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Geographical variation of persistent organochlorine concentrations in blubber of ringed seal (Phoca hispida) from the Canadian Arctic: univariate and multivariate approaches.

Geographical variation of organochlorine (OC) concentrations in ringed seal (Phoca hispida) in the Canadian Arctic was studied using univariate and multivariate statistical techniques. The dataset consisted of 80 individual OC components (58 PCB congeners plus DDT- and chlordane (CHL)-related compounds, toxaphene, hexachlorocyclohexanes (HCH), chlorobenzenes (CBz), and dieldrin) determined in 221 ringed seal blubber samples from 13 locations throughout the Canadian Arctic from the period 1983 to 1989. Mean concentrations of the major OC groups in ringed seal blubber (SigmaPCBs, SigmaDDT, SigmaCHL and toxaphene), adjusted for the age and sex of the seals, showed few significant geographical differences. Principal components analysis was used to examine geographical trends. Significant differences in mean factor scores for three of four principal components were found between sampling locations. Locations in the western and high Arctic could be distinguished from those in Hudson Bay by highest scores along principal component two which was associated principally with CBz. PCB congeners with six or more chlorine substitutions declined with increasing north latitude, whereas more volatile OCs (CBz, HCH, less chlorinated PCBs) increased in the proportion of total OCs with latitude. Proportions of less chlorinated PCBs also decreased with increasing longitude, whereas slopes of regressions for more highly chlorinated PCBs increased significantly. The results were generally consistent with the 'cold condensation' hypothesis of increasing proportions of more volatile OCs with increasing latitude and distance from sources.

Journal Article↗

Residues of chlorinated hydrocarbon insecticides in human milk of Jordanian women.

A total of 411 milk samples were screened for the residues of the following chlorinated hydrocarbon insecticides using chromatographic methods: DDT insecticides (P,P'-DDT, P,P'-DDE, P,P'-DDD, O,P' -DDT); cyclodiene insecticides (aldrin, endrin, dieldrin, heptachlor, heptachlorepoxide, cis-and trans-chlordane); hexachlorocyclohexane (alpha-HCH, gamma-HCH) and hexachlorobenzene (HCB). The milk samples were obtained from lactating women selected randomly from five different geographical regions in Jordan. These regions were North and Middle Jordan Valley, Amman, Irbid and Zarqa. All of the studied insecticides were found to contaminate human milk in Jordan, but with high variations in the concentration and percentage of population occurrence. P,P'-DDE was the predominant contaminant occurring in 80.3% of studied population, followed by P,P'-DDT occurring in 53.5%. The regional results showed that the DDT residues were also the predominant contaminant in all regions and that the North and Middle Jordan Valley regions were the most affected. Infant's age (i.e. lactation period) had a significant inverse relationship with the concentration of insecticides in the milk fat.

Journal Article↗

Residues of organochlorine pesticides in Alabama soils.

A survey was made of 36 Alabama agricultural soils to assess residues of formerly used organochlorine pesticides. Compounds determined comprised alpha- and gamma-hexachlorocyclohexane, heptachlor, heptachlor-exo-epoxide, trans- and cis-chlordane, trans-nonachlor, dieldrin, toxaphene, DDT and DDE. Concentrations varied by several orders of magnitude among farms and appeared to be log-normally distributed. Highest concentrations (ng g(-1) dry soil, arithmetic means) were found for toxaphene (285+/-390) and DDTs (p,p'-DDE, 22.7+/-21.4; p,p'-DDT, 24.6+/-30.5; o,p'-DDT, 4.00+/-5.86; p,p'-DDD, 2.40+/-2.41) which were once heavily used in the southern USA. Pesticide residues were not proportional to soil organic carbon content indicating that residue concentrations were a reflection of pesticide application history and dissipation rates rather than air-soil equilibrium. Mean ratios of DDT/DDE in six regions of the state ranged from 0.39 to 1.5, and compound ratios for chlordanes and toxaphene were different from those in the technical mixtures.

