苏南某市叶类蔬菜含氯有机农药残留状况分析及风险评估

目的了解苏南某市叶类蔬菜中含氯有机农药的残留状况及其质量安全现状。方法利用气相色谱法对采集自该市农贸市场、大型超市、种植基地及散户的6种主要叶类蔬菜中5种代表性的含氯有机农药(百菌清、三唑酮、氟氯氰菊酯、氯氰菊酯和氰戊菊酯)进行定量检测分析,采用食品安全指数开展暴露风险评估。结果 5种含氯有机农药在蔬菜样本中均有不同程度的检出,平均检出率为13.8%,百菌清、氯氰菊酯2种农药在部分蔬菜样本中的残留超标,超标率分别为0.4%和0.9%。6种叶类蔬菜的农药安全指数平均值均小于1,说明被检蔬菜的安全状态可为消费者所接受。但百菌清在菠菜和生菜中的安全指数均大于1,表明百菌清对菠菜和生菜质量安全的影响风险超过了可接受的限度。结论该地区主要叶类蔬菜的整体质量较安全,被检农药的残留状况总体良好,但对菠菜和生菜生产中百菌清的使用需加大监督管理力度,确保消费者食用蔬菜的安全性。     

Determination of organic acids in fruits and vegetables by liquid chromatography with tandem-mass spectrometry

A method using liquid chromatography coupled to tandem-mass spectrometry (LC-MS/MS) with triple quadrupole in selective reaction monitoring mode was developed to determine organic acids (glutamic, tartaric, quinic, malonic, malic, shikimic, α-ketoglutaric, pyruvic, citric, succinic and fumaric acids) in fruits (melon, grape, peach, orange, lemon) and vegetables (green and red pepper, tomato, lettuce and lamb’s lettuce). The negative ion mode of ESI was used. All the validation parameters were found to be within the range of acceptance for all the compounds. Different matrix effects were observed in the studied vegetables and samples were quantified by the standard additions approach. The main advantages of this method are its selectivity, which is one of the main weaknesses of most methods when analysing organic acid in complex matrices, and its simplicity since little sample preparation is needed.     

Application of a UV–vis detection-HPLC method for a rapid determination of lycopene and β-carotene in vegetables

The purpose of this paper is to optimize an HPLC method for the determination of lycopene and β-carotene in vegetables and compare it with a spectrophotometric standard method. Among the different conditions studied the most suitable ones for our samples were: extraction with hexane/acetone/ethanol (50:25:25 v/v/v), evaporation of the hexane layer, dissolution of the dry extract in THF/ACN/methanol (15:30:55 v/v/v) and injection on a C18 column with methanol/ACN (90:10 v/v) + TEA 9 μM as mobile phase (Φ = 0.9 ml/min) and λ_detection = 475 nm. Samples considered for analysis were: tomato, carrot, pepper, watermelon, persimmon and medlar. The HPLC method proposed showed adequate reproducibility (RSD < 10.5%), accuracy (100–109% recovery) and sensitive detection limits (0.6 μM for lycopene; 0.3 μM for β-carotene), with a simple preparation of the samples (one step direct extraction) and short run times (10 min) for the quantification of lycopene and β-carotene.     

Trace mineral content of conventional,organic and courtyard eggs analysed by inductively coupled plasma mass spectrometry (ICP-MS)

We investigated the contents in yolk and albumen of the trace minerals Se, Zn, Mn, Co, Cu, Mo, V, Cr, Ni, Tl, As and Cd in eggs from hens from three husbandry systems by ICP-MS. Conventional hens were given a commercial feed with added minerals, organic hens were given a feed based on organic feedstuffs also with added minerals, and courtyard hens were fed on cereals, legumes, grass and swill. Dietary Se, Zn, Mn, Co and Cu concentrations were lower in courtyard compared to conventional and organic diets; Cr concentration was highest in courtyard compared to organic diet. Trace element contents in yolks were higher than those in albumen. The highest content of Se in yolks was in organic, followed by conventional eggs. Zn contents were highest in courtyard yolk, followed by conventional, which in turn was higher than organic. Mn yolk contents were lowest in courtyard eggs; Cr contents were highest in courtyard eggs. The differences in albumen were in Zn and Cr values, which were highest in courtyard eggs. Τhe results provide baseline measurements of trace mineral contents of eggs and suggest measurable differences amongst eggs from hens in different husbandry systems; the physiological significance of these differences are discussed.     

