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We studied the mechanisms of microbial transformation in functional bacteria on 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) in two different field soils, Haiyan (HY) and Chenghai (CH). The results showed that microbial activities had a steady dechlorination effect on DDT and its metabolites (DDx). Adding lactate or glucose as carbon sources increased the amount of Desulfuromonas, Sedimentibacter, and Clostridium bacteria, which led to an increase in adsorbed Fe(II) and resulted in increased DDT transformation rates. The electron shuttle of anthraquinone-2,6-disulfonic disodium salt resulted in an increase in the negative potential of soil by mediating the electron transfer from the bacteria to the DDT. Moreover, the DDT-degrading bacteria in the CH soil were more abundant than those in the HY soil, which led to higher DDT transformation rates in the CH soil. The most stable compound of DDx was 1,1-dichloro-2,2-bis(p-chloro-phenyl)ethane, which also was the major dechlorination metabolite of DDT, and 1-chloro-2,2-bis-(p-chlorophenyl)ethane and 4,4'-dichlorobenzo-phenone were found to be the terminal metabolites in the anaerobic soils.

A fermentative facultative anaerobe, strain HS01 isolated from subterranean sediment, was identified as Aeromonas hydrophila by 16S rRNA sequence analysis. The biotransformation of 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT), 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (DDD), and 1,1-dichloro-2,2-bis (4-chlorophenyl) ethane (DDE) by HS01 was investigated in the presence of goethite and anthraquinone-2,6-disulphonic disodium salt (AQDS). The results demonstrated that HS01 was capable of reducing DDTs, goethite and AQDS. And goethite can significantly enhance the reduction of DDT, DDD and DDE to some extent, while the addition of AQDS can further accelerate the reduction of Fe(III) and DDTs. The products of DDT transformation were identified as a large amount of dominant DDD, and small amounts of 1-chloro-2,2-bis-(p-chlorophenyl)ethane (DDMU), unsym-bis(p-chlorophenyl)-ethylene (DDNU), and 4,4'-dichlorobenzophenone (DBP). The results of cyclic voltammetry suggested that AQDS could increase the amounts of reactive biogenic Fe(II), resulting in the enhanced transformation of DDTs. This investigation gives some new insight in the fate of DDTs related to iron- and humic-reducing bacteria.

Dichlorodiphenyltrichloroethanes (DDTs) are persistent organic pollutants that were widely used in China, especially eastern China, as insecticides. This work investigated the concentration, dissipation, and volatilization of DDTs and enantiomeric fractions (EFs) of o,p'-DDD and o,p'-DDT in agricultural soils collected in 2006 from 58 sites in Zhejiang province. Correlations between DDT residues and soil properties were assessed to determine the effect of soil properties on the environmental attenuation of DDTs. High concentrations and detection frequencies were found for DDTs in agricultural soils in the region even though large-scale use of DDTs was banned over 20 years ago. The amount of DDTs was about 485 tons in the upper 20 cm of the soil column of cropland in the province in 2010, with a dissipation half-life of ~9 years. The mass flux of DDTs was 43 ng m(-2) h(-1), which corresponds to emissions of 7.6 tons with an emission factor of 1.6% in 2006. The low p,p'-DDT/p,p'-DDE ratios and high o,p'-DDT/p,p'-DDT ratios suggest that there were no recent inputs of DDTs but fresh application of dicofol, which contains DDT (o,p'-DDT in particular) impurities. The significant positive correlation between concentrations of DDTs and total organic carbon content (TOC) indicates the distribution of DDTs fit a typical "secondary distribution" pattern. DEVrac of o,p'-DDD, which is defined as the absolute value of EFs subtracted from 0.5, was significantly related with most of the physicochemical and microbial soil properties. The most significant correlation is that between DEVrac of o,p'-DDD and soil pH (p < 0.001), indicating that the soil pH plays a key role in enantioselective residues of DDTs.

