The effect of oxygen on chemical dechlorination of dieldrin using iron sulphides

The degradation of dieldrin by ferric sulphide (FeS₂) in aqueous solution was investigated when shielded against sunlight. An oxidative dechlorination process was observed under aerobic and anaerobic conditions; oxygen volume changed the degradation rate of dieldrin and the generation rate of reaction products. The dechlorination rate under microaerophilic conditions was fastest among the anaerobic to air oxygen concentrations. For this experiment, over 99% of the dieldrin was degraded, and 90% of the released chloride was detected after 30 d under 10 μmol oxygen. The major reaction products were different depending on the dose of oxygen. In the case of aerobic conditions, low molecular weight organic acids, such as formic acid, lactic acid, and oxalic acid, were generated as major reaction products. However, under anaerobic conditions, C₁₆H₂₂O₄ (dibutyl phthalate) and C₆H₁₃ClO (3-chloro-4-methyl-2-pentanol) were detected as reaction intermediates, and small amounts of succinic acid, malonic acid, and formic acid were also generated. These reactions proceed by FeS₂ interface reactions with H₂O under anaerobic condition, or O₂ under aerobic condition.     

Photochemical processing of aldrin and dieldrin in frozen aqueous solutions under arctic field conditions

Organochlorine (OC) contaminants are transported to the Polar Regions, where they have the potential to bioaccumulate, presenting a threat to the health of wildlife and indigenous communities. They deposit onto snowpack during winter, and accumulate until spring, when they experience prolonged solar irradiation until snowmelt occurs. Photochemical degradation rates for aldrin and dieldrin, in frozen aqueous solution made from MilliQ water, 500 μM hydrogen peroxide solution or locally-collected melted snow were measured in a field campaign near Barrow, AK, during spring-summer 2008. Significant photoprocessing of both pesticides occurs; the reactions depend on temperature, depth within the snowpack and whether the predominant phase is ice or liquid water. The effect of species present in natural snowpack is comparable to 500 μM hydrogen peroxide, pointing to the potential significance of snowpack-mediated reactions. Aldrin samples frozen at near 0 °C were more reactive than comparable liquid samples, implying that the microenvironments experienced on frozen ice surfaces are an important consideration.     

Dieldrin uptake by vegetable crops grown in contaminated soils

The aim of these trials was to study the distribution of dieldrin in soil and its translocation to roots and the aerial parts of vegetable crops grown in greenhouses and fields. The main objectives were to characterize dieldrin accumulation in plant tissues in relation to the levels of soil contamination; uptake capability among plants belonging to different species, varieties and cultivars. The presence of the contaminant was quantified by gas chromatography-electron capture detector (GC-ECD) and confirmed by gas chromatography-mass spectrometer (GC-MS). The results showed a translocation of residues in cucurbitaceous fruits and flowers confirming that zucchini, cucumber and melon are crops with high uptake capability. The maximum level of dieldrin residue at 0.01 mg/kg was found to be a threshold value to safeguard the quality production of cucurbits. Tomato, lettuce and celery were identified as substitute crops to grow in contaminated fields.     

Novel metabolic pathways of organochlorine pesticides dieldrin and aldrin by the white rot fungi of the genus Phlebia

White rot fungi can degrade a wide spectrum of recalcitrant organic pollutants, including polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated biphenyls (PCBs). In this experiment, 20 white rot fungi, belonging to genus Phlebia, were investigated for their ability to degrade dieldrin. Based on the screening results, we further investigated Phlebia acanthocystis, Phlebia brevispora, and Phlebia aurea to determine their degradation capacity and metabolic products towards dieldrin and aldrin. The three fungi were able to remove over 50% of dieldrin in a low nitrogen medium, after 42 d of incubation. Three hydroxylated products were detected as metabolites of dieldrin, suggesting that in Phlebia strains, hydroxylation reactions might play an important role in the metabolism of dieldrin. In contrast to dieldrin, aldrin exhibited higher levels of degradation activity. Over 90% of aldrin was removed after 28 d of incubation, and several new metabolites of aldrin in microorganisms, including 9-hydroxyaldrin and two carboxylic acid products, were detected in fungal cultures. These results indicate that the methylene moiety of aldrin and dieldrin molecules might be prone to enzymatic attack by white rot fungi. In this study, we describe for the first time a new metabolic pathway of both compounds by fungi of genus Phlebia.     

