Interactions of chlorinated hydrocarbon insecticides with membranes

Chlorinated hydrocarbon insecticides quench the fluorescence of N-alkyl derivatives of carbazole. We used phospholipids with covalently attached carbazole as probes for the interactions of chlorinated hydrocarbon insecticides with lipid bilayers, the object being to understand better the toxicities of chlorinated hydrocarbons. Fluorescence quenching measurements revealed the lipid-water partition coefficients of the chlorinated hydrocarbons, their diffusion coefficients in the membranes, and the binding capacities of the membranes for the chlorinated hydrocarbons. Active insecticides were compared with inactive analogues to test whether activities correlated with chlorinated hydrocarbon-membrane interactions. Thus DDT and methoxychlor were compared with inactive DDE, and insecticidal γ-lindane was compared with three less active stereoisomers. The partition coefficients, diffusion coefficients and membrane saturation capacities did not correlate with insecticidal potency. The partition coefficients of these chlorinated hydrocarbons were larger in bilayers containing unsaturated fatty acyl chains as compared to bilayers containing saturated fatty acyl chains. Interestingly, neural membranes are known to contain a large percentage of unsaturated lipids. Our results indicate that the activities of chlorinated hydrocarbons are not a result of specific interactions of these compounds with the lipids of membranes. However, the neurotoxicity of chlorinated hydrocarbons may be amplified by selective partitioning in the unsaturated neural membranes.     

PAHs污染土壤植物修复对酶活性的影响

PAHs作为一类持久性有机污染物对土壤环境质量产生深刻的影响。选用了中国亚热带城市普遍采用的4个树种(樟树、栾树、广玉兰、马褂木),利用盆栽试验,研究了PAHs污染土壤植物修复对酶活性影响。结果表明,多酚氧化酶活性定量抑制率为-94.98%—16.29%,过氧化氢酶为-76.71%—13.19%,磷酸酶为-49.62%—56.38%。土壤酶活性对PAHs污染的响应受到不同树种的影响。方差分析表明,过氧化氢酶活性在不同污染水平间差异显著,3种酶活性在不同时间下差异性显著,3种酶活性在不同树种×污染水平、不同时间×污染水平二因素作用下差异都不显著。主成分分析表明,PAHs污染对土壤酶活性的影响大于树种的影响,多酚氧化酶和磷酸酶对土壤反映敏感。     

Radiation-induced volatile hydrocarbon production in platelets

Generation of volatile hydrocarbons (ethane, pentane) as a measure of lipid peroxidation was followed in preparations from platelet-rich plasma irradiated in vitro. The hydrocarbons in the headspace of sealed vials containing irradiated and nonirradiated washed platelets, platelet-rich plasma, or platelet-poor plasma increased with time. The major hydrocarbon, pentane, increased linearly and significantly with increasing log radiation dose, suggesting that reactive oxygen species induced by ionizing radiation result in lipid peroxidation. Measurements of lipid peroxidation products may give an indication of suboptimal quality of stored and/or irradiated platelets.     

Bacteria produce the volatile hydrocarbon isoprene

Various bacterial species, both Gram-negative and Gram-positive, were found to produce the volatile hydrocarbon isoprene (2-methyl-1,3-butadiene). Out of the tested cultures, Bacillus produced the most isoprene. The production of isoprene from bacteria was confirmed by gas chromatography-mass spectrometry. Media and growth effects on isoprene production were investigated: growth in rich media led to higher levels of isoprene than growth in minimal media, and highest isoprene emission rates were seen in log-phase cultures. Temperature profiles for bacterial isoprene production showed an optimum of 45°C and were suggestive of an enzymatic mechanism for isoprene formation.     

Bacterial bioconcentration of chlorinated hydrocarbon insecticides from aqueous systems

The prevalence of chlorinated hydrocarbon insecticide uptake by chemoorganotrophic bacteria has been investigated. Thirteen bacterial species were observed to sorb and concentrate (bioconcentratc)α-chlordane,β-chlordane, dieldrin, heptachlor epoxide, and lindane from aqueous systems. Bioconcentration, as expressed by the ratio of cellular insecticide in ng/mg (dry wt) to supernatant insecticide in ng/μl, ranged from 10 for lindane byEnterobacter aerogenes to a high of 55,900 forβ-chlordane byCaulobacter vibrioides var.limonus. Amounts of cellular chlorinated hydrocarbon insecticides (CHI) detected and the bioconcentration ratios were observed to have the following order in magnitude:α- orβ-chlordane > dieldrin > heptachlor epoxide > lindane. This decreasing order was the inverse of reported water solubilities for the CHI and the inverse relationship was mathematically defined. The CHI were not easily removed from cells by washing (desorbing) and desorption was directly proportional to insecticide water solubility. Uptake of the CHI was rapid, near-maximum amounts being sorbed within 15 min, and pH 7 appeared optimal for bioconcentration as examined over the range pH 6 to 8. Implications of this investigation are that bioconcentration of CHI by bacteria might serve as a means of introducing these toxic compounds into aquatic food chains and that the bioconcentration phenomenon might lend itself as a treatment procedure for the intentional removal of residual CHI from water supplies and wastewater.     

