桃中农药残留分析及膳食暴露评估研究

为明确并量化食用桃途径的农药膳食摄入风险水平,通过对19个桃主产区采集的98份样品进行农药残留检测,对桃中的农药残留急/慢性膳食摄入风险进行评估,并借鉴英国兽药残留委员会兽药残留风险排序矩阵进行农药和样品风险排序。结果在桃中检出了38种农药残留,98个样品的检出率为95.9%,检出的农药含量为0.007 4～3.399 3 mg/kg;检出农药的慢性膳食摄入风险(%ADI)和急性膳食摄入风险(%ARfD)的平均值分别为0.89%和11.09%,风险均低于100%,不会对人体产生慢性或急性风险;风险排序结果表明桃果品中氟虫腈、硫丹、灭多威、丁硫克百威、毒死蜱、联苯菊酯为6种为高风险农药,应在生产和质量安全监管中予以重点关注。该文为桃安全消费、农药残留监管和农药最大残留限量(MRLs)制修订提供了科学依据。     

Detection and Risk Assessments of Multi-Pesticides in Traditional Chinese Medicine Chuanxiong Rhizoma by LC/MS-MS and GC/MS-MS

With the internationalization of traditional Chinese medicines (TCMs) and the increasing use of herbal medicines around the world, there are concerns over their safety. In recent years, there have been some sporadic reports of pesticide residues in Chuanxiong Rhizoma (CX), although the lack of systematic and comprehensive analyses of pesticide residues and evaluations of toxicological risks in human health has increased the uncertainty of the potential effects of pesticides exposure in humans. This study aimed to clarify the status of pesticide residues and to determine the health risks of pesticide residues in CX. The findings of this study revealed that 99 batches of CX samples contained pesticide residues ranging from 0.05 to 3013.17 μg/kg. Here, 6–22 kinds of pesticides were detected in each sample. Prometryn, carbendazim, dimethomorph, chlorpyrifos, chlorantraniliprole, pyraclostrobin, and paclobutrazol were the most frequently detected pesticides, with detection rates of 68.69–100%. Insecticides and fungicides accounted for 43.23% and 37.84% of the total pesticides detected, respectively. Here, 86.87% of the pesticide content levels were lower than 50 μg/kg, and a small number of samples contained carbofuran, dimethoate, and isofenphos-methyl exceeding the maximum residue levels (MRLs). A risk assessment based on the hazard quotient/hazard index (HQ/HI) approach revealed that the short-term, long-term, and cumulative risks of pesticide residues in CX are well below the levels that may pose a health risk. Worryingly, six banned pesticides (carbofuran, phorate sulfone, phorate-sulfoxide, isofenphos-methyl, terbufos-sulfone, and terbufoxon sulfoxide) were detected. This study has improved our understanding of the potential exposure risk of pesticide multi-residues in CX. The results of the study will have a positive impact on improving the quality and safety of CX and the development of MRLs for pesticide residues.     

气相色谱法测定小麦粉中有机磷类和拟除虫菊酯类农药残留量

应用气相色谱法测定了小麦粉中4种有机磷和拟除虫菊类农药的残留量.样品中的残留农药用乙腈提取分离,所得提出液减压蒸发至近干,再用吹氮法蒸干.残渣用正己烷-乙酸乙酯(9+1)混合溶液2 mL溶解,所得溶液经中性氧化铝固相萃取柱净化.收集洗脱液,再用上述混合溶液10 mL淋洗固相萃取柱,收集洗脱液与上次洗脱液合并,减压蒸发至...     

Use patterns and residual levels of organophosphate pesticides on vegetables in Trinidad, West Indies.

