Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco,Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-α,α,α -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g^{? 1}; short-term experiment) to 200 days (initial concentration = 689 ng g^{? 1}; long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

Unusual polar metabolites in the groundwater of a contaminated waste site indicate a new pathway of mononitrotoluene transformation

At a mononitrotoluene-contaminated waste disposal site, the groundwater was screened for polar transformation products of mononitrotoluenes, by means of HPLC-MS, HPLC-NMR and further off-line NMR and MS techniques. Besides expected metabolites such as aminotoluenes (ATs) and nitrobenzoic acids (NBAs), three unknowns (di- and tetrahydro-derivatives of (2-oxo-quinolin-3-yl) acetic acid) could be identified which, in the context of explosives and related compounds, are new metabolites. Evidence could be provided by microcosm experiments with 2-nitrotoluene (2-NT) that these metabolites are microbial transformation products of 2-NT under anaerobic conditions. The NMR and MS data are presented and the possible pathway for the formation of these metabolites after addition of 2-NT to fumarate is discussed.     

广州人群尿液有机磷阻燃剂的暴露与健康风险

针对广州480名普通群众,利用尿液作为检测基质,研究人体内有机磷酸酯阻燃剂(OPFRs)代谢物的浓度水平,暴露的潜在来源,阐明其健康风险,并与其他包括邻苯二甲酸酯在内的多种有机污染物的健康风险对比筛选出高风险污染物.结果表明,广州居民体内普遍检出OPFRs代谢物,其平均浓度为6.59ng/mL,尤其是二-β,β-氯乙基...     

Genotypic Variation in the Phytoremediation Potential of Indian Mustard for Chromium

The term “phytoremediation” is used to describe the cleanup of heavy metals from contaminated sites by plants. This study demonstrates phytoremediation potential of Indian mustard (Brasicca juncea (L.) Czern. & Coss.) genotypes for chromium (Cr). Seedlings of 10 genotypes were grown hydroponically in artificially contaminated water over a range of environmentally relevant concentrations of Cr (VI), and the responses of genotypes in the presence of Cr, with reference to Cr accumulation, its phytotoxity and anti-oxidative system were investigated. The Cr accumulation potential varied largely among Indian mustard genotypes. At 100 μM Cr treatment, Pusa Jai Kisan accumulated the maximum amount of Cr (1680 μg Cr g⁻¹ DW) whereas Vardhan accumulated the minimum (107 μg Cr g⁻¹ DW). As the tolerance of metals is a key plant characteristic required for phytoremediation purpose, effects of various levels of Cr on biomass were evaluated as the gross effect. The extent of oxidative stress caused by Cr stress was measured as rate of lipid peroxidation. The level of thiobarbituric acid reactive substances (TBARS) was enhanced at all Cr treatments when compared to the control. Inductions of enzymatic and nonenzymatic antioxidants were monitored as metal-detoxifying responses. All the genotypes responded to Cr-induced oxidative stress by modulating nonenzymatic antioxidants [glutathione (GSH) and ascorbate (Asc)] and enzymatic antioxidants [superoxide dismutase (SOD), ascorbate peroxidase (APX), and glutathione reductase (GR)]. The level of induction, however, differed among the genotypes, being at its maximum in Pusa Jai Kisan and its minimum in Vardhan. Pusa Jai Kisan was grown under natural field conditions with various Cr treatments, and Cr-accumulation capacity was studied. The results confirmed that Pusa Jai Kisan is a hyperaccumulator of Cr and hypertolerant to Cr-induced stress, which makes this genotype a viable candidate for use in the development of phytoremediation technology of Cr-contaminated sites.     

利用HS-SPME-GC技术分析环境水样中超痕量的六氯苯,DDT及其代谢产物

利用顶空固相微萃取(HS-SPME)和气相色谱检测技术,通过对三种不同的SPME萃取头(PDMS,PMPVS,PA)实验条件的优化,并参照液液萃取的方法,对水相中六氯苯,DDT及其代谢产物的萃取效果进行了比较．结果表明,SPME方法比液液萃取方法在检测限和回收率上有很大的提高,其中PDMS对检测六氯苯,DDT及其代谢产物的效果较其它两种萃取头好．     

Potential environmental fate of elsinochrome A,a perylenequinone toxin produced in culture by bindweed biocontrol fungus Stagonospora convolvuli LA39

The photosensitizing perylenequinone toxin elsinochrome A (EA) is produced in culture by the bindweed biocontrol fungus Stagonospora convolvuli LA39 where it apparently plays a pathogenicity related role. We investigated the fate of EA with reference to its stability under different temperature and light conditions. EA remained stable when boiled in water at 100^∘C for 2 h. Similarly, exposing EA to 3–27^∘C in the dark for up to 16 weeks did not affect its stability either in dry or in aqueous form. However, results from irradiation experiments indicate that direct photolysis may be a significant degradation pathway for EA in the environment. EA either in dry form or dissolved in water was degraded by different irradiation wavelengths and intensities, with degradation plots fitting a first order rate kinetics. EA degraded faster if exposed in aqueous form, and at higher quantum flux density (μmol s⁻¹ m⁻²). Sunlight was more effective in degrading EA than artificial white light and ultraviolet radiations (UV-A or UV-B). Exposing EA to natural sunlight, particularly, during the intense sunshine (1,420– 1,640 μmol s⁻¹ m⁻²) days of 30 July to 5 August 2004 in Zurich caused the substance to degrade rapidly with half-life under such condition only 14 h. This implies that should EA gets into the environment, particularly on exposed environmental niches, such as on plant surfaces through biocontrol product spray, or released from shed diseased leaves, it may have no chance of accumulating to ‘level of concern’. Furthermore, a toxicity assay using Trichoderma atroviride P1 as biosensor showed that photo-degraded EA was not toxic, indicating that no stable toxic by-products were left.     

