Headspace solid phase microextraction method for determination of triazine and organophosphorus pesticides in soil

A headspace solid phase microextraction method (HS-SPME) for simultaneous determination of five pesticides belonging to triazine and organophosphorus pesticide groups in soil samples was developed. Microextraction conditions, such as temperature, extraction time and sodium chloride (NaCl) content were investigated and optimized using 100 μ m polydimethyl-siloxane (PDMS) fiber. Detection and quantification were done by gas chromatography-mass spectrometry (GC-MS). Relative standard deviation (RSD) and recovery values for multiple analysis of soil samples fortified at 30 μ g kg^{? 1} of each pesticide were below 13 % and higher than 70 %, respectively. Limits of detection (LOD) for all the compounds studied were less than 3.2 μ g kg^{? 1}. The proposed method was applied in the analysis of some agricultural soil samples.     

Application of a novel cold activated carbon fiber-solid phase microextraction for analysis of organochlorine pesticides in soil

A novel and simple analytical procedure using cold activated carbon fiber-solid phase microextraction (CACF-SPME) was applied to determine organochlorine pesticides (OCs) in soil samples. The pesticides in this study consist of α -, β -, γ -, and δ -hexachlorocyclohexane (HCH). By heating the sample while cooling the fiber, the developed method not only provides better performance in terms of sensitivity, linearity and recovery but also offers shorter adsorption procedure than that of traditional headspace-solid phase microextraction (HS-SPME). The experimental conditions such as the amount of water, adsorption time and adsorption temperature were optimized. Matrix effects were investigated with different types of soils. We concluded that using the standard addition method was required for quantification purposes. The limits of detection obtained using the proposed method range from 0.01 to 0.05 ng/g, and the recoveries for CACF-SPME are in the range of 80.01% to 89.68% with relative standard deviation (RSDs) better than 8.60%. The proposed method was further applied to determine OCs in real agricultural soil. The results are in good agreement with those obtained using traditional ultrasonic extraction. The research demonstrates the suitability of the CACF-SPME for the analysis of OCs in soil.     

Rapid screening for organochlorine and organophosphorus pesticides in milk using C18 and graphitized carbon black solid phase extraction cleanup

Abstract

A rapid, multiresidue, solid phase extraction (SPE) technique for the isolation and gas chromatographic determination of organochlorine and moderately polar organophosphorus pesticide residues in milk is described. Milk is sonicated with an acetonitrile‐acetone‐methanol mixture and centrifuged. The supernatant is subjected to a cleanup using both C₁₈ and graphitized carbon black SPE columns. The pesticide residues are determined by gas chromatography with electron capture and flame photometric detection. The method required minimal volumes of solvent and resulted in the production of minimal volumes of hazardous waste.     

Concentration and fate of persistent organochlorine pesticides in estuarine sediments using headspace solid-phase microextraction

The concentration and fate of persistent organochlorine pesticides (OCPs) in estuarine surface sediments in Erh-jen and Lan-yang rivers, Taiwan were investigated using headspace solid-phase microextraction (HSSPME) method to evaluate the possible pollution potential and guideline for OCP concentrations in Taiwan. The HSSPME method exhibits a good analytical performance with low detection limits for OCP determination in sediment. In addition, results obtained using the developed HSSPME method were in good agreement with those obtained using Soxhlet extraction in a certified sample. The developed analytical method was further applied to the determination of concentrations of OCP residues in surface sediments from the estuaries of the selected rivers in Taiwan. A total of 20 surface sediments from each river was collected from 10 sampling stations. The total OCP concentrations in sediments from Erh-jen River ranged from 0.17 to 5.04 ng/g-dw with the mean values of 0.25–1.24 ng/g-dw for HCHs, 0.10–0.89 ng/g-dw for cyclodienes and 0.16–0.64 ng/g-dw for DDTs. The concentrations of OCPs in sediments from Lan-yang River were in the range 0.37–0.9 ng/g-dw with an average of lower than 0.5 ng/g-dw. HCHs and DDTs were abundant in the estuarine sediments from the selected rivers. Results obtained in this study show that the origin of OCPs in the surface sediments from Erh-jen River is a combination of erosion of the weathered soils and long-range atmospheric transport, while the OCP concentrations found in Lan-yang River could be regarded as the background levels of OCPs in Taiwan.     

Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean

The purpose of this study was to develop an analytical method for the determination of organophosphorus and pyrethroid pesticides in soybean by pressurized liquid extraction (PLE). Two organic solvents, acetone and acetonitrile, were evaluated as extraction solvents. In both cases, the amount of extract was enhanced with increasing extraction temperature. The extracts obtained using acetonitrile were measured by gas chromatography/mass spectrometry after a cleanup process based on the analytical method for the Japanese Positive List System for Agricultural Chemicals Remaining in Foods. The effect of extraction temperature (range: 40– 130°C) on extraction efficiency was evaluated by a recovery study using 21 organophosphorus pesticides and 10 pyrethroid pesticides as target analytes and acetonitrile as the solvent. The results indicated that at 130°C, some organophosphorus pesticides might be degraded, whereas extraction temperatures between 70°C and 100°C were optimal. Next, a prepared sample containing fenitrothion and permethrin was analyzed. Although the sample was not soaked in water prior to analysis, PLE provided analytical results comparable to those obtained by solvent extraction with homogenization. Therefore, PLE is considered a simple and alternative technique for the extraction of organophosphorus and pyrethroid pesticides in soybean.     

Simultaneous determination of organophosphorus and organonitrogen pesticides residues in Angelica sinensis

Gas chromatography with nitrogen phosphorus detector (GC-NPD) was applied to the simultaneous determination of 15 organophosphorus and 6 organonitrogen pesticides residues in Angelica sinensis. The pesticides were extracted by microwave-assisted extraction (MAE) and ultrasound-assisted extraction (UAE) techniques, respectively. The experimental variables were optimized through orthogonal array experimental design. Cleanup of extracts was performed with column chromatography using florisil and neutral aluminum as the sorbents. The determination of pesticides in the final extracts was carried out by GC-NPD. Under optimized conditions, the average recoveries obtained from MAE and UAE are in the range of 75.1–129% and 70.6–129%, respectively, and the relative standard deviations of MAE and UAE were 3.1–10.6% and 1.0–17.8%, respectively.     

碳纳米管顶空固相微萃取-气相色谱法测定土壤中有机氯农药

采用碳纳米管顶空固相微萃取-气相色谱法测定了土壤中有机氯农药,探讨了萃取时间、萃取温度、搅拌速度、离子强度、有机溶剂和土壤加水量对萃取效率的影响.该方法的线性范围为0.5～50.0 ng/g,r0.991 5,检出限为0.03～0.33 ng/g.样品的加标回收率为91.4%～120.0%,相对标准偏差不大于12.7%.     

Environmental monitoring of complex hydrocarbon mixtures in water and soil samples after solid phase microextraction using PVC/MWCNTs nanocomposite fiber

A novel nanocomposite based on incorporation of multiwalled carbon nanotubes (MWCNTs) in polyvinyl chloride (PVC) was prepared. Proposed nanocomposite was coated on stainless steel wire by deep coating. Composition of nanocomposite was optimized based on results of morphological studies using scanning electron microscopy. The best composition (83% MWCNTs:17% PVC) was applied as a solid phase microextraction fiber. Complex mixture of aromatic (BTEX) and aliphatic hydrocarbons (C₅–C₃₄) were selected as model analytes, and performance of proposed fiber in extraction of the studied compounds from water and soil samples was evaluated. Analytical merits of the method for water samples (LODs = 0.10–1.10 ng L⁻¹, r² = 0.9940–0.9994) and for soil samples (LODs = 0.10–0.77 ng kg⁻¹, r² = 0.9946–0.9994) showed excellent characteristics of it in ultra trace determination of petroleum type environmental pollutants. Finally, the method was used for determination of target analytes in river water, industrial effluent and soil samples.     

