Review of advances in the thin layer chromatography of pesticides: 2008–2010

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 other related compounds are reviewed for the period from November 1, 2008 to November 1, 2010. 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 plant pesticides and synthesized pesticides, metabolism, degradation, mobility, identification of biomarkers for detection of herbicide effects in plants, and lipophilicity are covered.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

Carbofuran degradation in soil profiles

Abstract

Two soils, Puyallup fine sandy loam from Puyallup, WA, and Ellzey fine sand from Hastings, FL, each with a prior history of carbofiiran exposure but with different pedological and climatological characteristics, were found to exhibit enhanced degradation toward carbofiiran in surface and subsurface soil layers. The treated Puyallup and Ellzey soils exhibited higher mineralization rates for both the carbonyl and the aromatic ring of carbofiiran when compared to untreated soils. Disappearance rates of [¹⁴C‐URL (uniformly ring labeled)] carbofiiran in the treated Ellzey soil was faster than in untreated soil, and also faster in surface soil than in subsurface soil. Initial degradation patterns in the treated Ellzey soil were also different from those in the untreated soil. The treated Ellzey soil degraded carbofuran mainly through biological hydrolysis, while untreated soil degraded carbofuran through both oxidative and hydrolytic processes.     

Complete mineralization of benzene by a methanogenic enrichment culture and effect of putative metabolites on the degradation

Microbial degradation of benzene under anaerobic conditions plays an important role in remediation of contaminated sites but the microorganisms and metabolic pathways involved remain poorly understood. In this study, we evaluated degradation of benzene by a methanogenic enrichment culture obtained from non-contaminated lotus field soil, alone and in the presence of several putative metabolic intermediates, that is, toluene, benzoate and phenol. Using stable isotope (¹³C) labeled substrate, benzene was shown to be degraded almost completely to equimolar concentrations of methane and carbon dioxide, without detectable accumulation of extracellular metabolites. Concurrently, toluene, benzoate and phenol were also effectively mineralized, but probably by microorganisms other than the benzene degraders. The latter included Hasda-A, which is putative benzene-degrading deltaproteobacterium present in the culture. While toluene and benzoate did not affect benzene degradation, phenol had a moderate inhibitory effect although it was not a major metabolic intermediate of benzene in our culture. Finally, 4-hydroxycoumarin was detected as a compound formed from phenol but further experiments are required to elucidate its relationship to degradation of phenol.     

Toxicity of dispersant application: Biomarkers responses in gills of juvenile golden grey mullet (Liza aurata)

Dispersant use in nearshore areas is likely to increase the exposure of aquatic organisms to petroleum. To measure the toxicity of this controversial response technique, golden grey mullets (Liza aurata) were exposed to mechanically dispersed oil, chemically dispersed oil, dispersant alone in seawater, water-soluble fraction of oil and to seawater as a control treatment. Several biomarkers were assessed in the gills (enzymatic antioxidant activities, glutathione content, lipid peroxidation) and in the gallbladder (polycylic aromatic hydrocarbons metabolites). The significant differences between chemically dispersed oil and water soluble fraction of oil highlight the environmental risk to disperse an oil slick when containment and recovery can be conducted. The lack of significance between chemically and mechanically dispersed oil suggests that dispersant application is no more toxic than the natural dispersion of the oil slick. The results of this study are of interest in order to establish dispersant use policies in nearshore areas.     

Multibiomarker approach in fish to assess the impact of pollution in a large Brazilian river, Paraiba do Sul

This article examines the advantages of the use of biomarkers as environmental indicators by applying it to Paraiba do Sul watershed, one of the most important Brazilian water bodies, which is in a critical environmental situation. We use a multibiomarker approach in fish as an integrated strategy to assess the impact of pollution. It comprehends a general biomarker of fish health, the condition factor (CF), and specific biomarkers of contaminant exposure such as metallothionein (MT), acetylcholinesterase (AChE) activity and biliary polycyclic aromatic hydrocarbons (PAH) metabolites. Our results revealed different effects in the fish from diverse locations with varying degrees of pollution. Furthermore, fish located just upstream of the water-treatment plant of the metropolitan area of Rio de Janeiro has shown to be affected by metals. This study indicates the usefulness of integrating a set of biomarkers to define the effects of anthropogenic inputs in aquatic bodies under complex polluted situations.     

Volatile sesquiterpenes from Stachybotrys chartarum: Indicators for trichothecene producing mold species?

