Organophosphorus pesticide residues in Greek virgin olive oil: levels,dietary intake and risk assessment

The occurrence of organophosphorus pesticide (OPs) and their metabolite residues was investigated in 167 samples of Greek virgin olive oil during a 2-year (2004–2005) sampling campaign. A total of 30.5% of samples contained detectable residues, although only one sample contained dimethoate residues above the maximum residue limit. Among the seven detected OPs, fenthion and fenthion sulfoxide residues were detected in 10.8 and 14.4% of the samples, respectively, at levels of 0.003–0.61 mg kg^?1. Dimethoate was detected in 10.2% of the samples at 0.003–0.057 mg kg^?1. The acute dietary risk assessment was undertaken by determining the national estimated short-term intake (NESTI); for chronic dietary risk assessment, the national theoretical maximum daily intake (NTMDI) and national estimated daily intake (NEDI) were calculated. The estimated intakes (NESTI and NEDI) of each pesticide were <7 and <0.86% of the corresponding acute reference doses (ARfDs) and acceptable daily intakes (ADIs), respectively. A cumulative risk assessment was performed using the hazard index (HI) and toxicity equivalence factor (TEF), taking into account that OPs share the same toxicological mechanism. The determined HI and TEF values were found to represent only a small portion of the respective ADIs or ARfDs. These results indicate that there is neither acute nor chronic risk for the Greek population through olive oil consumption.     

Pigments in Greek virgin olive oils: occurrence and levels

Fifty‐two samples of virgin olive oil from various regions of Greece were examined for the presence and levels of chlorophyll and carotenoid pigments using normal phase liquid chromatography and spectrometry. Pheophytin α (Pheo α) was the main pigment in all the oils examined (>10 mg kg^?1 in more than 70% of samples). Two pheophytin α derivatives (peaks A and B), eluted close to Pheo α, may potentially be used to examine handling conditions and length of storage of oil until analysis. Analysis of 25 Greek commercial oils obtained from retail stores verified the above observations. Chlorophyll α may be present in a virgin olive oil just after production. Its absence should not be exclusively attributed to cultivar characteristics or extraction conditions, since pheophytinisation occurs rapidly. Lutein content varied between 0.2 and 3.9 mg kg^?1 and β‐carotene content from 0.4 to 5.1 mg kg^?1. The lutein/β‐carotene ratio was characteristic (<1) for samples from Koroneiki, the major Greek cultivar for oil production. The total Pheo α (Pheo α + peak A + peak B)/total carotenoid (lutein + β‐carotene) ratio ranged between 2 and 11 owing to prevailing green hues. This ratio may be used as an indicator of oil typicality along with other analytical parameters. © 2001 Society of Chemical Industry     

Pesticide residue assessment in different types of olive oil and preliminary exposure assessment of Greek consumers to the pesticide residues detected

In this study the occurrence and levels of multi-class pesticides in different types of virgin olive oil quality and origination were determined and the contribution of olive oil in the chronic risk of pesticide residues consumption in the Mediterranean diet was estimated. For this purpose, a multiresidue method for the determination of 35 pesticides in olive oil was evaluated and applied to a total number of 100 olive oil samples. Ten percent of the samples produced from fruits of conventional cultivations contained no detectable residues whereas in the rest samples were detected residues of 20 insecticides. The highest detection rates were observed for the residues of fenthion, dimethoate and endosulfan. The highest occurrence and levels of pesticides were observed in extra virgin olive oil whereas results pointed that residues in olive oil from variety of olives with high oil yield may be higher. Furthermore, olive oil from organic cultivations could be contaminated with pesticide residues and/or contain low levels of pesticide residues that are not registered for use in olive cultivations. For there were multiresidues of pesticides present in olive oil, there is no zero risk in consumption of olive oil. However, the exposure of olive oil consumers to each detected residue is far below the acceptable daily intake (ADI).     