Journal Article↗

Organochlorine and organophosphorus pesticide residues in the Atoya river basin, Chinandega, Nicaragua.

The hydrographic basin of the Atoya river, located in the Department of Chinandega, one of the main cotton producing regions in Nicaragua, is intensively contaminated by pesticides. Samples of river waters and sediments, as well as strategically selected wells have been analyzed to study variations in the concentrations of organochlorine and organophosphorus pesticide residues between the dry season (November-April) and the rainy season (May-June). Generally, higher concentrations of pesticides have been detected in the river waters and sediments in the dry season. DDT, DDD, DDE compounds and toxaphene are the most frequent organochlorine residues found in the water and sediment samples, while endrin, aldrin, dieldrin and lindane are mainly found in the waters of rivers and wells. Organophosphorus compounds were rarely detected. However, residues of ethion, methyl-parathion and ethyl-parathion were found in high concentrations in some river and well water samples. Generally, organochlorine compounds tend to accumulate in the fine grain-size fractions, rich in organic matter, except DDE, which concentrates basically in the coarse grain-size fractions.

Journal Article↗

Impact of protein binding on the availability and cytotoxic potency of organochlorine pesticides and chlorophenols in vitro.

In vitro toxicity data are generally based on nominal concentrations and thus depend on both activity and availability of a compound. The aims of the present study were to examine the influence of protein binding on the cytotoxicity of selected organochlorine pesticides and chlorophenols in Balb/c 3T3 cell cultures and to determine parameters of protein binding which can be used to estimate protein bound fractions and to model distribution in vitro. EC(50)-values derived from concentration-effect relationships determined in the presence of various concentrations of bovine serum albumin (BSA) were linearly correlated to BSA concentration. Increasing the BSA concentration from about 1.2 to 40 mg/ml increased the EC(50)-values by factors between 3.4 and 34.4. Molar ratios of substance bound to albumin ranged from 0.11 to 2.42. Calculated fractions bound to albumin in the normal growth medium were 0.075-0.17 (p,p'-DDT, p,p'-DDE, dieldrin, lindane), 0.09-0.1 (4-mono- and 2,4-dichlorophenol), 0.68 (2,4,5-trichlorphenol) and almost 1.0 (pentachlorophenol). At 40 mg/ml BSA any compound was largely bound to albumin (fractions bound > or = 0.74). Distribution modelling revealed that the availability of the highly hydrophobic organochlorines additionally was significantly reduced by partitioning into lipids. The results clearly demonstrate that nominal and relative toxic potencies of organochlorine pesticides and chlorophenols determined in vitro are substantially influenced by effects of protein binding on availability.

3T3 Cells↗

Detection of tumor promoters by early antigen expression of EB virus in Raji cells using a fluorescence microplate-reader.

As an in vitro assay for possible tumor promoters, we designed a quantitative immunofluorometric method to detect Epstein-Barr virus early antigen (EBV-EA) expression in Raji cells. In this method, anti-EBV-EA monoclonal antibody, a fluorogenic substrate and a fluorescence microtiterplate-reader were employed. 12-O-Tetradecanoylphorbol-13-acetate (TPA) was shown to be a potent inducer. EBV-EA induction by TPA was related to the activation of protein kinase C and phospholipase A2. The chemicals that reacted positively were okadaic acid, diethylstilbestrol, progesterone, sodium phenobarbital, aldrin and dieldrin. Lithocholic acid, testosterone and DDT were equivocal in the present experiments. Eight other chemicals tested did not react.

Acetophenones↗

Analysis of organochlorine pesticides in human milk: preliminary results.

In the face of evidence of human milk contamination by organochlorine pesticides, an analysis was performed on samples of milk obtained from healthy lactating women in the provinces of Granada and Almeria in Southern Spain. The samples were obtained by the Neonate Section of the Department of Pediatrics of Granada University Hospital (Neonatology Division) and by the Neonatal Service of Poniente Hospital in El Ejido, Almería. A liquid-liquid extraction procedure was performed. The cleaning of the sample before gas chromatography-mass spectrometry (GC-MS) used silica Sep-Pak. Among other pesticides, aldrin, dieldrin, DDT and its metabolites, lindane, methoxychlor and endosulfan were identified. The presence of these products was confirmed by mass spectrometry. The identification and quantification of these organochlorine molecules is important because they have estrogenic effects.

