Association between toxic organochlorine levels in human serum and systemic lupus erythematosus.

Organochlorines (OCs) are groups of highly toxic pesticides with known immunotoxicity. The present work aimed to study the potential association between serum residues of OCs and the risk of developing systemic lupus erythematosus (SLE) as well as correlating to the clinical-laboratory manifestations in a sample of Egyptian SLE patients. A cross-sectional study was conducted on 132 patients environmentally exposed to OCs. Patients were diagnosed as SLE based on the American College of Rheumatology (ACR) revised criteria. Systemic Lupus Erythematosus Disease Activity Index-2000 (SLEDAI-2K) score was calculated to stratify the disease severity. Blood and urine samples were collected to measure the levels of OCs, serological markers, and urinary protein. The most frequently detected OCs were p,p'-DDE; lindane; and hexachlorobenzene (HCB). The risk of developing SLE was significantly associated with detected p,p'-DDE and HCB (B value 7.704 and 14.33, respectively). Hexachlorobenzene, in addition, was significantly associated with increased SLEDAI-2K score and polycythemia. Lindane was significantly associated with hypocomplementemia, cardiac manifestations of SLE, anemia, and leucopenia. In conclusion, the detected OCs p,p'-DDE and HCB are associated with increased risk of SLE in Egyptian patients and correlates to the manifestations of disease severity.

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.

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.

Enhanced organic contaminants accumulation in crops: Mechanisms, interactions with engineered nanomaterials in soil.

The mechanism of enhanced accumulation of organic contaminants in crops with engineered nanomaterials (ENMs) were investigated by co-exposure of crops (Ipomoea aquatica Forsk (Swamp morning-glory), Cucumis sativus L. (cucumber), Zea mays L. (corn), Spinacia oleracea L. (spinach) and Cucurbita moschata (pumpkin))to a range of chemicals (polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polybrominated diphenyl ether (PBDE)) and ENMs (TiO2, Ag, Al2O3, graphene, carbon nanotubes (CNTs)) in soil. Induced by 50 mg kg-1 graphene co-exposure, the increase range of BDE-209, BaP, p,p'-DDE, HCB, PYR, FLU, ANT, and PHEN in the plants were increased in the range of 7.51-36.42, 5.69-32.77, 7.09-59.43, 11.61-66.73, 4.58-57.71, 5.79-109.07, 12.85-109.76, and15.57-127.75 ng g-1, respectively. The contaminants in ENMs-spiked and control soils were separated into bioavailable, bound and residual fractions using a sequential ultrasonic extraction procedure (SUEP) to investigate the mechanism of the enhanced accumulation. The bioavailable fraction in spiked soils showed no significant difference (p > 0.05) from that in the control, while the bound fraction increased in equal proportion (p > 0.05) to the reduction in the residual fraction. These results implied that ENMs can competitively adsorbed the bound of organic contaminants from soil and co-transferred into crops, followed by a portion of the residual fraction transferred to the bound fraction to maintain the balance of different fractions in soils. The mass balance was all higher than 98.5%, indicating the portion of degraded contaminants was less than 1.5%. These findings could expand our knowledge about the organic contaminants accumulation enhancement in crops with ENMs.

Influence of soil γ-irradiation and spiking on sorption of p,p'-DDE and soil organic matter chemistry.

The fate of organic chemicals and their metabolites in soils is often investigated in model matrices having undergone various pre-treatment steps that may qualitatively or quantitatively interfere with the results. Presently, effects associated with soil sterilization by γ-irradiation and soil spiking using an organic solvent were studied in one freshly spiked soil (sterilization prior to contamination) and its field-contaminated (sterilization after contamination) counterpart for the model organic compound 1,1-Dichloro-2,2-bis(4-chlorophenyl)ethene (p,p'-DDE). Changes in the sorption and potential bioavailability of spiked and native p,p'-DDE were measured by supercritical fluid extraction (SFE), XAD-assisted extraction (XAD), and solid-phase microextraction (SPME) and linked to qualitative changes in soil organic matter (SOM) chemistry measured by diffuse reflectance infrared Fourier-transform (DRIFT) spectroscopy. Reduced sorption of p,p´-DDE detected with XAD and SPME was associated more clearly with spiking than with sterilization, but SFE showed a negligible impact. Spiking resulted in an increase of the DRIFT-derived hydrophobicity index, but irradiation did not. Spectral peak height ratio descriptors indicated increasing hydrophobicity and hydrophilicity in pristine soil following sterilization, and a greater reduction of hydrophobic over hydrophilic groups as a consequence of spiking. In parallel, reduced sorption of p,p´-DDE upon spiking was observed. Based on the present samples, γ-irradiation appears to alter soil sorptive properties to a lesser extent when compared to common laboratory processes such as spiking with organic solvents.

