The concentrations of aldrin and dieldrin and their photoisomers in the atmosphere

Air samples taken in 1973 at a point remote from areas of organochlorine pesticide usage, Bantry Bay in S.W. Ireland, were analysed for aldrin and dieldrin in the vapour state and in association with particupate matter. In addition, some of the samples were analysed for the photoisomers of aldrin and dieldrin, and for pp'-DDT, 1,1-dichloro-2,2-di-(4-chlorophenyl) ethylene (pp'-DDE) and pp'-IDE. Detection and quantitation of all compounds were by gas-liquid chromatography with electron capture detection (g.l.c./e.c.). Confirmatory evidence for the presence of dieldrin and pp'-DDE was obtained with some samplesusing gas-liquid chromatography with mass fragmento-graphic detection (g.l.c./m.f.). Dieldrin was detected in all seventeen samples of air taken, but the mean concentration was 0.36 ng/kg and the range of concentrations was 0.06–1.60 ng/kg. Aldrin was not detected in the samples examined, neither were the two photoisomers. Only pp'-DDE of the pp'-DDT group of compounds was detected in the nine samples examined, and the apparent mean concentration was 0.14 ng/kg. None of the compounds was detected in particulate matter.     

Cytochrome P-450 content and aldrin epoxidation to dieldrin in isolated rat hepatocytes

A rat hepatocyte suspension effectively epoxidized aldrin to dieldrin with a V_max of 7.19 mol/mol P-450/min and a K_m of 9.27 μM. Viability and metabolic activity were stable for 6 hr after isolation when cells were maintained at room temperature (20°C) with the gentle introduction of $\text{O}{}_2\text{CO}{}_2$ onto the surface of the suspension. The cytochrome P-450 content of the suspension was 303 pmol/10⁶ cells. Primary maintenance culture of the cells also epoxidized aldrin. During culture for 3 days, metabolic activity decreased slowly day by day. Metabolic activity of microsomal fraction from rat liver was also examined. Microsomes epoxidized aldrin with a V_max of 5.11 mol/mol P-450/min and a K_m of 1.64 μM. Significant loss of some subspecies of cytochrome P-450 during fractionation of liver homogenate was indicated.     

The weathering of ant baits containing aldrin,dieldrin and meirx in trinidad

Sufficinent amounts of insecticide remained in baits to be effecitive against ants over the period when baits retained their attractiveness. Aldrin was lost at similar rates from waterproofed and non-waterproofed baits, but the former had advantages over the latter. Dieldrin and mirex were lost at slower ratesthan aldrin, and insecticide losses were governed by temperature and not by rainfall.     

The effects of dieldrin and isomeric aldrin diols on synaptic transmission in the American cockroach and their relevance to the dieldrin poisoning syndrome

Dieldrin and two of its metabolites, 6,7-trans-dihydroaldrindiol, and 6,7-cis-dihydroaldrindiol, were studied with regard to their toxicity to the American cockroach, effects on ganglia of the ventral nerve cord, and penetration into the ventral nerve cord of poisoned cockroaches. An approximate LD₅₀ for injected doses of dieldrin was 0.45 mg/kg. After injection at 115 mg/kg, the trans isomer of aldrin diol caused about 70%, and the cis isomer about 50% mortality. Injected doses of 40 mg/kg of the three compounds appeared in the ventral nerve cord to the extent of 0.13–0.26% of the doses. Dieldrin was more potent, but slower acting than the diols in causing synaptic after-discharge and elevated spontaneous activity in isolated nerve cords. The results are discussed in relation to other studies on these compounds. It was concluded that, in the American cockroach, dieldrin, rather than either of the diols, is the insecticidal agent in dieldrin poisoning, and that metabolic conversion of dieldrin to the cis and/or trans aldrindiol constitutes a detoxification.     

The uptake of [14C] dieldrin via the roots of young cotton plants

The stems and leaves of young cotton plants growing in nutrient solution containing a radioactive dieldrin suspension became radioactive. After 2 weeks, dieldrin was taken up at a constant rate which differered slightly in different environments probably because the plants transpired at different rates.     

Metabolism of [14C]dieldrin in bluegill fish

The exposure of bluegill fish to 50 parts per billion [¹⁴C]dieldrin in a static system resulted in the absorption of 73.00% of the radioactivity in 48 hr. Following transfer of the fish to clean water, only 16.20% of the absorbed radiolabel was eliminated in 23 days. Out of the 93.65% of the absorbed radioactivity recovered, 9 radioactive spots were isolated which included unchanged dieldrin (74.39%), pentachloroketone (8.17%), and aldrin-trans-diol (8.04%) as major metabolites.     

