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A solvent tolerant bacterium Serratia marcescens NCIM 2919 has been evaluated for degradation of DDT (1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane). The bacterium was able to degrade up to 42% of initial 50 mg L -1 of DDT within 10 days of incubation. The highlight of the work was the elucidation of DDT degradation pathway in S. marcescens. A total of four intermediates metabolites viz. 2,2-bis (chlorophenyl)-1,1-dichloroethane (DDD), 2,2-bis (chlorophenyl)-1,1-dichloroethylene (DDE), 2,2-bis (chlorophenyl)-1-chloroethylene (DDMU), and 4-chlorobenzoic acid (4-CBA) were identified by GC-Mass and FTIR. 4-CBA was found to be the stable product of DDT degradation. Metabolites preceding 4-CBA were not toxic to strain as reveled through luxuriant growth in presence of varying concentrations of exogenous DDD and DDE. However, 4-CBA was observed to inhibit the growth of bacterium. The DDT degrading efficiency of S. marcescens NCIM 2919 hence could be used in combination with 4-CBA utilizing strains either as binary culture or consortia for mineralization of DDT. Application of S. marcescens NCIM 2919 to DDT contaminated soil, showed 74.7% reduction of initial 12.0 mg kg -1 of DDT after 18-days of treatment.

Concentrations of isomers of hexachlorocyclohexane (α-, β-, γ-HCH) and dichlorodiphenyltrichloroethane (DDT) and its metabolites (dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethylene (DDE) were assessed in organs of the pink (Oncorhynchus gorbuscha), chum (Oncorhynchus keta), chinook (Oncorhynchus tshawytscha), and sockeye salmon (Oncorhynchus nerka), caught near the Kuril Islands (the northern-western part of the Pacific Ocean), in the Sea of Okhotsk and the Bering Sea. Pesticides have been found to accumulate in fish organs in the following: muscles < liver < eggs < male gonads. The highest concentrations in muscles and liver have been recorded from sockeye. Of the DDT group, only DDE has been detected. The average concentration of HCHs + DDE in the muscles of pink, chum, chinook, and sockeye was 141, 125, 1241, 1641 ng/g lipids, respectively; and in the liver, 279, 183, 1305, 3805 ng/g lipids, respectively. The total concentration of HCHs isomers was higher than that of DDE. Average HCHs + DDE concentration in organs of salmon from study area is lower than that in salmon from Pacific coast of North America., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The bioremediation of a long-term contaminated soil through biostimulation and surfactant addition was evaluated. The concentrations of 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) and its metabolites 1,1-dichloro-2,2-bis(4-chlorophenyl) ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (DDE) were monitored during an 8-week remediation process. Physicochemical characterization of the treated soil was performed before and after the bioremediation process. The isolation and identification of predominant microorganisms during the remediation process were also carried out. The efficiency of detoxification was evaluated after each bioremediation protocol. Humidity and pH and the heterotrophic microorganism count were monitored weekly. The DDT concentration was reduced by 79% after 8 weeks via biostimulation with surfactant addition (B+S) and 94.3% via biostimulation alone (B). Likewise, the concentrations of the metabolites DDE and DDD were reduced to levels below the quantification limits. The microorganisms isolated during bioremediation were identified as Bacillus thuringiensis, Flavobacterium sp., Cuprivadius sp., Variovorax soli, Phenylobacterium sp. and Lysobacter sp., among others. Analysis with scanning electron microscopy (SEM) allowed visualization of the colonization patterns of soil particles. The toxicity of the soil before and after bioremediation was evaluated using Vibrio fischeri as a bioluminescent sensor. A decrease in the toxic potential of the soil was verified by the increase of the concentration/effect relationship EC50 to 26.9% and 27.2% for B+S and B, respectively, compared to 0.4% obtained for the soil before treatment and 2.5% by natural attenuation after 8 weeks of treatment., (Copyright © 2014. Published by Elsevier B.V.)

In the 1950s and 60s, discharges from a DDT manufacturing plant contaminated a tributary system of the Tennessee River near Huntsville, Alabama, USA. Regulatory action resulted in declaring the area a Superfund site which required remediation and extensive monitoring. Monitoring data collected from 1988, after remediation, through 2011 showed annual decreases approximating first-order decay in concentrations of total DDT and its six principal congeners (p,p'-DDT, o,p'-DDT, p,p'-DDD, o,p'-DDD, p,p'-DDE and o,p'-DDE) in filets from three species of fish. As of 2013, these concentrations met the regulatory requirements of 5 mg/kg or less total DDT for each fish tested. The enantiomer fractions (EF) of chiral o,p'-DDD in smallmouth buffalo and channel catfish were always below 0.5, indicating preferential decay of the (+)-enantiomer of this congener; this EF did not change significantly over 15 years. The often-neglected DDT metabolite p,p'-DDA was found at a concentration of about 20 μg/l in the ecosystem water., (Published by Elsevier Ltd.)

Contamination levels of coplanar polychlorinated biphenyls (Co-PCBs), polycyclic aromatic hydrocarbons (PAHs), and dichlorodiphenyltrichloroethane (DDTs) were measured in the entire body of the large Japanese field mouse (Apodemus speciosus) collected from Hokkaido (Ishikari and Rankoshi) and Aomori prefecture (Takko) in Japan. Higher concentrations of PCBs including Co-PCBs, were observed in the mice collected from Ishikari than those from Rankoshi. The concentration of PAHs in the soil from Ishikari was also higher than that in the other sampling sites. The findings suggest that Ishikari is the most polluted area, probably because of human activities, depending on the population distribution. However, the observed contaminant levels were extremely lower compared to those in previous studies. The ratio of testis weight to body weight (TW/BW) was the lowest in the mice collected from Ishikari, which is the area contaminated with PAHs and p,p'-dichlorodiphenyldichloroethylene (DDE). However, the serum testosterone levels of mice from the Ishikari area were higher than those from the non-contaminated other areas although no significant differences. Previous studies have shown that a low-level exposure to dioxin related compounds (DRCs) disturbances in sexual function, resulting in the production of testosterone. This study showed that POPs exposure is one of the possibility of the high testosterone concentration in the mice of the Ishikari area in addition to a cause of biological and environmental factors such as habitat density, age, temperatures and/or food riches.

