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。     

Uncertainty estimation in the analysis of pesticide residues in olive oil using data from proficiency tests

In this work we report the results for estimating the measurement uncertainty (MU) following up the application of two different approaches, relatively the top-down procedure, by using proficiency test data. We have focused the estimation on the olive oil matrix. We used the analytical data obtained from five selected editions of the Proficiency Tests (PTs, from 2007 to 2011) on pesticide residues in olive oil to estimate the MU. These PTs have been organized by Istituto Superiore di Sanità annually in cooperation with International Olive Council (IOC) since 1997. The number of participants in each trial ranged from 10 to 43. We used a total of 34 pesticide results. The expanded uncertainty U _(c) was calculated using a covering factor k = 2 for a confidence interval of 95%. In the approach 1, the within–laboratory reproducibility standard deviation is combined with estimates of the method and laboratory bias using PTs data. In the approach 2, the way of estimating the MU is based only on the bias that the laboratory has obtained participating in a sufficient number of the IOC proficiency tests. Comparing the relative expanded uncertainty based on these different approaches we notice values quite constant and close, from 42% to 48%. Moreover, these calculated expanded uncertainties are less than the default value of 50% (corresponding to a 95% confidence level), adopted from European guidance document SANCO based on the fit-for-purpose relative standard deviation (FFP-RSD).     

The persistence of insecticidal chemicals in soils treated with granular formulations of disulfoton and their uptake by potato plants

Abstract

Potatoes were grown from cut seed in Plainfield sand treated in‐furrow with disulfoton (Di‐Syston 15G, 3.36 kg Al/ha) in 1983 and from whole seed in similarly treated loam in 1991. Soils were contained in 2 m² field plots. Soil, seed potato and foliage were analyzed for the insecticide and its sulfoxide and sulfone metabolites during the 8–12 wk following planting. Disulfoton disappeared at different rates from the two soils (k_sand=0.024 day^‐1, k_loam=0.056 day^‐1) with partial conversion to the sulfoxide and sulfone in both. Larger quantities of the three insecticidal components were absorbed by the seed potato in the cut‐seed/sand combination. The relative amounts of these components in the seed potato also differed between treatments with disulfoton being the largest component of the cut‐seed/sand and smallest in the whole‐seed/loam. Disulfoton sulfoxide and sulfone were the major insecticidal components of the foliage and concentrations in the initial foliage (each ca. 10 ppm) were similar for both treatments. Sulfoxide concentrations in the foliage decreased more rapidly than the sulfone and the decrease in concentration of each of the components was similar for the two treatments.     

Reducing the pollution risk of pesticide using nano networks induced by irradiation and hydrothermal treatment

Traditional pesticides (TP) often do not adhere tightly to crop foliage. They can easily enter the surrounding environment through precipitation and volatilization. This can result in the pollution of the surrounding soil, water, and air. To reduce pesticide pollution, we developed a loss-control pesticide (LCP) by adding attapulgite with a nano networks structure fabricated using high energy electron beam (HEEB) irradiation and hydrothermal treatment to TP. HEEB irradiation effectively dispersed originally aggregated attapulgite through modified thermal, charge, and physical effects. Hydrothermal treatment further enhanced the dispersion of attapulgite to form nano porous networks via thermal and wet expansion effects, which are beneficial for pesticide binding. An LCP has improved retention on crop leaf surfaces. It has a higher adhesion capacity, reduced leaching and volatilization, and extended residual activity compared with the TP formulation. The treatment increases the residual activity of pesticides on crop foliage and decreases environmental pollution.     

Uptake,translocation, and control of trumpet flower (Tecoma stans) with aminocyclopyrachlor

To gain a better understanding of the physiology of the herbicide aminocyclopyrachlor in young plants of trumpet flower, the uptake and translocation were evaluated after the application of herbicide. This was determined by treating individual leaves with formulated herbicides plus ¹⁴C-aminocyclopyrachlor after the application of the formulated herbicide. This experiment used a randomized experimental design with three replications. In addition, field studies were conducted to assess the effectiveness of foliar applications of aminocyclopyrachlor in association with metsulfuton-methyl. The plant absorbed 20% of the herbicide applied. The translocation percentage did not surpass 5% of the total amount applied. Only 1% of the herbicide applied was translocated to the roots. Rate of 40 + 13 g a.i. 100 L^?1 of aminocyclopyrachlor+metsulfuron-methyl was effective to control T. stans.     

