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

The present work reports microwave-assisted synthesis of SnO2 nanoparticles via green route using Psidium Guajava extract. For the enhancement of catalytic activity, nanohybrids of SnO2 were formulated using different ratios of polyaniline (PANI) via ultrasound-assisted chemical polymerization. Formation of nanohybrids was confirmed via IR and XPS studies. The UV-vis DRS spectra of PANI/SnO2 revealed significant reduction in the optical band gap upon nanohybrid formation. Microwave-assisted catalytic efficiency of pure SnO2, PANI, PANI/SnO2 nanohybrids was investigated using DDT as a model persistent organic pollutant. The degradation efficiency of PANI/SnO2 was found to increase with the increase in the loading of PANI. Around 87% of DDT degradation was achieved within a very short period of 12 min under microwave irradiation using PANI/SnO2-50/50 as catalyst. The effect of DDT concentration was explored and the degradation efficiency of PANI/SnO2-50/50 catalyst was noticed to be as high as 82% in presence of 100 mg/L of DDT. The effect of microwave power on the degradation efficiency revealed 79% degradation using the same nanohybrid when exposed to microwave irradiation for 5 min under 1110 W microwave power. Scavenging studies confirmed the generation of OH, O2- radicals. The fragments with m/z values as low as 86 and 70 were confirmed by LCMS analysis. Recyclability tests showed that PANI/SnO2-50/50 nanohybrid exhibited 81% degradation of DDT (500 mg/L) even after the third cycle, which reflected high catalytic efficiency as well as remarkable stability of the catalyst. This green nanohybrid could therefore be effectively utilized for the rapid degradation of persistent organic pollutants.

Levels and patterns of DDTs in maternal colostrum from an island population and exposure of neonates.

Dichlorodiphenyltrichloroethane (DDT) was heavily used in the past in many regions of the world. The occurrence of DDTs in island populations may be elevated if the island is adjacent to major DDT consumption estuaries, such as the Yangtze River Delta. In this study, colostrum samples were collected from maternal-neonate pairs (n = 106) from the Shengsi Island, located directly downstream from the Yangtze River outlet. DDT isomers and enantiomer compositions were analyzed by gas chromatography equipped with mass spectrometer (GC/MS) and GC/MS-MS. The average levels of p,p'-DDE, o,p'-DDD, p,p'-DDD, o,p'-DDT, p,p'-DDT and total DDTs were 1.32, 0.03, 0.09, 0.08, 0.48, and 1.93 µg g(-1) lipid weight, respectively. Maternal age and pregnancy body mass index (BMI) were positively associated with levels of DDTs (p < 0.05). High (DDE+DDD)/DDT and p,p'-DDE/p,p'-DDT ratios suggested that current DDT residues originated primarily from historical use of DDT products, but new sources may also contribute partially to some high o,p'-DDT/p,p'-DDT ratios. Enantiomeric enrichment was found for the (-)-enantiomer of o,p'-DDD and the (+)-enantiomer of o,p'-DDT, suggesting stereoselective attenuation. Based on breast milk consumption, the average daily intake of DDTs by neonates was 8.33 ± 7.34 µg kg(-1)bw per day, which exceeded the WHO's tolerable daily intake guideline of 0.01 mg kg(-1) bw per day by 25%, implying some neonates in the Yangtze River region are potentially at high risk from exposure to DDTs.

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.

Enhanced solubilization and desorption of organochlorine pesticides (OCPs) from soil by oil-swollen micelles formed with a nonionic surfactant.