Pesticide removal through wastewater and advanced treatment: full-scale sampling and bench-scale testing.

Dieldrin and DDx removal through wastewater treatment, ozonation, and microfiltration was assessed for a water reuse project for groundwater replenishment in Monterey, California, USA. Full-scale sampling was conducted at the wastewater treatment plant, and physical wastewater treatment processes, ozonation, and microfiltration were tested at the bench scale. Removals observed through wastewater treatment, ozonation, and microfiltration were 84%, 44% to 63%, and 97% to 98%, respectively, for dieldrin, and 93%, 36% to 48%, and 92% to 94% for DDx. These were sufficient to meet California Ocean Plan water quality objectives after wastewater treatment alone. Levels in the secondary effluent, ahead of ozonation, microfiltration, reverse osmosis and advanced oxidation in the advanced water purification facility, met drinking water standards. Removal of dieldrin and DDx through wastewater treatment occurred by physical treatment processes; removal through the full-scale wastewater treatment plant, which included biological and physical treatment processes, matched removal through the physical bench-scale wastewater treatment processes. Dieldrin and DDx removal correlated with removal of volatile suspended solids, suggesting that volatile suspended solids could be used as an indicator for pesticide removal through wastewater treatment. Dieldrin and DDx concentrations were highest in the solids contact process, where biomass is accumulated for carbon removal.

Serum concentrations of selected organochlorine pesticides in a Lebanese population and their associations to sociodemographic, anthropometric and dietary factors: ENASB study.

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

Levels and Determinants of DDT and DDE Exposure in the VHEMBE Cohort.

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

Modeling the dynamics of DDT in a remote tropical floodplain: indications of post-ban use?

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

Organic amendments for risk mitigation of organochlorine pesticide residues in old orchard soils.

Performance of compost and biochar amendments for in situ risk mitigation of aged DDT, DDE and dieldrin residues in an old orchard soil was examined. The change in bioavailability of pesticide residues to Lumbricus terrestris L. relative to the unamended control soil was assessed using 4-L soil microcosms with and without plant cover in a 48-day experiment. The use of aged dairy manure compost and biosolids compost was found to be effective, especially in the planted treatments, at lowering the bioavailability factor (BAF) by 18-39%; however, BAF results for DDT in the unplanted soil treatments were unaffected or increased. The pine chip biochar utilized in this experiment was ineffective at lower the BAF of pesticides in the soil. The US EPA Soil Screening Level approach was used with our measured values. Addition of 10% of the aged dairy manure compost reduced the average hazard quotient values to below 1.0 for DDT + DDE and dieldrin. Results indicate this sustainable approach is appropriate to minimize risks to wildlife in areas of marginal organochlorine pesticide contamination. Application of this remediation approach has potential for use internationally in areas where historical pesticide contamination of soils remains a threat to wildlife populations.

Occurrence of organochlorine pesticides in the environmental matrices from King George Island, west Antarctica.

