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Efficient decomposition of environmentally persistent perfluorooctanesulfonate and related fluorochemicals using zerovalent iron in subcritical water.

Decomposition of perfluorooctanesulfonate (PFOS) and related chemicals in subcritical water was investigated. Although PFOS demonstrated little reactivity in pure subcritical water, addition of zerovalent metals to the reaction system enhanced the PFOS decomposition to form F-ions, with an increasing order of activity of no metal approximately equal Al < Cu < Zn << Fe. Use of iron led to the most efficient PFOS decomposition: When iron powder was added to an aqueous solution of PFOS (93-372 microM) and the mixture was heated at 350 degrees C for 6 h, PFOS concentration in the reaction solution fell below 2.2 microM (detection limit of HPLC with conductometric detection), with formation of F-ions with yields [i.e., (moles of F- formed)/(moles of fluorine content in initial PFOS) x 100] of 46.2-51.4% and without any formation of perfluorocarboxylic acids. A small amount of CHF3 was detected in the gas phase with a yield [i.e., (moles of CHF3)/(moles of carbon content in initial PFOS) x 100] of 0.7%, after the reaction of PFOS (372 microM) with iron at 350 degree C for 6 h. Spectroscopic measurements indicated that PFOS in water markedly adsorbed on the iron surface even at room temperature, and the adsorbed fluorinated species on the iron surface decomposed with rising temperature, with prominent release of F- ions to the solution phase above 250 degrees C. This method was also effective in decomposing other perfluoroalkylsulfonates bearing shorter chain (C2-C6) perfluoroalkyl groups and was successfully applied to the decomposition of PFOS contained in an antireflective coating agent used in semiconductor manufacturing.

Alkanesulfonic Acids↗

Exposure to 4-tert-octylphenol, an environmentally persistent alkylphenol, enhances interleukin-4 production in T cells via NF-AT activation.

4-tert-Octylphenol (OP) is a representative endocrine disruptor that may have adverse effects on human health. The influence of this compound on allergic immune responses remains unclear. In this study, we have examined the effects of OP on production of interleukin-4 (IL-4), a pro-inflammatory cytokine closely associated with allergic immune responses. OP significantly enhanced IL-4 production in antigen-primed T cells in a dose-dependent manner. Treatment with OP in vivo resulted in significant increase of IL-4 production in T cells and of IgE levels in sera of antigen-primed mice. Furthermore, OP enhanced the activation of IL-4 gene promoter in EL4 T cells transiently transfected with IL-4 promoter/reporter constructs, and the enhancing effect mapped to a region in the IL-4 promoter containing binding sites for nuclear factor of activated T cell (NF-AT). Activation of T cells by phorbol-12-myristate-13-acetate (PMA) resulted in markedly enhanced binding activities to the NF-AT site, which significantly increased upon addition of OP, indicating that the transcription factor NF-AT was involved in the enhancing effect of OP on IL-4 production. The enhancement of IL-4 production by OP was blocked by FK506, a calcineurin inhibitor, but not by the estrogen receptor (ER) antagonist ICI 182780. FK506 inhibited the NF-AT-DNA binding activity and IL-4 gene promoter activity enhanced by OP in a dose-dependent manner. These findings demonstrate that OP enhances IL-4 production in T cells via the stimulation of calcineurin-dependent NF-AT activation.

Animals↗

Environmental health assessment of deltamethrin in a malarious area of Mexico: environmental persistence, toxicokinetics, and genotoxicity in exposed children.

We reported previously that children are exposed to deltamethrin in malarious areas. In the present work we explored the levels of this insecticide in soil samples and also obtained relevant toxicokinetic data of deltamethrin in exposed children. Results show that, after spraying, indoor levels of deltamethrin in soil samples were higher than outdoor levels. The mean half-life estimated with these data was 15.5 days for outdoor samples and 15.4 days for indoor samples. Children's exposure to deltamethrin was assessed using as biomarkers the urinary concentrations of the metabolites 3-phenoxybenzoic acid (3-PBA) and cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (Br2CA). The mean level of both biomarkers reached a peak within the first 24 hr postexposure; 6 months after the initial exposure, urinary levels of 3-PBA and Br2CA were found at levels observed before exposure. Approximately 91% of the total 3-PBA or Br2CA was excreted during the first 3 days after exposure. Therefore, we estimated a half-life for this period, the values for 3-PBA and Br2CA being almost identical (13.5 vs. 14.5 hr). Finally, considering reports about the genotoxicity of deltamethrin, we assessed DNA damage in children before and 24 hr after indoor spraying of deltamethrin; we found no differences in the comet assay end points. In conclusion, we observed exposure to deltamethrin in children, but we did not find any relationship between soil concentrations of deltamethrin and urinary levels of the metabolites. At least for genotoxicity, the exposed children appeared not to be at risk.