The twin-island state of Trinidad and Tobago produces much of the fresh fruit and vegetables consumed locally, although some are exported to Europe and North America. On average, approximately 1500 tons of pesticides are imported annually, of which about 10-15% are organophosphates. A survey of local farmers revealed that a wide range of pesticides are used and that the same pesticides are used on several crops to control different pests. Application rates exceeding manufacturers' recommendations are also common, as is the disregard of recommended preharvest intervals after pesticide application. Praedial larceny and subsequent sale of freshly sprayed crops also contribute to the risks posed to consumers by pesticide residues. A market basket survey of produce conducted between October 1996 and May 1997 in Trinidad for organophosphate pesticides showed that 10% of produce exceeded the internationally acceptable maximum residue limits (MRLs) for the respective pesticides. Celery constituted 6.5% of all such samples, with over 83% of celery samples exceeding the MRL. Organophosphate pesticides detected were methamidophos, triazophos, prophenofos, diazinon, ethion, pirimiphos methyl, malathion, and dimethoate, with the first 4 being the most commonly detected. There is an urgent need for comprehensive monitoring and control of pesticides on produce by local regulatory agencies, especially because the above data relate only to one class of pesticides. The education of farmers on safe operating practices regarding pesticide application and observation of recommended preharvest intervals for applied pesticides is also required.     

陈皮中农药残留分析及风险评估研究

通过分析中药陈皮的农药残留问题开展风险评估研究。采用气相色谱-串联质谱(GC-MS/MS)和高效液相色谱-串联质谱(HPLC-MS/MS)对198批陈皮中的117种农药进行检测;采用点评估方式计算陈皮中农药残留的急性和慢性摄入风险;采用英国兽药残留委员会提出的兽药残留风险排序矩阵计算各农药的风险得分;采用危害指数(HI)法计算有机磷农药的慢性累积风险。198批陈皮中共检出30种农药(含13种禁用农药),总检出率为98.5%,农药检出量为0.001~11.7 mg/kg。检出农药的慢性膳食摄入风险(%ADI)为0.003%~3.142%,急性膳食摄入风险(%ARfD)为0.022%~26.667%,风险均远低于100%,表明陈皮中农药的膳食暴露风险处于较低水平。6种有机磷农药的慢性累积暴露危害指数为0.942,略小于1,表明风险虽可控但需要关注。风险排序结果表明,陈皮中有16种为中高风险农药,应在生产和安全监管中重点关注。     

Response surface methodology for the microwave-assisted extraction of insecticides from soil samples

The extraction of two pyrethroid insecticides (deltamethrin and α-cypermethrin) together with three organophosphorus insecticides (dimethoate, diazinon and malathion) from soil samples was carried out with microwave-assisted technology. Experimental designs showed that extraction temperature, addition of water to the extractant and solvent/soil ratio were the variables that affected the recoveries of the pesticide the most. Response surface methodology was applied to find the optimum values of the variables involved in the extractions of the analytes. In addition, in order to achieve near-optimal extraction conditions, a desirability function was used to optimize the five pesticides simultaneously. The optimized conditions were applied to different types of soils.     

Effect of Coconut and Chestnut Flour Supplementations on Texture,Nutritional and Sensory Properties of Baked Wheat Based Bread

Wheat bread, produced by the single-phase method, is a common food consumed all over the world. Due to changes in lifestyle and nutritional trends, alternative raw materials are sought to increase the nutritional value and improve the taste of daily consumed products. Additionally, customers seek a wide variety of foods, especially when it comes to basic foods. Nuts, such as coconuts or chestnuts, might provide an attractive flavour with benefits to the nutritional quality. In this study, the effect of substituting wheat flour with coconut or chestnut flour (flour contribution level: 5, 10, 15, 30, 50% w/w), was evaluated in terms of the breads specific volume, texture, colour, nutritional composition, and dietary fibre fraction contents. Moreover, a sensory evaluation was conducted to assess potential consumer acceptance. Based on the consumer’s perception, the overall acceptance of bread with 15% w/w of coconut and chestnut flour was in privilege compared to the control sample. As a result, taking all of the tested parameters into account, the breads with 5, 10, and 15% supplementation of chestnut or coconut flour were still of good quality compared to the wheat bread and their fibre content was significantly higher.     