The effect of oil-swollen micelles formed with nonionic surfactant polyoxyethylene sorbitan monooleate (Tween 80), cosurfactant 1-pentanol, and linseed oil on the solubilization and desorption of organochlorine pesticides (OCPs) including DDT and γ-HCH from both loam soil and clay soil were investigated. Results showed that the solubilizing capacities of oil-swollen micelles were dependent on the critical micelle concentration (CMC) of Tween 80. Once the concentrations of oil-swollen micelles exceeded the CMC of Tween 80, the oil-swollen micelles exhibited much higher solubilizing capacity than empty Tween 80 micelles for the two OCPs. Desorption tests revealed that oil-swollen micelles could successfully enhance desorption of OCPs from both loam soil and clay soil. However, compared with the efficiencies achieved by empty Tween 80 micelles, oil-swollen micelles exhibited their superiority to desorb OCPs only in loam soil-water system while was less effective in clay soil-water system. Distribution of Tween 80, 1-pentanol and linseed oil in soil-water system revealed that the difference in the sorption behavior of linseed oil onto the two soils is responsible for the different effects of oil-swollen micelles on the desorption of OCPs in loam soil and clay soil systems. Therefore, oil-swollen micelles formed with nonionic surfactant Tween 80 are better candidates over empty micelle counterparts to desorb OCPs from soil with relatively lower sorption capacity for oil fraction, which may consequently enhance the availability of OCPs in soil environment during remediation processes of contaminated soil.

Heating of BDE-209 and BDE-47 in plant oil in presence of o,p'-DDT or iron(III) chloride can produce monochloro-polybromo diphenyl ethers.

Heating processes of food can alter the concentrations and composition of organohalogen compounds. In this study the fate of two polybrominated diphenyl ether (PBDE) congeners, decabromodiphenyl ether (BDE-209) and 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) was analyzed when heated in plant oil with and without additional compounds. When the PBDEs were heated in pure plant oil, no transformation was observed. Heating of decabromodiphenyl ether (BDE-209) together with ortho,para'-dichlorodiphenyltrichloroethane (o,p'-DDT) or iron(III) chloride in plant oil resulted in the formation of monochloro-nonabromodiphenyl ethers (Br(9)Cl-DEs). Almost 10% of the initial amount of BDE-209 was transferred into Br(9)Cl-DEs. Heating BDE-47 in the presence of iron(III) chloride produced two monochlorinated transformation products which were tentatively identified as 2,2',4-tribromo-4'-chlorodiphenyl ether (4'-Cl-BDE-17) and 2,4,4'-tribromo-2'-chlorodiphenyl ether (2'-Cl-BDE-28). However, the reactivity was smaller and no Br→Cl exchange was observed with o,p'-DDT. The conditions used in our experiments (200 °C; heating 30 min-3 h) indicate that such reactivity may also occur during cooking of fish, meat and other food samples.

Role of non-ionic surfactants and plant oils on the solubilization of organochlorine pesticides by oil-in-water microemulsions.

Screening low-cost, high efficacy and environmentally safe surface active agents is critical for achieving successful surfactant-enhanced remediation (SER) of soil contaminated with hydrophobic organic compounds. This study reports the solubilization of organochlorine pesticides (DDT or gamma-HCH) in oil-in-water (Winsor I) microemulsions (microE) composed of non-ionic surfactant (Tween 80 or Triton X-100), plant oil (linseed oil or soybean oil), and the cosurfactant (1-pentanol). Results show that the cosurfactant to surfactant ratio (C/S ratio, w/w) is the major factor influencing the microemulsion formation, and C/S ratios of 1:3 and 1:6 are superior to 1:1 for microemulsion formation. 66.9-95.6% and 51.9-80.9% of DDT solubilization enhancements were achieved by microemulsions based respectively on Tween 80 or Triton X-100 as compared to their respective surfactant solution alone, indicating the higher solubilizing capacities of microemulsion systems. The solubilization of gamma-HCH also increased by 40.6-57.5% in microemulsion formed with Tween 80 and 43.0-65.8% in microemulsion formed with Triton X-100, compared with that in corresponding surfactant solutions only. Further studies revealed that both cosurfactant content and oil content could influence the solubilizing capacity of microemulsions system, and higher solubilizing capacity could be obtained when more cosurfactant or oil were emulsified in microemulsion system. Between the two, oil content is more influential than cosurfactant content. The present results affirm the effective role of microemulsions formed with Tween 80 and Triton X-100 in enhancing the solubilization of DDT and gamma-HCH which would facilitate remediation of soils contaminated with these compounds.