One strain of ectomycorrhizal fungi, Xerocomus chrysenteron, had been investigated for its ability to degrade 1,1,1-trichloro-2,2-bis(4-chlorophe-nyl) ethane (DDT) by measuring unlabeled DDT and identifying its metabolites, and determining the mineralization of [(13)C]DDT in pure cultures. After 45d incubation, about 55% of the added DDT disappeared from the culture system, less than 5% remained in the nutrient solution, and about 44% was retained in the mycelium. Inoculation with mycelium enhanced the degradation of DDT in soil, and alleviated enrichment of DDT in plants. The metabolites identified by gas chromatography-mass spectrometry were 1,1-dichloro-2,2-bis(4-chlorophenyl) ethane (DDD), 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE), and 4,4'-dichlorobenzophenone (DBP). There were significant differences in the δ(13)C of released CO2 between [(13)C]DDT and DDT cultures, which indicated X. chrysenteron was able to mineralize DDT to CO2., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The purpose of this study was to investigate the effect of 1,1,1-trichloro-2,2-bis-(chlorophenyl)ethane (DDT), 1,1-bis-(chlorophenyl)-2,2-dichloroethene (DDE), and 1,1-dichloro-2,2-bis(chlorophenyl)ethane (DDD) isomers on COX-2 expression in a human trophoblast-derived cell line. Cultured HTR-8/SVneo trophoblast cells were exposed to DDT isomers and its metabolites for 24 h, and COX-2 mRNA and protein expression were assessed by RT-PCR, Western blotting, and ELISA. Prostaglandin E₂ production was also measured by ELISA. Both COX-2 mRNA and protein were detected under control (unexposed) conditions in the HTR-8/SVneo cell line. COX-2 protein expression and prostaglandin E₂ production but not COX-2 mRNA levels increased only after DDE and DDD isomers exposure. It is concluded that DDE and DDD exposure induce the expression of COX-2 protein, leading to increased prostaglandin E2 production. Interestingly, the regulation of COX-2 by these organochlorines pesticides appears to be at the translational level., (© 2012 Wiley Periodicals, Inc.)

In the companion paper, solid phase microextraction (SPME) fiber concentrations were used as a dose metric to evaluate the toxicity of hydrophobic pesticides, and concentration-response relationships were found for the hydrophobic pesticides tested in the two test species. The present study extends the use of fiber concentrations to organism body residues to specifically address biotransformation and provide the link to toxic response. Test compounds included the organochlorines p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT), p,p'-dichlorodiphenyldichloroethane (p,p'-DDD), and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE); two pyrethroids, permethrin and bifenthrin; and an organophosphate, chlorpyrifos. Toxicity, body residues, and biotransformation of the target compounds were determined for the midge Chironomus dilutus and the amphipod Hyalella azteca. Significant regression relationships were found without regard to chemical, extent of biotransformation, or whether the chemical reached steady state in the organisms. The equilibrium SPME fiber concentrations correlated with the parent compound concentration in the biota; however, the regressions were duration specific. Furthermore, the SPME fiber-based toxicity values yielded species-specific regressions with the parent compound-based toxicity values linking the use of SPME fiber as a dose metric with tissue residues to estimate toxic response., (Copyright © 2012 SETAC.)

A study to assess the level of organochlorine pesticides (OCPs) and bisphenol A (BPA) in edible marine biota collected from coastal waters of Malaysia was conducted using GC-MS and SPE extraction. An analytical method was developed and validated to measure the level of 15 OCPs and BPA simultaneously from five selected marine species. It was observed that some samples had low levels of p,p'-DDE, p,p'-DDT and p,p'- DDD ranging from 0.50 ng g(-1) to 22.49 ng g(-1) dry weight (d.w) but significantly elevated level of endosulfan I was detected in a stingray sample at 2880 ng g(-1) d.w. BPA was detected in 31 out of 57 samples with concentration ranging from below quantification level (LOQ: 3 ng g(-1)) to 729 ng g(-1) d.w. The presence of OCPs is most likely from past use although there is also indication of illegal use in recent times. The study also reveals that BPA is more widely distributed in coastal species caught off the coast of the most developed state. The potential health risk from dietary intakes of OCPs and BPA from the analysed fish species was negligible., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

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.

This study evaluated the interactions of flight, fasting, and 1,1,1-trichloro-bis(4-chlorophenyl)ethane (p,p'-DDT) loading on residue metabolism and distribution in recently exposed white-crowned sparrows (Zonotrichia leucophrys). Female sparrows were dosed with 5 mg p,p'-DDT per kg body weight over 3 d. Following 1 d of recovery, sparrows were flown in a wind tunnel for up to 140 min, in 15-min blocks. Food was withheld from the start of the flight period until birds were euthanized. DDT, 1,1-dichloro-2,2-bis(4 chlorophenyl)ethane (DDD), and 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE) were present in all tissues examined. 1-Chloro-2,2-bis(4-chlorophenyl)ethene (DDµ), 1,1-bis(4-chlorophenyl)ethane (p,p'-DDη), and 2,2-bis(4-chlorophenyl)ethanol (p,p'-DDOH) were not found. Fasting did not significantly affect the rate of residue increase over time in any of the tissues examined. When sparrows flew and fasted simultaneously, fasting seldom contributed to an increase in tissue residues. However, the length of time flown was significantly correlated with increasing toxicant concentrations in the brain, kidney, and liver, effectively demonstrating the potential for brief flights to enhance mobilization of DDT and its metabolites. Dose, flight, and fasting also increased residues in brain tissue. These contaminant redistributions may have important ramifications on the stresses experienced by migratory birds., (Copyright © 2011 SETAC.)

Environmental contamination caused by obsolete pesticide stocks was assessed using the Nile monitor (Varanus niloticus) as a sentinel species. Organochlorines and organophosphates were quantified by gas chromatography in abdominal fat and the liver, respectively. Results were compared to those obtained from three other sites, characterized by different histories of contamination. None of the previously stocked pesticides were recovered. Low to moderate levels of 4,4'-dichlorodiphenyldichloroethylene (4,4'-DDE) were quantified in monitors from all sites. Malathion and 4,4'-dichlorodiphenyldichloroethane (4,4'-DDD) also were detected sporadically. Interindividual variability was substantial. Correlations between pesticide loads and individual characteristics were considered. The nondetection of previously stocked pesticides in the monitors' tissues, their contamination by other pesticides, and the value of V. niloticus as a monitoring tool for environmental contamination are discussed. The results indicate a situation of low concern and draw attention to the importance of local conditions in determining environmental dangers associated with potential pollution sources., (Copyright © 2011 SETAC.)