Levels of organochlorine pesticides in Amazon turtle (Podocnemis unifilis) in the Xingu River,Brazil

Abstract

Due to the toxicity and high environmental persistence of organochlorine pesticides in aquatic organisms, turtles have been studied as environment biomonitors. These animals are important sources of protein for the riverside and indigenous peoples of the Brazilian amazon. In the present study, organochlorine pesticide contamination was investigated in Podocnemis unifilis. Liver, muscle and fatty tissue samples were removed from 50 specimens collected from five sampling points located in the Xingu River basin. Fourteen organochlorine pesticides were analysed via gas chromatography with an electron capture detector (CG-ECD). Eight organochlorine pesticides were detected with average concentrations of ∑DDT, ∑Endossulfan and ∑HCH which were 26.17?±?26.35, 14.38?±?23.77 and 1.39?±?8.46?ng g^?1 in moisture content, respectively. DDT compounds were the most predominant, with a greater concentration of pp′-DDT in the liver and pp′-DDD in the muscle. Significant differences were noted between the types of tissues studied, and the concentration of OCPs varied between sampling sites.     

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.     

Simple analytical method for determination of pesticide residues in human serum by liquid chromatography tandem mass spectrometry

The aim of this study was to develop an analytical method for the determination of residues of organophosphorus and carbamate pesticides which are widely used in Tunisia. This method involves a liquid-liquid extraction procedure followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for the identification and quantification of compounds. Ionization of molecules was performed by the electrospray mode. Multiple reactions monitoring (MRM) was the acquisition mode used for the monitoring of two MS/MS transitions for each compound. The average recoveries obtained, at three different fortification levels, ranged between 65% and 106% for most of the pesticides studied, except for methamidophos (lower than 25%).The linearity of the method was in the range of 5 to 50 μ g/L with a correlation coefficient from 0.995 to 0.999, depending on the analyte. The estimated limit of detection and limit of quantification were 2 μ g/L and 5 μ g/L, respectively. The precision of the analytical procedure was satisfactory and the coefficients of variation, evaluated at three concentration levels were lower than 15% for most pesticides studied. The application of the method was investigated in a population of agricultural workers chronically exposed to various pesticides some of which, such as carbofuran, carbendazim, methomyl and pirimicarb, were detected in some serum samples.     

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.     

Determination of 28 pesticides applied on two tomato cultivars with a different surface/weight ratio of the berries,using a multiresidue GC-MS/MS method

The behavior of 28 pesticides on two tomato cultivars with a different surface/weight (S/W) ratio of the berries (S/W, Birikino vs. Tombola) was studied, in order to provide appropriate indications about their persistence on crops reaching the pre-harvest interval (PHI). Quantitative analysis was performed using a GC MS/MS method. Birikino cv. (BIR) was a “cherry type tomato” with a double S/W ratio compared with Tombola cv. (TOM). The results showed a different pesticide behavior. Azoxystrobin, Boscalid, Bupirimate, Difenoconazole, Etofenprox, Iprodione, Mepanipyrim, Myclobutanil, Tebuconazole, Zoxamide, Metalaxyl M, Pyrimethanil, Tetraconazole, Benalaxyl, Cyprodinil, Fenamidone, Famoxadone and Fludioxonil immediately after treatments showed residues on BIR higher than TOM, and this behavior is consistent with its greater exposed surface. BIR showed higher decay rates of these pesticides during the whole trial, nevertheless residue averages remained higher than TOM reaching the time of harvest. Residues at the PHI were all below their Maximum Residue Levels (MRLs), but data indicated that they could exceed their legal limits especially if the above-mentioned active ingredients were employed more than once per crop cycle on cherry type tomatoes. As regards to Chlorpyrifos, Chlorpyrifos methyl, Triadimenol, Pyridaben and Tebufenpyrad, no different residual behavior related to S/W ratio of the cultivars was observed. Even in this case, residues at the PHI were all below MRLs. As for Cyfluthrin, Deltamethrin, Lambda cyhalothrin, Etoxazole and Cyproconazole, residues were lower than the limit of quantitation (LOQ) of the analytical method just after the treatment, according to their low doses of employment.