Pesticide residue determination in vegetables from western China applying gas chromatography with mass spectrometry

In this study,an effort has been made to evaluate the pesticide residues in vegetables from western China. Fifty‐one pesticides, including organophosphorus, organochlorine, carbamate and pyrethroid, were detected in 369 commonly used vegetables by GC‐MS. Concentrations of organophosphorus pesticides were detected ranging from 0.0008 to 18.8200 mg/kg, among which organophosphorus pesticide concentrations exceeded their maximum residue levels (MRLs) in five samples. Carbamate and organochlorine pesticides were determined to have concentrations in the range of 0.0012–0.7928 mg/kg. The residual concentrations of carbamate pesticides in six samples and organochlorine pesticides in four samples exceeded their MRLs. The residual concentrations of five pyrethroid pesticides were within the range of 0.0016–6.0827 mg/kg and the pyrethroid residues in two samples exceeded their MRLs. The results revealed that pesticide residues in 70.73% of the vegetables samples were not detected, while in the rest of vegetables there were one or more pesticide residues and some even exceeded their MRLs, which would threaten the health of consumers. Our work provides significant information for the food safety regulations to control the excessive use of some pesticides on those kinds of vegetables from western China. Copyright © 2016 John Wiley & Sons, Ltd.     

What are we determining using gas chromatographic multiresidue methods: tralomethrin or deltamethrin?

The analytical behaviour of the relatively new pyrethroid insecticide tralomethrin has been evaluated by using gas chromatography (GC) with electron-capture and mass spectrometry (MS) detectors, and liquid chromatography (LC)-atmospheric pressure ionization mass spectrometry with electrospray interfacing. Under the GC conditions commonly used in pesticide residue analysis, it was found that tralomethrin is transformed into deltamethrin (in a reproducible way) in the injector port of the GC system. Results obtained in this work indicate that the GC multiresidue methodologies routinely applied in the analysis of pyrethroid pesticides in foods cannot distinguish between these two pesticides, and the chromatographic signal obtained at the retention time of deltamethrin/tralomethrin can be really quantified as either deltamethrin or tralomethrin, including when it is confirmed as deltamethrin by MS. Under the LC-MS conditions assessed in this work, deltamethrin and the two diasteroisomers of tralomethrin were well separated and identified.     

Determination of multiresidue pesticides in green tea by using a modified QuEChERS extraction and ion-trap gas chromatography/mass spectrometry

The pesticide residues in exported and imported tea products must not exceed the maximum residue limits (MRLs) regulated by the import countries. Tea is a complex matrix that obfuscates the determination of pesticide residues. Many available methods for multiresidue pesticide analysis of tea are time-consuming and require many cleanup steps. The objective of this study was to develop a simple multiresidue method by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction and ion-trap GC/MS/MS, which can identify, confirm, and quantify pesticides in complex matrixes. A tea product was homogenized with water, and the pesticides were extracted with acetonitrile containing 1% acetic acid. The extract was subjected to centrifugation, initial cleanup with dispersive SPE (dSPE), solvent exchange, and final cleanup with dSPE. Diethyl-d10-parathion and triphenyl phosphate were used as the internal standard and surrogate, respectively. The final extract was injected into an ITQ 700 gas chromatograph/mass spectrometer. Quantitation of individual pesticides was based on matrix-matched calibration curves with a correlation coefficient of > 0.9930 for the 22 pesticides selected for the study. The recoveries of the 22 pesticides ranged from 78 to 115%, except those for diazinon (130%) and malathion (122%), with an average RSD of 8.7%. The LOD values of all of the pesticides, except for terbufos, were below the MRLs set by the European Union and Japan.     

Analysis of Malathion pesticide residues in rice samples using ultrasound-assisted emulsification-microextraction coupled to UV photoionization source ion mobility spectrometry

The present paper describes the validation of ultrasound-assisted emulsification-microextraction method followed by ion mobility spectrometry (IMS) for determination malathion pesticides. Ultrasound radiation was applied for accelerating the emulsification of microliter organic solvent in aqueous solutions and enhancing the microextraction efficiency. This preconcentration step combined with IMS detection provided a precise and accurate method for determination of trace amounts of malathion pesticides. The effect of parameters influencing the extraction efficiency such as sonication time, type of extraction solvent, extraction solvent volume, and salt concentration were investigated and discussed. Under the optimum conditions, enrichment factors was 270 with corresponding LOD of 4 μg/L. Linearity with a coefficient of estimation (r²) were >0.99 in the concentration level range of 6–750 μg/L for extraction of Malathion in water samples. The applicability of the proposed method was evaluated by determination of the residues of the investigated pesticide in rice paddy water gathered from four stations during 60 days after spraying (June 2014), and in storage rice samples in Mazandaran province, Iran.     