Pesticide residues in conventional, integrated pest management (IPM)-grown and organic foods: insights from three US data sets

An analysis of pesticide residue data was performed to describe and quantify differences between organically grown and non-organic fresh fruits and vegetables. Data on residues in foods from three different market categories (conventionally grown, integrated pest management (IPM)-grown/no detectable residues (NDR), and organically grown) were compared using data from three test programmes: The Pesticide Data Program of the US Department of Agriculture; the Marketplace Surveillance Program of the California Department of Pesticide Regulation; and private tests by the Consumers Union, an independent testing organization. Organically grown foods consistently had about one-third as many residues as conventionally grown foods, and about one-half as many residues as found in IPM/NDR samples. Conventionally grown and IPM/NDR samples were also far more likely to contain multiple pesticide residues than were organically grown samples. Comparison of specific residues on specific crops found that residue concentrations in organic samples were consistently lower than in the other two categories, across all three data sets. The IPM/NDR category, based on data from two of the test programmes, had residues higher than those in organic samples but lower than those in conventionally grown foods.     

Preliminary evaluation of fumonisins by the Nordic countries and occurrence of fumonisins (FB1 and FB2) in corn-based foods on the Danish market

Experts from the Nordic countries (Denmark, Norway, Sweden, Finland and Iceland) have carried out an evaluation of fumonisins. The working group members concluded that, at that time point, it was not possible to carry out a complete risk assessment. However, it was recommended that the human daily' intake of fumonisins should be less than 1 microg/kg bw/day. Subsequently, the presence of the Fusarium mycotoxins fumonisin B1 and B2 (FB1 and FB2) in corn-based food on the Danish retail market has been determined. A total of 70 samples were analysed and 37% contained FB1 and 21% contained FB2. No fumonisins were found in sweet corn (canned or frozen), corn-on-the-cob, corn starch or gruel powder for babies. FB1 was found in about half of the corn flakes, corn snack and popcorn (not popped) samples, whereas FB2 was seen to a lesser extent. Both FB1 and FB2 were found in 75% or more of the corn flour, tacos and polenta samples. In general, the content of FB1 was in the range of 1-1000 micro/kg and the content of FB2 was in the range of 4-250 microg/kg. Corn-based foods are consumed in rather low amounts and irregularly among the Danish population and therefore it is not meaningful to calculate an average daily funonisin intake. An estimate for an 'eater' shows that the intake of fumonisins will not exceed 0.4 microg/kg bw/day.     

Determination of metronidazole and hydroxymetronidazole in trout by a high-performance liquid chromatographic method

A high-performance liquid chromatographic (HPLC) method based on solid phase extraction was developed for determination of metronidazole (MNZ) and its metabolite hydroxymetronidazole (MNZ-OH) in muscle and skin tissues of rainbow trout. Tinidazole (TNZ) was used as internal standard. The compounds were extracted with acetonitrile and the extract was evaporated and redissolved in a mixture of ethyl acetate and hexane (1:2). The extract was cleaned up by solid phase extraction on a silica cartridge. The extract was analysed by reverse phase gradient HPLC on a C18 column followed by ultraviolet detection at 325nm. The limit of detection was 2.8 μg/kg for both compounds in muscle. The estimated limits of detection in skin tissue were 3 μg/kg for MNZ and 5 μg/kg for MNZ-OH. The mean recoveries of MNZ in muscle calculated without use of internal standard were 93% and 81% at levels of 10 μg/kg and 25-100 μg/kg respectively. The mean recovery of MNZ-OH in muscle was 79% at a level of 10-100 μg/kg. The mean relative repeatability standard deviations on spiked muscle tissue were 3.3% for MNZ and 3.2% for MNZ-OH at a level of 10-100 μg/kg. The method was applied to trout given feed containing MNZ in an aquaculture pilot plant. Residues of MNZ and MNZ-OH were detected in muscle and skin tissues shortly after the administration period but not 3 weeks later.     