Existing evidence indicated that dichlorodiphenyltrichloroethane (DDT)-containing antifouling paints were an important source of DDT residues to mariculture zones. However, the magnitude of the impact on aquafarming environment has remained largely unknown. In the present study, the concentrations of DDT and its metabolites (designated as DDXs) were determined in harbor sediment and antifouling paint samples collected from a typical mariculture zone in South China. Compositional and concentration correlation analyses implicated the DDT-containing antifouling paints for fishing boat maintenance as an important source of DDT in the mariculture zone. The annual emission of DDXs to the study region was estimated at 0.58 tons/yr. Furthermore, a comparison of the expected DDT loadings in pelagic fish and field measurements indicated that fish feed especially trash fish was a major source of DDTs in the fish body. Nevertheless, the use of DDT-containing antifouling paints should be limited to prevent further deterioration in aquafarming environment., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

One hundred and two basidiomycete strains (93 species in 41 genera) that prefer a soil environment were examined for screening of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) biodegradation. Three strains within two litter-decomposing genera, Agrocybe and Marasmiellus, were selected for their DDT biotransformation capacity. Eight metabolites; 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (DDD), two monohydroxy-DDTs, monohydroxy-DDD, 2,2-dichloro-1,1-bis(4-chlorophenyl)ethanol, putative 2,2-bis(4-chlorophenyl)ethanol and two unidentified compounds were detected from the culture with Marasmiellus sp. TUFC10101. A P450 inhibitor, 1-ABT, inhibited the formation of monohydroxy-DDTs and monohydroxy-DDD from DDT and DDD, respectively. These results indicated that oxidative pathway which was catalyzed by P450 monooxygenase exist beside reductive dechlorination of DDT. Monohydroxylation of the aromatic rings of DDT (and DDD) by fungal P450 is reported here for the first time.

This study examined the potential sources of persistent halogenated compounds (PHCs), including organochlorine pesticides, mainly DDXs (sum of o,p'- and p,p'-DDT, -DDD, and -DDE and p,p'-DDMU) and polybrominated diphenyl ethers, to typical aquaculture environments of South China, determined the relative importance of gill diffusion and fish feeding for exposure of fish to these contaminants and assessed potential health risk for global consumers via consumption of fish from South China. Fish feed is generally a direct and important source of PHCs in both freshwater and seawater aquaculture. In addition, gill diffusion is the predominant uptake route for PHCs (except p,p'-DDMU, o,p'-DDD and -DDT) in farmed freshwater fish, whereas accumulation from the diet is the major route for farmed marine fish. Risks to health of global consumers via consumption of fish from South China are minimal. However, increased risk can be foreseen due to continuous use of brominated fire retardants and electronic waste importation to China., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

This paper presents a comprehensive study of pesticide levels and bio-accumulation characteristics in human adipose tissues among residents of Southeast China. A large number of adipose samples (n=633) were selected for 58 pesticides and were analyzed by high sensitive Gas Chromatography-Tandem Mass Spectrometry (GC-MS/MS). The results showed that POPs pesticides were frequently detected, including 2,4'-DDD, 2,4'-DDE, 2,4'-DDT, 4,4'-DDD, 4,4'-DDE, 4,4'-DDT, α-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), and mirex. Other detected pesticide species were dicofol, methamidophos and chlordimeform, which have rarely been reported. Comparing to different countries, the concentrations of total DDT and HCH in these three Chinese southeastern sites were in the middle range, whereas the HCB and mirex were in the lower end. A significant correlation was observed between region as well as age and POPs pesticide levels. Some pesticide residue levels were also found significantly correlated to occupation. However, there was no significant correlation between gender and pesticides. Meanwhile, it is interesting to find that mortality of malignant tumors tends to associate with the pesticides levels in human adipose tissue. More importantly, the measured data presented in this study provide realistic information which is useful for assessing human exposure to pesticides in the general population of Southeast China., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Some organochlorine compounds, such as polychlorinated biphenyls (PCBs), have a tendency to bioaccumulate in humans and predators at the top of the food chain. We have recently confirmed the transplacental transfer of these compounds and the present study has been designed on the same material with the aim of investigating their potential health effects on newborns from 70 pregnant women, resident in a Northern Italy industrial town. Organochlorine compounds [namely, p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT), p,p'-dichlorodiphenyldichloroethene (p,p'-DDE), hexachlorobenzene (HCB), and PCBs] have been analyzed both in cord and maternal serum, placenta, and maternal subcutaneous adipose tissue by GC-MSD. p,p'-DDT levels in the adipose tissue resulted significantly (p<0.05) related to birth length. Mothers of neonates born by preterm programmed caesarean delivery showed significantly (p<0.005 for both) higher serum p,p'-DDE serum concentrations and p,p'-DDT levels in the adipose tissue, as compared to mothers delivering at term., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Air, rain, pond water, bank soil, pond sediment, fish feed, and fish were sampled from four freshwater cultured fish ponds (FWCFPs) in rural areas within the Pearl River Delta (PRD) of South China. Compositional analyses indicated that historical residues were the main sources of DDXs (defined as the sum of dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane (DDD), and dichlorodiphenyldichloroethylene (DDE) and 1-chloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDMU)), and hexachlorocyclohexanes (HCHs) in the FWCFPs. The input fluxes to the FWCFPs were estimated at 4.0, 1.6, 15, and -0.92 µg/m(2) ·year for DDXs and 3.8, 0.92, 2.9, and -1.4 µg/m(2) ·year for HCHs for dry deposition, wet deposition, feeding, and net air-water exchange in Dongguan, and 3.8, 1.2, 137, and -1.2 µg/m(2) ·year for DDXs and 3.6, 0.66, 5.0, and -1.0 µg/m(2) ·year for HCHs in Shunde, respectively. These results indicated that fish feed was the dominant input source of DDXs to the FWCFPs. As for HCHs, fluxes via dry deposition and feeding were similar and slightly higher than those via wet deposition. Biological effects due to the occurrence of DDXs in the FWCFPs were minimal, and consumption of freshwater fish from the PRD appeared to pose insignificant risk to human health based on some existing regulations and guidelines., (Copyright © 2011 SETAC.)

