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Gas chromatographic resolution of organochlorine insecticides on OV-1/OV-17, OV-210/OV-17, and OV-225/OV-17 mixed phase systems.

The resolution of organochlorine insecticides and their related compounds on OV-1/OV-17, OV-210/OV-17, and OV-225/OV-17 mixed phase column systems was investigated. Four BHC isomers and p,p'-DDT, its isomer, and their metabolites (except p,p'-DDE and o,p'-DDE) were resolved on the OV-210/OV-17 system. Heptachlor and heptachlor epoxide were separated on 5% OV-1/2% OV-17 or OV-225/2% OV-17. Resolution of aldrin, dieldrin, and endrin was obtained on 5% OV-210/2% OV-17, p,p'-DDE and o,p'-DDE could not be separated by any of the systems studied.

Aldrin↗

[Preparation and characterization of a novel adsorbent made by cellulose acetate].

A novel adsorbent made by cellulose acetate was developed. Preparation method, structure, and adsorbing characterization of the adsorbent were discussed. SEM results showed that the surface of round adsorbent was stable membrane of cellulose acetate, free from obvious cracks, holes, or other defects; while the cross section of the adsorbent was meshy and a lot of cavities were found. The adsorption results of 4 organochlorinated pesticides, such as Dieldrin, Aldrin, Endrin and Heptachlor, show that the adsorbent has higher efficient for organic pollutants, the adsorption rate is about 85% after 12 h. The adsorption rate is faster with the higher lgKow, and the removal efficiency of Heptachlor and Aldrin is up to 99% after 0.5h. The adsorbent can be used to remove persistent organic pollutants effectively.

Adsorption↗

Screening of nonfatty fish for organochlorine pesticide residues by solid-phase extraction cleanup: interlaboratory study.

Six U.S. Food and Drug Administration laboratories participated in an Interlaboratory trial of a solid-phase extraction cleanup method for determination of pesticides in nonfatty seafood products. The participants analyzed control and fortified (about 0.050 ppm lindane, heptachlor epoxide, p,p'-DDE, and endrin) croaker and flounder samples and a sea trout sample containing incurred p,p'-DDE residues. Mean recoveries of the fortified residues from the fish ranged from 89.1 to 107.8%. The within-laboratory coefficients of variation (CVs) ranged from 4.2 to 8.5%, and the among-laboratory CVs ranged from 10.9 to 26.5%. The 6 laboratories reported a mean value of 0.040 ppm p,p'-DDE in a fish sample which contained incurred residues. The same value (0.040 ppm) was obtained by using official methodology. The within-laboratory CVs ranged from 3.5 to 18.3%, and the among-laboratory CV was 17.3%.

Analysis of Variance↗

Responses of the L5178Y mouse Lymphoma cell forward mutation assay. V: 27 coded chemicals.

Twenty-seven chemicals were tested for their mutagenic potential in the L5178Y tk+/tk- mouse lymphoma cell forward mutation assay using procedures based upon those described by McGregor et al. (McGregor DB, Martin R, Cattanach P, Edwards I, McBride D, Caspary WJ (1987): Environ Mol Mutagen 9:143-160). Cultures were exposed to the chemicals for 4 hr, then cultured for 2 days before plating in soft agar with or without trifluorothymidine (TFT), 3 micrograms/ml. The chemicals were tested at least twice. Statistically significant responses were obtained with acid orange 10, aniline, benzaldehyde, o-chloroaniline, chlorodibromomethane, cytembena, 1,2-dibromo-4-(1,2-dibromomethyl) cyclohexane, dieldrin, lithocholic acid, oxytetracycline, phenazopyridine HCl, 1-phenyl-3-methyl-5-pyrazolone, sodium diethyldithiocarbamate, solvent yellow 14, tetraethylthiuram disulfide (disulfiram), 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. Apart from phenazopyridine HCl, acid orange 10, and solvent yellow 14, rat liver S9 mix was not a requirement for the mutagenic activity of these compounds. Chemical not identified as mutagens were N-4-acetylaminofluorene, chlorpheniramine maleate, chloropropamide, 1,4-dioxane, endrin, ethylene glycol, iron dextran, methapyrilene, sodium(2-ethylhexyl)alcohol

Animals↗

Relative genotoxic activities of pesticides evaluated by a modified SOS microplate assay.