Microemulsion-enhanced remediation of soils contaminated with organochlorine pesticides.

Soil contaminated by organic pollutants, especially chlorinated aromatic compounds such as DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane), is an environmental concern because of the strong sorption of organochlorine pesticide onto the soil matrix and persistence in the environment. The remediation of organochlorine pesticide contaminated soils through microemulsion is an innovative technology to expedite this process. The remediation efficiency was evaluated by batch experiments through studying the desorption of DDT and hexachlorocyclohexane (y-HCH) and sorption of microemulsion composed of Triton X-100, 1-pentanol and linseed oil in the soil-surfactant-water suspension system. The reduction of desorption efficiency caused by the sorption loss of microemulsion components onto the soil could be corrected by the appropriate adjustment of C/S (Cosurfactant/Surfactant) and O/S (Oil/Surfactant) ratio. The C/S and O/S ratios of 1:2 and 3:20 were suitable to desorb DDT and gamma-HCH from the studied soils because of the lower sorption of Triton X-100 onto the soil. Inorganic salts added in microemulsion increased the pesticides desorption efficiency of pesticides and calcium chloride has a stronger ability to enhance the desorption of DDT than sodium chloride. From the remediation perspective, the balance of surfactant or cosurfactant sorbed to soil and desorption efficiency should be taken into consideration to enhance the remediation of soils contaminated by organochlorine pesticides.

Residues of 18 organochlorine pesticides in 30 traditional Chinese medicines.

We analyzed 30 different traditional Chinese medicines (TCMs) to determine levels of contamination with organochlorine pesticides (OCPs). We tested for 18 pesticides: benzene hexachloride (BHC, including alpha-BHC, beta-BHC, gamma-BHC, delta-BHC), heptachlor, heptachlor epoxide, tecnazene, pentachloronitrobenzene (PCNB), hexachlorobenzene, aldrin, methyl pentachlorophenyl sulphide (MPCPS), alpha-endosulfan, trans-chlorodane, cis-chlorodane, p,p'-DDE, o,p'-DDT, p,p'-DDD, and p,p'-DDT. The sample extracts were analyzed by GC-ECD. A total of 280 samples of 30 different TCMs were analyzed. Our results showed that 75.8% of samples contained at least one of the above pesticides. The pesticides detected were tecnazene, hexachlorobenzene, PCNB, heptachlor, aldrin, alpha-BHC, beta-BHC, gamma-BHC, delta-BHC, p,p'-DDE, o,p'-DDT, p,p'-DDD p,p'-DDT. More than 50% of samples contained alpha-BHC (55.8%) and PCNB (55.8%); hexachlorobenzene was detected in 40.9% of samples, tecnazene in 19.5%, gamma-BHC in 16.7% and p,p'-DDE in 16.0%. Less than 10% of samples contained beta-BHC, delta-BHC, heptachlor, aldrin, o,p'-DDT, p,p'-DDT and p,p'-DDD. None of the 280 samples contained heptachlor epoxide, MPCPS, alpha-endosulfan, trans-chlorodane, or cis-chlorodane. Concentrations of OCPs in four samples exceeded the maximum allowable residue limits (MRLs) specified in the PRC Pharmacopoeia 2005. The results indicate that the most common contaminants among the 280 samples were alpha-BHC, PCNB, hexachlorobenzene, and tecnazene. Our results suggest that contamination of TCMs with OCPs is widespread. The MRLs for other OCPs commonly found in TCMs (e.g. hexachlorobenzene and tecnazene) should be set as quickly as possible, and the MRLs of OCPs in other TCMs should be established.

Studies on dechlorination of DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) using magnesium/palladium bimetallic system.