In the present study, five soil samples with organic carbon contents ranging from 0.23% to 7.1% and aged with technical dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH) for 15 months were incubated in a sealed chamber to investigate the dynamic changes of the OCP residues. The residues in the soils decreased over the incubation period and finally reached a plateau. Regression analysis showed that degradable fractions of OCPs were negatively correlated with soil organic carbon (SOC) except for α-HCH, while no correlation was found between degradation rate and SOC, which demonstrated that SOC content determines the OCP sequestration fraction in soil. Analysis of the ratio of DDT and its primary metabolites showed that, since it depends on differential sequestration among them, magnitude of (p,p'-DDE + p,p'-DDD)/p,p'-DDT is not a reliable criterion for the identification of new DDT sources., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

The fungi Aspergillus sydowii Ce15, Aspergillus sydowii Ce19, Aspergillus sydowii Gc12, Bionectria sp. Ce5, Penicillium miczynskii Gc5, Penicillium raistrickii Ce16 and Trichoderma sp. Gc1, isolated from marine sponges Geodia corticostylifera and Chelonaplysylla erecta, were evaluated for their ability to grow in the presence of DDD pesticide. Increasing concentrations of DDD pesticide, i.e., 5.0 mg (1.56 × 10⁻¹² mmol), 10.0 mg (3.12 × 10⁻²) mmol) and 15.0 mg (4.68 × 10⁻² mmol) in solid and liquid culture media were tested. The fungi Trichoderma sp. Gc1 and Penicillium miczynskii Gc5 were able to grow in the presence of up to 15.0 mg of DDD, suggesting their potential for biodegradation. A 100% degradation of DDD was attained in liquid culture medium when Trichoderma sp. Gc1 was previously cultivated for 5 days and supplemented with 5.0 mg of DDD in the presence of hydrogen peroxide. However, the quantitative analysis showed that DDD was accumulated on mycelium and biodegradation level reached a maximum value of 58% after 14 days.

Ionic liquids are a kind of environmentally friendly solvents which have drawn great attention in many fields. The potential of ionic liquid as dispersive liquidphase microextraction (DLPME) solvent for the enrichment of typical persistent organic pollutants, dichlorodiphenyltrichloroethane (DDT), and its metabolites including 1,1-dichloro-2,2-bis-(4'-chlorophenyl)ethane and 1,1-dichloro-2,2-bis-(4'-chlorophenyl)ethylene has been investigated. Parameters that may influence the extraction efficiency, such as the type and volume of ionic liquid, the type and volume of disperser solvent, extraction time, and sample pH, were investigated and optimized in detail. The experimental results showed the excellent linear relationship between peak area and the concentration of DDT and its metabolites over the range of 1-50 μg L⁻¹, and the precisions (RSDs) were 5.27-6.73% under the optimal conditions. The limits of detection could reach 0.33-0.63 μg L⁻¹. Satisfied results were achieved when the proposed method was applied to determine the target compounds in real-world water samples with spiked recoveries over the range 94.4-115.3%. All these facts indicated that ionic liquid DLPME coupled to HPLC was an environmentally friendly alternative for the rapid analysis of DDT and its metabolites at trace level in environmental water samples.

Background: In the present study, we report the analytical results of pp'DDT, pp'DDE and pp'DDD determination in lake water, plankton and zooplanktivorous fish of Lake Maggiore (Northern Italy), rather recently polluted by DDT of industrial origin, in order to understand the bottom-up pollution transfer among the abiotic and biotic components of the lake ecosystem., Materials and Methods: Fourteen water sampling campaigns were carried out from March 2003 to January 2009 in the water column of the deepest point (Ghiffa) of Lake Maggiore. Suspended and dissolved pollutants were determined separately. Three sampling campaigns were carried out from July 2008 to January 2009 for zooplankton and pelagic fish, and DDT residues were analysed by HRGC coupled with ECD and MS. Moreover, food items were detected in fish stomachs., Results and Discussion: Starting from 2007, the DDT contamination along the water column became rather homogeneous, probably because no flooding or other relevant hydrological events occurred; although steady-state condition should be expected, lipid normalised concentrations of pp'DDE and pp'DDD in zooplankton exceeded the levels of the same compounds in zooplanktivorous fishes., Conclusion: As this finding represents a thermodynamic paradox since bioaccumulative pollutant concentrations are expected to increase along the trophic chain, it was supposed that the abiotic and biotic lake components were not in a steady-state condition in Lake Maggiore.

The transformation of DDT was studied in an anaerobic system of dissimilatory iron-reducing bacteria (Shewanella decolorationis S12) and iron oxide (alpha-FeOOH). The results showed that S. decolorationis could reduce DDT into DDD, and DDT transformation rate was accelerated by the presence of alpha-FeOOH. DDD was observed as the primary transformation product, which was demonstrated to be transformed in the abiotic system of Fe(2+)+alpha-FeOOH and the system of DIRB+alpha-FeOOH. The intermediates of DDMS and DBP were detected after 9 months, likely suggesting that reductive dechlorination was the main dechlorination pathway of DDT in the iron-reducing system. The enhanced reductive dechlorination of DDT was mainly due to biogenic Fe(II) sorbed on the surface of alpha-FeOOH, which can serve as a mediator for the transformation of DDT. This study demonstrated the important role of DIRB and iron oxide on DDT and DDD transformation under anaerobic iron-reducing environments., (Copyright 2009 Elsevier Ltd. All rights reserved.)

Although the estrogenic properties of numerous chloroorganic pesticides have been widely recognized, population studies do not give clear results indicating the link between the exposure to these compounds and breast cancer development. Because of the weak affinity of these pesticides to estrogen receptors, they probably act by affecting the expression of CYP genes encoding cytochromes P450 engaged in the metabolism of environmental as well as natural estrogens. To examine the possible correlation between environmental estrogen levels in adipose tissue and breast cancer stage, grade, receptor status and onset of the disease, adipose tissue was isolated from 54 breast cancer patients and 23 healthy individuals. Clinical characteristics were obtained from the medical records, while the information concerning exposure to environmental estrogens where obtained from questionnaires. The environmental estrogens were identified and quantified by GC-chromatography. The data was analyzed with the use of Student t-test and Spearman correlation. The levels of most environmental estrogens did not differ between the patients and the controls, except the beta-HCH (beta-hexachlorocyclohexane) level, which was higher in the patients than in the healthy individuals. Significantly higher levels of DDE (1,1-bis(4-chlorophenyl)-2,2-dichloroethene) and DDT (1,1,1-trichloro-2,2-bis(4-chlorophenol)ethane) (P < 0.05) were observed in the patients with late onset of the disease which was probably due to the time of exposure. Moreover, in the patients exposed to environmental estrogens, significantly higher concentrations of DDD (1,1-bis(4-chlorophenyl)-2,2-dichloroethane) were found (P < 0.05). We also evidenced that estrogen-independent cancer was more frequent in the patients exposed to numerous risk factors in which higher levels of HCB (hexachlorobenzene), gamma-HCH (gamma-hexachlorocyclohexane), DDD and DDT in adipose tissue were detected. Breast cancer development is probably related to the accumulation of DDT and its derivatives, but the effect appears only in older patients. We postulate that environmental estrogens acting together with other risk factors might influence the progress and exacerbate the prognosis of breast cancer.