The genotoxic activities of 47 pesticides were determined using a modified SOS microplate assay in which the induction of beta-galactosidase in E. coli PQ37 was used as a quantitative measure of genotoxic activity. The results were compared with those obtained with anethole, curcumin, and capsaicin, a few examples of naturally occurring compounds present in foods. The assays were conducted with pesticides dissolved either in a suitable solvent, such as 10% DMSO in physiological saline or dispersed in sodium taurocholate micelles, to simulate conditions in the small intestine from where these substances are normally absorbed from the diet. 4-Nitroquinoline oxide (4-NQO) served as the reference standard of a direct acting mutagen. In micellar form, 4-NQO and 25 of the 47 pesticides tested showed significantly higher genotoxic activities than when they were tested in an organic solvent. In micellar form the SOS inducing potency of 4-NQO was almost twice as high as in 10% DMSO in physiological saline. In taurocholate micelles, the five most active compounds had activities in the range of 1,234-3,765 units/mumol and in the order of decreasing activities they were ranked as follows: malathion > dichlorvos > lindane > chlordane > endrin. They were significantly less active than 4-NQO (less than 40%). In micellar solution the naturally occurring compounds, anethole, curcumin, and capsaicin gave activities of 4,594, 928, and 809 units/mumol, respectively. These studies show that genotoxicity may depend upon the environment in which cells are exposed to these potential genotoxins. It appears that testing of the more hydrophobic compounds, both synthetic and naturally occurring, are needed.

DNA Damage↗

[Residues of organochlorine pesticides, PCB's and chlorophenols in fish from commercial ponds and fish hatcheries from the waters in the area of Frankfurt (Oder)].

Fishes from fish-hatcheries, lakes and the river Oder in the area of the former district Frankfurt (Oder) were analysed for organochlorine pesticides (HCB, aldrin, HCH-isomeres, DDD, DDE, DDT, endrin, toxaphen and dieldrin), polychlorinated biphenyles and penta- and tetrachlorophenole. A clean up-procedure using acidic digestion mixture has been compared with a column-extraction-procedure followed by column chromatography on aluminia. Furthermore the simultaneous determination of the organochlorine pesticides, PCB's and chlorophenoles by acidic silicagel-extraction is described. The identification and quantification was realized by packed-column and capillary-gaschromatography including electron-capture-detection. The investigations show, that the permissible levels were only reached up to 2 to 10% with exception of toxaphen and pentachlorophenole. Average 50% of the toxaphen- and pentachlorophenole-values were found near the tolerance levels settled for these substances. The application of both substances in the area of the former German Democratic Republic until today can be regarded as a reason for this. The results of our investigations are comparable to last publications on fish contamination in the area of the previous Federal Republic of Germany.

Animals↗

Role of molecular geometry, valence charge distribution and vibrational modes in bioactivity of cyclodiene insecticides.

Fourier transform infrared spectral measurement and complete normal mode calculations have been carried out for heptachlor and wedge modes have been identified. In addition, valence charge distributions have been obtained for aldrin, endrin, heptachlor, beta-endosulfan, cis-chlordane, trans-chlordane, photo-cis-chlordane and photo-trans-chlordane using CNDO/2 (complete neglect of differential overlap) molecular orbital calculations. A toxicity parameter has been defined as the product of the charge distribution and surface area of the corresponding active wedges, depending on the interacting structural features. The variation of this toxicity parameter is generally in order and in agreement with the reported measurements based on the corresponding order of observed LD50 values. Because of the structural features, the toxicity in these cases is a surface phenomenon rather than a volume effect as in the case of Gammexane, wherein the insecticide binds itself to membrane channels. Because the biological activity is a dynamic rather than a static phenomenon, it is expected that the normal modes involving the wedge atoms play an important role.

