-advanced oxidation technologies (AOTs) have been attracted great attention in the remediation of contaminated soil and groundwater. In the present study, Co(2+) ions activated peroxymonosulfate (PMS) system was used to degrade 1, 1, 1-trichloro-2, 2'bis(p-chlorophenyl) ethane (DDT) in aqueous solutions. It was found that DDT was efficiently degraded in the PMS/Co(II) solutions within several hours, and the degradation efficiency of DDT was dependent on the concentrations of PMS and Co(II), and the optimum molar ratio of PMS and Co(II) was 50:1. The degradation kinetics of DDT were well described with pseudo-first-order equations over a range of temperature (10-40 °C), and the activation energy that was calculated with Arrhenius equation was 72.3 ± 2.6 kJ/mol. Electron paramagnetic resonance (EPR) and GC-MS techniques were applied to identify the intermediates and reactive species for DDT degradation. The results indicated that [Formula: see text] and OH were the main reactive species accounting for DDT degradation. Dichlorobenzophenone, 4-chlorobenzoic acid and benzylalcohol were the dominant intermediates for DDT degradation, and the likely degradation pathway of DDT was proposed on the basis of these identified products. Increasing pH inhibited the formation of [Formula: see text] and OH, and thus decreased the catalytic degradation of DDT. Cl(-) ion was found to significantly inhibit, while [Formula: see text] and dissolved oxygen had limited effects on DDT degradation., (Copyright © 2016 Elsevier Ltd. All rights reserved.)