Anaerobic biodegradation of the pesticides: gamma-hexachlorocyclohexane, methoxychlor, o,p'- and p,p'-DDT in field polluted soil was tested at 12, 22 and 30 degrees C, using methanogenic granular sludge as inoculum. The contaminants were removed quite effectively at all temperatures and their removal rates increased 1.2-1.7 times with the increase in temperature. In most cases pesticide concentrations after an initial substantial decline remained almost constant until the end of experiment. These residual concentrations were also temperature dependent and they were 1.4-8.2 times higher at 12 degrees C than at 30 degrees C. DDT was degraded via DDD and accumulation of this metabolite was lower (19-64%) than the corresponding amount of removed DDT, especially at higher temperatures. Further transformation of DDD was confirmed by formation of p,p'-dichlorobenzophenone. Additional experiment demonstrated that removal was limited to readily desorbing fractions of pesticides, while their desorption-resistant fractions persisted in the soil. However, DDD metabolite was only partially removed despite its good desorbability.

Methanogenic granular sludge and wastewater fermented sludge were used as inocula for batch tests of anaerobic bioremediation of chlorinated pesticide contaminated soil. Results obtained for both types of biomass were similar: 80 to over 90% of gamma -hexachlorocyclohexane (gamma-HCH), 1,1,1-trichloro-2,2-bis-(4-methoxyphenyl)ethane (methoxychlor) and 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane (DDT) removed in 4-6 weeks. Residual fractions of these pesticides persisted till the end of the 16-week experiment. DDT was degraded through 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethane (DDD). Accumulation of this product corresponded stoichiometrically only to 34-53% of removed DDT, supposedly due to its further transformations, finally resulting in formation of detected 4,4'-dichlorobenzophenone (DBP). Addition of 0.5 mM Tween 80 nonionic surfactant resulted in about a twofold decrease of gamma -HCH and methoxychlor residual concentrations, as well as considerably lower DDD accumulation (7-29%) and higher DBP production. However, 1.25 mM dose of this surfactant applied together with granular sludge brought DDD levels back to that observed for treatments with the sludge alone, also impairing DBP formation.

Blue mussels (Mytilus edulis) and Pacific oysters (Crassostrea gigas) collected at seven locations in the Lower Saxonian Wadden Sea in January and February 2007 were analysed for organochlorine compounds. Contaminants were present in all samples, albeit with variable amounts and composition. The highest values were found in the Jade Bay. Congener PCB 153 was the contaminant which had the highest content of all organochlorines tested (475.75-937.39 ng/g lipid). DDT was detected in one sample only while DDD and DDE were found in all samples, the latter with contents up to 351.34 ng/g lipid. No clear differentiation could be made in terms of accumulation of organochlorines for M. edulis and C. gigas. Comparison with data from 2001 to 2006 showed an increase in 2007, which may be due to the different season the samples were taken.

This paper examines the concentration levels of organochlorine pesticides (OCPs) such as hexachlorocyclohexane (HCH) (alpha, beta and gamma), Aldrin, Endosulfan (alpha, beta), DDE, DDD, and DDT in the leaf, root and sediment part of Avicennia marina, a dominantly distributed mangrove species in Mumbai. The overall pattern of accumulation of OCPs was observed as sigmaHCH> sigmaDDT> sigmaEndosulfan>Aldrin. The occurrence of alphaHCH was found to be frequent in all the samples. The leaf and root samples showed better uptake of organochlorine pesticides whereas lower concentration levels of OCPs was observed in case of sediment samples. The mean concentration of OCPs was observed highest in case of root samples. This study indicated towards the capability of A. marina in bioaccumulation of the OCPs. The present data will serve as the baseline against which future study of OCPs uptake in the mangrove plant species may be assessed.

The biokinetics of p,p'-dichlorodiphenyltrichloroethane (DDT) and its metabolites, p,p'-dichlorodiphenydichloroethylene (DDE) and p,p'-dichlorodiphenyldichloroethane (DDD), in the green-lipped mussel Perna viridis were characterized in this study. We exposed the mussels to DDT in aqueous or dietary sources and then compared and evaluated the absorption, accumulation, distribution and elimination of DDT and its metabolites (DDD and DDE) in the mussels. In addition, a dynamic model was employed to quantify the depuration kinetics of each DDT compound in various organs of the mussels. The potential biotransformation pathway in the mussels after dietary exposure to DDT was also analyzed. Differing accumulation and elimination patterns of each DDT compound (DDT, DDD and DDE) in various organs were observed. Most of the DDT was confined to the hepatopancreas following either aqueous or dietary exposure, although the biological fate and biokinetics of DDT were differed significantly between routes of exposure. In addition, the elimination of dietary DDT was markedly slower than that following aqueous uptake. The biotransformation of DDT to DDE was rare in the mussels, suggesting that any DDE in the mussels came primarily from the ambient environment instead of through biotransformation process. Nevertheless, DDE may be retained in the mussels because of its exceptionally low elimination rate. In contrast, DDT was biotransformed to DDD in the mussels following dietary uptake, and this biotransformation may facilitate DDT elimination from the mussels.

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.

Dynamics of DDMS and DDMU in soils with DDT application under rice and ryegrass planting by pot experiment in greenhouse was conducted. Results show that DDE/DDD is slightly increased, and only about 20 ng x g(-1) DDMU or DDMS could be found in ryegrass soil at the end of the experiment. However, the DDD, DDMS and DDMU are formed very rapidly in rice soil. By the 84th day of the experiment of rice planting, DDT residue is 70-80 ng x g(-1), about 2% of the concentration added at the first of the experiment, meanwhile, concentrations of DDD, DDMS and DDMU are increased to the highest level. Concentration of DDMS and DDMU is detected at 28 and 115 ng x g(-1) respectively. On the other hand, above phenomena are not observed in the aged DDT of soils, which implies that submerging could increase degradation of DDT added newly to DDD and DDMS/DDMU, but not for the aged DDT of soils.