Determination of pesticides by solid phase extraction followed by gas chromatography with nitrogen–phosphorous detection in natural water and comparison with solvent drop microextraction

The European Union specificies that drinking water can contain pesticide residues at concentrations of up to 0.1 μg/L each and 0.5 μg/L in total, and that 1–3 μg/L of pesticides can be present in surface water, but the general idea is to keep discharges, emissions and losses of priority hazardous substances close to zero for synthetic substances. Therefore, in order to monitor pesticide levels in water, analytical methods with low quantification limits are required. The method proposed here is based on solid phase extraction (SPE) followed by gas chromatography with a nitrogen–phosphorous detector (GC-NPD). During method development, six organophosphate pesticides (azinphos-ethyl, chlorfenvinphos, chlorpyriphos, ethoprophos, fenamiphos and malathion) and two organonitrogen pesticides (alachlor and deltamethrin) were considered as target analytes. Elution conditions that could influence the efficiency of the SPE were studied. The optimized methodology exhibited good linearity, with determination coefficients of better than 0.996. The analytical recovery for the target analytes ranged from 70 to 100%, while the within-day precision was 4.0–11.5 %. The data also showed that the nature of the aqueous matrice (ultrapure, surface or drinking water) had no significant effect on the recovery. The quantification limits for the analytes were found to be 0.01–0.13 μg/L (except for deltamethrin, which was 1.0 μg/L). The present methodology is easy, rapid and gives better sensitivity than solvent drop microextraction for the determination of organonitrogen and organophosphate pesticides in drinking water at levels associated with the legislation.     

Gas chromatographic determination of pesticide residues in malt, spent grains, wort, and beer with electron capture detection and mass spectrometry

A method for the simultaneous determination of 9 pesticides (dinitroanilines, organophosphorus, triazoles, and pyrimidines) in several products (malt, spent grains, wort, and beer) of the beer industry is reported. Solid samples (malt and spent grains) are extracted by homogenization with a water-hexane mixture, and the pesticides are partitioned with dichloromethane. Liquid samples (wort and beer) are extracted by sonication with a hexane-dichloromethane mixture. Determination of pesticide residues was made by capillary gas chromatography with an electron capture detector (ECD). Confirmation of the compounds was performed by gas chromatography/ion trap mass spectrometry in the selected ion monitoring mode. Detection limits for GC-ECD varied from 0.2 to 5.5 pg for trifluralin and malathion, respectively. Recoveries of the pesticides from spiked samples ranged from 81.2 to 113.7% with a relative standard deviation between 3.4-7.5%. The method presents good linearity over the studied range (0.005-2 microg/mL). The proposed method is rapid and reliable and can be useful for routine monitoring during brewing.     

Multiresidue analysis of 47 pesticides in cooked wheat flour and polished rice by liquid chromatography with tandem mass spectrometry

Liquid chromatography in conjunction with tandem mass spectrometry was used to directly quantify of 47 pesticide residues from cooked wheat flour and polished rice, which are the most widely consumed cereals in the Republic of Korea. The sample clean‐up was carried out according to the method established by the Korea Food and Drug Administration. The mobile phase for liquid chromatograpy separation consisted of water and 5 mm methanolic ammonium formate. Tandem mass spectroscopy experiments were performed in electrospray ionization positive mode and the multiple reaction monitoring mode. The matrix effects estimated for the 47 pesticides had a mean value of 99% and ranged from 45 to 147%. High recoveries (70–140%) and relative standard deviations (≤20%) were achieved for most of the pesticides tested. The method used in this study allowed for rapid quantification and identification of low levels of pesticides in cooked wheat flour and polished rice samples. Of the screened pesticide residues, only tricyclazole and fenobucarb were found in polished rice samples. However, no samples contained residues above the MRL established by the Korea Food and Drug Administration. Copyright © 2008 John Wiley & Sons, Ltd.     