Metabolism of methylated analogs of aldrin and dieldrin by liver preparations from male and female rat

Analogs of aldrin and dieldrin have been synthesized, the molecules of which lack a methylene bridge but have two methyl groups attached to olefinic or oxirane ring carbon atoms. Their metabolism was studied using NADPH-supplemented 12,000g × 30-min supernate of livers from Wistar and CD strains of rats. The dimethylated olefin was not metabolized to its epoxide but was converted by supernate of liver from rats of both sexes to a labile hydroxylated metabolite. Exogenous NADPH increased the rate at which the olefin was metabolized, but concentrations of NADPH which increased the yield of the labile metabolite when added to female rat liver preparations decreased the yield when added to those from the male. This metabolite had a mass spectrum which was consistent with it being a hydroxymethyl derivative. The dimethylated epoxide was metabolized more slowly than the olefin, and a notable sex difference in the route of metabolism was evident. With supernate from livers of female rats the only metabolite detected by gas-liquid chromatography had a mass spectrum consistent with it being a ring-hydroxylated epoxide. Male rat liver supernate formed small quantities of the same compound, but the major metabolite had a mass spectrum indicative of a hydroxymethyl epoxide. No hydrolysis of the oxirane ring of the epoxide has been detected. The relevance of these results to the planned synthesis of cyclodienes of optimal biodegradability is mentioned.     

Bioconversion of dieldrin by wood‐rotting fungi and metabolite detection

BACKGROUND: Dieldrin is one of the most persistent organochlorine pesticides, listed as one of the 12 persistent organic pollutants in the Stockholm Convention. Although microbial degradation is an effective way to remediate environmental pollutants, reports on aerobic microbial degradation of dieldrin are limited. Wood‐rotting fungi can degrade a wide spectrum of recalcitrant organopollutants, and an attempt has been made to select wood‐rotting fungi that can degrade dieldrin, and to identify the metabolite. RESULTS: Thirty‐four isolates of wood‐rotting fungi were investigated for their ability to degrade dieldrin. Strain YK543 degraded 39.1 ± 8.8% of dieldrin during 30 days of incubation. Phylogenetic analysis demonstrated that strain YK543 was closely related to the fungus Phlebia brevispora Nakasone TMIC33929, which has been reported as a fungus that can degrade chlorinated dioxins and polychlorinated biphenyls. 9‐Hydroxydieldrin was detected as a metabolite in the cultures of strain YK543. CONCLUSION: It is important to select the microorganisms that degrade organic pollutants, and to identify the metabolic pathway for the development of bioremediation methods. Strain YK543 was selected as a fungus capable of degrading dieldrin. The metabolic pathway includes 9‐hydroxylation reported in rat's metabolism catalysed by liver microsomal monooxygenase. This is the first report of transformation of dieldrin to 9‐hydroxydieldrin by a microorganism. Copyright © 2010 Society of Chemical Industry     

Biliary secretion of 14C and identification of 5,6-dihydro-5,6-dihydroxycarbaryl glucuronide as a biliary metabolite of [14C]carbaryl in the rat

The biliary secretion of ¹⁴C was observed in conscious, bile-fistulated rats given single oral doses of [¹⁴C]carbaryl (1.5, 30, and 300 mg/kg). Over 94% of the ¹⁴C was absorbed after 12 hr. From 15 to 46% of the ¹⁴C was secreted in bile, 10–40% in urine, and less than 1% in feces 12 hr after dosing. Three metabolites were isolated from bile and identified by mass and/or NMR spectrometric methods. These metabolites were: 5,6-dihydro-5,6-dihydroxycarbaryl glucuronide (12–18% of the biliary ¹⁴C), a conjugate(s) of carbaryl (12% of the biliary ¹⁴C), and conjugated isomers of hydroxy-carbaryl (2% of the biliary ¹⁴C). The majority of the biliary ¹⁴C remains to be identified.     