Benzoates↗

Biofilm formation, extracellular polysaccharide production, and cell-to-cell signaling in various Enterobacter sakazakii strains: aspects promoting environmental persistence.

Enterobacter sakazakii is considered an opportunistic pathogen and has been implicated in food-associated cases of meningitis or enteritis, especially in neonates and infants. The organism has been detected in various types of food and in food production units, but so far only powdered infant formula has been linked to outbreaks of disease. Survival and persistence in such environments requires the ability to adapt to high osmotic potentials and/or dry conditions. Fifty-six E. sakazakii strains were evaluated for several features important for persistence and survival: (i) biofilm formation and the putative production of cellulose as one of the components of the extracellular matrix, (ii) adherence to hydrophilic and hydrophobic surfaces, (iii) the production of extracellular polysaccharides, and (iv) the ability of E. sakazakii to produce cell-to-cell signaling molecules. Pellicle and flock formation was observed in 21 of the strains grown in Luria-Bertani broth and in 44 of the strains grown in brain heart infusion broth. Calcofluor-stained fibrils, observed microscopically in every (fragile or rigid) pellicle, suggested the presence of cellulose as an extracellular compound in this type of biofilm. Twelve isolates did not form any pellicle or flocks under either condition. Twenty-three of the isolates exhibited the potential to adhere to glass surfaces in shaken cultures, and 33 strains showed biofilm formation at the air-solid interface of polyvinyl chloride microtiter wells. Sixteen isolates adhered to both surfaces. Twenty-four of the isolates tested produced a milky, viscous mass, considered as extracellular polysaccharide. High-performance liquid chromatography analysis of the polysaccharide revealed the presence of glucose, galactose, fucose, and glucuronic acid. Thin-layer chromatography analyses performed on ethyl acetate extracts of cell-free supernatants of the 56 strains indicated the presence of two different types of acylated homoserine lactones (3-oxo-C6-HSL and 3-oxo-C8-HSL). These findings illustrate the ability of E. sakazakii to produce cell-to-cell signaling molecules.

Bacterial Adhesion↗

Fluoroacetate content of some species of the toxic Australian plant genus, Gastrolobium, and its environmental persistence.

Gas chromatography confirmed the relatively high concentrations of fluoroacetate found in toxic Gastrolobiums, a genus of indigenous Australian plants. Fluoroacetate concentration in these plants ranged from 0.1 to 3875 micrograms/g (ppm) dry weight, with young leaves and flowers containing the highest concentrations. However, there was considerable intrastand variation between individual plants of at least two species with coefficients of variation ranging from 94% to 129%. Despite the high concentrations of fluoroacetate in many species, only one of nine soil samples collected from beneath these plants contained fluoroacetate. None of the 16 water samples collected from nearby streams and catchment dams contained fluoroacetate. This suggests that fluoroacetate does not persist in this environment. Fluoroacetate was also found in the genus Nemcia, and very low levels of fluoroacetate (ng/g) were detected in the foodstuffs, tea and guar gum. The latter indicates that other plant species may produce biologically insignificant amounts of fluoroacetate.

Australia↗

Environmental persistence of Bacillus thuringiensis spores following aerial application.

Soil and leaf populations of Bacillus thuringiensis (Bt) were monitored following aerial application of commercial Bt formulations at the rate of 72 billion international units per acre per year during a 5-year period. Data from soil sample spore counts suggested that Bt spores persisted in Wasatch forest soils for up to 2 years but they did not proliferate. Bt isolates were recovered from leaf samples 12 months post application from sprayed, previously sprayed and from nonsprayed areas. The frequency and diversity of Bt isolates recovered from leaves was independent of sample area spray history. In accordance with U.S. Forest Service criteria, aerial application of Bt during a 5-year period resulted in the eradication of gypsy moth (Lymantria dispar, L) from the Wasatch Front region of the Wasatch Mountain Range, Utah.