Fast gas chromatography for pesticide residues analysis using analyte protectants

Fast GC-MS with narrow-bore columns combined with effective sample preparation technique (QuEChERS method) was used for evaluation of various calibration approaches in pesticide residues analysis. In order to compare the performance of analyte protectants (APs) with matrix-matched standards calibration curves of selected pesticides were searched in terms of linearity of responses, repeatability of measurements and reached limit of quantifications utilizing the following calibration standards in the concentration range 1-500 ng mL(-1)(the equivalent sample concentration 1-500 microg kg(-1)): in neat solvent (acetonitrile) with/without addition of APs, matrix-matched standards with/without addition of APs. For APs results are in a good agreement with matrix-matched standards. To evaluate errors of determination of concentration synthetic samples at concentration level of pesticides 50 ng mL(-1) (50 microg kg(-1)) were analyzed and quantified using the above given standards. For less troublesome pesticides very good estimation of concentration was obtained utilizing APs, while for more troublesome pesticides such as methidathion, malathion, phosalone and deltamethrin significant overestimation reaching up to 80% occurred. According to presented results APs can be advantegously used for "easy" pesticides determination. For "difficult" pesticides an alternative calibration approach is required for samples potentially violating MRLs. An example of real sample measurement is shown. In this paper also the use of internal standards (triphenylphosphate (TPP) and heptachlor (HEPT)) for peak areas normalization is discussed in terms of repeatability of measurements and quantitative data obtained. TPP normalization provided slightly better results than the use of absolute peak areas measurements on the contrary to HEPT.     

Detection of malathion in food peels by surface-enhanced Raman imaging spectroscopy and multivariate curve resolution

An analytical methodology was developed for detection of malathion in the peels of tomatoes and Damson plums by surface-enhanced Raman imaging spectroscopy and multivariate curve resolution. To recover the pure spectra and the distribution mapping of the analyzed surfaces, non-negative matrix factorization (NMF), multivariate curve calibration methods with alternating least squares (MCR-ALS) and MCR with weighted alternating least square (MCR-WALS) were utilized. Error covariance matrices were estimated to evaluate the structure of the error over all the data. For the tomato data, NMF-ALS and MCR-ALS presented excellent spectral recovery even in the absence of initial knowledge of the pesticide spectrum. For the Damson plum data, owing to heteroscedastic noise, MCR-WALS produced better results. This methodology enabled detection below to the maximum residue limit permitted for this pesticide. This approach can be implemented for in situ monitoring because it is fast and does not require extensive manipulation of samples, making its use feasible for other fruits and pesticides as well.     

p-Nitro-N-propylaniline/silica: synthesis, characterization, and its application in matrix solid phase dispersion for multiresidue analysis of pesticides in carrots

A new material for matrix solid phase dispersion (MSPD) was synthesized -- p-nitro-N-propylaniline/silica (pNNPASi) by grafting reactions, characterized by elemental analysis and N(2)-adsorption-desorption isotherms, and tested for multiclass multiresidue analysis of pesticides in wet and freeze-dried carrots. Results obtained applying this new solid phase sorbent to MSPD extraction of ten pesticides (trichlorphon, trifluralin, dicloran, chlorothalonil, prometryn, linuron, captan, procymidone, prochloraz, and deltametrin) in wet carrots showed better results than the ones obtained for freeze-dried samples. Recoveries were in the range of 48-106% and precisions varied from 6 to 20% when wet samples were employed. Comparison between pNNPASi sorbent and C(18) showed better performance of pNNPASi for eight out of ten pesticides tested. The LOQs show that the developed method can be used to detect the pesticides investigated in carrots at concentrations below the maximum residue levels (MRL) established by EU, USEPA, and National Sanitary Surveillance Agency (ANVISA). Linuron, captan, prochloraz, and deltamethrin were found in at least one of the two commercial samples studied in concentrations above the LOQ of this method. Concentrations of the last three pesticides were above the European MRL in one of the commercial samples.     