Electrons↗

Chlordecone interaction of calmodulin binding with phosphodiesterase.

The effects of organochlorine (O.C.) compounds, such as aldrin, dieldrin, endrin, isodrin, chlordecone and mirex, on calmodulin (CaM) activity were investigated. Changes induced by O.C. compounds on biological and physical properties of CaM were monitored in terms of phosphodiesterase stimulation and tyrosine fluorescence, respectively. None of the O.C. compounds altered tyrosine fluorescence of CaM in the presence of Ca2+. Except for chlordecone, none of the O.C. compounds inhibited CaM-activated phosphodiesterase (PDE). Chlordecone significantly decreased (P less than 0.05) CaM-activated PDE in a concentration-dependent manner without affecting the basal enzyme. Combination of chlordecone with W-7 (CaM antagonist) increased the inhibitory effect of W-7 on CaM activity. These results suggest that O.C. compounds may not be changing the tyrosine fluorescence of CaM. Among the O.C. compounds tested, chlordecone is a specific inhibitor of CaM-activated PDE.

Binding, Competitive↗

The Ca(2+)-transport-ATPase of human erythrocytes as an in vitro toxicity test system--acute effects of some chlorinated compounds.

Investigations to determine the inhibitory activity on the Ca(2+)-transport-ATPase of human erythrocyte membranes were performed with various compounds of toxicological significance, mostly chlorinated and mainly used as biocides, such as phenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 2,3,4-trichlorophenol, 2,3,4,5-tetrachlorophenol, pentachlorophenol (PCP), captan, folpet, captafol, (+)-camphene, toxaphene, dichlorodiphenyltrichloroethane (DDT), lindane, endrin, dieldrin, alpha-endosulfan, beta-endosulfan, paraquat, diallate, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). Some of the compounds investigated display an inhibitory effect on the Ca(2+)-transport-ATPase at very low concentrations. The in vitro results obtained in this enzyme assay can be correlated directly with the results of other in vitro assays and with the results of in vivo investigations in different species in which an inhibitory effect on various biological functions is observed. Therefore, an inhibitory effect on the Ca(2+)-transport-ATPase indicates a toxic effect of these compounds to cell functions. Since the inhibitory effect of these compounds can be measured rapidly and the enzyme is easy to handle, it might be a useful tool to screen the toxic effects of various compounds on cell function. The aim of the authors was to investigate the usefulness of this screening test system for the characterization of the cellular toxicity of various compounds.

Calcium-Transporting ATPases↗

Ultratraces analysis of organochlorine pesticides in drinking water by solid phase extraction coupled with large volume injection/gas chromatography/mass spectrometry.

This study describes an SPE coupled with large volume injection (LVI) analytical method for the analysis of organochlorine pesticides, BHC (alpha, beta, delta), aldrin, endosulfan (alpha, beta), endrin, dieldrin, and DDT, from aqueous samples. Determination was carried out by GC with MS. The LODs of organochlorine pesticides were determined at 10 ng/L concentration levels, and the results show that SPE-LVI-GC/MS has the potential to accurately determine organochlorine pesticides in water, as it avoids analyte classes in the various steps of a typical extraction procedure.

Chromatography, Gas↗

Benzene-assisted atmospheric-pressure chemical ionization: a new liquid chromatography/mass spectrometry approach to the analysis of selected hydrophobic compounds.

Charge-exchange reactions involving benzene have been successfully exploited to increase the sensitivity of atmospheric-pressure chemical ionization mass spectrometry (APCI-MS) towards hydrophobic compounds of significant environmental relevance which are not detectable with the ordinary APCI techniques. Among them, good sensitivity have been found for (a) highly chlorinated biphenyl derivatives such as dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethene (DDE); (b) cyclopentadienes such as Aldrin and its epoxy derivatives Dieldrin and Endrin; and (c) dibenzofurans and dibenzo-para-dioxins such as 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF) and 2,3,7,8-tetrachloro-dibenzo-para-dioxin (2,3,7,8-TCDD). The reactant benzene molecules were introduced into the source either through the nebulizer gas or by direct post-column addition of neat liquid, whereas the targeted compounds were analyzed using a high-performance liquid chromatography (HPLC) RP-18 column using methanol/water solutions as mobile phase. By using benzene as post-column reagent, positive ion mode detection was proven to be significantly enhanced as compared with APCI measurements carried out without benzene assistance.