Determination of glucosinolate profiles in Chinese vegetables by precursor ion scan and multiple reaction monitoring scan mode (LC-MS/MS)

Liquid chromatography-electrospray ionization (ESI) mass spectrometry was used to describe the glucosinolate (GSL) profiles in three Chinese vegetables. The strategy was based on first screening for possible glucosinolates via precursor ion scan mode (PreIS). Further validating was done using the multiple reaction monitoring scan mode (MRM). The obtained fragment ions [S=C=NOH]^– for m/z 75 and [SO₄H]^– for m/z 97 were used in both scan modes to reveal the masses of the GSL precursor ions [M-H]^– which were further validated by the mostly known chromatographic behavior of the resulting intact GSL. The feasibility of the strategy was first demonstrated using crude extracts of broccoli. The tandem mass spectrometric experiments in negative ion ESI proved to be sensitive and selective enough to rapidly examine the GSL profiles even of crude plant extracts. The results adequately characterize the target differences between various GSL distributions in vegetables induced by treatment of methyl jasmonate.     

Electrochemical Determination of Phenothrin in Agricultural Formulations, Vegetables, and Storage Bags of Wheat and Rice by Differential Pulse Adsorptive Stripping Voltammetry (DP-AdSV)

An electroanalytical method has been developed for the determination of the pesticide phenothrin by differential pulse adsorptive stripping voltammetry on a hanging mercury drop electrode in universal buffer as supporting electrolyte. The best adsorption conditions were found to be pH 6.0, an accumulation potential of −0.6 V, and an accumulation time of 75 s. Effects of stirring rate, scan rate, pulse amplitude, and purge time were examined for the optimization of instrumental conditions. Calibration curve is linear in the range 2 × 10⁻⁹ to 2 × 10⁻⁷ mol l⁻¹ with a detection limit of 1.9 × 10⁻¹⁰ mol l⁻¹. The correlation coefficient and relative standard deviation were 0.995% and 1.1%. The method is applied to the determination of the phenothrin in agricultural formulations, vegetables, and storage bags of wheat and rice under Food Corporation of India’s storage system.     

Determination of endogenous concentrations of nitrites and nitrates in different types of cheese in the United States: method development and validation using ion chromatography

Nitrites and nitrates can be present in dairy products from both endogenous and exogenous sources. In the European Union (EU), 150 mg kg^–1 of nitrates are allowed to be added to the cheese milk during the manufacturing process. The CODEX General Standard for Food Additives has a maximum permitted level of 50 mg kg^–1 residue in cheese, while in the United States (U.S.) nitrates are unapproved for use as food additives in cheese. In order to be able to investigate imported cheeses for nitrates intentionally added as preservatives and the endogenous concentrations of nitrates and nitrites present in cheeses in the U.S. marketplace, a method was developed and validated using ion chromatography with conductivity detection. A market sampling of cheese samples purchased in the Washington DC metro area was performed. In 64 samples of cheese, concentrations ranged from below the method detection limit (MDL) to 26 mg kg^–1 for nitrates and no concentrations of nitrites were found in any of the cheese samples above the MDL of 0.1 mg kg^–1. A majority of the samples (93%) had concentrations below 10 mg kg^–1, which indicate the presence of endogenous nitrates. The samples with concentrations above 10 mg kg^–1 were mainly processed cheese spread, which can contain additional ingredients often of plant-based origin. These ingredients are likely the cause of the elevated nitrate concentrations. The analysis of 12 additional cheese samples that are liable to the intentional addition of nitrates, 9 of which were imported, indicated that in this limited study, concentrations of nitrate in the U.S.-produced cheeses did not differ from those in imported samples.     