Metabolism of volatile chlorinated aliphatic hydrocarbons by Pseudomonas fluorescens

A Pseudomonas fluorescens strain designated PFL12 was isolated from soil and water that were contaminated with various chloroaliphatic hydrocarbons. The isolate was able to metabolize 1,2-dichloroethane, 1,1,2-trichloroethane, 1,2-dichloropropane, 2,2-dichloropropane, and trichloroethylene.     

Residues of chlorinated hydrocarbon insecticides in the North Sea environment

Summary 1. Sandwich terns(Sterna sandvicensis) of a colony in the Dutch Wadden Sea, which were seen dying in tremors and convulsions, were analysed for their contents of chlorinated hydrocarbon insecticides. These proved to be present in considerable concentrations.2. The concentrations found were compared to those present in chickens of hens, poisoned in the laboratory. The amounts present in the dying or dead Sandwich terns were high enough to cause their death.3. Tern eggs from different coastal places in Ireland, Great Britain, The Netherlands and West Germany were sampled and analysed for these compounds. The amounts of dieldrin, telodrin and endrin in the eggs from the first two countries were much lower than those in the eggs from the last two ones. The amounts of DDE were quite the same.4. Tern food fishes(Clupea sprattus, Clupea harengus andAmmodytes lanceolatus) were sampled in the Dutch Wadden Sea and analysed. They contained considerable amounts of chlorinated hydrocarbon insecticides.5. Mussels(Mytilus edulis) were sampled at a series of locations alongside the Dutch coast. The highest concentrations of the insecticides were found on places near the mouth of the river Rhine. Also telodrin, an insecticide not used in Europe, was found.6. A big insecticide producing industry near the mouth of the river Rhine was informed of these facts. Measures taken by this form resulted in a decrease of the amounts of telodrin in the coastal North Sea environment.

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Rückstände von chlorierten Kohlenwasserstoff-Insektiziden im Lebensraum der Nordsee

Kurzfassung In einer großen Brutkolonie von Brandseeschwalben(Sterna sandvicensis) auf der Insel Griend im holländischen Wattenmeer war die Anzahl der Brutvögel von > 20 000 Paaren im Jahre 1955 auf etwa 1000 Paare im Jahre 1965 zurückgegangen. Viele Vögel wurden tot oder sterbend mit Krampfsymptomen aufgefunden. Organe und Blut dieser Vögel wurden auf ihren Gehalt an nerventoxischen Stoffen, insbesondere an chlorierten Kohlenwasserstoff-Insektiziden, untersucht. Die Konzentrationen wurden mit denen von Jungvögeln verglichen, die im Laboratorium auf künstliche Weise mit diesen Stoffen versehen worden waren und daran auch starben. Es konnte somit nachgewiesen werden, daß die in den Brandseeschwalben gefundenen Konzentrationen zum Tod der Tiere geführt haben. Die an verschiedenen Orten gesammelten Eier der Brandseeschwalben wurden ebenfalls untersucht. Eier aus den Niederlanden und aus Deutschland enthielten deutlich mehr Endrin, Dieldrin und Telodrin als Eier aus England und Irland. Verschiedene Fischarten(Clupea sprattus, Clupea harengus, Ammodytes lanceolatus), die von den Brandseeschwalben gefressen werden, wurden im holländischen Wattenmeer gesammelt und analysiert; sie enthielten beträchtliche Mengen an chlorierten Kohlenwasserstoff-Insektiziden. Der Herkunft dieser Stoffe wurde durch Untersuchungen von Miesmuscheln(Mytilus edulis) nachgegangen, die an verschiedenen Stellen entlang der holländischen Küsten gesammelt wurden. Die größten Insektizid-Konzentrationen wurden in Miesmuscheln gefunden, die aus dem Gebiet der Rheinmündung stammten. Einem dort gelegenen chemischen Werk, das diese Insektenvertilgungsmittel herstellt, wurden die Untersuchungsergebnisse mitgeteilt. Zugleich wurden geeignete Maßnahmen vorgeschlagen, um das Einleiten von insektizidhaltigen Abwässern zu verhindern. Augenscheinlich hat inzwischen die Konzentration einiger dieser Stoffe inMytilus edulis abgenommen.