Residues of organochlorine pesticides and PCBs in some Brazilian municipal solid waste compost

Persistent organic pollutants (POPs), organochlorine pesticides and polychlorinated biphenyls (PCBs), listed as per the Stockholm Convention (α -HCH, β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, p,p′-DDE, aldrin, endrin, dieldrin, PCBs 28, 52, 118, 138, 153, and 180), were analyzed in municipal solid waste (MSW) compost samples from three different Brazilian composting plants located in three São Paulo State cities: Araras, Araraquara and São Paulo (Vila Leopoldinha). Quantitative and qualitative analyses were carried out using gas chromatography electron capture detection (GC-ECD) and gas chromatography mass spectrometry (GC-MS) (Ion Trap, electron impact ionization), respectively. The samples were analyzed in triplicate and the target POPs were not detected by GC-ECD. Twelve pollutants were identified in two samples when qualitative analysis (GC-MS) was used (β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, and p,p′-DDE, PCBs 28, 118, 138, 153 and 180). The composting process has advantages such as urban solid waste reduction and landfill life-span increase, however the MSW compost quality, which can be utilized for agricultural purposes, should be evaluated and be controlled. This kind of study is the first step in making available information to answer questions regarding MSW compost for sustainable agricultural use, such as the pollutants accumulation in soil and in groundwater, and plants uptake.     

Influence of pesticides on acetylene reduction and growth of microorganisms in an organic soil 1

Abstract

The effects of 32 pesticides at two concentrations on acetylene reduction (non‐symbiotic nitrogen fixation), nitrogen fixers, bacteria and fungi in an organic soil were assessed. None of the pesticide treatments suppressed C H reduction as compared to controls. No significant inhibition of the population of non‐symbiotic nitrogen fixers occurred. However, stimulatory effects were observed with treatments of fensulfothion, fonofos, oxamyl, DD^R , Telone^R and Telone C^R . Bacterial and fungal populations showed temporary declines but all recovered within 7 days to levels similar to or higher than those in the controls.     

Packed in-tube solid phase microextraction with graphene oxide supported on aminopropyl silica: Determination of target triazines in water samples

On-line in-tube solid phase microextraction (in-tube SPME) coupled to high performance liquid chromatography and tandem mass spectrometry (HPLC-MS/MS) was successfully applied to the determination of selected triazines in water samples. The method based on the employment of a packed column containing graphene oxide (GO) supported on aminopropyl silica (Si) showed that the extraction phase has a high potential for triazines extraction aiming to its physical-chemical properties including ultrahigh specific surface area, good mechanical and thermal stability and high fracture strength. Injection volume and loading time were both investigated and optimized. The method validation using Si-GO to extract and concentrate the analytes showed satisfactory results, good sensitivity, good linearity (0.2–4.0 µg L^?1) and low detection limits (1.1–2.9 ng L^?1). The high extraction efficiency was determined with enrichment factors ranging from 1.2–2.9 for the lowest level, 1.3–4.9 intermediate level and 1.2–3.0 highest level (n = 3). Although the analytes were not detected in the real samples evaluated, the method has demonstrated to be efficient through its application in the analysis of spiked triazines in ground and mineral water samples.     

Solid phase extraction with silicon dioxide microsphere adsorbents in combination with gas chromatography-electron capture detection for the determination of DDT and its metabolites in water samples

