Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.     

Persistent organochlorine pesticides in internal organs of coypu,Myocastor coypus

A highly selective and sensitive method based on gas chromatography-tandem mass spectrometry (GC-MS/MS) to identify and quantify persistent organochlorine pesticides, (18 compounds including primary compounds and metabolites), in animal internal organs (kidneys, liver, and brain) has been developed. Tandem mass spectrometric conditions were individually optimized for each target compound in Multiple Reaction Monitoring (MRM) mode to obtain maximum sensitivity. Prior to instrumental analysis, a sample preparation method based on matrix solid phase dispersion (MSPD) followed by acidic digestion with sulfuric acid to reduce matrix co-extractives was employed. Analyses of real samples were carried out on coypus (Myocastor coypus) from the autumn slaughter of 19 animals. In the analyzed samples, three of the target compounds, namely DDE-pp′ (DDT metabolite), HCB and lindane, were detected. Their concentration levels fell in the ranges of 0.003–0.007, 0.003–0.025, and 0.003–0.021 mg kg^?1 (0.005, 0.010, and 0.010 mg kg^?1 on average) in the case of DDE-pp′, HCB and lindane, respectively. Although low quantities of organochlorine pesticides do not pose an immediate danger to consumers' health, they should be of public health concern considering long-term, low-dose exposure.     

The destruction of ground water threatening pesticides using high intensity UV light

Abstract

A high‐intensity short‐wavelength UV light system was studied for its ability to degrade the pesticides carbofuran, fenamiphos sulfoxide (nemacur sulfoxide), and propazine in aqueous solutions. Half‐lives, rate constants, and breakdown products were determined for all chemicals. The presence of hydrogen peroxide, an oxidant and potential source of hydroxyl radicals, had no effect on the rate of breakdown of any of the chemicals investigated. Short‐wavelength UV light appears to be solely responsible for the observed pesticide breakdown. The breakdown of all three pesticides followed first order kinetics. Carbofuran, nemacur sulfoxide, and propazine had half lives of 3.9, 1.1, and 3.9 minutes, respectively. Breakdown product analysis was performed using capillary gas chromatography/mass spectrometry.     

Application of chemometric analysis based on physicochemical and chromatographic data for the differentiation origin of plant protection products containing chlorpyrifos

The aim of this study was to investigate the similarities and dissimilarities between the pesticide samples in form of emulsifiable concentrates (EC) formulation containing chlorpyrifos as active ingredient coming from different sources (i.e., shops and wholesales) and also belonging to various series. The results obtained by the Headspace Gas Chromatography–Mass Spectrometry method and also some selected physicochemical properties of examined pesticides including pH, density, stability, active ingredient and water content in pesticides tested were compared using two chemometric methods. Applicability of simple cluster analysis and also principal component analysis of obtained data in differentiation of examined plant protection products coming from different sources was confirmed. It would be advantageous in the routine control of originality and also in the detection of counterfeit pesticides, respectively, among commercially available pesticides containing chlorpyrifos as an active ingredient.     

Analysis of lipid peroxidation in animal and plant tissues as field-based biomarker in Mediterranean irrigated agroecosystems (Extremadura,Spain)

ABSTRACT

The development of field-based biomarkers can allow for a more reliable assessment of the exposure of organisms to pollutants. Different sampling sites, along two streams running through an irrigable agricultural area, were selected to evaluate the effect of agrochemical load on the measured endpoints. The levels of lipid peroxidation were evaluated in several organs of Procambarus clarkii. The same method was applied to leaves of two woody species. Determining levels of MDA (malonaldehyde) by thiobarbituric acid reactive substances assay allows measuring the levels of lipid peroxidation. Differences in lipid peroxidation levels were observed in P. clarkii individuals collected at different sites; however, the patterns varied depending on the organ (when accounting for variations due to sex). The use of a MDA-gills/MDA-hepatopancreas index allowed for discrimination between reference and polluted sites. Significant differences in oxidative damage between sites were found in the leaves of Quercus rotundifolia but not in Salix sp. The lipid peroxidation of crayfish organs and holm oak leaves as a suitable biomarker of environmental pollution deserves further investigation.     

Rapid determination of polar pesticides and plant growth regulators in fruits and vegetables by liquid chromatography/tandem mass spectrometry

ABSTRACT

A simple high-throughput liquid chromatography/tandem mass spectrometry (LC-MS/MS) multiresidue analysis method was developed for the simultaneous determination of polar pesticides, plant growth regulators and other polar compounds. These included amitrole, chlormequat, mepiquat, cyromazine, ETU, PTU, perchlorate, and daminozide using a mixed-mode column. A 10 g test portion was shaken with acidified methanol for 10 min. After centrifugation, the sample extract was injected and analyzed within 11 min by LC-MS-MS. This column eliminated the need for derivatization or the use of ion paring reagent. Two MS-MS transitions were monitored in the method for each target compound to achieve true positive identification. Eight isotopically-labeled internal standards corresponding to each analyte were used to correct for matrix suppression effect and/or instrument signal drift. The average recovery for all analytes at 20, 40, and 250 ng/g (n = 6) ranged from 73–136%, with a relative standard deviation of ≤ 20%.     