The aim of our investigation was to compare the rates of dechlorination of DDT using Mg0/Pd4+ system in two different reaction phases, namely, water-acetone and 0.05% biosurfactant in water. Since palladium is expensive and its toxicity effects are not well known we also examined the reuse efficiency of Pd0 immobilized on alumina for dechlorinating DDT. Studies on the dechlorination of DDT in water-acetone (1:1, v/v) and 0.05% biosurfactant phases revealed that the reaction followed second order kinetics and rate of reaction is dependent upon both initial concentrations of the target compound and Mg0/Pd4+. The presence of acid enhanced the rate of reaction by providing protons and preventing passivation of metal that occurs due to deposition of magnesium hydroxide. GC-MS analyses revealed the formation of completely dechlorinated hydrocarbon skeleton of DDT namely, diphenylethane (DPE), as the end product in both reaction phases (water-acetone and 0.05% biosurfactant in water) thereby implying the removal of all five chlorine atoms (three alkyl and two aryl) of DDT. The optimum ratio of water and acetone to facilitate successful dechlorination reaction was found to be 9:1. Results suggested that salt form (K2PdCl6) of palladium had higher potential to dechlorinate DDT as compared to pellet (Pd0-alumina) form (efficiencies of 95 and 36%, respectively, for 100 ppm initial concentration of DDT). We noted that Pd0-alumina pellets could be reused at least four times for successful dechlorination of DDT provided Mg0 granules are present in sufficient quantity. Technical grade DDT (50 ppm) containing significant amounts of DDD was dechlorinated almost completely by the Mg0/Pd4+ (10mg/0.2mg/ml) within 1h in water-biosurfactant phase. Our studies reveal that Mg/Pd system is a promising option due to its high reactivity and its ability to achieve complete dechlorination of DDT. This bimetallic system may be useful for designing indigenous permeable barriers or reactors for the treatment of DDT contaminated water.

Systematic evaluation of organochlorine pesticide residues in Chinese materia medica.

A systematic evaluation on the levels of organochlorine pesticide residues (OCP) was conducted on four selected, authentic Chinese materia medica, namely: Radix Angelicae Sinensis, Radix Notoginseng, Radix Salviae Miltiorrhizae and Radix Ginseng. Altogether ten representative batches of samples were analysed for each herb. Six batches were collected in the major cultivation areas of the Mainland whilst the remaining four batches were procured in the Hong Kong herbal market. All except Radix Angelicae Sinensis have been identified as containing quintozene and hexachlorocyclohexane in various levels. Hexachlorobenzene and lindane were also reported in samples of Radix Ginseng. The banned pesticide, DDT and its derivatives, was also observed in one of the Radix Notoginseng samples. The investigation will be continued for a target list of common used herbs in Hong Kong. All the results will be gathered and analysed for setting up regulatory permissible limits of OCP residues in Chinese materia medica used in Hong Kong.

Control de calidad de residuos de biocidas en frutos de Silybum marianum L / Quality control of organochlorine biocide residues in fructus from Silybum marianum L

Los estudios analíticos de los biocidas organoclorados demuestran que su nivel de concentración en las raíces de plantas es mayor que la concentración en el suelo, y especialmente en las plantas medicinales utilizadas en las industrias farmacéutica y medicinal. Los fármacos búlgaros más utilizados (Carsil, Tribestan y Nivalin) contienen extractos de plantas y deben ser analizados de acuerdo con las directivas de la Comunidad Europea EEC/76/895 y EEC/90/642 1998; Por ello, se ha estudiado el método de cromatografía de gases para la determinación cuantitativa de biocidas organoclorados (HCH e isómeros, DDT y metabolitos). Se han analizado conforme a las regulaciones de la Pharmacopoeia Europea materiales procedentes de plantas de distintas regiones de Bulgaria (frutos de Silybum marianum, L) y grageas de Carsil producidas por Sopharma Ltd. El método ha sido validado y se han estudiado parámetros analíticos de especificidad, linealidad, precisión, replicabilidad y rango