Young leaves of Mangifera indica (mango tree) from nine sites were used as bioindicators of local atmospheric contamination by organochlorine pesticides and metabolites from a point source, an old storage site at Vikuge farm in Tanzania. Sample extracts were analysed by GC-ECD and GC-MS. The concentrations ranged 2.7-649 ng g(-1)p,p'-DDT, below detection limit (bdl)-290 ng g(-1) o,p'-DDT, 0.4-13 ng g(-1) p,p'-DDE, bdl to 4 ng g(-1) o,p'-DDE, 1-231 ng g(-1) p,p'-DDD and 0.5-55 ng g(-1) o,p'-DDD. The concentrations of other compounds were up to 3.9 ng g(-1) pentachloroanisole, 1.3 ng g(-1) alpha-HCH, 12 ng g(-1) beta-HCH and 2 ng g(-1) gamma-HCH, on fresh weight basis. The compounds p,p'-DDT, p,p'-DDE, p,p'DDD and o,p'-DDD were found in 100% of the samples, while pentachloroanisole, o,p'-DDT and o,p'-DDE were detected in 78%, 56% and 67% of the samples, respectively. The low DDE/DDT ratios (0.01-0.20) in all samples indicate recent input of significantly non-degraded DDT from the point source. The low alpha-/gamma-HCH ratios (<0.3-0.7) in most samples indicate recent input of lindane (99% gamma-HCH). The slightly high alpha-/gamma-HCH ratios in some samples might be due to photochemical or bacterial transformation of gamma-HCH to alpha-HCH, or could reflect input of technical HCH. The very strong positive correlations in the concentrations of p,p'-DDT, p,p'-DDE, p,p'-DDD, o,p'-DDT, o,p'-DDE and o,p'-DDD (r=0.91-0.98, n=18, p<0.01) indicate that they have a common source. The results suggest that young mango leaves are suitable bioindicators of recent inputs of organochlorine contaminants from a point source.

A three-step sequential extraction procedure was applied to measure the concentrations of dichlorodiphenyltrichloroethane (DDT) on rice root surface and in root tissues collected from two sites in Tianjin. Bulk and rhizosphere soils were also analyzed. The measured DDXs in the rhizosphere soils were significantly higher than those in the bulk soils. On average, p,p'-DDT, p,p'-DDD, and p,p'-DDE in the soil accounted for 38%, 47% and 15% of the total. For total DDXs, approximately one third remained on the outer surface of the roots. The partition of DDXs between rhizosphere soil and root surface depend on contaminant affinity to soil organic matter, soil organic matter content and root specific area. A case specific equation was developed to quantitatively describe the partition of DDXs between soil and root surface.

Three Cucurbitaceae, Cucurbita pepo L. subsp. pepo (cv. Black Beauty, true zucchini), Cucurbita pepo L. intersubspecific cross (cv. Zephyr, summer squash), and Cucumis sativis (cv. Marketmore, cucumber), were grown in rhizotrons containing soil contaminated with three classes of highly weathered, hydrophobic organic contaminants: (1) technical chlordane, (2) dichlorodiphenylethanes (DDT and DDD) and -ethene (DDE), (3) polyaromatic hydrocarbons (PAHs), and heavy metal residues. Movement of the contaminants through the soil/plant system was studied by comparing contaminant concentration in the bulk soil, the rhizosphere soil pore water, the xylem sap, and aerial tissue. This permitted, for the first time, calculation of bioconcentration factors (BCFs) based on concentration in the xylem sap versus that in the rhizosphere soil pore water. The bioconcentration factors so determined for the sum of five chlordane residues (two enantiomers of trans-chlordane, TC; two enantiomers of cis-chlordane, CC; and achiral trans-nonachlor, TN) were 36, 40, and 23 for Black Beauty, Zephyr, and Marketmore, respectively. In addition, the xylem sap of each cultivar had a consistent enantioselective profile for some of the chiral chlordane components. For the sum of dichlorodiphenylethanes and -ethene, comparable BCF values were 19, 4, and 0.8, respectively. In the case of PAHs, different BCF patterns among the cultivars were noted for three- versus four-ring compounds. Similarly, movement of heavy metals was cultivar-dependent, with cadmium BCF values 9.5, 3.5, and 0.6for Black Beauty, Zephyr, and Marketmore, respectively; the analogous BCFs for zinc were 9, 11, and 2. Thus, passage from ex planta to in planta regions of the soil/plant system is dependent not only on properties of the plant, but also on those of the pollutant. Such data will provide insight into transport mechanisms of highly hydrophobic organic contaminants, as well as heavy metal contaminants, in the soil/plant system.

Harbor porpoises from the German North and Baltic Seas exhibit a higher incidence of bacterial infections compared to whales from less polluted arctic waters. The potential adverse effect of environmental contaminants such as polychlorinated biphenyls (PCBs) and heavy metals on the immune system and the health status of marine mammals is still discussed controversially. The aim of the present study was to investigate the possible influence of PCB, polybrominated diphenyl ether (PBDE), toxaphene, (p,p'-dichlorodiphenyl)trichlorethane (DDT), and (p,p'-dichlorodiphenyl)dichlorethene (DDE) on the immune system of harbor porpoises. Lymphoid organs are influenced by a variety of factors, and therefore special emphasis was given to separating the confounding effect of age, health status, nutritional state, geographical location, and sex from the effect of contaminant levels upon thymus and spleen. Contaminant analysis and detailed pathological examinations were conducted on 61 by-caught and stranded whales from the North and Baltic Seas and Icelandic and Norwegian waters. Stranded harbor porpoises were more severely diseased than by-caught animals. Thymic atrophy and splenic depletion were significantly correlated to increased PCB and PBDE levels. However, lymphoid depletion was also associated with emaciation and an impaired health status. The present report supports the hypothesis of a contaminant-induced immunosuppression, possibly contributing to disease susceptibility in harbor porpoises. However, further studies are needed to determine if lymphoid depletion is primarily contaminant-induced or secondary to disease and emaciation in this cetacean species.

The southern bent-wing bat (Miniopterus schreibersii bassanii) is an insectivorous, obligate cave dwelling species found in south-eastern South Australia and western Victoria, Australia. In recent times, the finger of blame for an apparent population decline at Bat Cave, Naracoorte (one of only two known maternity roosts for this species, the other being Starlight Cave, Warrnambool) has been pointed at pesticide use in the region, following the finding of organochlorine and organophosphate insecticide residues in bat guano. This study sampled juvenile southern bent-wing bats from Bat Cave and Starlight Cave, and determined DDT, DDD and DDE concentrations in liver, pectoral muscle, brain and back-depot fat tissues. DDT was detected in only three tissue samples (highest concentration, 126 microg kg(-1) (wet weight) in back-depot fat), DDD was detected only in brain tissue (highest concentration, 115 microg kg(-1) (wet weight)), but DDE was detected in most tissues (highest concentration, 24,200 microg kg(-1) (wet weight) in back-depot fat). A minimum DDE body burden was estimated for each bat, and then for each sex at each site, from the data from all tissues sampled. The DDE body burdens estimated were highest in male bats from Starlight Cave (114 microg kg(-1)), then females from Starlight Cave (54.5 microg kg(-1)), and males from Bat Cave (53.2 microg kg(-1)). Female bats at Bat Cave contained the lowest estimated body burden (24.2 microg kg(-1)). Comparisons of DDE concentrations between the sexes showed that contamination was not statistically different within each maternity site. The different chemical concentrations observed in the Bat Cave and Starlight Cave bats is suggestive of different feeding locations, and perhaps an emerging population split, further threatening a species already at risk as a result of landscape scale changes to land use across their range.