Air Pollutants↗

Organochlorine pesticides in wolves from Galicia.

Levels of seven organochlorine pesticides (heptachlorepoxide, dieldrin, endrin, p,p'-DDE, o-p'-DDT, p,p'-DDT, and methoxychlor) and DDE/DDT ratios were determined in spleen, liver, muscle, kidney and suprarenal from 12 wolves from three provinces of Galicia (eight male and four female). Analysis was carried out by GC-ECD. Heptachlorepoxide was in found only 25% of samples, while p,p'-DDE was the most dominant of the organochlorine compounds analyzed. DDE/DDT ratios higher than 1 were found in liver and muscle.

Adrenal Glands↗

Perinatal metabolism of dichlorodiphenyldichloroethylene in Nicaraguan mothers.

Umbilical cord and venous blood samples were collected at the time of delivery from 52 mothers living in urban and rural areas of the Atoya River basin, Nicaragua. In a subsample of 24 mothers that delivered by Cesarean section, abdominal adipose tissue samples were also collected, as was breast milk later in lactation. Cord and venous blood sera were analyzed for 13 organochlorine pesticides: 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (pp'-DDT); 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (pp'-DDE); pp'-dichlorophenyldichlorodiene (pp'-DDD); alpha-hexachlorocyclohexane (alpha-HCH); beta-hexachlorocyclohexane (beta-HCH); gamma-hexachlorocyclohexane (gamma-HCH); delta-hexachlorocyclohexane (delta-HCH); toxaphene; dieldrin; endrin; aldrin; heptachlor; and heptachlor epoxide. In venous blood only pp'-DDE (100% of samples), pp'-DDT (1.92%), dieldrin (15.38%), heptachlor (15.38%), gamma-HCH (7.69%), beta-HCH (11.53%), and delta-HCH (1.92%) were found, whereas in cord blood only pp'-DDE (100%), pp'-DDT (3.84%), dieldrin (19.23%), and heptachlor (9.16%), were found. The persistent DDT metabolite pp'-DDE, present in all samples of blood serum, adipose tissue, and breast milk, was studied in relation to maternal characteristics such as body mass index (BMI), age, lactation experience, and fetal pesticide acquisition. Mean venous (7.12 microg/g) and cord (6.39 microg/g) pp'-DDE concentrations were not significantly different but were significantly correlated. pp'-DDE in maternal adipose tissue was positively correlated with pp'-DDE in cord blood (P=0.0001) and breast milk (P<0.0001) and marginally correlated with changes in BMI (r=-0.03088; P=0.06). There was a higher proportion of samples (58%) with a greater concentration of DDE in venous than in cord blood. Although DDE accumulation may be less during fetal development than during breast feeding, exposure during embryogenesis may be more important than during the postnatal period.

Adipose Tissue↗

Organochlorine residues and elemental contaminants in U.S. freshwater fish, 1976-1986: National Contaminant Biomonitoring Program.