Trichodiene, a volatile sesquiterpene which is structurally related to trichothecene mycotoxins, has been identified in the headspace of growing Stachybotrys chartarum by GC/MS. It is possible that volatile sesquiterpene patterns can be used to characterize S. chartarum and related mold isolates as trichothecene producers, thus providing clear criteria for decisions concerning the occupancy and renovation of contaminated buildings.     

Biologically active secondary metabolites in white clover (Trifolium repens L.) – a review focusing on contents in the plant, plant–pest interactions and transformation

Summary.  To exploit biologically active compounds from white clover (Trifolium repens L.) for suppressing weeds and soil-borne diseases, either as isolated products (biopesticides) or through cultivars with enhanced production of these compounds, the biologically active compounds must be identified, plant content measured, and their fate in soil known. The present review summarizes the published knowledge needed for such exploitation; providing essential information on structure and concentration of flavonols, flavones, condensed tannins, isoflavones, isoflavanones, pterocarpans, coumestans, cyanogenic glucosides, and saponins in healthy and stressed white clover plants. Various stresses and particular cultivars affect the concentrations of several of the compounds. Information on biological effects and the degradation/transformation of these compounds in plants or by microorganisms is available. There is no information on the degradation pathway in soil, the mechanisms of exudation and leaching of compounds from plants, and soil sorption properties of the compounds. The clover soil fatigue problem is increasing in grasslands and causes problems especially in organic farming. Research efforts focused on biological elements of clover soil fatigue have not explained it, and the influence of secondary metabolites has not been investigated. There are few investigations into the interaction between beneficial fungi/fungal-diseases and the occurrence of biologically active secondary metabolites in white clover plants. Such studies are critical to better understand beneficial fungi and pathogens.     

聚乙烯和聚乳酸微塑料对大豆生长和生理生化及代谢的影响

为揭示生物可降解性不同的微塑料对农作物的毒性效应,选择聚乳酸(polylactic acid可生物降解)和聚乙烯(polyethylene难生物降解)微塑料(microplastics)为供试材料,以大豆为供试植物,深入探究了不同暴露水平(0.1%,1%,W/W)下两种不同的微塑料对大豆(Glycine max)生长、光合作用、抗氧化性、营养品质以及代谢方面的影响.结果表明,聚乙烯微塑料(PEMPs)对大豆根部鲜重有促进作用,而0.1%聚乳酸微塑料(PLAMPs)则抑制根部长度.大豆的叶绿素含量在0.1% PEMPs作用下能够显著提高.PLAMPs则能够导致大豆过氧化氢酶(CAT)活性显著下降,而过氧化氢(H₂O₂)含量在0.1% PEMPs和1% PLAMPs下显著升高.此外,微塑料的暴露能够改变大豆根部中锰、铁以及铜的含量,其中0.1% PEMPs的效应最为显著.大豆叶片中的氨基酸代谢在PEMPs的作用下上调,而0.1% PLAMPs则引起有机酸以及糖类代谢下调.综上,微塑料的植物毒性效应与其生物可降解性及浓度密切相关,低浓度可生物降解微塑料的效应最强.这些发现有望为微塑料的植物毒理研究提供新的方向.     

中国红豆杉内生放线菌En-1的分离、鉴定及其次生代谢物的研究

采用选择性分离方法对药用植物红豆杉Taxus chinensis嫩枝和叶进行内生菌分离,得到一株放线菌En-1,经鉴定为链霉菌Streptomyces sp.;并对该菌进行液体培养条件优化、次生代谢物初筛及其抗菌活性的研究。通过添加宿主植物浸出物至En-1液体培养中以考察宿主对后者生长的影响,结果表明红豆杉叶浸出物能促进En-1的体外生长;而且En-1次生代谢物对5株供试菌中的黑曲霉具有抑制活性。通过En-1菌培养基优化并联合波谱法检测其发酵产物,显示8#配方（淀粉25 g.L-1,KNO3 1 g.L-1,K2HPO4.3H2O 0.5 g.L-1,NaCl 0.5 g.L-1,FeSO4.7H2O 0.01 g.L-1,MgSO4.7H2O 0.5 g.L-1）培养液中,En-1所产的次生代谢物最具结构多样性;同时8#配方也有利于该菌产生抗菌活性产物。本研究提示红豆杉内生放线菌可作为寻求药物先导化合物的资源菌。