Bacillus thuringiensis↗

Efficient decomposition of environmentally persistent perfluorocarboxylic acids by use of persulfate as a photochemical oxidant.

Photochemical decomposition of persistent perfluorocarboxylic acids (PFCAs) in water by use of persulfate ion (S2O8(2-)) was examined to develop a technique to neutralize stationary sources of PFCAs. Photolysis of S2O8(2-) produced highly oxidative sulfate radical anions (SO4-), which efficiently decomposed perfluorooctanoic acid (PFOA) and other PFCAs bearing C4-C8 perfluoroalkyl groups. The major products were F- and CO2; also, small amounts of PFCAs with shorter than initial chain lengths were detected in the reaction solution. PFOA at a concentration of 1.35 mM (typical of that in untreated wastewater after an emulsifying process in fluoropolymer manufacture) was completely decomposed by a photochemical system with 50 mM S2O8(2-) and 4 h of irradiation from a 200-W xenon-mercury lamp. The initial PFOA decomposition rate was 11 times higherthan with photolysis alone. All sulfur-containing species in the reaction solution were eventually transformed to sulfate ions by this method. This method was successfully applied to the decomposition of perfluorononanoic acid contained in a floor wax solution.

Carboxylic Acids↗

Biofilm formation by mycoplasma species and its role in environmental persistence and survival.

Although mycoplasmas possess a very limited genome, little is known about their virulence mechanisms and methods of persistence in the host. Examination of a wide range of mycoplasma species found considerable variation in their ability to form a biofilm. Mycoplasma putrefaciens, M. cottewii, M. yeatsii, M. agalactiae and M. bovis produced prolific biofilms. Conversely, the highly pathogenic mycoplasma and causative agent of contagious bovine pleuropneumonia, Mycoplasma mycoides subsp. mycoides SC, was unable to produce a biofilm. Biofilms were found to be considerably more resistant to stress, including heat and desiccation, than planktonic cells. A link between the biofilm phenotype and genotype as determined by molecular typing was found for M. bovis. Analysis of biofilms using fluorescent staining combined with confocal microscopy demonstrated that mycoplasma biofilms formed a highly differentiated structure with stacks and channels. Biofilm formation may indicate that mycoplasmas are capable of surviving in the environment.

Anti-Bacterial Agents↗

Oxidation of persistent environmental pollutants by a white rot fungus.

The white rot fungus Phanerochaete chrysosporium degraded DDT [1,1,-bis(4-chlorophenyl)-2,2,2-trichloroethane], 3,4,3',4'-tetrachlorobiphenyl, 2,4,5,2',-4',5'-hexachlorobiphenyl, 2,3,7,8-tetrachlorodibenzo-p-dioxin, lindane (1,2,3,4,5,6-hexachlorocylohexane), and benzo[a]pyrene to carbon dioxide. Model studies, based on the use of DDT, suggest that the ability of Phanerochaete chrysosporium to metabolize these compounds is dependent on the extracellular lignin-degrading enzyme system of this fungus.

Carbon Dioxide↗

Environmentally persistent alkylphenolic compounds are estrogenic.

We show that a number of alkylphenolic compounds, used in a variety of commercial products and found in river water, are estrogenic in fish, birds, and mammals. 4-Octylphenol (OP), 4-nonylphenol, 4-nonylphenoxycarboxylic acid, and 4-nonylphenoldiethoxylate were each capable of stimulating vitellogenin gene expression in trout hepatocytes, gene transcription in transfected cells, and the growth of breast cancer cell lines. The most potent of the chemicals is OP, which was able to stimulate these biological responses to a similar extent as 17 beta-estradiol itself, albeit at a 1000-fold greater concentration. The action of alkylphenols is mediated by the estrogen receptor, as their effects depended on its presence and was blocked by estrogen antagonists. OP, 4-nonylphenol, and 4-nonylphenoxycarboxylic acid appear to possess intrinsic estrogenic activity, because they compete for binding to the estrogen receptor. Moreover, it is likely that they interact with a similar region of the hormone-binding domain as 17 beta-estradiol, because the mutant receptor G-525R, which is defective in estrogen binding, is also insensitive to OP. Like 17 beta-estradiol, OP is capable of stimulating the activity of both transcriptional activation functions, TAF-1 and TAF-2, in the receptor, as judged by analyzing the activity of the wild-type and mutant receptors in transiently transfected cells. The significance of our results will depend to a large extent on the degree of exposure of wildlife and humans to these estrogenic alkylphenolic compounds.