Levels of selected urinary metabolites of volatile organic compounds in a representative sample of US adolescents

Data from National Health and Nutrition Examination Survey for the years 2011–2012 were used to evaluate the variability in the observed levels of 20 urinary metabolites of 16 parent volatile organic compounds by age, gender, race/ethnicity, and smoking status for adolescents aged 12–19 years. Smokers were found to have statistically significantly higher adjusted levels than nonsmokers for selected urinary metabolites of acrylonitrile (p < 0.05) and 1,3-butadiene (p < 0.05). For example, for N-Acetyl-S-(2-cyanoethyl)-L-cysteine, the adjusted levels for smokers were 29.2 ng/mL and 2.0 ng/mL for nonsmokers (p < 0.05). Females were found to have higher adjusted levels of selected metabolites of crotonaldehyde (p < 0.05), cyanide (p < 0.05), and tetrachloroethylene (p < 0.05) than males. For example, the adjusted levels of 2-Aminothiazoline-4-carboxylic acid or ATCA were 218.9 and 108.6 ng/mL for females and males, respectively (p < 0.05). Non-Hispanic whites (NHW) had higher adjusted levels than non-Hispanic blacks (NHB) for selected metabolites of N,N-dimethylformamide (p < 0.05) and ethylbenzene, styrene (p < 0.05). For example, for N-Acetyl-S-(N-methylcarbamoyl)-L-cysteine or AMCC, the adjusted levels for NHW and NHB were 122.7 and 80.2 ng/mL, respectively (p < 0.05). The reverse was true for selected metabolites of carbon-disulfide and tetrachloroethylene. For example, for N-Acetyl-S-(benzyl)-L-cysteine or BMA, adjusted levels for NHW and NHB were 6.7 and 10.3 ng/mL, respectively (p < 0.05).     

酞酸酯暴露及风险评价研究进展

酞酸酯的暴露及健康风险研究日趋深入。在综述了酞酸酯的物化性质、接触机会两方面特性,以及体内代谢、健康危害两方面的最新研究进展基础上,比较了其国内外相关标准现状,总结了酞酸酯暴露评估现状及健康风险研究现状,提出并分析了存在的问题,并对其今后的研究进行了展望。     

Evaluation of 3-hydroxy-benzo[a]pyrene levels in Nile tilapia (Oreochromis niloticus) after waterborne exposure to Benzo[a]pyrene

3-Hydroxy-benzo[a]pyrene (3-OH-BaP), a toxic compound with the ability to covalently bind with the macromolecules (proteins and DNA), is one of the major phenolic metabolites of benzo[a]pyrene (BaP). The purpose of this study was to evaluate the presence of 3-OH-BaP in the bile and plasma of Nile tilapia by HPLC with fluorescence detection, after waterborne exposure to BaP (10 and 100?µg?L^?1). Metabolites were detected in bile and plasma, and conjugates of 3-OH-BaP (glucuronide and/or sulphate conjugates) were the majority forms in both biological fluids, glucuronide 3-OH-BaP being the main metabolite in bile. Our data suggest that extrahepatic tissues as intestine or gill are important in BaP metabolism and need to be the considered sources of metabolites released into the blood. Although, low levels of 3-OH-BaP in toxic form (free form) were detected in plasma, one cannot exclude the possibility of circulating the levels leading to adverse effects.     

Biodegradation of 2-naphthol and its metabolites by coupling Aspergillus niger with Bacillus subtilis

To explore biodegradation of 2-naphthol and its metabolites accumulated in wastewater treatment, a series of bio-degradation experiments were conducted. Two main metabolites of 2-naphthol, 1,2-naphthalene-diol and 1,2-naphthoquinone, were identified by high-performance liquid chromatography with standards. Combining fungus Aspergillus niger with bacterium Bacillus subtilis in the treatment enhanced 2-naphthol degradation e ciency, lowered the accumulation of the two toxic metabolites. There were two main phases during the degradation process by the kinetic analysis: 2-naphthol was first partly degraded by the fungus, producing labile and easily accumulated metabolites, and then the metabolites were mainly degraded by the bacterium, attested by the degradation processes of 1,2-naphthalene-diol and 1,2-naphthoquinone as sole source of carbon and energy. Sodium succinate, as a co-metabolic substrate, was the most suitable compound for the continuous degradation. The optimum concentration of 2-naphthol was 50 mg/L. The overall 2-naphthol degradation rate was 92%, and the CODCr removal rate was 80% on day 10. These results indicated that high degradation rate of 2-naphthol should not be considered as the sole desirable criterion for the bioremediation of 2-naphtholcontaminated soils/wastewater.