Pesticide Residues and Effect of Household Processing in Commonly Consumed Vegetables in Jimma Zone, Southwest Ethiopia.

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.

Validation of a Modified QuEChERS Method for the Determination of Selected Organochlorine Compounds in Honey.

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.

Prediction and Understanding: Quantum Chemical Framework of Transition Metals Enclosed in a B12N12 Inorganic Nanocluster for Adsorption and Removal of DDT from the Environment.

Emission of harmful pollutants from different sources into the environment is a major problem nowadays. Organochlorine pesticides such as DDT (C14H9Cl5) 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 (B12N12) 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 B12N12-DDT nanocluster have been reported. Further, analysis of the dipole moment, frontier molecular orbitals, molecular electrostatic potential plots, energy band gap, QNBO, and Fermi level suggested that the late-transition-metal-encapsulated inorganic B12N12 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.

Electron Attachment to Isolated Molecules as a Probe to Understand Mitochondrial Reductive Processes.

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.

Investigation of pesticides on honey bee carbonic anhydrase inhibition.

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 IC50 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.

Accelerated remediation of organochlorine pesticide-contaminated soils with phyto-Fenton approach: a field study.

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-Fe3O4 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-Fe3O4 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 (R2 > 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-Fe3O4, respectively, indicating that the degradation of DDE correlated positively with Fe3O4 concentration in the soil. Additionally, the presence of vetiver and nano-Fe3O4 in the soil increased DDT removal rates, which might be linked to the involvement of Fenton/Fenton-like reactions.

Interaction of zero-valent iron and carbonaceous materials for reduction of DDT.

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).

First evaluation of DDT (dichlorodiphenyltrichloroethane) residues and other Persistence Organic Pollutants in soils of Rwanda: Nyabarongo urban versus rural wetlands.

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.

Microwave-assisted rapid degradation of DDT using nanohybrids of PANI with SnO2 derived from Psidium Guajava extract.

The present work reports microwave-assisted synthesis of SnO2 nanoparticles via green route using Psidium Guajava extract. For the enhancement of catalytic activity, nanohybrids of SnO2 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/SnO2 revealed significant reduction in the optical band gap upon nanohybrid formation. Microwave-assisted catalytic efficiency of pure SnO2, PANI, PANI/SnO2 nanohybrids was investigated using DDT as a model persistent organic pollutant. The degradation efficiency of PANI/SnO2 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/SnO2-50/50 as catalyst. The effect of DDT concentration was explored and the degradation efficiency of PANI/SnO2-50/50 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, O2- radicals. The fragments with m/z values as low as 86 and 70 were confirmed by LCMS analysis. Recyclability tests showed that PANI/SnO2-50/50 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.

Detection and functional characterization of sigma class GST in Phlebotomus argentipes and its role in stress tolerance and DDT resistance.

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, H2O2 and temperature induction assays demonstrated stress-dependent induction of Parg-GSTσ expression indicating its important role in oxidative stress redressal.

Manipulating Solid Forms of Contact Insecticides for Infectious Disease Prevention.

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.

Persistent organic pollutants are still present in surface marine sediments from the Seto Inland Sea, Japan.

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.

Concentration, distribution and sources of perfluoroalkyl substances and organochlorine pesticides in surface sediments of the northern Bering Sea, Chukchi Sea and adjacent Arctic Ocean.

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 Σ14PFAS in surface sediments (0.85 ±â€¯0.22 ng g-1) of the Bering Sea were lower than that in the Chukchi Sea and adjacent Arctic Ocean (1.27 ±â€¯0.53 ng g-1). Perfluoro-butanoic acid (PFBS) and perfluoro-octanoic acid (PFOA) were the dominant PFAS in these areas. The concentrations of Σ15OCPs in the sediment of the Bering Sea (13.00 ±â€¯6.17 ng g-1) was slightly higher than that in the Chukchi and Arctic Ocean (12.05 ±â€¯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.

Full-Life Cycle Toxicity Assessment of Sediment-Bound DDT and Its Degradation Products on Chironomus dilutus.

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.

Risk of breast cancer and adipose tissue concentrations of polychlorinated biphenyls and organochlorine pesticides: a hospital-based case-control study in Chinese women.

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.

Dichlorodiphenyltrichloroethane (DDT) levels in rat livers collected from a malaria vector control region.

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.

Magnetic Solid-Phase Extraction of Dichlorodiphenyltrichloroethane and Its Metabolites from Environmental Water Samples Using Ionic Liquid Modified Magnetic Multiwalled Carbon Nanotube/Zeolitic Imidazolate Framework-8 as Sorbent.

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 m2 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.

The synergistic interaction between sulfate-reducing bacteria and pyrogenic carbonaceous matter in DDT decay.

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 ±â€¯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.

Evidence of non-DDD pathway in the anaerobic degradation of DDT in tropical soil.

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 (CH4 and CO2) 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.

Effect of mixing on reductive dechlorination of persistent organic pollutants by Fe/Pd nanoparticles.

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.