Organophosphorus pesticide residues in milled rice ( Oryza sativa ) on the Chinese market and dietary risk assessment

The present study investigates the occurrence of acetylcholinesterase (AChE)-inhibiting organophosphorus (OP) pesticide residues in milled rice samples obtained form local markets in China during the period 2004–2006 and estimates their cumulative exposure. Concentrations of OP pesticides were determined by gas chromatography with flame photometric detection (GC–FPD). The results showed that 9.3% of the samples contained detectable residues of at least one of the seven target OP pesticides (chlorpyrifos, dichlorvos, omethoate, methamidophos, parathion-methyl, parathion and triazophos) mainly used for agriculture in China, with concentrations ranging 0.011–1.756 mg kg^?1. Rice consumption data was obtained from an individual food consumption survey. Relative potency factors (RPFs) for each pesticide were calculated with methamidophos as the index compound (IC), using 1- or 2-year chronic non-observed adverse effect levels (NOAEL) for AChE inhibition, mostly in rat brain, obtained from international evaluations of pesticides. Exposure to AChE-inhibiting pesticides for the population above 7 years old at P99.9 represented 52–94.5% of the acceptable daily intake (ADI) expressed as methamidophos. Estimated exposure for children aged 2–4 and 4–7 years at P99.9 were 119 and 104.3% of the ADI level, respectively. This study suggests that a yearly monitoring program for OP pesticide residues and strict implementation of the national safety standard for milled rice is necessary.     

Survey of organophosphorus pesticide residues in virgin olive oils produced in Chile

Dimethoate, diazinon, parathion methyl, pirimiphos methyl, malathion, fenthion, chlorpyriphos, methidathion and azinphos methyl were determined in 71 olive oil samples produced in Chile from different varieties of olives (arbequina, frantoio, picual, lechino and blend) at three different harvest periods (2007, 2008 and 2009). The target pesticides were determined using a validated analytical method based on microwave-assisted liquid–liquid and solid-phase extraction with subsequent GC–FPD detection and GC–MS/MS for confirmation purposes. In 79% of the samples, five of the nine pesticides tested were detected with a frequency of one pesticide per sample. The highest detection rates were observed for the residues of chlorpyriphos and diazinon. The average concentration of chlorpyriphos, diazinon, azinphos methyl and methidathion were 0.084, 0.057, 0.024 and 0.010 µg g^?1, respectively. Higher contents of organophosphorus pesticides (OPPs) were found in regions where intensive agriculture is practiced. However, the levels of OPPs were reassuringly low and indicate that olive oil produced and exported from Chile does not currently represent any risk for consumers.     

慈溪市葡萄农药残留膳食摄入风险评估

目的开展葡萄农药残留膳食摄入风险评估工作,为葡萄食用、农药残留监管和农药最大残留限量提供科学依据。方法在2008~2013年对慈溪市生产的169批次葡萄样品进行了23种农药残留定量检测分析,分别用%ADI和%ARf D进行农药残留慢性膳食摄入风险评估和急性膳食摄入风险评估,用ADI值、大份餐和体重等参数计算最大残留限量估计值(eMRL)。结果近6年葡萄农药检出率为24.85%,超标率为0.59%。检出的7种农药慢性膳食摄入风险(%ADI)为0.010%~1.34%,平均值为0.23%;急性膳食摄入风险(%ARf D)为0.98~28.30%,平均值为8.90%。葡萄农药残留慢性膳食摄入风险和急性膳食摄入风险均很低。结论检出的7种农药最大残留限量(MRLs)均过严,建议将敌敌畏、乙酰甲胺磷、百菌清、氯氟氰菊酯、氯氰菊酯、氰戊菊酯、腐霉利等7种农药的最大残留限量分别定为0.5、3.5、2.5、2.5、2.5、2.5、11 mg/kg。     

Survey of pesticide residues in table grapes: Determination of processing factors, intake and risk assessment

The differences in residue pattern between Italy and South Africa, the main exporters of table grapes to the Danish market, were investigated. The results showed no major differences with respect to the number of samples with residues, with residues being found in 54-78% of the samples. Exceedances of the European Union maximum residue limit (MRL) were found in five samples from Italy. A number of samples were rinsed to study the possible reduction of residues. For copper, iprodione, procymidone and dithiocarbamates a significant effect of rinsing was found (20-49% reduction of residues). However, no significant effect was found for organophosphorus pesticides and pyrethroids, whereas the number of samples with residues of benzilates, phenylamids and triazoles was insufficient to demonstrate any significant effects. An intake calculation showed that the average intake from Italian grapes was 3.9 µg day^-1 for pesticides and 21 µg day^-1 for copper. Correspondingly, the intakes from South African grapes were 2.6 and 5.7 µg day^-1, respectively. When the total exposure of pesticides from grapes were related to acceptable daily intake, expressed as the sum of Hazard Quotients, the exposure were approximately 0.5% for Italian samples and 1% for South African samples.     

