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.     

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％。     

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.     

柚园间种作物及施用不同有机肥对土壤与柚果的影响

柚树间种短期经济作物在提高柚园经济效益的同时,还可提高土壤的有机质和N、P、K养分质量分数,改善柚园小区气候,增加有机肥来源。间种物残余体作为绿肥,可显著地提高柚果产量和质量。     

湖北野生食果资源特点及其开发途径

野生食果为营养丰富的食用资源植物。在深入调查的基础上，分析了湖北野生食果资源的特点，提出了野生食果资源开发的对策以及产品深加工的途径，为野生食果资源的开发利用打下了坚实的基础。     

海南省集约化种植园中谷物、蔬菜和水果中重金属累积程度及健康风险

集约化种植园中植物有害元素的累积会危及人类健康.本研究共采集海南省典型集约化种植园中谷物、蔬菜和水果样品673份.分析了7种重金属（Cu、Pb、Zn、Cr、Cd、As和Hg）的分布特征,并采用单因子指数和内梅罗指数进行污染物评价.同时,结合中国营养学会推荐的日常膳食摄入量,分析重金属的膳食暴露风险.结果表明,673件农作物的Cu、As和Hg含量均低于国家食品限量标准,Pb、Zn、Cr和Cd的超标率分别为2.67%、3.71%、2.53%和3.71%.6类农作物的重金属综合污染程度表现为：叶类蔬菜 > 薯类 > 非叶类蔬菜类 > 豆类 > 水果 > 谷类.其中,叶类蔬菜中Cr的风险系数（HQ）显著高于其它类型农作物,并且大于1,表明通过叶类蔬菜摄入重金属具有潜在健康风险.薯类、非叶菜蔬菜类、豆类、水果类和谷类农作物的危害指数（HI）较低,表明这几类农作物更适合集约化生产模式.     

辽东半岛自然资源的优势及其在农业中的利用

辽东半岛是东北东部山地的南延部分,属于暖温带落叶阔叶林景观。由于受到海洋的影响,气候比我国同纬地区温和、湿润,为太区农业、林业及果蚕业的发展提供了有利条件,同时本区海岸曲折,港湾众多,富海上交通和渔业之利。在东北地区,本区是一个自然环境较优越,自然资源较丰富的区域。本文主要阐述辽东半岛自然地理的基本特征和自然资源的优势,并对其利用方向作了初步探讨。     

新鲜蔬菜和水果中亚硝酸盐测定方法研究

本文研究了消除新鲜蔬菜和水果中抗坏血酸对亚硝酸盐测定原方法，在样品提取时加入醋酸锌和活性炭，以消除抗坏血酸对测定的干扰，提高了测定的灵敏度和准确必     

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.     

Monitoring of Pesticide Residues in Fruits

Fruit samples of ber, grapes and guava analysed for pesticide residues employing multiresidue analysis by gas liquid chromatography equipped with ECD and NPD detectors and capillary columns showed contamination with organochlorine, synthetic pyrethroid and organophosphate insecticides. Among organochlorines, HCH, DDT and endosulfan were detected in almost all the samples. Residues of HCH and DDT were maximum in ber followed by grapes and guava where as of endosulfan were maximum in guava followed by grapes and ber. All the fruit samples showed the presence of residues with one or the other group of pesticides. Residues of none of the pesticides exceeded the MRL values in any sample. On the basis of these studies, it is suggested that monitoring studies should be extended to other fruits grown in different agro climatic regions which may serve as basis for future policy in chemical use.