Ecological Risk Assessment of Neem-Based Pesticides

Abstract

A tiered process was used to evaluate the risks of pure azadirachtin (AZA) and two neem-based insecticides (Neemix? and Bioneem?) on six aquatic animals [crayfish (Procambarus clarkii), white shrimp (Penaeus setiferus), grass shrimp (Palaemonetes pugio), blue crabs (Callinectes sapidus), water fleas (Daphnia pulex), and mosquito larvae (Culex quinquefasciatus)] through short term acute toxicity tests. The risk was calculated using the level of concern endpoints (Q values) and relative hazard index (RHI) for acute and chronic exposure scenarios. The Q values of Neemix?, Bioneem?, and pure AZA derived from acute exposure tests indicated that D. pulex is the only sensitive species to the test pesticides. Furthermore, the RHI values of Neemix? and Bioneem? for D. pulex were above the critical limit of 10 indicating that these pesticides may pose a moderate hazard to this species and related crustaceans in acute exposure scenarios. The RHI values of the two pesticides and pure AZA were all below the critical limit of 10 for P. clarkii, P. setiferus, P. pugio, C. sapidus, and C. quinquefasciatus. The aquatic risk assessment process showed that the risk values of tested pesticides did not exceed the criteria, and therefore, no ecological hazard is likely to result from their use.     

百菌清农药残留的SPE-GC检测

对环境水样中百菌清农药残留进行了SPE-GC分析方法研究。环境水样通过Florisil柱富集、净化,3 mL乙酸乙酯洗脱,GC-ECD进行分析检测。实验表明,百菌清农药残留在0.01~10 mg/L范围内线性关系良好,相关系数为0.9993。外标法定量,检出限为0.0035 mg/L,对实际水样进行加标回收,回收率范围在93.47%~100.14%之间,6次重复测定相对标准偏差在3.97%~4.96%之间,并将方法应用于周边环境地表水的检测。该方法具有简便,快速,准确,灵敏度高等特点,能满足环境水样中农药残留分析要求。     

浅谈串联四极杆质谱（GC—QqQ-MS／MS）在土壤样品有机污染物分析中的应用

建立了ASE-GPC—GC-QqQ—MS／MS测定土壤中17种有机氯农药和19种多氯联苯以及MAE-SPE—GC-QqQ—MS／MS测定土壤中16种多环芳烃和18种邻苯二甲酸酯的方法。多环芳烃和邻苯二甲酸酯定量限在0．02～2．81μg／kg之间,有机氯农药和多氯联苯定量限在0．01～0．51μg/kg之间。样品加标浓度在5μg/kg时多环芳烃和邻苯二甲酸酯的平均回收率在66．6％～122．1％之间,相对标准偏差均小于20％;有机氯农药和多氯联苯平均回收率在79．6％～93．2％之间,相对标准偏差均小于15％。     

Adsorption of Pb and Cd on the natural surface coatings (NSCs) in the presence of organochlorine pesticides: a preliminary investigation

Adsorption of Pb and Cd in the presence and absence of organochlorine pesticides (OCPs) on natural surface coatings (NSCs), which were collected in the Nanhu Lake in Changchun, China, was measured in order to investigate the effect of the OCPs on the adsorption of heavy metals on the NSCs. Adsorption of Pb/Cd was carried out under controlled laboratory conditions (mineral salt solution with defined species, ionic strength 0.05 mol/l, 25 degrees C and pH 6.0) with initial Pb and Cd concentrations ranging from 0.2 to 2.5 mol/l. The classical Langmuir adsorption isotherm was applied to estimate the equilibrium coefficients of the adsorption of Pb and Cd on the NSCs. Adsorption interference between Pb/Cd and the OCPs on the NSCs indicated that the adsorption of Pb/Cd on the NSCs was influenced by the OCPs, and competitive adsorption between Pb and the OCPs was observed while adsorption of Cd was enhanced by addition of the OCPs. Adsorption data fit the Langmuir isotherm well for the NSCs treated with the OCPs at different equilibrium concentrations. The results showed that the amount of adsorbed Pb decreased by more than 40% while the amount of adsorbed Cd increased by over 60% with an increase in the initial concentrations of the OCPs ranging from 0 to 5.0 microg/l and that adsorption of Pb/Cd on the NSCs was strongly affected by the OCPs. This preliminary study highlights the importance of the OCPs on the NSCs in controlling the transport, fate, biogeochemistry, bioavailability and toxicity of trace metals in aquatic environments.