The grafting of melon plants onto cucurbit rootstocks is a common commercial practice in many parts of the world. However, certain cucurbits have been shown to accumulate large quantities of weathered persistent organic pollutants from the soil, and the potential contamination of grafted produce has not been thoroughly evaluated. Large pot and field experiments were conducted to assess the effect of grafting on accumulation of weathered DDX (the sum of p,p'-DDT, p,p'-DDD, and p,p'-DDE) from soils. Intact squash (Cucurbita maxima × moschata) and watermelon (Citrullus lanatus), their homografts, and compatible heterografts were grown in pots containing soil with weathered DDX at 1480-1760 ng/g soil or under field conditions in soil at 150-300 ng/g DDX. Movement of DDX through the soil-plant system was investigated by determining contaminant levels in the bulk soil and in the xylem sap, roots, stems, leaves, and fruit of the grafted and nongrafted plants. In all plants, the highest DDX concentrations were detected in the roots, followed by decreasing amounts in the stems, leaves, and fruit. Dry weight concentrations of DDX in the roots ranged from 7900 ng/g (intact watermelon) to 30100 ng/g (heterografted watermelon) in the pot study and from 650 ng/g (intact watermelon) to 2430 ng/g (homografted squash) in the field experiment. Grafting watermelon onto squash rootstock significantly increased contaminant uptake into the melon shoot system. In the pot and field studies, the highest stem DDX content was measured in heterografted watermelon at 1220 and 244 ng/g, respectively; these values are 140 and 19 times greater than contaminant concentrations in the intact watermelon, respectively. The xylem sap DDX concentrations of pot-grown plants were greatest in the heterografted watermelon (6.10 μg/L). The DDX contents of the leaves and fruit of watermelon heterografts were 3-12 and 0.53-8.25 ng/g, respectively, indicating that although the heterografted watermelon accumulated greater pollutant levels, the resulting contamination is not likely a food safety concern.

1,1-Dichloro-2,2-bis(p-chlorophenyl) ethylene (p,p'-DDE) is the major metabolite of insecticide 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane (p,p'-DDT) and a persistent organic pollutant (POPs) with concerns regarding its bioaccumulation and persistence in the environment and food chain. In the present study, an indirect competitive enzyme-linked immunosorbant assay (ic-ELISA) specific for the detection of p,p'-DDE is described. In hapten synthesis, 2,2'-bis(4-chlorophenyl)ethanol and glutaric anhydride were used as precursor and spacer arm, respectively. The hapten was then conjugated to bovine serum albumin (BSA) as immunogen for mouse immunization and also conjugated to ovalbumin as coating antigen for ELISA. The developed ic-ELISA was used for detecting p,p'-DDE in human milk samples and validated against the results from conventional gas chromatography-electron capture detection (GC-ECD). Coefficients of variation (%CV) of ELISA were 5.7-10.4% for intra-assay and 10.6-19.6% for interassay variations. The Pearson correlation coefficient of p,p'-DDE concentrations between ic-ELISA and GC-ECD was r = 0.766, which was in an acceptable range. The results indicate that the developed assay could be an alternative analytical tool for monitoring p,p'-DDE in lipimic matrices such as human milk.

This study presents a reductive transformation method that combines zerovalent iron (ZVI) and Aeromonas hydrophila HS01 with iron oxide reduction property to degrade DDT (1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) under anoxic conditions. The results suggest that HS01 has weak capability in terms of reducing DDT to DDD (1,1-dichloro-2,2-bis(p-chlorophenyl)ethane) and nearly failed to reduce DDD or its transformed intermediates. The coexistence of ZVI and HS01 results in a slight enhancement of DDT degradation compared with the ZVI system alone. The reduction of intermediates by ZVI, however, can be obviously accelerated in the presence of HS01, and the addition of anthraquinone-2,6-disulfonic disodium salt (AQDS) can accelerate the transformation rates further, especially for intermediate reduction. The analysis of the amount and electrochemical properties of Fe(III)/Fe(II) indicates that the presence of HS01 with or without AQDS is beneficial to the reduction of Fe(III) to Fe(II), resulting in the removal of passivating ferric precipitates on the ZVI surface. A mechanism and pathway that clarify the roles of ZVI, HS01, and AQDS in the ZVI + HS01 + AQDS system for DDT transformation are proposed. The quick removal of surface ferric precipitates is thought to be the reason for the enhancement of the transformation of DDT and its intermediates.