Breast Feeding↗

Analysis of pesticides and PCB congeners in serum by GC/MS with SPE sample cleanup.

This paper describes a simple procedure for the quantitative analysis of 25 polychlorinated biphenyl congeners (PCB) in serum. They are PCB 70, 74, 77, 87, 99, 101, 118, 126, 128, 138, 151, 153, 156, 169, 170, 180, 183, 187, 191, 194, 205, 206, 208 and 209. In addition, 15 pesticides are analyzed in the same extract: aldrin, p,p'-DDE, p,p'-DDT, dieldrin, endrin, endosulfan I, heptachlor, hexachlorobenzene, alpha-hexachlorocyclohexane, beta-hexachlorocyclohexane, lindane, methoxychlor, mirex, pentachlorobenzene, and 1,2,3,4-tetrachlorobenzene. The procedure involved sample cleanup using a combination of C18 and NH(2) solid phase extraction cartridges. The instrumental technique was gas chromatography/mass spectrometry with both electron ionization and negative chemical ionization in the selected ion monitoring mode. Concentration of sub-ng/ml level was attainable with 2 ml of serum sample.

Environmental Monitoring↗

Pesticide monitoring and its health problems in Egypt, a Third World country.

Health profiles for 300 pesticide formulators and 300 pesticide applicators revealed peripheral neuritis (> 40%), psychiatric manifestations (> 40%), electroencephalographic (EEG) changes (> 25%), and hepatorenal dysfunction (> 80%); all these manifestations were confirmed by different diagnostic tools. The frequency of carrier state of hepatitis (HbsAg) was 7.4% and of transitory state was 21.5%. The cytogenetic changes were confirmed by measuring chromosomal aberrations (CAs) among formulators and applicators, and proved to be more than twice those of controls. Pesticides residues among 130 milk, cheese, butter, yoghurt and milk powder samples (DDT, HCH and Dieldrin) were confirmed. Registration schemes, and post-registration programs (monitoring requirements, training needs and control of pesticide and fertilizer imports) should be mandatory.

Adult↗

Determination of endosulfan and its metabolites in human urine using gas chromatography-tandem mass spectrometry.

A method was developed for determining the occupational exposure to endosulfan and its main metabolites (endosulfanether, -lactone and -sulfate) in human urine using dieldrin as an internal standard. Solid phase extraction (SPE) and gas chromatography-tandem mass spectrometry (GC-MS-MS) have been used due to their high sensitivity and selectivity in avoiding most matrix interferences. The recovery efficiencies of the tested compounds yielded more than 89.2% at the fortification level of 10 ng ml(-1) in urine and their relative standard deviations were between 9.1 and 12.8%. The detection limit of each compound ranged between 6 and 18 pg ml(-1). Urine samples from nine pest control operators were analysed and total endosulfan concentrations between 94 and 2038 pg ml(-1) were found.

Calibration↗

Is exposure to endocrine disrupting compounds during fetal/post-natal development affecting the reproductive potential of farm animals?