Antarctica is considered as a final sink of many persistent organic pollutants (POPs). This work aims to investigate the levels, distributions and potential sources of organochlorine pesticides (OCPs) with HRGC/HRMS technique. Twenty-three OCPs were measured in various environmental matrices from King George Island, west Antarctica. The total concentrations (Σ23OCPs) were at quite low levels, ranging 93.6-1260 pg g(-1) dry weight (dw) in soil and sediment, 223-1053 pg g(-1) dw in moss and 373-812 pg g(-1) dw in lichen. Hexachlorobenzene (HCB), dichloro-diphenyl-trichloroethane (DDT) and its metabolites (especially p,p'-DDE) and hexachlorocyclohexanes (HCHs) were the main contaminants in all samples. Lower α-HCH/γ-HCH and higher p,p'-DDE/p,p'-DDT ratios compared with the technical products indicated long-range atmospheric transport (LRAT) of recent lindane and aged technical DDT. Significant dependence of many OCPs concentrations on total organic carbon (TOC) was observed. Apart from LRAT, local biotic activities could also contribute and influence the spatial distribution of the contaminants.

Simulation of Observed PCBs and Pesticides in the Water Column during the North Atlantic Bloom Experiment.

The dynamics of persistent organic pollutants in the oceans are not well constrained, in particular during a bloom formation and collapse. Polychlorinated biphenyls (PCBs) and some pesticides were measured in air, water, and zooplankton tracking the North Atlantic Bloom in May 2008. Lower weight PCBs were entering the water column from the atmosphere during the main bloom period but reached equilibrium after the bloom collapsed. The PCBs in the lipids of zooplankton Calanus were in equilibrium with those in the dissolved phase. A Lagrangian box model was developed to simulate the dissolved phase PCBs and pesticides by including the following processes: air-water exchange, reversible sorption to POC, changes in mixed layer depth, removal by sinking particles, and degradation. Results suggest that sorption to (sinking) POC was the dominant removal process for hydrophobic pollutants from seawater. Statistical test suggested simulated results were not significantly different from observed values for hydrophobic pollutants (p,p'-DDE).

DDT and HCH, two discontinued organochlorine insecticides in the Great Lakes region: isomer trends and sources.

The uses of the insecticides 1,1'-(2,2,2-trichloroethylidene)bis[4-chlorobenzene] (p,p'-DDT) and γ-hexachlorocyclohexane (γ-HCH) have been discontinued for several years, but they are still consistently detected in air samples collected on the shores of the Great Lakes. Although the agricultural uses of DDT have been restricted in the United States since 1972, DDT continued to be used to manufacture the miticide, dicofol, up until 2011. The use of the technical HCH mixture in North America was restricted in the 1970s, when it was replaced by one of its purified conformers, γ-HCH, also known as lindane. In this study, we have focused on isomer-specific data to gain insights on the temporal trends and possible sources of these compounds. In particular, we calculated ratios of the concentrations of p,p'-DDE+p,p'-DDD versus the sum of the concentrations of the three p,p' isomers. These ratios are about the same at all five of our sampling sites and are about the same as observed globally. We also calculated the ratio of the concentrations of o,p'-DDT versus the sum of concentrations of o,p'-DDT+p,p'-DDT. This ratio has increased significantly at all five sites over the last 15-20 years. We suggest that dicofol, which contained about 11% o,p'-DDT, may now be a significant, additional source of DDT to the Great Lakes. The average ratio of the concentration of γ-HCH (lindane) versus the sum of the concentrations of γ-HCH+α-HCH did not vary significantly with time, but it did show an urban signature, suggesting that cities may be more important sources of these compounds than previously suspected.

Multiwalled carbon nanotubes and c60 fullerenes differentially impact the accumulation of weathered pesticides in four agricultural plants.

