通过式固相萃取/超高效液相色谱-串联质谱法测定蔬菜中18种农药残留

建立了超高效液相色谱-串联质谱(UPLC-MS;MS)快速测定蔬菜中18种农药残留的方法.样品经乙腈提取后,经Oasis PRiME HLB固相萃取柱净化,采用ACQUITY UPLC HSS T3 C18(50 mm×2.1 mm,1.8μm)色谱柱进行分离,以0.1%甲酸水溶液和乙腈作为流动相进行梯度洗脱.采用电喷雾电离源、正离子模式下以多反应监测(MRM)进行定性和定量分析.结果表明,18种农药在0.5—50μg·L^-1范围内线性关系良好(r2>0.995),方法最低检出限为0.4—1.5μg·kg^-1,最低定量限为1.4—5.0μg·kg^-1.在韭菜、芹菜、番茄、白菜基质中,5、10、50μg·kg^-1添加水平下的加标回收率为60.2%—126.9%,相对标准偏差(RSD)为0.4%—21.6%(n=3).     

LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.     

南京市蔬菜中滴滴涕和六六六的残留及摄食暴露分析

为研究有机氯农药在食物中的残留及人群的摄食暴露,在2015年5月采集了南京市居民普遍食用的10种蔬菜,利用气相色谱-质谱联用仪(GC-MS)进行检测。研究表明滴滴涕(DDTs)和六六六(HCHs)在蔬菜中均有检出,∑DDTs的残留量为1.78~5.29 ng·g~(-1),∑HCHs的残留量为0.21~4.77 ng·g~(-1),其中∑10OCPs(有机氯农药)含量最高的蔬菜是藕(10.07 ng·g~(-1)),含量最低的是青菜(2.32 ng·g~(-1))。通过来源分析发现,蔬菜中DDTs可能有新的输入,而HCHs则主要源于历史残留。通过对不同人群的每日摄取量(EDI)进行摄食暴露分析发现,儿童的摄食暴露量要高于同性别其他年龄段人群,在儿童和未成年阶段,男性的暴露量普遍高于女性,而在成年和老年阶段,男性的暴露量低于女性。平均而言,各年龄段人群对γ-HCH和DDTs的日均口摄暴露量(EDI)值远低于联合国粮农组织和世界卫生组织(FAO/WHO)所规定的ADI值,表明在目前蔬菜消费量下,南京市居民通过摄入蔬菜引起的健康风险水平较低。     

成都平原农用土壤重金属污染现状及防治对策

随着工业化进程的加快和农业生产中化肥和农药不合理施用使得农用土壤重金属污染风险逐渐增大。本文对成都平原农用土壤和农作物重金属污染现状进行了综述，发现农用土壤和蔬菜中重金属污染均以Pb、Cd和Hg三种元素为主。分析了重金属离子在土壤一植物系统中迁移的一般规律及其影响因子，分析了农用土壤重金属污染的主要原因，为预防和防治污染提供了一些建议。     

贵阳和万山地区部分蔬菜中的重金属含量及其健康风险

以贵州省贵阳市和万山地区为例,对购自当地自由市场的部分蔬菜中的重金属Cd、Hg、Pb、Mn、As的含量进行了测定,并以国际放射防护委员会(ICRP,International Commissionon Radiological Protection)给出的限定值为标准,对某些重金属含量超标的蔬菜进行了健康风险评价.结果表明:除个别蔬菜的As和Mn外,万山地区蔬菜中的重金属含量均明显高于贵阳地区;两地蔬菜中的As、Pb含量均低于国家限定值(GB4810-1994、GB14935-1994),而部分蔬菜中的Cd、Hg含量均明显超出国家限定值(GB15201-1994、GB2762-1994).风险评价结果表明贵阳和万山两地的蔬菜可能存在重金属Cd、Hg、Pb的中、轻度污染;存在Cd污染的蔬菜对人体的年致癌风险为3.40×10-7·a-1,非致癌物Hg和Pb对人体的总健康风险分别为3.63×10-7·a-1、1.69×10-6·a-1,均低于ICRP标准.     