2018—2021年陕西省市售水果中农药残留状况调查及膳食摄入风险评估

目的 调查分析陕西省市售水果中杀虫剂和杀菌剂类农药残留情况,评估当地居民通过摄入水果的农药残留暴露风险。方法 采集2018—2021年陕西省10个地市共6大类486份市售水果样品,依据国家风险监测工作手册《植物性样品中农药多组分残留的气相色谱-串联质谱（GC-MS）法测定的标准操作程序》和《植物性样品（含食用菌）中农药多组分残留的液相色谱质谱-串联质谱（LC-MS）法测定标准操作程序》对水果中13种杀虫剂和15种杀菌剂残留水平进行检测,依据GB 2763—2021《食品安全国家标准 食品中农药最大残留限量》评价多组分农药残留的检出和超标状况。采用点评估法对各类农药残留进行急性、慢性膳食暴露风险评估,通过食品安全指数模型对检出农药开展总体风险判定。结果 本次监测的28种农药除吡唑醚菌酯、恶霜灵、腈菌唑、异菌脲4种杀菌剂和灭线磷、灭蝇胺、氟氯氰菊酯3种杀虫剂未检出,其余21种农药均有不同程度的检出,检出率在0.77%~21.54%,共7份样品4种农药残留超标,超标率在0.28%~1.27%,且有禁用的高毒农药检出。核果类（39.24%）、热带及亚热带水果（28.33%）、柑橘类（26.47%）及仁果类（25.96%）水果的农药残留检出率较高,浆果类（2.54%）的超标率较高,且均存在多种农药联合使用的情况。各类农药的急性和慢性膳食暴露量均低于其健康指导值,单项农药的食品安全指数均小于1,水果总体食品安全指数小于1。结论 陕西省市售水果中农药残留检出率较高,但超标率较低,本次监测的水果膳食摄入风险在可接受范围内,整体安全质量良好。     

济南市市售蔬菜中农药残留及慢性膳食暴露风险评估

目的了解济南市市售蔬菜中农药残留情况,评估蔬菜中农药残留的慢性膳食暴露风险。方法对2010—2012年济南市市售蔬菜的农药残留情况进行分析,以2002年山东省居民营养与健康状况调查和中国居民膳食指南中推荐的蔬菜摄入量及JMPR制定的ADI为参数,应用国际每日膳食摄入评估法对济南市居民蔬菜中农药残留的慢性膳食暴露风险进行评估。结果共监测样品675份,有机磷类农药(乐果和乙酰甲胺磷)的检出率为3.93%(13/331),超标率为2.11%(7/331);拟除虫菊酯类农药(甲氰菊酯和氯菊脂)的检出率为9.91%(21/212),超标率为6.60%(14/212);氨基甲酸酯类农药(抗蚜威和异丙威)的检出率为7.58%(10/132),超标率为5.30%(7/132)。经评估各类农药的摄入量均小于ADI。结论济南市市售蔬菜农药残留量在安全限制之内,居民蔬菜中农药残留的慢性膳食暴露风险小,但农药残留超标现象普遍,应规范和加强农药的使用和管理。     

Unit to unit variation of pesticide residues options for acute dietary risk assessment

Within the context of the current UK policy for those commodities where the potential variability of residues in individual commodity units is taken into account, a variability factor nu , which reflects the ratio of a high level residue in the individual commodity unit to the corresponding composite residue level, is used. Data gathered from supervised industry trials in which individual items were analysed following treatment, although limited, show that variability is typically lower than that reflected by the default factors currently used and that the range of variability is reproducible over the limited range of different a.i./crop/method of application combinations investigated. In order to improve the accuracy of the acute dietary exposure estimate, the European Crop Protection Association (ECPA) proposes the following alternative to the current Tier I approach. The residue level input from a 'hot' unit within the dietary risk assessment should be determined using the highest composite sample residue from supervised field trials and a generic variability factor (nu) determined experimentally from supervised trials. The variability factor itself should be calculated as the 95th percentile level of the residue level found in an individual unit (or single serving portion for large crops) divided by sample mean for data produced from supervised trials. This would improve the accuracy of the Tier I approach and allow attention to be focused on particular a.i./crop/method of application combinations where the NESTI> acute RfD (based on a Tier I assessment) and generation of individual unit residue data for the particular outlet or other mitigation may be appropriate.     