As part of the National Contaminant Biomonitoring Program (NCBP, formerly a component of the National Pesticide Monitoring Program), the U.S. Fish and Wildlife Service periodically determined concentrations of organochlorine chemical residues and elemental contaminants in freshwater fish collected from a nationwide network of stations. In late 1986 and early 1987, the last time the network was sampled, a total of 319 composite fish samples were collected from 97 NCBP stations. The samples were analyzed for residues of organochlorine chemicals and the elements As, Cd, Cu, Hg, Pb, Se, and Zn. The mean concentration of total DDT and its homologs (p,p'-constituents) declined from 1984 to 1986, thus continuing a trend that began in 1970. The most persistent DDT homolog (p,p'-DDE) was detected at all stations sampled in 1986, and averaged 74% of total DDT residues, up from 70% in 1974-1979 but essentially unchanged from 1984. Collectively, these findings indicated a low rate of influx and continued weathering of DDT in the environment; nevertheless, DDT concentrations in fish from some stations in the South remained high enough to constitute a threat to piscivorous wildlife. Residues of polychlorinated biphenyls (PCBs) also remained widespread, but a significant downward trend in total PCB concentrations and incidence was evident, and PCB mixtures containing early eluting components were present at fewer stations than in the past. PCB concentrations were generally highest in fish from the industrialized rivers of the Northeast and Midwest and from the Great Lakes. Concentrations of toxaphene also declined, as did its incidence, from 88% of the stations sampled in 1980-1981 to 64% in 1986; however, analytical problems with the 1986 samples may have contributed to the latter. The risks represented by PCBs and toxaphene could not be evaluated on the basis of our data. Among cyclodiene insecticides, dieldrin and chlordane-related residues were the most widespread. Mean concentrations of dieldrin declined through 1986, but remained consistently highest in the Great Lakes. For chlordane-related residues, mean concentrations were lower that reported previously, and trans-nonachlor continued to replace cis-chlordane as the most abundant component. Collectively, these findings suggested a lower rate of chlordane influx to the aquatic environment; however, a point source of cyclodiene insecticides to the Mississippi R. near Memphis, TN, remained evident. Residues of mirex, PCA, BHC isomers, endrin, heptachlor, and HCB were either found at relatively few (< 25%) of the stations sampled in 1986 or were characterized by relatively low concentrations. Concentrations of the herbicide Dacthal (DCPA) were also low, but incidence increased from 46% of the stations sampled in 1984 to 61% in 1986. In general, organochlorine chemical concentrations were lower in 1986 than at any time reported previously. For elemental contaminants, the geometric mean, maximum, and 85th percentile concentrations (respectively, all in microgram/g wet weight) in 1986 samples were as follows: As, 0.083, 1.53, 0.24; Cd, 0.011, 0.32, 0.04; Cu, 0.794, 11.0, 1.7; Hg, 0.087, 0.44, 0.18; Pb, 0.058, 1.90, 0.21; Se, 0.417, 3.41, 0.66; and Zn, 21.191, 94.5, 31.7. Mean concentrations of Cu increased and concentrations of As decreased relative to the 1984 collection, but these changes may reflect subtle differences in the species composition of the 1986 collection relative to other collections; concentrations of both elements differ greatly among fishes. There were no other statistically significant changes from 1984 to 1986; however, mean concentrations of As, Cd, Pb, and Zn declined from 1976, when elemental contaminants in fish were first measured in the NCBP, and 1986. In contrast, mean concentrations of Hg and Se did not change appreciably. Moreover, and in contrast to the other elements measured in 1986, concentrations of Hg and Se were high enough to constitute a threat to pisc

Animals↗

Organochlorine pesticides and polychlorinated biphenyls in human adipose tissue.

Halogenated organic compounds are highly lipophilic chemicals that are persistent in the environment as a result of their use and chemical stability. Some of these compounds are also present in the environment as metabolites or oxidation products of a parent compound or as by-products formed in the production of chlorinated compounds. Chronic exposure to the general population results mainly through the food chain. Because they are lipophilic, and because many are metabolized slowly, these chemicals tend to concentrate in body fat tissue. This contribution has described these halogenated organic compounds, discussed their use, regulation and prohibition throughout the world, and reviewed published studies on the levels of these chemicals found in the adipose tissue of humans and animals. For many years, residues of halogenated organic compounds have been detected in the human adipose tissue of individuals in a number of countries, including those in Europe, Asia, and Africa, as well as in the U.S. The levels detected have been used as an index of the level of general population exposure of these compounds over time. Over the past two decades, most countries have observed a steady decline of this level of exposure, reflecting a reduction in the use of these compounds, restrictions on or banning of their use, and a corresponding decrease in their environmental levels. The levels of concentrations vary from chemical to chemical as well as from isomer to isomer. Since the use of aldrin and dieldrin has now been banned or restricted in the U.S. and a number of other countries, residue levels have slowly decreased. Mean values in human adipose tissue in the U.S. and some foreign countries ranged from 0.04 to 0.40 ppm for dieldrin. Aldrin was detected only in Argentina and Poland in the 1970s and endrin was not detected anywhere at anytime. By 1978, all products containing BHC registered in the U.S. has been either discontinued or reformulated to incorporate lindane rather than BHC. The potential for exposure to BHC is virtually nonexistent in the U.S.; however, exposure to lindane is possible since products containing this chemical are still marketed, and used particularly in the manufacture of human medicine. DDT was banned for agricultural purposes in the U.S. in 1972, although it is still used elsewhere for public health vector control. Since the decline in use of DDT, however, the average levels of concentration have also declined. Heptachlor, chlordane, and trans-nonachlor (a component of both heptachlor and chlordane) are chlorinated cyclodienes.(ABSTRACT TRUNCATED AT 400 WORDS)