Three point mutations R335S, L336V and V476L, distinguish the sequence of a cytochrome P450 CYP6A2 variant assumed to be responsible for 1,1,1-trichloro-2,2-bis-(4'-chlorophenyl)ethane (DDT) resistance in the RDDT(R) strain of Drosophila melanogaster. To determine the impact of each mutation on the function of CYP6A2, the wild-type enzyme (CYP6A2wt) of Cyp6a2 was expressed in Escherichia coli as well as three variants carrying a single mutation, the double mutant CYP6A2vSV and the triple mutant CYP6A2vSVL. All CYP6A2 variants were less stable than the CYP6A2wt protein. Two activities enhanced in the RDDT(R) strain were measured with all recombinant proteins, namely testosterone hydroxylation and DDT metabolism. Testosterone was hydroxylated at the 2beta position with little quantitative variation among the variants. In contrast, metabolism of DDT was strongly affected by the mutations. The CYP6A2vSVL enzyme had an enhanced metabolism of DDT, producing dicofol, dichlorodiphenyldichloroethane and dichlorodiphenyl acetic acid. The apparent affinity of the enzymes CYP6A2wt and CYP6A2vSVL for DDT and testosterone was not significantly different as revealed by the type I difference spectra. Sequence alignments with CYP102A1 provided clues to the positions of the amino acids mutated in CYP6A2. These mutations were found spatially clustered in the vicinity of the distal end of helix I relative to the substrate recognition valley. Thus this area, including helix J, is important for the structure and activity of CYP6A2. Furthermore, we show here that point mutations in a cytochrome P450 can have a prominent role in insecticide resistance.

A comparative study on the reliability of toxicokinetic parameters for predicting hepatotoxicity was conducted in male F344 rats receiving a single (106 mg/kg by gavage) or 7-day repeated (1000 ppm in feed, 97 mg/kg/day) administration of p,p'-DDT. DDT was selected as the test substance because it is known as a hepatotoxic agent and its metabolic pathway is well documented. Concentrations of DDT and its metabolites (DDE and DDD) in the plasma, brain, and liver were measured at various time intervals during the study and the results were compared with the area under the concentration-time curve (AUC) in relation to hepatotoxic response. Increases in the absolute and relative (ratio to body weight) liver weights were observed as a typical toxic response after a single or repeated exposure to DDT. The coefficient (R2) of correlation between the increases in the relative liver weight and the concentrations or AUC of DDT and its metabolites in the plasma and liver was estimated. The values of R2 between the relative liver weight and AUC of DDT or the total DDT (T-DDT) in the plasma and liver were found to be more consistent and higher than those with their concentrations in the repeated dose study. In addition, the R2 values in correlation with their AUCs after a single exposure were lower than those in the repeated dose study. These results indicate that the AUC of DDT or T-DDT in the plasma and liver would be more reliable than their concentrations for predicting hepatotoxicity caused by DDT, especially in the repeated dose study.

Uptake of sediment-associated contaminants by the oligochaete Lumbriculus variegatus was evaluated after 1, 3, 7, 14, 28, and 56 d of exposure to a field-collected sediment contaminated with DDT and its metabolites, dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethylene (DDE), or to a field-collected sediment contaminated with polycyclic aromatic hydrocarbons (PAHs). Depuration of contaminants by oligochaetes in a control sediment or in water was also evaluated over a 7-d period after 28 d of exposure to the field-collected sediments. Accumulation of PAHs with a log octanol-water partitioning coefficient (log Kow) <5.6 typically reached a peak at day 3, followed by a lower plateau between days 7 and 56 of the sediment exposure. Similarly, 4,4'-DDT exhibited a peak in accumulation at day 14 followed by a decline at days 28 and 56. In contrast, accumulation of PAHs with a log Kow >5.6 or DDD and DDE typically exhibited a steady increase from day 1 to about day 14 or 28, followed by a plateau. Therefore, exposures conducted for a minimum of 14 to 28 d better reflected steady-state concentrations for DDT and its metabolites and for PAHs. Depuration rates for DDT and its metabolites and high-Kow PAHs were much higher in organisms held in clean sediment relative to both water-only depuration and model predictions. This suggests that depuration in clean sediment may artificially accelerate depuration of hydrophobic compounds. Comparisons between laboratory-exposed L. variegatus and oligochaetes collected in the field from these sediments indicate that results of laboratory tests can be extrapolated to the field with a reasonable degree of certainty.

The impacts of arsenic co-contamination on the natural breakdown of 1,1,l1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) in soil are investigated in a study of 12 former cattle dip sites located in northeastern NSW, Australia. This study examines the relationship between the intrinsic breakdown of DDT to 1,1 -dichloro-2,2-bis(4-chlorophenyl)ethane (DDD) and 1,l-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE), and the impacts of arsenic co-contamination on this breakdown. Between-site analysis demonstrated that arsenic at 2000 mg/kg gave a 50% reduction in the concentration of DDD compared to background arsenic of 5 mg/kg.Within-site analysis also showed the ratio of DDT:DDD increased in soils as arsenic concentrations increased. This within-site trend was also apparent with the DDT:DDE ratio, suggesting inhibition of DDT breakdown by arsenic co-contamination. Microbial activity was inhibited as residues of total DDTs and arsenic increased. Hence arsenic co-contamination and high concentrations of DDT in soil may result in an increased persistence of DDT in the environment studied.