Gamma radiation influence on technological characteristics of wheat flour

This study aimed at determining the influence of gamma radiation on technological characteristics of wheat (Triticum sativum) flour and physical properties of pan breads made with this flour. The bread formulation included wheat flour, water, milk, salt, sugar, yeast and butter. The α-amylase activity of wheat flour irradiated with 1, 3 and 9 kGy in a Gammacell 220 (AECL), one day, five days and one month after irradiation was evaluated. Deformation force, height and weight of breads prepared with the irradiated flour were also determined. The enzymatic activity increased—reduction of falling number time—as radiation dose increased, their values being 397 s (0 kGy), 388 s (1 kGy), 343 s (3 kGy) and 293 s (9 kGy) respectively, remaining almost constant over the period of one month. Pan breads prepared with irradiated wheat flour showed increased weight. Texture analysis showed that bread made of irradiated flour presented an increase in maximum deformation force. The results indicate that wheat flour ionizing radiation processing may confer increased enzymatic activity on bread making and depending on the irradiation dose, an increase in weight, height and deformation force parameters of pan breads made of it.     

Gas‐phase copper and silver complexes with phosphorothioate and phosphorodithioate pesticides investigated using electrospray ionization mass spectrometry

Efforts to improve agricultural productivity have led to a growing dependency on organophosphorus pesticides. Phosphorothioate and phosphorodithioate pesticides are organophosphorus pesticide subclasses with widespread application for the control of insects feeding on vegetables and fruits. However, even low doses of these pesticides can cause neurological problems in humans; thus, their determination and monitoring in agricultural foodstuffs is important for human health. Phosphorothioate and phosphorodithioate pesticides may be poorly ionized during electrospray, adversely affecting limits of detection. These pesticides can form complexes with Cu²⁺ and Ag⁺, however, potentially improving ionization. In the present work, we used electrospray ionization/mass spectrometry (ESI/MS) to study fenitrothion, parathion, diazinon, and malathion coordination complexes with silver and copper ions. Stable 1 : 1 and 1 : 2 metal/pesticide complexes were detected. Mass spectra acquired from pesticide solutions containing Ag⁺ or Cu²⁺ showed a significant increase in signal‐to‐background ratio over those acquired from solutions containing only the pesticides, with Ag⁺ improving detection more effectively than Cu²⁺. Addition of Ag⁺ to a pesticide solution improved the limit of detection by ten times. The relative affinity of each pesticide for Ag⁺ was related to complex stability, following the order diazinon > malathion > fenitrothion > parathion. The formation of Ag⁺–pesticide complexes can significantly improve the detection of phosphorothioate and phosphorodithioate pesticides using ESI/MS. The technique could potentially be used in reactive desorption electrospray ionization/mass spectrometry to detect phosphorothioate and phosphorodithioate pesticides on fruit and vegetable skins. Copyright © 2015 John Wiley & Sons, Ltd.     

Comparison of the In Vitro Bioavailability of Selected Minerals from Gluten-Free Breads Enriched with Grains and Synthetic Organic and Non-Organic Compounds

Introduction: Despite the constant efforts of scientists to improve the texture, sensory properties, and nutritional value of gluten-free bread, obtaining high bioavailability of minerals is still a huge challenge. Gluten-free bakery products are characterized by a low bioavailability of minerals. The aim of this study was to design gluten-free bread with high bioavailability of minerals commonly found in deficiencies in people struggling with gluten intolerance. Material and methods: The material consisted of gluten-free breads designed to obtain the highest possible content of minerals in the bread while maintaining a good structure and taste. Results: Higher contents of all the analyzed minerals were obtained in breads with natural and synthetic additives, both in rice and buckwheat bread, compared to basic bread. There was also a higher content of the analyzed minerals in buckwheat bread in comparison to rice bread for each type of additive. Higher bioavailability of iron, copper, calcium, and magnesium was noted in rice bread, while the bioavailability of zinc was higher in buckwheat bread. Conclusion: The additives used increased the bioavailability of the analyzed minerals from the gluten-free breads. The use of various variants of flour (rice, buckwheat) influenced the bioavailability of iron, zinc, copper, calcium, and magnesium. The release of minerals from gluten-free bread depends on the element and added components (seeds or synthetic additives).