Animals↗

Joint persistence of transformation products in chemicals assessment: case studies and uncertainty analysis.

The joint persistence (JP) quantifies the environmental persistence of a parent compound and a selection of relevant transformation products. Here, the importance as well as the uncertainty of the JP in comparison to the persistence of the parent compound alone (primary persistence, PP) are investigated. To demonstrate the effect of transformation products on the environmental persistence of organic chemicals, three case studies of parent compounds (nonylphenol ethoxylates, perchloroethylene, atrazine) and transformation products are investigated in detail with a multimedia fate model. Comparison of the PP and JP values shows that transformation products can significantly increase the persistence. In addition to the point estimates of PP and JP, the associated uncertainties are investigated. For each of the case studies, the chemical-specific input parameters of all compounds are varied and the corresponding variance of the PP and JP is determined by Monte Carlo simulations. Interestingly, the higher number of input parameters required for the JP does not necessarily increase the uncertainty of the JP as compared to that of the PP alone. An exact mathematical expression specifying the contribution of each transformation product to the JP is given. When transformation products are grouped in different generations, it becomes discernible that the first generation increases the JP most; the later generations are of decreasing importance. Finally, the effect of incomplete knowledge of the transformation products and their properties on the JP results is discussed. For reliable JP estimates, knowledge of the first generation transformation products and their degradation rate constants is required.

Journal Article↗

Quantitative genetics and the persistence of environmental effects in clonally propagated organisms.

Phenotype is often viewed as a product of genes and the environment in which these genes are expressed. However, numerous studies have shown that environment can cause lasting changes in phenotype that can be passed from one generation to the next, much as genes are transmitted. In clonally propagated organisms, persistence of environmental effects has been observed in a range of plant and animal species, but has rarely been the object of study. We measured the persistence and magnitude of environmental effects on phenotype over three clonal generations in the arctic sedge Eriophorum vaginatum. We found that the environment in which tillers developed had large effects on their later performance (parental effects) and that these effects were in part independent of the size of tillers. The magnitude and persistence of environmental effects did not differ between environmental treatments or among genotypes. However, after 52 weeks of growth and two rounds of clonal propagation, grandparental treatment effects were not significant. We describe methods that can be used in quantitative genetics studies of clonal organisms to reduce bias in estimates of genotypic and environmental variance and argue that the persistence of environmental effects in clonal plant material has ecological and evolutionary consequences similar to those described for maternal environmental effects in sexual organisms.

Environment↗

Inhibition of E2-induced expression of BRCA1 by persistent organochlorines.

BACKGROUND: Environmental persistent organochlorines (POCs) biomagnify in the food chain, and the chemicals are suspected of being involved in a broad range of human malignancies. It is speculated that some POCs that can interfere with estrogen receptor-mediated responses are involved in the initiation and progression of human breast cancer. The tumor suppressor gene BRCA1 plays a role in cell-cycle control, in DNA repair, and in genomic stability, and it is often downregulated in sporadic mammary cancers. The aim of the present study was to elucidate whether POCs have the potential to alter the expression of BRCA1. METHODS: Using human breast cancer cell lines MCF-7 and MDA-MB-231, the effect on BRCA1 expression of chemicals belonging to different classes of organochlorine chemicals (the pesticide toxaphene, 2,3,7,8-tetrachlorodibenzo-p-dioxin, and three polychlorinated biphenyls [PCB#138, PCB#153 and PCB#180]) was measured by a reporter gene construct carrying 267 bp of the BRCA1 promoter. A twofold concentration range was analyzed in MCF-7, and the results were supported by northern blot analysis of BRCA1 mRNA using the highest concentrations of the chemicals. RESULTS: All three polychlorinated biphenyls and 2,3,7,8-tetrachlorodibenzo-p-dioxin reduced 17beta-estradiol (E2)-induced expression as well as basal reporter gene expression in both cell lines, whereas northern blot analysis only revealed a downregulation of E2-induced BRCA1 mRNA expression in MCF-7 cells. Toxaphene, like E2, induced BRCA1 expression in MCF-7. CONCLUSION: The present study shows that some POCs have the capability to alter the expression of the tumor suppressor gene BRCA1 without affecting the cell-cycle control protein p21Waf/Cip1. Some POCs therefore have the potential to affect breast cancer risk.

Blotting, Northern↗