Concerns have been raised about the potential adverse effects on reproductive health and immune status of farm animals following exposure to a range of natural and synthetic environmental compounds that disrupt normal hormonal actions. These compounds range from natural plant oestrogens (e.g. genistein, coumesterol) and mycoestrogens (e.g. Aflatoxins, zearalenone) to growth promoting pharmaceuticals (e.g. trenbolone acetate, melengastrol acetate) to chemicals spread in water, sewage sludge or the atmosphere such as detergents and surfactants (e.g. octylphenol, nonylphenol), plastics (e.g. bisphenol-A, phthalates), pesticides (e.g. methoxychlor, dieldrin, DDT) and industrial chemicals (e.g. PCB, TCDD). These compounds are commonly termed 'endocrine disrupting compounds' (EDCs) or 'endocrine disruptors' due to their ability to act as either hormone agonists or antagonists or the ability to disrupt hormone synthesis, storage or metabolism. A similar group of compounds are called 'immunotoxicants' and are thought to affect the immune system mainly by disrupting B and T cell homeostasis. As more studies are performed it is becoming clear that many compounds can directly or indirectly affect both the endocrine and immune systems. The susceptibility of target tissues is related to the stage of development, the cumulative exposure dose and the immune status of the individual. While some of the effects of the EDCs on the endocrine and immune systems are quite distinct, many are subtle and identifying the causative agent from the vast array of environmental challenges including EDCs, nutrition, temperature, etc. can be problematic. Identifying the causative agent is confounded by the possibility that effects that are observed in the adult may be due to exposure to EDCs during fetal life. This has major implications for the determination of universal end-point measurements to assess exposure to EDCs in farm animals.

Animals↗

Factors influencing nominal effective concentrations of chemical compounds in vitro: cell concentration.

In vitro potency data (e.g. EC(50) values), used to characterise the biological activity of chemicals, are generally based on nominal effective concentrations and thus depend on any factor influencing the availability of a compound. In this study the significance of cell binding for the availability of chemicals in vitro is (i) theoretically investigated by means of a simple equilibrium distribution model and (ii) experimentally examined using a bull sperm assay to measure the cytotoxic potency of selected compounds at different cell concentrations. Compounds were selected either to cover a wide range of hydrophobicity (log K(ow)=2.52-5.69) or to represent modes of cell binding other than partitioning into cellular lipids. With the exception of xylene, the EC(50) values increased with increasing cell concentration. The ratios of EC(50) values determined at about 120 x 10(6) and 15 x 10(6) cells/ml were: pentachlorophenol. 1.2, 1-nitronaphthalene: 1.9, thioridazine: 2.7, dieldrin: 4.1, hexachlorophene: 4.1, digitonin: 5.1, methylmercury chloride: 7.9, antimycin A: 10.1 and p,p'-dichlorodiphenyl dichloroethylene (p,p'-DDE): >19.1. The influence of partitioning into cell lipids was rather well predicted by the equilibrium distribution model, except for p,p'-DDE. The results show that cell binding can significantly affect the availability of compounds in vitro and thus toxic potencies and toxic equivalency factors.

Animals↗

The presence of environmental pollutants in the follicular fluid of farm animals (cattle, sheep, goats, and pigs).

Organochlorine pesticides and polychlorinated biphenyls are widely used in agriculture and industry, respectively. The present study assessed the burden of environmental pollutants in the follicular fluid of farm animals (cattle, sheep, goats, and pigs). An analytical method combining a solid-phase extraction with (C(18)) for clean-up and GC-electron capture detection using a capillary column was implemented for isolation and determination of organochlorine pesticides and polychlorinated biphenyls (PCBs). Of the organochlorine pesticides, hexachlorobenzene (HCB), hexachlorocyclohexane (HCH, alpha-, beta-, and gamma-isomers), dieldrin, heptachlor epoxide, and the DDT-related chemicals (o,p'-DDE, p,p'-DDE, p,p'-DDD, p,p'-DDT) were detected and of the PCBs, the congeners PCB-52, -101, -138, -153, and -180 were detected. In all species of farm animals, the most frequently detected pollutant was gamma-HCH (90-100% of samples) followed by HCB (80-100%), and p,p'-DDE (75-90.91%). Species differences in the concentrations of HCB, beta-HCH, heptachlor epoxide, and DDT-related chemicals in follicular fluid were noted as well as differences in the concentrations of some pollutants within the same species.

Animals↗

Isolation of four aquatic streptomycetes strains capable of growth on organochlorine pesticides.