     

Efficiency of alfalfa and reed in the phytoremediation of hydrocarbon polluted soil

The efficacy of plants as means of decontaminating hydrocarbon-polluted soil has been studied. Ditch reed (Phragmites australis) and alfalfa (Medicago sativa) markedly intensified processes of pollutant destruction, the effect being particularly pronounced in the case of polycyclic aromatic hydrocarbons (PAHs). Comparative analysis of microflora in soils (including those devoid of plants and rhizosphere) demonstrated that, in addition to preventing the pollutant-induced decrease in the amount of heterotrophic microorganisms, the plants stimulated their development, significantly increasing the population of destructors. Effects of plants on major physiological groups of soil microorganisms under conditions of pollution were ambiguous. The rhizosphere consortium of alfalfa was less susceptible to effects of pollutants than that of reed.     

Metabolism of volatile chlorinated aliphatic hydrocarbons by Pseudomonas fluorescens.

A Pseudomonas fluorescens strain designated PFL12 was isolated from soil and water that were contaminated with various chloroaliphatic hydrocarbons. The isolate was able to metabolize 1,2-dichloroethane, 1,1,2-trichloroethane, 1,2-dichloropropane, 2,2-dichloropropane, and trichloroethylene.     

Treatment of chlorinated volatile organic compounds in upflow wetland mesocosms

Sorption, biodegradation and hydraulic parameters were determined in the laboratory for two candidate soil substrate mixtures for construction of an upflow treatment wetland for volatile organic compounds (VOCs) at a Superfund site. The major parent contaminants in the groundwater at the Superfund site were cis-1,2-dichloroethene (cis-1,2-DCE) and 1,1,1-trichloroethane (1,1,1-TCA). The two mixtures; one a mixture of sand and peat, the other a mixture of sand, peat and Bion Soil, a product derived from agricultural wastes; were selected from ten possible mixtures based on the results of hydraulic and geotechnical testing. The sand and peat mixture had an average hydraulic conductivity of 4.95×10⁻⁴ cm/s with a critical flow of 39.5 gpm/acre (368 l/min/ha) without fluidization of the bed. The sand, peat and Bion Soil mixture had an average hydraulic conductivity of 3.02×10⁻⁴ cm/s with a critical flow of 36.8 gpm/acre (344 l/min/ha) without fluidization of the bed. Retardation coefficients ranged from 1 to 7.3 for target VOCs with higher coefficients observed in the mixture containing the Bion Soil. Consistently higher spatial and temporal first-order removal rate constants were observed in the sand, peat and Bion Soil mixture (cis-1,2-DCE, 0.84±0.36/day; 1,1,1-TCA, 6.52±3.12/day) than in the sand and peat mixture (cis-1,2-DCE, 0.37±0.13/day; 1,1,1-TCA, 1.48±0.42/day). Results from anaerobic microcosm studies confirmed that biodegradation was occurring in the columns and that the sand, peat and Bion Soil mixture had higher degradation rate than the sand and peat mixture. Vinyl chloride (VC) was identified as a ‘design’ contaminant since it is a proven carcinogen and had the lowest removal rate constant for both substrate mixtures. Effective wetland bed depths for VC removal of 900 and 210 cm will be required for peat and sand alone and sand, peat and Bion Soil mixtures, respectively.     

Engineered endophytic bacteria improve phytoremediation of water-soluble, volatile, organic pollutants

Phytoremediation of highly water soluble and volatile organic xenobiotics is often inefficient because plants do not completely degrade these compounds through their rhizospheres. This results in phytotoxicity and/or volatilization of chemicals through the leaves, which can cause additional environmental problems. We demonstrate that endophytic bacteria equipped with the appropriate degradation pathway improve the in planta degradation of toluene. We introduced the pTOM toluene-degradation plasmid of Burkholderia cepacia G4 into B. cepacia L.S.2.4, a natural endophyte of yellow lupine. After surface-sterilized lupine seeds were successfully inoculated with the recombinant strain, the engineered endophytic bacteria strongly degraded toluene, resulting in a marked decrease in its phytotoxicity, and a 50-70% reduction of its evapotranspiration through the leaves. This strategy promises to improve the efficiency of phytoremediating volatile organic contaminants.     