Contaminant concentrations in whole-body fish and shellfish from US estuaries

Persistent bioaccumulative and toxic (PBT) pollutants are chemical contaminants that pose risks to ecosystems and human health. For these reasons, available tissue contaminant data from the US EPA Environmental Monitoring and Assessment Program’s National Coastal Assessment were examined to estimate to what areal extent PBTs are found in US estuarine resources. The data document composite, whole-body tissue chemical concentrations for 736 sampling sites across Northeast, Southeast, Gulf of Mexico, and West Coast estuaries. Tissue chemical concentrations were compared to US EPA non-cancer risk guidelines for recreational fishers, because of a lack of ecological guidelines for these chemical concentrations. Samples were analyzed for 23 PAH compounds, 21 PCB congeners, 6 DDT derivatives and metabolites, 14 chlorinated pesticides (other than DDT) and 13 metals, including mercury. Total PCBs were found to exceed recreational fisher guidelines most frequently (31% of samples evaluated), followed by mercury (29%), total PAHs (21%), and DDT and its metabolites, DDD and DDE (11%). Toxaphene, cadmium and dieldrin were found but in fewer than 1% of the samples.     

Removal of Aldrin,Dieldrin, Heptachlor,and Heptachlor Epoxide Using Activated Carbon and/or Pseudomonas fluorescens Free Cell Cultures

Degradation of aldrin (1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5-8-dimethanonaphthalene), heptachlor (1H-1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methano indene), dieldrin (1aα,2β,2aα,3β,6β,6aα,7β,7aα)-3,4,5,6,9,9-Hexachloro-1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-d-methanonaphtha[2,3-b]oxirene, and heptachlor epoxide (1aα, 1bβ,2α,5α,5αβ,6β,6aα-2,3,4,5,6,7,7-Heptachloro-1a,1b,5,5a,6,6a-hexahydro-2,5-methano-2H-inden[1,2-b]-oxirene) was tested using free cultures of Pseudomonas fluorescens under controlled conditions. Pesticide concentrations were monitored by gas chromatography during 120 h. Percentages of degradation and biodegradation rates (BDR) were calculated. Data showed a trend suggesting a relation between chemical structure and degradability. Degradation kinetics for each pesticide tested showed that the highest degradation rates were found in the first 24 h. Kinetics data were adjusted to an empirical equation in order to predict their behavior, and the correlation coefficients obtained were satisfactory. Gas chromatography/mass spectrometry (GC/MS) analysis of the final extracts allowed the identification of chlordene and monodechlorodieldrin, which have been reported as final metabolite produced in the biodegradation of this kind of compounds. Regarding adsorption of pesticides on activated vegetal carbon, we concluded that removal efficiencies between 95.45 and 97.18% can be reached, depending on the pesticide and the carbon dose applied. The values for K from the Freundlich equation were quite similar for the four pesticides (between 1.0001 and 1.04), whereas the n values were quite different for each pesticide in the following order of affinity: dieldrin > aldrin > heptachlor epoxide > heptachlor. Equilibrium times, very important for scaling up the process, were between 43 min and 1 h, for the heptachlor epoxide and the heptachlor, respectively.     

Synergistic increase in cell lethality by dieldrin and H2O2 in rat thymocytes: Effect of dieldrin on the cells exposed to oxidative stress

Dieldrin, one of persistent pesticides, is highly resistant to biotic and abiotic degradation. It is accumulated in organisms. Recent studies suggest that dieldrin exerts a potent cytotoxic action on cells exposed to oxidative stress. In this study, the effect of dieldrin on rat thymocytes exposed to hydrogen peroxide (H₂O₂)-induced oxidative stress was examined. Dieldrin at 5 μM and H₂O₂ at 300 μM slightly increased cell lethality from a control value of 5.4 ± 0.5% (mean ± standard deviation of four experiments) to 7.8 ± 1.3% and 9.0 ± 0.3%, respectively. Simultaneous application of dieldrin and H₂O₂ significantly increased cell lethality to 46.2 ± 1.8%. The synergistic increase in cell lethality was dependent on dieldrin concentration (0.3–5 μM) but not on H₂O₂ concentration (30–300 μM). Dieldrin accelerated H₂O₂-induced cell death, which was estimated with the help of annexin V-FITC and propidium iodide. Presence of either dieldrin or H₂O₂ decreased the cellular content of nonprotein thiol and increased intracellular Zn²⁺ concentration. The combination of dieldrin and H₂O₂ further pronounced these effects. TPEN, a chelator of intracellular Zn²⁺, significantly attenuated the synergistic increase in cell lethality induced by dieldrin and H₂O₂. It is, therefore, suggested that dieldrin augments the cytotoxicity of H₂O₂ in a Zn²⁺-dependent manner.     

The stability of dieldrin,aldrin, lindane,chlorpyrifos and prothiofos in stored roof water

Abstract

The stability of dieldrin, aldrin, lindane, chlorpyrifos and prothiofos was determined in distilled water and in roof water from either galvanised or concrete tanks. Samples were stored in the dark at 23°C. Dieldrin and lindane were stable for the 36 week period. Aldrin dissipated rapidly with a half‐life of 4–5 weeks, with no dieldrin being formed. Chlorpyrifos and prothiofos also broke down, with half‐lives ranging 12–18 weeks and 11–14 weeks respectively. No significant effect of water type was found. For the purpose of domestic usage, an activated carbon filter would be essential otherwise all contaminated water would have to be disposed of safely.