The effect of multiwalled carbon nanotubes (MWCNT) or C60 fullerenes on the uptake of weathered chlordane or DDx (DDT + metabolites) by Cucurbita pepo (zucchini), Zea mays (corn), Solanum lycopersicum (tomato), and Glycine max (soybean) was investigated. The plants were grown in 50 g of soil with weathered chlordane (2150 ng/g) and DDx (118 ng/g) that was amended with 0, 500, 1000, or 5000 mg/kg MWCNT or C60. After 28 d, the root and shoot content of chlordane components and DDx was determined by GC-MS. Zucchini and tomato growth were unaffected by carbon nanomaterial coexposure, although C60 at 500 mg/kg reduced corn and soybean biomass by 36.5-45.0%. Total chlordane content ranged from 1490 (tomato) to 4780 (zucchini) ng; DDx amounts ranged from 77.8 (corn) to 395 ng (zucchini). MWCNT coexposure decreased chlordane and DDx accumulation 21-80% across all crops, depending on species and nanotube concentration. Conversely, C60 had species- and contaminant-specific effects on pesticide uptake, ranging from complete suppression of DDx uptake (corn/tomato) to 34.9% increases in chlordane accumulation (tomato/soybean). The data show that pesticide accumulation varies greatly with crop species and carbon nanomaterial type/concentration. These findings have implications for food safety and for the use of engineered nanomaterials in agriculture.

Can mitochondrial dysfunction be initiated by dissociative electron attachment to xenobiotics?

Resonance attachment of low-energy electrons to xenobiotic molecules, 2,4-dichlorophenoxyacetic acid (2,4-D), dichlorodiphenyltrichloroethane (DDT) and dichlorodiphenyldichloroethylene (DDE), was investigated under gas-phase conditions by means of complementary experimental techniques. Electron transmission spectroscopy (ETS) and dissociative electron attachment spectroscopy (DEAS), in the 0-6 eV and 0-15 eV energy range, respectively, were applied with the aim of modeling the behavior of these pesticide molecules under reductive conditions in vivo. Formation of long-lived parent molecular anions and fragment negative ions was observed at incident electron energies very close to zero, in agreement with the results of density functional theory calculations. The gas-phase DEA process, analogous to dissociative electron transfer in solution, was considered as a model for the initial step which occurs in the intermembrane space of mitochondria when a xenobiotic molecule captures an electron "leaked" from the respiratory chain. A possible involvement of the fragments produced by DEA to the pesticides under investigation into cellular processes is discussed. It is concluded that the free radicals and potential DNA adducts formed by DEA are expected to be dangerous for mitochondrial functionalities, while several of the products observed could act as messenger molecules, thus interfering with the normal cellular signaling pathways.

Influence of climate and land use change on spatially resolved volatilization of persistent organic pollutants (POPs) from background soils.

The subject of this study is the assessment of the influence of climate and land use change on the potential re-emission of organochlorine pesticides (OCPs) from background and agricultural soils. A deterministic spatially and temporally explicit model of the air-surface exchange was created, fed with distributed data of soil and atmospheric concentrations from real measurements, and run under various scenarios of temperature and land use change for a case study area representative of central European conditions. To describe land use influence, some important features were implemented including effect of plowing, influence of land cover, temperature of soil, and seasonal changes of air layer stability. Results show that volatilization of pesticides from soil largely exceeded dry gas deposition in most of the area. Agricultural soils accounted for more than 90% of the total re-emissions both because of the generally higher soil fugacities (higher loads of chemicals and relatively low organic carbon content), but also due to physical characteristics and land management practices enhancing the dynamics of the exchange. An increase of 1 °C in air temperature produced an increase of 8% in the averaged total volatilization flux, however this effect can be neutralized by a change of land use of 10% of the arable lands to grassland or forest, which is consistent with projected land use change in Europe. This suggests that future assessment of climate impact on POP fate and distribution should take into consideration land use aspects.

Effect of C60 fullerenes on the accumulation of weathered p,p'-DDE by plant and earthworm species under single and multispecies conditions.