Ninety-three wild-type isolates identified as actinomycetes were tested against 11 organochlorine pesticides (OPs): aldrin, chlordane, DDD, DDE, DDT, dieldrin, heptachlor, and heptachlor epoxides, lindane, and methoxychlor. Qualitative screening agar assays displayed 62-78% tolerance of strains to OPs. Four strains designed M4, M7, M9 and M15 were selected based on multi-OP-tolerance, and identified as members of the streptomycetes group. Different growth profiles were observed in cultures of the four selected streptomycetes cultured in synthetic medium containing 5-50 microg x l(-1) aldrin or chlordane or lindane. Increase of aldrin removal by the selected microorganisms was concomitant with the 4.8-36.0 microg x l(-1) pesticide concentration range. After 72 h of streptomycete M7 growth in synthetic medium containing 48.0 microg x l(-1) aldrin, the remaining OP concentration in the supernatant was approximately 10% of the initial concentration. Also, in stationary growth phase less than 2.5 microg x l(-1) aldrin residual concentration was detected in the medium.

Biodegradation, Environmental↗

Content of 8-oxodG in chromosomal DNA of Sparus aurata fish as biomarker of oxidative stress and environmental pollution.

The 8-oxodG content has been measured in chromosomal DNA of gilthead seabream (Sparus aurata) by HPLC-EC. Susceptibility of different tissues to oxidative DNA damage was studied by exposing fish to model pollutants. Cu(II), paraquat (PQ) and malathion failed to promote DNA oxidation in liver, while dieldrin significantly increased the 8-oxodG content in this organ, but not in gills or blood. After PQ exposure, fish liver showed high levels of glucose-6-P dehydrogenase (G-6PDH) and GSSG reductase activities. The increased antioxidant status and the lack of a specific transport system could explain the lack of susceptibility of liver to DNA oxidative damage induced by PQ. Increased levels of 8-oxodG were detected in the gills of PQ-exposed fish after 8 and 24 h. In contrast, after 48 h exposed fish contained lower 8-oxodG levels than controls. The existence of a PQ transport system in this O2-rich organ and the lack of a significant increase in antioxidant defenses would explain the sensitivity of gills to DNA damage promoted by PQ. Elimination of this soluble chemical and the putative induction of DNA-repair enzymes specific for oxidative damages could explain the drop of 8-oxodG levels at longer times. Fish exposed to moderate levels of urban and industrial pollution showed significantly high 8-oxodG content in hepatic DNA. We conclude that 8-oxodG determination in chromosomal DNA by HPLC-EC is a potentially useful biomarker of environmental pollution, although its response is still somewhat lower than that of other well-established biomarkers of oxidative stress.

8-Hydroxy-2'-Deoxyguanosine↗

Immunomodulatory effect of various anti-parasitics: a review.

This paper reviews the immunomodulatory effects (immunosuppression or immunoactivation) of various anthelmintics including levamisole, fenvalerate, dieldrin, carbofuran, aminocarb, thiabendazole, fenbendazole, oxfendazole and ivermectin. The induced modulation of immune function may occur via direct and/or indirect mechanisms. The immunomodulatory effects of these anti-parasitics have been studied in a variety of bacterial (e.g. brucellosis, salmonellosis, paratuberculosis, mastitis), viral (e.g. infectious bovine rhinotracheitis, Herpes, foot and mouth disease), parasitic (e.g. onchocerciasis, coccidiosis, ascariasis, schistosomiasis) and neoplastic diseases. Some antiparasitics have also been used to boost immunity in a number of human diseases including leprosy, Hodgkin's disease, rheumatoid arthritis, and in adjuvanted therapy of colorectal cancer. The ability to stimulate the immune response of animals offers a new means of disease intervention. Future research on immunomodulatory effects of anti-parasitics, for humans and domestic farm animals, will provide additional methods of treating immunosuppressed subjects. The immunopotentiating or immunosuppressing activity of anti-parasitics will dictate whether co-administration of vaccines and anthelmintics or administration of vaccines during the window of immunoactivation is justified or not.

Animals↗

Temporal trends of organochlorine pesticides in the Canadian Arctic atmosphere.