Von Baeyer/IUPAC names and abbreviated chemical names of metabolites and artifacts of aldrin (HHDN), dieldrin (HEOD) and endrin

The correct von Baeyer/IUPAC names of aldrin (HHDN), dieldrin (HEOD), and endrin, of 5 previously incorrectly-named compounds and of 18 other related compounds which have not hitherto been named in this way are presented in tabular form alongside their structural formulae. The von Baeyer ring systems present in some of these compounds were identified by inspection of Schlegel diagrams (planar representation of bridged hydrocarbons), a guide to the construction of which is presented. Also included in the tables (which have been indexed) are abbreviated chemical names; the suitability of the choices made is discussed. The alternative “polyhydroaromatic” names for 12 of these compounds have been abstracted from the literature and listed.     

Structural studies and photochemical re-arrangement of an animal metabolite of HEOD,the active component of dieldrin

The structure of 9-hydroxy HEOD was examined by spectroscopic methods and by photolysis. The hydroxyl group was found to be hydrogen bonded to the epoxy group, and the product of photolysis was a hydroxylated analogue of the previously described photoisomer of HEOD.     

Persistence of organochlorine insecticides on different substrates under different environmental conditions. I. The rates of loss of dieldrin and aldrin by volatilisation from glass surfaces

The losses of dieldrin and aldrin by volatilisation from crystalline deposits on glass surfaces in different environments were studied by using these insecticides labelled with the radioactive isotope ³⁶CL as a tracer. Volatilisation rates were very sensitive to changes in temperature and to a lesser extent to air movement, but not to change in relative humidity (the effect of which was measurable only on porous glass surfaces). All rates of loss from glass surfaces could be described mathematically in terms of single or double exponential equations, although many were better described by simple sigmoid (logistic) equations.     

Conversion of [14C]buturon in soil and leaching water under outdoor conditions

[¹⁴C]Buturon, a urea herbicide, was sprayed on soil and winter wheat as an aqueous formulation (2.98 kg/ha) under outdoor conditions. Three months after application, a total of 49.2% of the applied radiocarbon was recovered: 46.9% in the soil, 0.3% in the leaching water (depth > 50 cm), and 2.0% in the plants. Radioactive residues in the soil were distributed to a depth of 50 cm and decreased with increasing depth of the soil. An average of 47% of the radioactivity present in the soil could be extracted with cold chloroform; by this extraction method, the formation of artefacts was avoided. Between one and two thirds of the extracted radioactivity was unchanged buturon. In the soil extracts, the following eight conversion products were isolated and identified by combined gas chromatography/mass spectrometry: N-(p-chlorophenyl)-N-methyl-O-methyl carbamate; N-(p-chlorophenyl)-O-methyl carbamate; N-(p-chlorophenyl)-N′-methyl-N′-isobutenyl-urea; N-(p-chlorophenyl)-N′-methyl-urea, N-(p-chlorophenyl)-N′-methyl-N′-isobutenylol-urea; p-chloroaniline in “biologically bound” form; N-(p-chlorophenyl)-N′-methyl-N′-methoxyisobutenyl-urea; and N-(p-chlorophenyl)-N′-methyl-N′-ethoxyisobutenyl-urea. In the leaching water, which contained only 0.005–0.006 mg/liter of radioactive substances, the following three conversion products were isolated and identified by gas chromatography/mass spectrometry: p-chloroformanilide; N-(p-chlorophenyl)-N-methyl-O-methyl carbamate; and an N-hydroxyphenyl-N′-methyl-N′-isobutinyl-urea. The results are discussed in relation to the factors responsible for the formation of these products.     

Estimation of dieldrin in cured tobacco

Estimation of dieldrin in cured tobacco using published methods of clean-up followed by electron-capture g.l.c., suffers from serious interferences. Such interference can be eliminated by Storherr sweep codistillation and t.l.c. on alumina. The limit of detection is 0.01 part/million.     

Electrophysiological studies on the effect of sesamex upon the action of dieldrin in Blaberus discoidalis

Treatment of the metathoracic ganglion of the cockroach, Blaberus discoidalis, with dieldrin (HEOD) at a concentration of 10^?5M produced changes in spontaneous efferent activity and afterdischarge in efferent pathways. Pretreatment with sesamex markedly reduced the spontaneous activity caused by dieldrin and also reduced the latency of appearance of symptoms from 60 min to nearly 30 min. However, pretreatment with sesamex did not alter the intensity and duration of the dieldrin-induced synaptic afterdischarge. Pretreatment of cockroaches with sesamex did not measurably change the toxicity of dieldrin in vivo.     