The use of engineered nanomaterials has increased dramatically in recent years, but an understanding of nanomaterial fate and effects in the environment is lacking. In particular, the interaction of nanomaterials with coexisting organic contaminants and the subsequent implications for sensitive biota is almost completely unknown. Here, the effect of C60 fullerenes on the accumulation of weathered dichlorodiphenyldichloroethylene (p,p'-DDE; DDT metabolite) by Cucurbita pepo (pumpkin) and Eisenia fetida (earthworm) was determined under single and multispecies conditions. The plants, in the presence or absence of earthworms, were grown in soil containing weathered DDE (200 ng/g) and 0 or 1,670 mg/kg C60 fullerenes. Plants and earthworms were added either simultaneously or sequentially (earthworms after plants). Neither DDE nor C60 had an impact on survival or biomass of plants and earthworms, although fullerenes significantly decreased (29.6-39.0%) the relative root mass. Under single or multispecies conditions, C60 had little impact on DDE bioaccumulation by either species. The DDE concentrations in non-fullerene-exposed shoots, roots, and earthworms were 181, 7,400, and 8,230 ng/g, respectively. On fullerene exposure, the DDE content was nonsignificantly lower at 163, 7280, and 7540 ng/g, respectively. In the presence of the earthworms, C60 significantly decreased the shoot DDE content (28.6%), but no impact on root concentrations was observed. Root DDE content was unaffected by the presence of fullerenes and decreased by 21.6 to 37.5% during coexposure with earthworms. Earthworm DDE content was decreased by plant presence. Earthworms added to soils after plant harvest accumulated more DDE but were unaffected by the C60 exposure. Additional work is necessary, but these findings suggest that fullerenes may have minimal impact on the bioaccumulation of weathered cocontaminants in soil.

Gene cluster and regulation system for 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE) degradation in Janibacter sp. TYM3221.

A DDE-degrading bacterium, Janibacter sp. TYM3221, is able to grow on biphenyl and degrades 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE) via a meta-ring cleavage pathway. The bphAa gene, encoding a biphenyl dioxygenase large subunit, was previously demonstrated to be involved in the degradation of DDE in TYM3221. The bph gene cluster, containing orf2 and bphDAaAbAcAdBCST was cloned and characterized. Reverse transcription-PCR (RT-PCR) analysis indicated that these genes were transcribed as an operon. The real-time RT-PCR on orf2, bphAa, bphC, and bphS suggest the presence of the inducible orf2 promoter (orf2p) and constitutive bphAa promoter (bphAap). The TYM3221 bphST conducted biphenyl-dependent inducible activation plus constitutive basal activation of orf2p and constitutive activation of bphAap in a rhodococcal host strain, Rhodococcus erythropolis IAM1399, suggesting that expression of the TYM3221 bph operon depends on the bphST-coded two-component regulatory system. Both of these promoters were also induced by the bphS1T1 of a biphenyl degrader, Rhodococcus jostii RHA1, and contained the 24-bp consensus sequences of RHA1 bphS1T1-dependent promoters. The replacement of RHA1 bphS1 with TYM3221 bphS in combination with RHA1 bphT1 suggests that TYM3221 bphS is responsible for low inducible and high constitutive activation of orf2p in IAM1399 by the TYM3221 bphST-system. Expression of bphAaAbAcAdBC in IAM1399 resulted in the transformation of DDE to the meta-ring cleavage product via 2,3-hydroxylation, suggesting that these genes are involved in DDE degradation.

Use of solid phase microextraction to estimate toxicity: relating fiber concentrations to body residues--part II.

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.

Use of solid phase microextraction to estimate toxicity: relating fiber concentrations to toxicity--part I.

Use of solid-phase microextraction (SPME) fibers as a dose metric for toxicity testing was evaluated for hydrophobic pesticides to the midge Chironomus dilutus and the amphipod Hyalella azteca. Test compounds included p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT), p,p'-dichlorodiphenyldichloroethane (p,p'-DDD), p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE), permethrin, bifenthrin, tefluthrin, and chlorpyrifos. Acute water toxicity tests were determined for 4- and 10-d exposures in both species. Median lethal and sublethal concentrations were expressed both on a water concentration (LC50 and EC50) and on an equilibrium SPME fiber concentration (LC50(fiber) and EC50(fiber)) basis. A significant log dose-response relationship was found between log fiber concentration and organism mortality. It has been shown in the literature that equilibrium SPME fiber concentrations reflect the bioavailable concentrations of hydrophobic contaminants, so these fiber concentrations should be a useful metric for assessing toxic effects from the bioavailable contaminant providing a framework to expand the use of SPME fibers beyond estimation of bioaccumulation.