Characterization of distribution of pesticide residues in crop units

The characteristic features of distribution of pesticide residues in crop units and single sample increments were studied based on more than 19,000 residue concentrations measured in root vegetables, leafy vegetables, small-, medium- and large-size fruits representing 20 different crops and 46 pesticides. Log-normal, gamma and Weibull distributions were found to provide the best fit for the relative frequency distributions of individual residue data sets. The overall best fit was provided by lognormal distribution. The relative standard deviation of residues (CV) in various crops ranged from 15–170%. The 100–120 residue values being in one data set was too small to identify potential effects of various factors such as the chemical and physical properties of pesticides and the nature of crops. Therefore, the average of CV values, obtained from individual data sets, were calculated and considered to be the best estimate for the likely variability of unit crop residues for treated field (CV = 0.8) and market samples (CV = 1.1), respectively. The larger variation of residues in market samples was attributed to the potential mixing of lots and varying proportion of non-detects. The expectable average variability of residues in composited samples can be calculated from the typical values taking into account the sample size.     

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.     

TOTAL ARSENIC ACCUMULATION IN EDIBLE PODS AND SEEDS OF PHASEOLUS VULGARIS

The main objective of this study was to evaluate whether arsenic accumulated in the edible pods and seeds of Phaseolus vulgaris, cv. Helda, above the Spanish maximum recommended concentration for food crops, 1 mg kg^?1 on a fresh weight basis. Only organic arsenicals were used because they are: a) the only arsenic species allowed for agricultural applications and b) more mobile than inorganic species. Selection of French beans, a sensitive plant to arsenic, was based on the fact that arsenic upward translocation is higher in sensitive than in tolerant plants. A 2 × 3 factorial experiment was conducted with two organic arsenic species: methylarsonic acid (MAA) or dimethylarsinic acid (DMAA) and three arsenic concentrations: 0.2, 0.5, or 1.0 mg L^?1. Arsenic phytotoxicity was primarily determined by soluble arsenic concentration. Experimental results showed that the low bean plant tolerance to arsenic is possibly due to the high arsenic upward transport to shoots, which could result in profound negative metabolic consequences. Even under extremely adverse conditions, arsenic residues in edible beans were below the maximum statutory limit set by the Spanish legislation. It can be concluded that the major danger of organic arsenical herbicides is that of decreased productivity rather than high arsenic uptake by consumers.     

亚硒酸盐对四种蔬菜生长、吸收及转运硒的影响

采用土培盆栽试验和室内分析相结合的方法,研究了添加不同含量外源亚硒酸盐对小白菜、芥菜、生菜和菠菜的生长、吸收及转运硒的影响.结果表明,低含量硒(＜3.81 mg·kg-1)对供试的4种蔬菜的生长均有促进作用,而高含量硒(＞29.91 mg·kg-1)却显著抑制蔬菜的生长,并对供试蔬菜的茎、根产生明显的毒害作用.同等硒添...     

果蔬废弃物两相厌氧消化特征研究

厌氧消化在处理果蔬废弃物具有较高的处理效率,同时可获得甲烷等能源气体,具有很大的技术优势和广阔的应用前景。本文通过研究两相厌氧系统启动及试运行,深入分析了该系统处理果蔬废弃物的消化特征。酸化初期,苹果和白菜两种底物在酸化过程中均降解迅速。约10d即可分解70％80％的还原糖;当系统运行40d后,pH稳定在7．5左右,反应器已形成较好的缓冲体系：氧化还原电位稳定于-460--540mV之间。适宜产甲烷阶段的进行。挥发性脂肪酸的分析表明,果蔬废弃物置于循环反应体系中。仍有一段时间的酸化过程。该过程中丁酸由2000mg／L增加至2600mg／L,戊酸由600mg／L增加至1300mg／L。乙酸含量基本稳定在1000mg／L左右,丙酸含量略有提高,由450mg／L增加至600mg／L。此阶段发酵类型为丁酸型发酵．各挥发酸所占比例由高到低依次为丁酸、戊酸、乙酸和丙酸,所占比例分别为45％、23％、20％和10％。