The goal of the present study was to investigate the feasibility of silicon dioxide (SiO₂) microspheres without special modification to enrich dichlorodiphenyltrichloroethane (DDT) and its main metabolites, p,p′-dichlorodiphenyl-2,2-dichloroethylene (p,p′-DDD) and p,p′-dichlorodiphenyldichloroethylene (DDE) in combination with gas chromatography-electron-capture detection. The experimental results indicated that an excellent linear relationship between the recoveries and the concentrations of DDT and its main metabolites was obtained in the range of 0.2–30 ng mL^?1 and the correlation coefficients were in the range of 99.96–99.99%. The detection limits based on the ratio of signal to the baseline noise (S/N = 3) were 2.2, 2.9, 3.8 and 4.1 ng L^?1 for p,p′-DDD, p,p′-DDT, o,p′-DDT, and p,p′-DDE, respectively. The precisions of the proposed method were all below 10% (n = 6). Four real water samples were utilized for validation of the proposed method, and satisfactory spiked recoveries in the range of 72.4–112.9% were achieved. These results demonstrated that the developed method was a simple, sensitive, and robust analytical method for the monitoring of pollutants in the environment.     

Multiresidue determination of carbamate,organochlorine, organophosphorus,and dicarboximide pesticides in lettuce by GC/MS

An extraction method based on matrix solid-phase dispersion was developed to determine pirimicarb, methyl parathion, malathion, procymidone, α -endosulfan and β -endosulfan in lettuce using gas chromatography-mass spectrometry. The best results were obtained using 4.0 g of lettuce, 2.0 g of silica as dispersant sorbent, 0.1 g of activated carbon as clean up sorbent and acetonitrile as eluting solvent. The method was validated using lettuce samples fortified with pesticides at six different concentration levels (0.1 to 2.0 mg/kg). Average recoveries (7 replicates) ranged from 50 to 120 %, with relative standard deviations between 0.6 and 8.0 %. Detection and quantification limits for lettuce ranged from 0.01 to 0.02 mg/kg and 0.04 to 0.10 mg/kg, respectively.     

热解析-固相微萃取-气相色谱法测定空气样品中挥发性有机化合物

建立了热解析-固相微萃取-气相色谱法测定空气样品中挥发性有机化合物的分析方法,并对色谱分离条件、玻璃针筒保存样品的稳定性、固相微萃取萃取纤维、萃取时间、色谱进样时间等条件进行了优化,9种挥发性有机化合物的峰面积与其质量浓度在所测范围内有较好的线性关系,相对标准偏差＜8.8%,检出限为0.05～0.75 μg/100 mL,满足实际空气样品测定需要。     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'_W) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb_T) in pure water. Experimental breakthrough volumes (Vb_E) were first determined using purified and deionized water as the matrix for selected compounds having Vb_T < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4–5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb_E curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5–6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb_E in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

施用典型有机固废生物炭对土壤重金属生物有效性的影响

将有机固废经热解转化为生物炭,具有改良土壤、促进碳固定、钝化重金属等优点,但有机固废生物炭中被钝化重金属进入土壤后生物有效性尚不明确。采用盆栽方法评估了施用市政污泥、中药渣等典型有机固废生物炭对受纳土壤中重金属有效性及植物吸收、传输重金属的影响。结果表明,施用污泥炭、中药渣炭显著增加了土壤中As、Zn的化学提取有效态含量,从而降低了Cr、Pb有效态含量(P < 0.05),对Cd、Cu、Ni有效态含量也有不同程度的降低趋势;同时,抑制了除Zn以外As、Cd、Cr、Cu、Ni、Pb等6种重金属从土壤向植物的传输、累积,降幅最高达30%。中药渣炭联合污泥炭施用可进一步抑制7种重金属在植物地上部分以及除As、Cr外其他重金属在根中的吸收、累积。本研究结果可为评估有机固废生物炭土地利用的环境风险提供参考。     

Effects of the organic matter from swine wastewater on the adsorption and desorption of alachlor in soil

The application of swine wastewater to the soil for agricultural purposes results in the addition of total and dissolved organic matter to the soil, which may interfere with the dynamics of pesticides in the soil. The objective of this study was to evaluate the effects of the application of total and dissolved organic matter from a biodigester and a treatment lagoon of swine wastewater in the adsorption and desorption of alachlor [2-chloro-2,6-diethyl-N(methoxymethyl acetamide)]. The assay was performed by the batch equilibrium method, and the results were fitted to the Freundlich model. The curve comparison test revealed a greater adsorption of alachlor in the soil treated with swine wastewater from the biodigester. The adsorption and desorption of alachlor increased in the soils where swine wastewater was added, and hysteresis was observed in all of the treatments.     