Adipose Tissue↗

Transmitter-activated ion channels as the target of chemical agents.

The transmitter-activated ion channels are known to be important target sites of a variety of therapeutic and toxic agents. The GABA-activated chloride channel has been shown to be modulated by general anesthetics, alcohols, and the pyrethroid, cyclodiene and lindane insecticides. The general anesthetics halothane, enflurane and isoflurane greatly augmented the GABA-activated current before desensitization took place, and suppressed it after desensitization at clinically relevant concentrations equivalent to 1-2 minimum alveolar concentrations. The stimulating effect appears to be a mechanism of general anesthesia. It seems that general anesthetics have a specific affinity for the GABA receptor-channel complex. Ethanol also augmented the GABA-activated peak chloride current with little or no effect on the desensitized sustained current. Longer chain alcohols n-butanol, n-hexanol, n-octanol, and n-decanol also exerted the same type of effect, with the potency and efficacy increasing with lengthening of the carbon chain. The GABA receptor-channel complex has also been shown to be an important target site of certain insecticides. The type II pyrethroids deltamethrin and fenvalerate augmented the GABA-activated peak chloride current when applied concurrently with GABA, but the effect was diminished as the pyrethroids were applied for long periods of time prior to GABA application. The latter effect might explain the controversy in the literature regarding the pyrethroid action on the GABA system. The type I pyrethroid allethrin suppressed the GABA-activated peak chloride current when co-applied with GABA. Both types of pyrethroids suppressed the N-methyl-d-aspartate-induced current. Lindane and the cyclodienes dieldrin, endrin, heptachlor-epoxide, and isobenzan suppressed the GABA-activated chloride current. These effects can account for the convulsant action of lindane and the cyclodienes.

Alcohols↗

Organochlorine pesticide contaminations in human milk samples from women living in Amman, Jordan.

Concentration of 15 organochlorine pesticides were determined by capillary gas chromatography in 59 human milk samples collected from the general population during 1989/1990 in the Jordanian capital of Amman. In addition to hexachlorbenzene (HCB), three groups of organochlorine compounds namely, DDT and its metabolites, hexachlorcyclohexane (HCH-isomers) and the cyclopentadiene group (aldrin, dieldrin, endrin, heptachlor, and heptachlor epoxide) were analyzed. The results show that almost all samples contained HCB, beta-HCH, p,p'-DDE and p,p'-DDT, whereas p,p'-DDD, heptachlor, alpha-HCH, gamma-HCH and o,p'DDT were found in 42, 40, 33, 22 and 20 analyzed samples, respectively. The concentration of HCB, beta-HCH, p,p'-DDE, p,p'-DDT and heptachlor expressed on a milk-fat basis (median in mg/kg milk fat): 0.29, 0.4, 2.04, and 0.7 respectively. For the comparative purposes and in order to try to find the possible sources of mother-milk contaminations, different types of locally produced and imported cow milk samples were also analyzed for the same organochlorine compounds. Almost all types of tested milk were contaminated with p,p'-DDE.

Adult↗