Validation of a HPLC method for simultaneous determination of main organic acids in fruits and juices

A liquid chromatographic method for fast and simultaneous determination of tartaric, malic, ascorbic and citric acids was validated for further application to fruits and juices. Moreover, the organic acids content of commercial samples of fruits and juices were evaluated, as well as the ascorbic acid stability during the storage. Determination of organic acids was carried out using a liquid chromatograph coupled to a diode array detector, with reversed phase (C₁₈ column) and isocratic elution with 0.01 mol L⁻¹ KH₂PO₄ (pH = 2.60) mobile phase. The validation parameters showed efficiency, adequate linearity, relative standard deviation values between 0.4% and 2.3% (n = 10) for repeatability and from 1.2% to 5.0% (n = 18) for reproducibility, limits of detection (LD) were between 0.03 and 3.31 μg mL⁻¹ and quantification (LQ) were between 0.10 and 11.03 μg mL⁻¹, recovery rates were between 82% and 110%, for two levels. In addition, the method is fast (10 min) and generates low and non-toxic residues. The values found for vitamin C were about 10 times above the values declared at the package. Ready to drink juices have a composition similar to the fruit, concerning to organic acids, except for the powder juice, in which only ascorbic and citric acids were found, for all tastes. After opening the package, a decrease of 14.0% and 27.0% in ascorbic acid content was observed for orange powder and ready to drink juices, respectively.     

Multiresidue method for determination of pesticides in fruits and vegetables by GC/MS (SCAN) and LC/MS (SIM)

A rapid multiresidue method has been developed for determination of many pesticides in fruits and vegetables using GC/MS and LC/MS. The method of analysis was the same as that reported by Kakimoto et al. in 2003 except for the use of LC/MS. Good recoveries in the range of 70-120% were obtained for 70 (32 by GC/MS, 38 by LC/MS) of 113 pesticides spiked at 0.1 microg/g into fruits and vegetables. For screening purposes, the method could be appiled to 82 pesticides. Considering the report by Kakimoto et al. in 2004, 177 pesticides were suitable for screening by this method. The limits of detection were 0.001-0.015 microg/g (by GC/MS) and < 0.001-0.010 microg/g (by LC/MS). The calibration curves were linear for most pesticides, with correlation coefficients of 0.976-1.000 (by GC/MS) and 0.968-1.000 (by LC/MS). The values obtained for fruits and vegetables naturally contaminated with pesticides by this method were nearly equal to those by the official method.     

Determination of As(III) and As(V) in oilseeds by chronopotentiometric stripping analysis: development of a method

Chronopotentiometric stripping analysis (CSA) was used for selective determination of As(III) and As(V) in different oilseeds. After the optimization of experimental parameters an appropriate procedure for sample pretreatment was developed. A detection limit of 2 microg/dm3 for As(III) was obtained with an electrolysis time of 600 s. This method was used for arsenic determination in sunflower, pumpkin, and flax seed, as well as for soy flakes and almond.     

邻-（2,3,4,5,6-五氟苄基）羟胺盐酸盐衍生-HPLC法测定果蔬中甲醛含量

通过邻-（2,3,4,5,6-五氟苄基）羟胺盐酸盐与甲醛衍生,建立了测定果蔬中甲醛含量的高效液相色谱法。样品在温度为70℃超声波条件下直接提取衍生30 min,经离心纯化后液相色谱检测,外标法定量。优化的色谱条件为:Eelipse XDB-C₁₈柱（4.6 mm×250 mm,5μm）;流动相为乙腈和水（70∶30,v/v）,流速1.0 m L/min,柱温40℃,检测波长210 nm。结果表明,该方法的检出限可达到0.114 mg/kg,在0.57⁵7 mg/kg范围内呈良好的线性关系,平均回收率为82.3%⁹4.1%,相对标准偏差为4.0%⁷.1%（n=6）。该方法样品前处理简便,稳定性好,检测限低,适合果蔬中甲醛的快速定量检测。      

Quantification of organophosphate insecticides and herbicides in vegetable samples using the “Quick Easy Cheap Effective Rugged and Safe” (QuEChERS) method and a high-performance liquid chromatography-electrospray ionisation-mass spectrometry (LC-MS/MS) technique

A Quick Easy Cheap Effective Rugged and Safe (QuEchERS) extraction was developed and followed by selective analysis using a liquid chromatography-mass spectrometry method for the quantification of eighteen pesticides in vegetable samples. This method was accurate (?99.5%), and it exhibited limits of detection and quantification values in the 0.006-0.091 and 0.020-0.314 μg kg⁻¹ ranges, respectively. Furthermore, the coefficients of variations (?0.9999) were less than 1% at the low μg kg⁻¹ end of the method. Mean recoveries ranged between 94% and 102%, and relative standard deviations were below 10%. Based on these results, the methodology was proven to be highly efficient, robust, and suitable for monitoring the maximum residue limits (MRL) compliance of a wide range of commodity/pesticide combination. This method was successfully applied to the analysis of vegetable samples that were collected from different government farmers’ markets and street shops in urban areas. The presence of target pesticides was found in the range of 0.016 and 50.85 μg kg⁻¹.     