Temperature normalization (TN), multiple linear regression (MLR), and digital filtration (DF) were used to analyze the temporal trends of an atmospheric dataset on organochlorine pesticides (OCs) collected at the Canadian high arctic site of Alert, Nunavut. Details of these techniques have been presented before (Environ. Sci. Technol. 2001, 35, 1303-1311). Both the TN and DF methods revealed that the majority of OC pesticides declined over the 5 years of study, except endosulfan I and several of the pesticide metabolites, including dieldrin and p,p'-DDE. In comparison to studies conducted in the Great Lakes, atmospheric levels in the Arctic were less dependent on temperature, although seasonal variations were apparent. Generally, levels in the winter were lower than during the rest of the year. A notable exception was p,p'-DDE. Many compounds also showed a second minimum in concentrations during June/July and possible explanations are presented to account for this. The estimated first order half-lives for the decline in OC concentrations were generally found to be comparable or slightly longer than those obtained at temperate locations, with the exception of alpha-HCH, which displayed a much longer half-life in the Arctic (approximately 17 yrs). Sporadic increases in heptachlor as well as increases in the ratio of trans- to cis-chlordane suggest episodic input of chlordanes between 1995 and 1997, especially during the winter.

Arctic Regions↗

Fate of endocrine-disruptor, pharmaceutical, and personal care product chemicals during simulated drinking water treatment processes.

The potential occurrence of endocrine-disrupting compounds (EDCs) as well as pharmaceuticals and personal care products (PPCPs) in drinking water supplies raises concern over the removal of these compounds by common drinking water treatment processes. Three drinking water supplies were spiked with 10 to 250 ng/L of 62 different EDC/ PPCPs; one model water containing an NOM isolate was spiked with 49 different EDC/PPCPs. Compounds were detected by LC/MS/MS or GC/MS/MS. These test waters were subjected to bench-scale experimentation to simulate individual treatment processes in a water treatment plant (WTP). Aluminum sulfate and ferric chloride coagulants or chemical lime softening removed some polyaromatic hydrocarbons (PAHs) but removed <25% of most other EDC/ PPCPs. Addition of 5 mg/L of powder activated carbon (PAC) with a 4-h contact time removed 50% to >98% of GC/ MS/MS compounds (more volatile) and 10% to >95% of LC/ MS/MS compounds (more polar); higher PAC dosages improved EDC/PPCP removal. EDC/PPCP percentage removal was independent of the initial compound concentration. Octanol-water partition coefficients served as a reasonable indicator of compound removal under controlled PAC test conditions, except for EDC/PPCPs that were protonated or deprotonated at the test pH and some that contained heterocyclic or aromatic nitrogen. Separate chlorine or ozone experiments decreased the EDC/PPCP initial concentration by <10% to >90%; EDC/PPCPs were likely transformed to oxidation byproducts. Ozone oxidized steroids containing phenolic moieties (estradiol, ethynylestradiol, or estrone) more efficiently than those without aromatic or phenolic moieties (androstenedione, progesterone, and testosterone). EDC/PPCP reactivity with oxidants were separated into three general groups: (1) compounds easily oxidized (>80% reacted) by chlorine are always oxidized at least as efficiently by ozone; (2) 6 of the -60 compounds (TCEP, BHC, chlordane, dieldrin, heptachlor epoxide, musk ketone) were poorly oxidized (<20% reacted) by chlorine or ozone; (3) compounds (24 of 60) reacting preferentially (higher removals) with ozone rather than chlorine. Conventional treatment (coagulation plus chlorination) would have low removal of many EDC/PPCPs, while addition of PAC and/or ozone could substantially improve their removals. Existing strategies that predict relative removals of herbicides, pesticides, and other organic pollutants by activated carbon or oxidation can be directly applied for the removal of many EDC/PPCPs, but these strategies need to be modified to account for charged (protonated bases or deprotonated acids) and aliphatic species. Some compounds (e.g., DEET, ibuprofen, gemfibrozil) had low removals unless ozonation was used. Other compounds had low removals by all the WTP processes considered (atrazine, iopromide, meprobamate, TCEP), and removal processes capable of removing these types of compounds should be investigated.

Alum Compounds↗