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.     

Development of an efficient extraction method for oxytetracycline in animal manure for high performance liquid chromatography analysis

Oxytetracycline (2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a major member of the tetracycline antibiotics family of which are widely administered to animals in concentrated animal feeding operations for purposes of therapeutical treatment and health protection. With the disposal of animal manure as fertilizer into agricultural land, tetracyclines enter the environment. However, tetracyclines chelate with multivalent cations and proteins, resulting in low extraction efficiencies from animal manure for tetracycline residue analysis. In this study an efficient extraction method for oxytetracycline from steer manure using methanol/water solution amended with chelating organic acid was developed for the analysis of high performance liquid chromatography. The effect of species and amount of amendment acids, shaking time, methanol/water ratio, manure weight, and repeated times of extraction was investigated. It was optimized to amend 2.5 g citric acid and 1.1 g oxalic acid with 10.0 g manure sample in a 50-ml centrifuge tube and extract with 15 ml methanol/water (9:1 in volume) by vigorously shaking for 30 min in a reciprocating shaker. After centrifugation at 11,000 rpm, supernatant is collected. Sample was extracted for a total of 3 times. The developed extraction method was further applied to extract oxytetracycline from fresh and aged cow manure, swine and poultry manure, and soil. Satisfactory recoveries ranging from (84.1 ± 2.4) % to (102.0 ± 3.1) % were obtained, demonstrating that the optimized extraction method is robust for oxytetracycline from different manure sample matrixes.     

A method for the analysis of organophosphorus pesticide residues in Mexican axolotl

A method based on matrix solid-phase dispersion (MSPD) was developed for quantitative extraction of three organophosphorus pesticides (OPPs) from the Mexican axolotl, Ambystoma mexicanum. The determination was carried out using high- performance liquid chromatography (HPLC) with diode array spectrophotometric UV detection (DAD). The MSPD extraction with octadecylsilyl (C18) sorbent combined with a silica gel clean-up and acetonitrile elution was optimised for chlorpyrifos, fenthion and methyl parathion. The method was validated, yielding recovery values higher than 90%. The precision, expressed as the relative standard deviation (RSD), was less than or equal to 6% in muscle samples at spiking levels of 10 and 5 ppm. Linearity was studied from 15 to 60 ppm for chlorpyrifos and fenthion, and from 7.5 to 30 ppm for methyl parathion. The limits of detection (LODs) were found to be less than or equal to 0.5 ppm_.This method was applied to the analysis of samples from a chlorpyrifos-exposed axolotl, demonstrating its use as an analytical tool for toxicological studies.     

Spatio-temporal variations of selected pesticide residues in the Kurose River in Higashi-Hiroshima city,Japan

ABSTRACT

This study investigated spatio-temporal variations of selected pesticide residues in the Kurose River in Higashi-Hiroshima city (Hiroshima Prefecture), Japan. Water samples were collected from the river at seven sites every month for 1 year (March 2016 to February 2017). Pesticide residues were extracted from the samples by a solid phase extraction using Sep Pack C₁₈ cartridges. Once extracted, the samples were analyzed for cyanazine, simetryn, fenarimol, isoprothiolane, and diazinon using a reversed-phase high-performance liquid chromatography ultraviolet visible (HPLC-UV Vis) system. The limits of detection were 3.60, 4.10, 2.80, 6.50, and 7.30 ng L^-1 for cyanazine, simetryn, fenarimol, isoprothiolane, and diazinon, respectively. Good recovery rates (88%–102%), and mean percent relative standard deviation range (1.00%–5.70%) (n = 6) were obtained with a spiking at 0.20 µg L^-1. The maximum concentrations of 282, 391, 60, 1086, and 1194 ng L^-1 were obtained for cyanazine, simetryn, isoprothiolane, fenarimol, and diazinon, respectively. Cyanazine was the most frequently detected pesticide (64% of the samples, n = 84), followed by simetryn (58%), and then diazinon (57%). The highest and lowest pesticide concentrations were measured during the periods May–June, and January–February, respectively. Principal component analysis revealed three principal components in which the pesticides were linked to dissolved organic matter and total suspended solids. The major water quality parameters (electrical conductivity, pH, Na⁺, K⁺, Mg²⁺, Ca²⁺, NH₄⁺, NO₃^?, Cl^?, SO₄^2?, NO₂^?, and temperature) showed no clear trends for these pesticides. The presence of simetryn and isoprothiolane was largely attributed to rice paddy farms, whereas diazinon was associated mostly with vegetable farms and orchards. The diazinon and isoprothiolane patterns were consistent with their use of controlling insects and fungi in the prefecture. The maximum diazinon concentration detected was higher than the human safe level specified by the European Union (100 ng L^-1) in Council Directive 98/83/EC. This is of concern because of the bioconcentration potential of these residues in fish and other marine animals consumed by humans.     

