Review of advances in the thin layer chromatography of pesticides: 2012–2014

Publications reporting techniques and applications of thin layer chromatography (planar chromatography) for the separation, detection, qualitative, and quantitative determination, and preparative isolation of pesticides and their metabolites are reviewed for the period from November 1, 2012 to November 1, 2014. Analyses are described for a variety of sample types and pesticide classes. In addition to references on residue analysis, studies such as pesticide structure – retention relationships, identification and characterization of natural and synthesized pesticides, metabolism, bioactivity, degradation, soil mobility, and lipophilicity are covered.     

Review of advances in the thin layer chromatography of pesticides: 2010–2012

Techniques and applications of thin layer chromatography (planar chromatography) for the separation, detection, qualitative and quantitative determination, and preparative isolation of pesticides and their metabolites and some related pollutants are reviewed for the period from November 1, 2010 to November 1, 2012. Analyses are described for a variety of samples types and pesticide classes. In addition to references on residue analysis, studies such as pesticide structure – retention relationships, identification and characterization of natural and synthesized pesticides, metabolism, degradation, mobility, lipophilicity, and mechanism of action are covered.     

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.     

Catecholamine metabolites in amniotic fluid from fetuses with neural tube defects

Catecholamine metabolites were analysed in amniotic fluid from fetuses with neural tube defects and controls. HMPG (4-hydroxy-3-methoxyphenyl-glycol) assumed to originate mainly from the central nervous system and VMA (4-hydroxy-3-methoxymandelic acid) formed in the peripheral nervous system were determined by gas chromatography-mass spectrometry. The HMPG/VMA ratio was increased (more than 2 SD) compared with controls in ten out of fifteen cases of neural tube defects.     

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).     

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.     

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。     

1株氯苯高效降解菌的分离鉴定及降解特性

分离筛选到1株能以氯苯为唯一碳源和能源的菌株LW26,根据菌株的形态、生理生化特征、16S rRNA序列分析以及Biolog鉴定,确定该菌株为戴尔福特菌(Delftia tsuruhatensis),其为新发现的具有氯苯降解能力的菌株,并且该菌株能降解BETX、正己烷和环己烷等常见的有机污染物.实验考察了温度、pH、氯苯初始浓度、Cl-浓度等因素对菌株生长和降解性能的影响.结果表明,该菌株较为适宜的生长和降解条件为:温度25℃、pH 7.0;底物耐受浓度高达500 mg·L~(-1);当Cl-浓度超过0.14 mol·L~(-1)时,菌株生长会受到抑制.利用Haldane模型对实验数据拟合得到菌株LW26的最大比生长速率μmax和最大比降解速率γmax分别为0.42 h~(-1)和2.53 h~(-1).利用GC-MS进行中间产物分析,结果表明菌株LW26降解氯苯的过程中产生邻氯苯酚,结合邻苯二酚双加氧酶活性分析,推测氯苯经历邻位开环、脱氯、氧化等过程,最终矿化为CO2或转化为生物质.     

Characterization of phenanthrene degradation by strain Polyporus sp. S133

Polyporus sp. S133, a fungus collected from contaminated soil, was used to degrade phenanthrene, a polycyclic aromatic hydrocarbon, in a mineral salt broth liquid culture. A maximal degradation rate (92%) was obtained when Polyporus sp. S133 was cultured for 30 days with agitation at 120 r/min, as compared to 44% degradation in non-agitated cultures. Furthermore, the degradation was a ected by the addition of surfactants. Tween 80 was the most suitable surfactant for the degradation of phenanthrene by Polyporus sp. S133. The degradation rate increased as the amount of Tween 80 added increased. The rate in agitated cultures was about 2 times that in non-agitated cultures. The mechanism of degradation was determined through the identification of metabolites; 9,10-phenanthrenequinone, 2,2’-diphenic acid, phthalic acid, and protocatechuic acid. Several enzymes (manganese peroxidase, lignin peroxidase, laccase, 1,2-dioxygenase and 2,3-dioxygenase) produced by Polyporus sp. S133 were detected during the incubation. The highest level of activity was shown by 1,2-dioxygenase (187.4 U/L) after 20 days of culture.     

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.