Extending the theory of planned behavior to understand consumer purchase behavior for organic vegetables in Brazil: The role of perceived health benefits,perceived sustainability benefits and perceived price

This study explores the factors that influence consumer purchase intention and behavior for organic vegetables in Brazil. A conceptual model based on the theory of planned behavior (TPB) was developed. In addition to all standard relationships in the TPB, the candidate variables of perceived health benefits, perceived sustainability benefits, and perceived price were added to the TPB-based model. Attitude was expected to mediate the relation between perceived health benefits and intention and the relation between perceived sustainability benefits and intention. Perceived price was expected to moderate the relation between intention and behavior. An online survey was conducted, resulting in a sample size of 504 participants. Data were analyzed by partial-least squares structural equation modeling. The results indicate that intention and perceived behavioral control influence the purchase behavior for organic vegetables, with intention presenting the strongest impact on behavior. Attitude has the strongest impact on consumer intention to purchase organic vegetables, followed by perceived behavioral control and subjective norms. The results also indicate that attitude mediates the relations between perceived health benefits and intention and perceived sustainability benefits and intention. Perceived price moderates the relationship between intention and behavior. Based on the results, managerial implications are presented.     

Determination of theobromine,theophylline and caffeine in cocoa samples by a high-performance liquid chromatographic method with on-line sample cleanup in a switching-column system

A simple reversed-phase high-performance liquid chromatographic method was developed for the determination of theobromine, theophylline and caffeine in cocoa samples. In the sample cleanup step, the procedure involves an on-line solid-phase extraction of analytes from cocoa samples into a home-made dry-packed pre-column with ODS-C₁₈ using a column-switching system. The separation was performed on a C₁₈ Nova-Pak column (150 mm × 3.9 mm, 4 μm) using a mobile phase consisting of a solution of 20% of methanol in water under isocratic conditions, at a flow-rate of 1.4 ml/min. The validation method revealed quantitative recoveries (>95.0%) with a coefficients of variation <3.2% and it also provided a good precision for data validation. The overlap of sample cleanup, analysis and recondition of the precolumn increases the sample throughput to 8 samples/h. Furthermore, the proposed method was successfully applied to analysis of cocoa samples “Trinitario”, “Forastero” and “Criollo” grown in different seasons of the year and fermented for 3 and 7 days, respectively. The results showed a slight reduction in the theobromine and caffeine content according to the fermentation times. In the same way, the theobromine/caffeine ratio was assessed, with the purpose of establishing a correlation with the genotype of the studied samples.     

A rapid High Performance Liquid Chromatographic (HPLC) method for the simultaneous determination of seven UV filters found in sunscreen and cosmetics

A rapid High Performance Liquid Chromatographic (HPLC) method was developed for the simultaneous determination of seven Ultra Violet (UV) filters most commonly found in cosmetics and sunscreen. The object of the method development was to provide a reliable rapid method, that would simultaneously separate a combination of the UV Filters, most commonly found in cosmetics and sunscreen products, utilizing a minimum of environmentally friendly solvents. The compounds separated were: benzophenone 3 (BZ3), methylbenzildene camphor (MBC), octyl dimethyl PABA (ODP), octocrylene (OCR), octyl methoxycinnamate (OMC), butyl – methoxydibenzoylmethane (BDM) and octyl salicylate (OS). An adjusted mobile phase consisting of ethanol and 1% acetic acid, combined with a Thermo Hypersil C₁₈ BDS 3 micron column resulted in a method, which allowed the analysis of the seven compounds in seven minutes. The proposed method was validated utilising the International Congress on Harmonisation (ICH) and the Food and Drug Administration (FDA) guidelines. All parameters examined were found to be well within the stated guidelines.