Spectroscopic study of the degradation of antibiotics and the generation of representative EfOM oxidation products in ozonated wastewater

This study examined effects of ozonation on thirteen fluoroquinolone, macrolide and lincosamide antibiotics present in municipal wastewater. Transformations of effluent organic matter (EfOM) caused by ozonation were characterized using absorbance/fluorescence spectroscopy and high performance size exclusion chromatography (HPSEC). Concentrations of aldehydes and carboxylic acids generated via the oxidation of EfOM were also determined. The absorbance and fluorescence of ozonated wastewater decreased with increasing ozone dose or treatment time. HPSEC data showed that these phenomena corresponded to the oxidation of all EfOM fractions, with some preference towards the degradation of the EfOM molecules with high apparent molecular weight. The removal of antibiotics and production of aldehydes and carboxylic acids were strongly correlated with the changes in both EfOM absorbance and fluorescence. Applications of a model describing the concurrent degradation of trace level contaminants and relative changes of EfOM emission allowed achieving a good fitting between the experimental and modeled ΔC/C₀ vs. ΔA/A₀ and ΔC/C₀ vs. ΔF/F₀ data.     

Pilot scale application of a method for the analysis of perfluorinated compounds in surface soils

A growing number of studies now indicate that perfluorinated compounds (PFCs) are globally distributed in the environment. Their widespread distribution and presence in remote locations has led to questions about the importance of atmospheric and oceanic transport. Describing their distribution in surface soils is also an essential but neglected element in developing a comprehensive understanding of their occurrence in the environment. Soils are the critical link between global atmospheric and hydrologic processes where both local and distant contaminants can accumulate and be released into aquatic and terrestrial communities. Because PFC concentrations in soils will influence ground and surface water, wildlife, and crops, methods to accurately measure PFCs in soil are clearly needed. To help answer this need, we developed a method for the analysis of nine perfluorinated carboxylic acids and four perfluorinated sulfonic acids in soil. Samples from six nations (n = 10 per nation) were analyzed by LC-MS/MS to demonstrate the method performance parameters and to make preliminary observations about the occurrence of the PFCs in soils in different parts of the world. The resulting method shows acceptable performance characteristics for the target compounds in most soils while documenting the widespread occurrence of PFCs in surface soils.     

Determination of chlorinated paraffins in sediments from the Firth of Clyde by gas chromatography with electron capture negative ionisation mass spectrometry and carbon skeleton analysis by gas chromatography with flame ionisation detection

Short chain chlorinated paraffins (SCCPs) are a group of persistent organic pollutants (POPs) of increasing concern, but are to date not widely investigated in the environment, largely due to the challenges involved in their quantification. Here, SCCPs were quantified in marine sediments from the Firth of Clyde, Scotland, by gas chromatography with electron capture negative ionisation mass spectrometry (GC-ECNIMS) and through carbon skeleton analysis by gas chromatography with flame ionisation detection (GC-FID), and the analytical challenges encountered are discussed. Concentrations in the sediments ranged from 0.4 to 69 μg kg⁻¹ when determined by GC-ECNIMS, and from 5.6 to 379 μg kg⁻¹ when determined by GC-FID. For 8 out of 11 samples, analysis by GC-FID gave higher results than analysis by GC-ECNIMS. Unexpected aspects of the analysis, such as the presence of high concentrations of longer chain chlorinated paraffins in the samples, are also presented.     

顶空-毛细管柱气相色谱法测定气样中甲醇

对自动顶空进样器与气相色谱法联用技术测定环境空气和废气中甲醇的方法进行了研究。结果表明：当样品加入4g氯化钠,顶空平衡温度为80℃,平衡时间为20min,用HP—FFAP毛细管柱分离,氢火焰离子化检测器检测时,得到甲醇标准曲线方程为y=23415x＋237．2,相关系数（R）0．9994;检出限为0．002mg／m2,相对标准偏差（n=6）为0．5％,加标回收率为98．9％。该方法简单、灵敏、分离度好、检出限低。     

丙溴磷在稻田环境中的残留动态研究

确立了气相色谱法测定丙溴磷残留量的检测方法.采用该方法,丙溴磷在土壤、植株、糙米、稻壳和田水中的平均添加回收率为87.2％～103.6％,变异系数为3.20％～11.50％,最低检测质量浓度:田水为0.005 mg/kg;土壤、植株、糙米和稻壳为0.050 mg/kg.残留动态研究表明,丙溴磷在田水、植株和土壤中的半衰...     

采用气相色谱法测定土壤中有机磷农药

建立了一种用GC-FPD测定土壤中的5种有机磷农药的测定方法,经索氏提取,GPC净化浓缩后直接进样分析。用保留时间定性,外标法定量。5种有机磷农药的回收率为86.5%～103.2%,精密度(以相对标准偏差表示)为2.47%～5.70%;检测限为0.000 1～0.000 2 mg/kg。该方法准确度和灵敏度高,前处理简单,可同时测定土壤中的5种有机磷农药。