Analytical studies of organochlorine biocides show that their concentration in the plants (roots) is higher than in the ground and particularly in the medicinal plants used in the therapy and the pharmacy industry. The most favorite Bulgarian drugs (Carsil, Tribestan and Nivalin Nivalin) contain plant extracts and they have to be analyzed in respect to European Community Directives EEC/76/895 and EEC/90/642 1998; In view of that the gas chromatography method for quantitative determination of organochlorine biocides (HCH and isomers, DDT and metabolites) was studied. Plant material from different regions of Bulgaria (fructus from Silybum marianum, L) and Carsil dragee produced by Sopharma Ltd. were analyzed in respect to European Pharmacopoeia regulations. The method was validated and analytical parameters specificity, linearity, precision, repeatability and range were studied

[The effects of organic matter and hydrous metal oxides on the anaerobic degradation of gamma-666, p,p'-DDT in Liaohe River sediments].

Effects of organic matter and active Fe, Al, Mn oxides on the anaerobic degradation of gamma-666, p,p'-DDT were investigated by means of removing organic matter and hydrous metal oxides in Liaohe River sediments sequentially. The results showed that the anaerobic degradation of gamma-666, p,p'-DDT followed pseudo-first-order kinetics in different sediments; but, the extents and rates of degradation were different, even the other conditions remained same. Anaerobic degradation rates of gamma-666, p,p'-DDT were 0.020 d-1, 0.009 d-1 respectively for the sediments without additional carbon resources. However, with additional carbon resources, the anaerobic degradation rates of gamma-666, p,p'-DDT were 0.071 d-1 and 0.054 d-1 in the original sediments respectively. After removing organic matter, the rates were decreased to 0.047 d-1, 0.037 d-1. In the sediments removed organic matter and hydrous metal oxides, the rates were increased to 0.067 d-1, 0.059 d-1. This results indicated that organic matter in the sediments accelerated the anaerobic degradation of gamma-666, p,p'-DDT; the hydrous metal oxides inhibited the anaerobic degradation of gamma-666 and p,p'-DDT.

Estrogens and environmental estrogens.

The natural female sex hormone estrogens binds once inside the cell to a protein receptor to form a 'ligand-hormone receptor complex'. The binding activates the hormone receptor, which triggers specific cellular processes. The activated hormone receptor then turns on specific genes, causing cellular changes that lead to responses typical of a ligand-hormone receptor complex. Estrogens (especially estradiol) bring out the feminine characteristics, control reproductive cycles and pregnancy, influence skin, bone, the cardiovascular system and immunity. Natural hormones are more potent than any of the known synthetic environmental estrogens (except drugs such as diethylstilbestrol [DES]). Estrogen production varies according to different factors (gender, age and reproductive cycles). Women produce more estrogen than men and the production is more abundant during fetal development than in the postmenopausal period. Most natural estrogens are short-lived, do not accumulate in tissue and are easily broken down in the liver. In contrast to natural estrogens, estrogenic drugs such as ethynylestradiol diethylstilbestrol (DES), synthetic environmental estrogens such as beta-hexachlorocyclohexane (beta-HCH), polychlorinated biphenyls (PCBs), o, p, p'DDT, 4-nonylphenol (NP) and phytoestrogens such as isoflavones or lignans, are more stable and remain in the body longer than natural estrogens. Because most of these compounds are lipophilic, they tend to accumulate within the fat and tissue of animals and humans. Thus, depending on the natural estrogen levels, environmental estrogens may have different influences (mimicking, blocking or cancelling out estrogen's effects) on estrogen activities.

[Determination of residues of organic chloride pesticide in Chinese medicinal materials with capillary gas chromatography].

Residues of organic chloride pesticide were separated and detected successfully with high performance capillary column and high sensitive electron capture detector, such as hexachloro-cyclohexane, dichloro-diphenyl-trichloroethane, pentachloronitrobenzene. The method can be used for the determination of residues of organic chloride pesticide in Chinese medicinal materials, and the residue enriching in the different part of plant body was tested preliminary.