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.     

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.

     

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.     

The influence of some chlorinated hydrocarbon insecticides on the mineralization of N fertilizers and plant growth

Summary The variable effects, previously observed under field and laboratory conditions, resulting from the application of the widely used chlorinated hydrocarbon insecticides has stimulated further investigations. Because of the possible cumulative harmful effects of the insecticides on the activities of soil micro-organisms, several investigations have been concerned with the influence of these insecticides on the conversion of ammonia to nitrate.The present investigation is concerned with the relationship between the deleterious effect of certain pesticides on the activities of the soil microflora and the use of nitrogenous fertilizers; an aspect of the problem which has not previously been considered.The results of the investigation may allow the anomalous effects of the insecticides in the laboratory and in the field to be understood.The observations indicate that the basis of the effects of hexachlorocyclohexane on soils is as an inhibitor of nitrification.     

Oxygen transfer in mechanically agitated aqueous systems containing dispersed hydrocarbon

The effect of dispersed n -dodecane or n -hexadecane on the air-to-aqueous phase overall volumetric oxygen transfer coefficient in a simulated (cell-free) stirred-tank fermentor is described. The oil volume fraction ranged from zero to 0.10; the ionic strength of the aqueous phases was varied from 0 to 0.45. The air-to-aqueous phase coefficients in both oil-free (K_La) and oil-bearing (K_La*) systems were evaluated from unsteady-state experiments using a membrane-covered probe to follow the aqueous phase dissolved oxygen tension. For all systems studied, K_La*/K_La was found to be independent of P/V and v_s for all practical purposes. However, for a particular aqueous phase and at a given P/V and v_s, the ratio K_La*K_La generally differed from unity. Depending on the combination of hydrocarbon type and volume fraction and the aqueous-phase ionic strength employed, the dispersed hydrocarbon may, in some cases, reduce the rate of oxygen transfer and in others enhance it relative to that of the corresponding oil-free gas–liquid dispersion. Enhancement of the air-to-aqueous transfer rate by such negative spreading coefficient hydrocarbons has not been reported previously.     

Bacterial cometabolic degradation of chlorinated paraffins

Summary Cometabolic dechlorination of chlorinated paraffins was demonstrated in the presence of n-hexadecane by bacterial strains (HK-3, HK-6, HK-8, and HK-10) isolated from soil samples.Eleven per cent of chlorine of chlorinated paraffin-150 (CP-150) was released by strain HK-3. The mixed culture of strain HK-3, catalyzing the dechlorination of terminal chlorine of chloroalkane, and strain H15-4, capable of releasing the chlorine from 2-chlorinated fatty acids, dechlorinated CP-150 up to 13%. The mixed culture of the four strains (HK-3, HK-6, HK-8, and HK-10) performed the dechlorination of CP-150 by cometabolism in a jar fermentor pH at 7.0. The amount of chloride released from the chlorinated paraffins tested was in the range of 15–57%.The activated sludge acclimatized to n-hexadecane for 60 days showed a little dechlorination activity to CP-150.     

Mass balance studies of volatile chlorinated hydrocarbon phytoremediation

In field-scale mass balance studies of poplar remediation of carbon tetrachloride (CT), more than 95% of the mass of CT was degraded with all of the CT chlorine accountable as chloride ion accumulation in the soil. Atmospheric loss of CT through leaf transpiration and trunk diffusion was insignificant. These findings are consistent with previously reported uptake and degradation of trichloroethylene (TCE) by poplar. Poplar phytoremediation of CT and TCE results in little decrease in aqueous concentration, since water is taken up at about the same rate as the chlorinated compounds. From this result we predict that phytoirrigation--the application of pumped contaminated groundwater to planted systems--will result in concentrations of the pollutants at the bottom of the root zone that are higher than permitted regulatory levels. Such plantations will be susceptible to loss of contaminants during rainfall events, possibly resulting in pollution of uncontaminated soil. Greenhouse studies of pollutant profiles in the media beneath poplar trees that were surface irrigated with TCE and CT confirmed that regulatory concentrations of these pollutants were not achieved in the root zone of the poplar; rather concentrations fell by less than 50%.     

Bacterial diversity in marine hydrocarbon seep sediments

Marine seeps introduce significant amounts of hydrocarbons into oceans and create unusual habitats for microfauna and -flora. In the vicinity of chronic seeps, microbes likely exert control on carbon quality entering the marine food chain and, in turn, hydrocarbons could influence microbial community composition and diversity. To determine the effects of seep oil on marine sediment bacterial communities, we collected sediment piston cores within an active marine hydrocarbon seep zone in the Coal Oil Point Seep Field, at a depth of 22 m in the Santa Barbara Channel, California. Cores were taken adjacent to an active seep vent in a hydrocarbon volcano, on the edge of the volcano, and at the periphery of the area of active seepage. Bacterial community profiles were determined by terminal restriction fragment length polymorphisms (TRFLPs) of 16S ribosomal genes that were polymerase chain reaction (PCR)-amplified with eubacterial primers. Sediment carbon content and C/N ratio increased with oil content. Terminal restriction fragment length polymorphisms suggested that bacterial communities varied both with depth into sediments and with oil concentration. Whereas the apparent abundance of several peaks correlated positively with hydrocarbon content, overall bacterial diversity and richness decreased with increasing sediment hydrocarbon content. Sequence analysis of a clone library generated from sediments collected at the periphery of the seep suggested that oil-sensitive species belong to the gamma Proteobacteria and Holophaga groups. These sequences were closely related to sequences previously recovered from uncontaminated marine sediments. Our results suggest that seep hydrocarbons exert a strong selective pressure on bacterial communities in marine sediments. This selective pressure could, in turn, control the effects of oil on other biota in the vicinity of marine hydrocarbon seeps.