The degradation of mixed (DDT and chlorpyrifos) insecticides by mixed insecticide enriched cultures was investigated. The mixed fungal population was isolated from mixed insecticide acclimatized sewage sludge over a period of 90 days. Gas chromatography was used to detect the concentration of mixed insecticides and calculate the degradation efficiency. The results showed that the degradation capability of the mixed microbial culture was higher in low concentrations than in high concentrations of the mixed insecticides. After 12 weeks of incubation, mixed pesticide enriched cultures were able to degrade 79.5-94.4% of DDT and 73.6-85.9% of chlorpyrifos in facultative cometabolic conditions. The fungal strains isolated from the mixed microbial consortium were identified as Fusarium sp. isolates GFSM-4 (ITCC 6841) and GFSM-5 (ITCC 6842). The fungal culture GFSM-4 could not utilize mixed insecticides as source of carbon and nitrogen, probably due to high combined toxicity of the mixed insecticides. Liquid media deficient in carbon (1% mannitol) and nitrogen (0.1% sodium nitrate) source increased the degradation efficiency of DDT and chlorpyrifos to 69 and 45%, respectively. The media with normal carbon and deficient nitrogen (0.1% sodium nitrate) sources extensively increased the degradation efficiencies of DDT (94%) and chlorpyrifos (69.2%). Traces of p,p'-dichlorobenzophenone and desdiethylchlorpyrifos were observed in the liquid medium, which did not accumulate probably due to further rapid degradation. This fungal isolate (GFSM-4) was able to degrade simultaneously DDT (26.94%) and chlorpyrifos (24.94%) in sterile contaminated (50 mg of each insecticide kg(-1)) soil in aerobic conditions.

Chirality exists extensively in nature. Synthetic chiral plant growth regulators and other pesticides usually behave enantioselectively in phyto-biochemical processes. Chiral plant growth regulators regulate the physiological processes of plants enantioselectively, and chiral pesticides cause enantioselective toxicities or ecotoxicities to plants. On the other hand, these chiral agrochemicals can be absorbed and enantioselectively metabolized by plants. This review summarizes the enantioselective effects of chiral plant growth regulators on plants and the phytotoxic and biotransformation effects of chiral herbicides and several persistent organic pollutants (POPs) on plants. Together, this information on the interactions between chiral agrochemicals and plants might shed light on studies on the chemical and biological behaviors of chiral chemicals, and direct research into the selection of plants, which can potentially decontaminate the environment.

Horticultural soils can contain elevated concentrations of selected trace elements and organochlorine pesticides as a result of long-term use of agrichemicals and soil amendments. A glasshouse study was undertaken to assess the uptake of weathered SigmaDDT {sum of the p, p'- and o, p-isomers of DDT [1,1,1-trichloro-2,2- bis( p-chlorophenyl)ethane], DDE [1,1-dichloro-2,2- bis( p-chlorophenyl)ethylene] and DDD[1,1-dichloro-2,2- bis( p-chlorophenyl)ethane]}, arsenic (As), cadmium (Cd), copper (Cu), and lead (Pb) residues by lettuce ( Lactuca sativa) and radish ( Raphanus sativus) from field-aged New Zealand horticultural soils. Concentrations of SigmaDDT, DDT, DDE, Cd, Cu, and Pb in lettuce increased with increasing soil concentrations. In radish, similar relationships were observed for SigmaDDT, DDE, and Cu. The bioaccumulation factors were less than 1 with the exception of Cd and decreased with increasing soil concentrations. Lettuce Cd concentrations for plants grown on four out of 10 assayed soils were equivalent to or exceeded the New Zealand food standard for leafy vegetables of 0.1 mg kg (-1) fresh weight. Concentrations of As, Pb, and SigmaDDT did not exceed available food standards. Overall, these results demonstrate that aged residues of SigmaDDT, As, Cd, Cu, and Pb in horticultural soils have remained phytoavailable. To be protective of human health, site-specific risk assessments and soil guideline derivations for residential settings with vegetable gardens need to consider the produce consumption pathway.