水体中27种有机磷阻燃剂(OPFRs)的检测及风险评价

有机磷阻燃剂(organophosphorus flame retardants,OPFRs)具有致畸、致癌、致突变风险以及神经毒性作用。为了更好地研究其存在水平和健康风险,建立了固相萃取与高效液相色谱-串联质谱仪和气相色谱-质谱联用仪检测水体中27种OPFRs的分析方法,并对OPFRs进行了健康风险评价。20种OPFRs采用MCX固相萃取柱预处理和LC-MS/MS进行检测,以甲醇和含10 mmol·L⁻¹的甲酸水溶液作为流动相进行梯度洗脱,7种OPFRs采用HLB串联Envi-18固相萃取柱进行预处理并利用GC-MS进行检测。检测结果表明,27种OPFRs的检出限为0.02~2.53 ng·L⁻¹;定量限为0.06~8.43 ng·L⁻¹;回收率为65.82%~108.48%。2021年4月份,采集北京市潮白河地表水和地下水8个水样并检测其OPFRs。实测结果表明：除磷酸三(2-异丙基苯)酯、磷酸异癸基二苯酯、磷酸叔丁基苯二苯酯、磷酸二苄酯外,其余23种OPFRs均有不同程度检出,质量浓度为0~973.17 ng·L⁻¹;磷酸三(2-乙基己基)酯、磷酸三乙酯、磷酸三丙酯、磷酸三异丙酯含量相对较高,分别高达973.17、459.90、315.47、298.41 ng·L⁻¹。采用USEPA模型对水样中的OPFRs进行了健康风险评价, 13种OPFRs的非致癌风险值为0~6.17×10⁻⁴,4种OPFRs致癌风险值为1.37×10⁻⁹~1.07×10⁻⁷;在高暴露条件下,OPFRs的非致癌风险值为1.61×10⁻⁵~6.17×10⁻⁴,致癌风险值为1.00×10⁻⁸~1.07×10⁻⁷,均低于风险阈值。上述结果说明,水体中OPFRs产生的健康风险处于较低水平。此次采集的潮白河地表水和地下水水中OPFRs的致癌风险和非致癌风险均处于较低水平。本研究结果可为地表水和地下水水体中OPFRs的检测及风险评价提供参考。     

土壤有机质对铊在土壤中吸附-解吸行为的影响

研究了土壤有机质对Tl＋在红壤和黄土2种土壤中的吸附-解吸行为的影响。结果表明,去除土壤有机质后红壤和黄土对Tl＋的吸附量均明显下降,下降幅度最高分别达到24.7%和28.2%,黄土的下降幅度大于红壤;黄土对Tl＋吸附率最高下降幅度约为20%,也高于红壤的15%。土壤有机质对Tl＋吸附的贡献率平均值分别是黄土39.2%、红壤32.8%。2种土壤对Tl＋的解吸量在去除有机质之后都明显增大,在初始Tl＋浓度较高的情况下,增大幅度明显;并且Tl＋的初始浓度越高,土壤在去有机质前后的解吸率相差就越大,在Tl＋最大处理浓度为20 mg/L时,红壤和黄土的解吸率增加分别达到60.8%和65.5%。     

银纳米粒子作为二苯并噻吩固相萃取剂的研究

以银纳米粒子为对象,开展其作为新型固相萃取填料的二苯并噻吩类化合物的固相萃取-气相色谱快速分析方法的初步研究。采用液相化学还原法合成银纳米粒子及扫描电子显微镜表征银纳米粒子,研究了银纳米粒子对二苯并噻吩的吸附动力学和热力学特征;在前面的基础之上,用固相萃取法对样品中的二苯并噻吩进行快速定量。