Degradation of [14C]Terbuthylazine and [14C]Atrazine in Laboratory Soil Microcosms

The degradation and formation of major chlorinated metabolites of terbuthylazine and atrazine in three soils (loamy clay, calcareous clay and high clay) were studied in laboratory experiments using molecules labelled with ¹⁴C on the s-triazine ring. Soil microcosms were treated with the equivalent of 1 kg ha^-1 of herbicide and incubated in the dark for 45 days at 20(±1)°C. The quantity of [¹⁴C]carbon dioxide evolved in the soils treated with atrazine was negligible and could not be attributed to mineralization of the parent molecule. The mineralization of terbuthylazine accounted for 0·9–1·2% of the initial radioactivity. In the soils studied, the extrapolated half-lives varied from 88 to 116 days for terbuthylazine and 66 to 105 days for atrazine, with no significant differences for the three soils and the two molecules. The deethyl metabolites of the two s-triazines and the deisopropyl-atrazine metabolite appeared during the incubation in the three soils. The completely dealkylated metabolite was not detected in any of the soils. After 45 days of incubation, the non-extractable soil residues for the high clay, loamy clay and calcareous clay soils represented for terbuthylazine, 33·5, 38·3 and 43·1% and for atrazine, 19·8, 20·8 and 22·3% of the initial radioactivity. © 1997 SCI.     

The metabolism of [14C] cymoxanil in the rat

A rat, given a single oral dose of [¹⁴C] cymoxanil, 1-(2-cyano-2-methoxyimino-[2-¹⁴C]-acetyl)-3-ethylurea, eliminated 91% of the radioactivity within 72 h. The urine contained 71%, the faeces 11%, and the expired air about 7% of the radiolabel; no ¹⁴C residue was found in the internal organs. Greater than 70% of the radioactivity in the urine was identified. The major metabolite was characterised as glycine, both free and conjugated, as hippuric acid and phenylaceturic acid [N-(phenylacetyl)-glycine], and probably in the form of polypeptides of low molecular weight. The other metabolites identified included 2-cyano-2-methoxyiminoacetic acid, 2-cyano-2-hydroxyiminoacetic acid and 1-ethylimidazolidine-2, 4, 5-trione. The minor metabolites included succinic acid and 2-oxoglutaric acid which indicated reincorporation of metabolic ¹⁴C. Cymoxanil, as such, was not detected in the urine.     

Metabolism of [14C]parathion and [14C]paraoxon in isolated,perfused rat livers

Perfusion of ¹⁴C-(ring)-parathion or ¹⁴C-(ring)-paraoxon with blood through isolated, intact rat livers resulted in the rapid degradation of these insecticides. Degradation was negligible in the absence of rat liver (controls), thus demonstrating the capacity of the liver per se to effectively degrade these compounds. Of the total radiocarbon recovered after liver perfusion with [¹⁴C]parathion, 33 % could be attributed to unchanged [¹⁴C]parathion (similarly distributed between the liver and the blood) while 67.9 % was degraded to water soluble compounds and 2.5% was converted to organic soluble paraoxon and traces of p-nitrophenol. Nearly all of the [¹⁴C]paraoxon, however, was degraded by the intact rat liver, resulting in water soluble products that amounted to 98.5% of the total radiocarbon recovered. Unexplained losses of radiocarbon with the perfusion apparatus used were lower in the presence of rat liver which degraded the insecticides to more water soluble compounds. The water soluble degradation products produced from [¹⁴C]parathion and [¹⁴C]paraoxon were non-toxic to mosquito larvae (Aedes aegypti L.). These ring-labelled products were found to be conjugated p-nito-phenol. Nearly all of the water soluble radiocarbon was located in the perfused blood, while only small amounts (1.8 to 3.0% of recovered) were excreted via the bile or were associated with the liver tissue (1.3 to 1.8 % of recovered).     

Quick estimation of dieldrin in fresh cotton-leaf samples

Hexane was the most convenient extraction solvent. Consistent recoveries of 80% dieldrin were obtained after cold grinding with 10 mi hexane/g of leaf for 5 min. After filtering, solutions did not require a “clean-up” before g.l.c. analysis, provided they were not concentrated further. Radioactive dieldrin in such extracts could be directly counted with a simple scintillation apparatus if pre-treated with acidified potassium permanganate solution to eliminate the colour-quenching effect and stored in the dark for 24 h to allow phosphorescence from some leaf materials to decay. Extractions using other solvents would need a “clean-up” procedure before g.l.c. analysis, but radioactive dieldrin in hexane-isopropanol extracts could be quickly estimated by simple scintillation counting after decolorisation with sodium hypochlorite and storage in the dark for 24 h.