The potential for anaerobic biodegradation of 1,1,1-trichloro-2,2-bischlorophenylethane (DDT), 1,1-dichloro-2,2,-bischlorophenylethane (DDD), and dichlorodiphenylchloroethylene (DDE) in anoxic sediment slurries collected from the Keelung River was investigated in this study. o,p'- and p,p'-DDT were dechlorinated to o,p'- and p,p'-DDD, respectively, and then transformed to other compound(s). 1-Chloro-2,2-bis (p-chlorophenyl) ethylene (DDMU) and trace amount of dichlorobenzophenone (DBP) were detected in sediment slurries amended with p,p'-DDT or p,p'-DDD. DDMU was also detected in sediment slurries amended with p,p'-DDE. The relative transformation rates for both o,p'- and p,p'-isomers of DDT, DDD, and DDE were DDT>DDD>DDE. Re-addition of DDT, DDD, or DDE to the sediment slurries after initial removal enhanced the respective dechlorination rates. The transformation rates of the p,p'-isomers of both DDT and DDD were faster than those of the respective o,p'-isomers. p,p'-DDT dechlorination in the p,p'-DDT-adapted sediment slurries were inhibited by the addition of molybdate, or molybdate plus sulfate, but not inhibited by the addition of sulfate. Addition of bromoethane-sulfonic acid (BESA) slightly inhibited p,p'-DDT dechlorination. Non-adapted sediment slurries lost the ability to dechlorinate pentachlorophenol during adaptation to p,p'-DDT. p,p'-DDD was the major transformation product of p, p'-DDT in 3,4,4',5-tetrachlorobiphenyl-adapted sediment slurries, which suggested that the microbial community in the 3,4,4',5-CB-adapted sediment was unable to remove chlorine from the aromatic rings of p,p'-DDT.

Microbial analysis of contaminated soil and uncontaminated plant and faecal material resulted in the enrichment of a number of microbial communities capable of utilizing a range of environmental pollutants. Growth was observed on polycyclic aromatic hydrocarbons, polychlorinated biphenyls, heterocyclic aromatic compounds and organochlorine pesticides. However, none of the communities could grow on pentachlorophenol. Pure cultures were isolated from microbial communities using phenanthrene and pyrene as the sole carbon and energy source. Isolates were also obtained using DDT, DOH, DBH and PCPA when peptone was supplemented to the medium. Strain AJR39,504, isolated using DDT and peptone, could not be positively identified on the basis of substrate utilization tests. However, it most closely resembled Stenotrophomonas maltophilia (0.424 similarity) using the Microlog 3 database software. Isolate AJR39, 504 could also grow on polycyclic aromatic hydrocarbons, chlorinated- and nitro-aromatic compounds. In addition, the degradation of DDT (100 mg l(-1)) by isolate AJR39,504 resulted in a 35% decrease in DDT concentration after 28 days with a concomitant increase in DDD concentration.

Wildlife contamination studies found high levels of DDT and associated metabolites in bird eggs from Canadian orchard sites during the early 1990s. The present study investigated local dietary uptake of DDT and geographic variability in tissue concentrations in the same orchards. A soil-earthworm-robin food chain was chosen for study, as early surveys showed that robins contained the highest levels of DDT of several avian species and because published research indicated that earthworms were a probable dietary exposure route. Organochlorine pesticides and PCBs were measured in soil, earthworm, robin egg, and robin nestling samples collected from fruit orchards and reference sites. High average DDE (soil: 5.2 mg/kg; earthworm: 52 mg/kg; robin egg: 484 mg/kg dry weight) and DDT (soil: 9.2 mg/kg; earthworm: 21 mg/kg; robin egg: 73 mg/kg dry weight) concentrations in Okanagan (British Columbia) samples confirmed that previously recorded contamination was common in the region. Concentrations detected in Simcoe, Ontario, orchards were not as high but were still significantly elevated relative to levels in soils and robins from reference areas. Significant positive linear regressions between soil and earthworm concentrations and consistent trends in food chain accumulation suggested that robins were acquiring DDT and metabolite (DDTr) burdens locally. Low concentrations of DDT and DDTr in robin eggs collected from nests in nearby nonorchard and post-DDT orchard habitats suggested that the local sources were in orchards. Persistence of DDT in orchard food chains is likely due to a combination of retarded degradation rates for DDT in soil and its extensive use historically. DDT concentrations in some robin eggs and earthworms were at levels comparable to those observed in field studies where mortality or reproductive effects occurred.

Degradation of 14C-DDT was studied in a marine ecosystem for 60 days and in marine sediments under moist and flooded conditions using a continuous flow system for a period of 130 days. 14C-DDT residues were recovered in sediments of the marine ecosystem at uniform level of 60-65% of the applied 14C-activity throughout the incubation period. DDD was a major metabolite in sediments while DDMU was a major metabolite in clams. Clams brought about substantial degradation of DDT. However, 14C-residues recovered form clams are not suggestive of significant bioaccumulation. In the continuous flow experiment, under both moist and flooded conditions, DDT underwent degradation and about 22% of the applied 14C-activity was recovered as volatiles under both conditions. In sediments, extractable 14C-residues accounted for about 30 and 19% under moist and flooded conditions, respectively. DDT was the major compound in extractable residues as identified by TLC-autoradiographic procedures. More bound residues were formed under flooded than under moist conditions.

DDT is reductively dechlorinated to DDD and dehydrochlorinated to DDE; it has been thought that DDE is not degraded further in the environment. Laboratory experiments with DDE-containing marine sediments showed that DDE is dechlorinated to DDMU in both methanogenic and sulfidogenic microcosms and that DDD is dehydrochlorinated to DDMU three orders of magnitude more slowly. Thus, DDD does not appear to be an important precursor of the DDMU found in these sediments. These results imply that remediation decisions and risk assessments based on the recalcitrance of DDE in marine and estuarine sediments should be reevaluated.

The present study focuses on the distribution and accumulation of persistent organochlorine compounds in different tissues and organs of grey seal (Halichoerus grypus) pups. Thus, levels of drins (aldrin, dieldrin, endrin), chlordanes (heptachlor, heptachlorepoxide, oxychlordane, transnonachlor), DDTs (p,p'-DDE, o,p'-DDD, p,p'-DDD, o,p'-DDT, p,p'-DDT) and 22 PCB congeners were determined in samples of brain, fat, and liver of 0-10 days old grey seal pups from the species' main breeding site in Norway. Whereas 10 different compounds were detected in the blubber, 8 compounds were detected in the liver. The concentrations of the two major classes of OCs (PCBs and DDTs) in liver were both about 75% of that in blubber. In cerebral tissue, only two PCB congeners were detected, and sigma PCB was only about 1% of that measured in the blubber. The distribution pattern of PCB-congeners in liver and brain differed significantly from that in blood and blubber tissue, indicating that the physico-chemical properties of the individual congeners and the lipid composition of the tissue are decisive for the tissue-specific pattern of congener distribution. A significant increase of the sigma DDT/sigma PCB-ratio as a function of blubber thickness indicates that DDT compounds are more readily accumulated in older pups.