Binding of chlorinated benzidines to the rat hepatic aromatic hydrocarbon receptor

The binding of benzidine, 3,3'-dichlorobenzidine (3,3'-Cl2BZ), and the asymmetrically-substituted chlorinated benzidines 3,5-dichlorobenzidine (3,5-Cl2BZ) and 3,5,3'-trichlorobenzidine (Cl3BZ) to the rat hepatic cytosolic aromatic hydrocarbon (Ah) receptor was measured, in order to assess the mechanism of P-450I induction by 3,3'-Cl2BZ. Cl3BZ is the most mutagenic benzidine derivative in the Ames assay. Binding affinity to the Ah receptor protein was determined by displacement of labelled 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) from the receptor, measured with the sucrose density gradient centrifugation technique. The rank order of affinities and the apparent inhibitor constants were: Cl3BZ (4 microM) greater than 3,5-Cl2BZ (8.4 microM) greater than 3,3'-Cl2BZ (10 microM). Benzidine did not displace TCDD from the receptor protein. 4-Aminobiphenyl a structural link between the benzidine and biphenyl series competed weakly with TCDD. The 50% inhibition concentration was about 150 microM. The results are consistent with the hypothesis that the induction of P-450 enzymes by 3,3'-Cl2BZ in vivo is mediated by the Ah receptor.     

Obstructive jaundice due to a chlorinated hydrocarbon in breast milk.

A 6-week-old breast-fed infant had obstructive jaundice and hepatomegaly. When a dry-cleaning solvent, tetrachloroethylene, was detected in the mother''s milk and blood, breast-feeding was discontinued. Rapid clinical and biochemical improvement followed. The child grew normally and had normal liver function during 2 years of follow-up.     

Decline of chlorinated hydrocarbon insecticides residues in the tea-garden soils of Taiwan

Residues of chlorinated hydrocarbon insectidies and some of their metabolites, including p,p'-DDT, p,p'-DDD, p,p'-DDE, gamma-BHC, aldrin, dieldrin, heptachlor and heptachlor epoxide, were examined in the soils collected from 21 tea-gardens distributed in 15 countries of 6 prefectures in 1977, and from 100 locations distributed in 46 counties of 10 prefectures in 1984 in Taiwan. Although the use of these chlorinated hydrocarbon insecticides has been banned for many years, minor amounts of residues in the soils have still been detected. From 1977 to 1984, average residues of the chlorinated hydrocarbon insecticides and their metabolites in the soils of tea-gardens decreased from 5.64 to 0.06 ppb for gamma-BHC, 97 54 to 1.10 ppb for aldrin, 35.91 to 1.00 ppb for p,p'-DDE, 17.41 to 0.28 ppb for dieldrin, and 30.17 to 3.42 ppb for p,p'-DDT. But the number of positive cases increased for all chlorinated hydrocarbon insecticides tested, the residual levels were not significantly different among soils with different physiochemical properties or among soil layers. No significant amount of these insecticides was found in the processed tea.     

Dehalogenase gene detection and microbial diversity of a chlorinated hydrocarbon contaminated site

In recent years large quantities of mixtures of chlorinated hydrocarbons have accumulated in the environment due to the widespread use and production of these compounds. Microbes have been found to demonstrate a widespread and diverse potential to adapt to the dechlorination of such compounds. Therefore the aim of this study was to investigate the presence and diversity of reductive and hydrolytic dehalogenase genes in a site contaminated with a mixture of chlorinated hydrocarbons. Primers targeting reductive and hydrolytic bacterial dehalogenase genes were designed. In addition, DGGE analysis was performed in order to determine the presence of any known dehalogenase-producing organisms. Total DNA isolated from borehole water samples was used as the template for the amplification reactions. All PCR products obtained with the reductive and hydrolytic gene primers, as well as the dominant bands present on the DGGE gel were cloned and sequenced. Sequencing of the individual amplicons revealed significant identities to the tceA gene of Dehalococcoides ethenogenes 195, the vcrA gene of Dehalococcoides sp. VS as well as the dhlA and dhlB genes of Xanthobacter autotrophicus GJ10. DGGE analysis indicated a high level of commonality with the different sampling times and depths. However, sequence analysis revealed that 66% of the cloned fragments showed significant (95–99%) identity with uncultured microorganisms. Phylogenetic analysis of the sequences revealed that the DGGE clones clustered into two groups when compared to known bacteria having hydrocarbon degradative capabilities. This indicated that the sequences of the clones were diverse when compared to known microorganisms. This diversity represents a largely untapped genetic pool that can be exploited for the discovery of novel biocatalysts that can be employed in bioremediation. In addition, the presence of both hydrolytic and reductive dehalogenases provided strong evidence that bacteria capable of dehalogenation of chlorinated hydrocarbons may be present in sites contaminated with these compounds.