青岛市市售蔬菜中农残特征及膳食暴露风险评估

目的 了解青岛市市售蔬菜中农药残留污染水平,为青岛市蔬菜食用安全提供科学依据。方法 2020—2022年,在青岛10个区市随机采集7大类680份蔬菜样品,检测并分析蔬菜样品中28种农药残留的特征,对被检出农药进行急性、慢性膳食暴露风险评估。结果 680份蔬菜样品中,农药检出率为9.71%（66/680）;超标率为2.79%（19/680）。共检出10种农药,检出率最高的为联苯菊酯4.50%（27/600）;共超标6种农药,超标率最高的为毒死蜱1.18%（8/680）。各类农药检出率与超标率间的差异均具有统计学意义（P<0.001）。7类蔬菜间的检出率差异具有统计学意义（P<0.001）,茄果类农残检出率最高（27.68%,31/112）,检出农残种类的数量最多（8种）。7类蔬菜中均有禁限用农药的分布。10个区市均有农残检出,除黄岛区、胶州市、平度市外均有超标现象。城阳区检出率为19.44%（7/36）,李沧区超标率为7.02%（4/57）,市北区检出农残种类的数量最多为7种。检出的各类农药的急性、慢性膳食暴露风险评估aHQ、cHQ均小于1。结论 青岛市市售蔬菜样品中仍有部分禁限用农药存在,但农药残留水平较低,居民通过膳食途径摄入蔬菜中农残的健康风险较小。要继续加强对禁限用农药的监督管理,最大限度降低食用蔬菜中农药残留对人体健康造成的风险。     

Direct analysis of glucuronidated metabolites of main olive oil phenols in human urine after dietary consumption of virgin olive oil

In the present study we report on a UPLC-MRM validated method for the simultaneous direct analysis of main glucuronidated metabolites of olive oil phenols: tyrosol, hydroxytyrosol and its O-methyl metabolite homovanillyl alcohol in human urine after dietary olive oil ingestion. The developed method was linear within the concentration range 20–2000 ng/mL with adequate recovery of analytes (>86%). Intra- and inter-day precision and accuracy were according to standard requirements for method validation criteria. Using the developed method, urinary concentrations and excretion rates of glucuronides of olive oil phenols were successfully estimated in an intervention study with 11 healthy volunteers supplemented with a dietary dose of virgin olive oil (VOO) (50 mL). Therefore, about 13% of the consumed olive oil polyphenols were recovered in 24-h urine, where 75% of them were in the form of glucuronides (3′- and 4′-O-hydroxytyrosol glucuronides, 4′-O-glucuronides of tyrosol and homovanillyl alcohol) and 25% as free compounds.     

Geographical classification of Greek virgin olive oil by non-parametric multivariate evaluation of fatty acid composition

Fatty acid compositional data for Greek virgin olive oils from 24 years of harvest and various regions and cultivars were evaluated using chemometric methods. Non-parametric discriminant analysis after proper transformation of the data seems to be a suitable approach to characterise the oils according to the geographical origin and may produce a scientific basis for the assignment of an ‘appellation d'origine’ trade mark.     

信阳茶叶农药残留检测及其风险评估

目的 了解信阳地区茶叶农药残留情况及其风险程度.方法 2013—2020年连续8年收集信阳地区茶叶样品132个,在同一年按照国家标准、农业行业标准等规定的农药测定方法进行测定.运用危害物风险系数法进行农残风险评估.结果 132个信阳茶叶样品中,检测出农药残留样品100个,农药残留检出率为75.76％,共检测到农药种类1...     

桃胶中多农药残留分析及风险评估

目的:研究桃胶中农药残留及风险。方法:基于液相色谱—串联质谱法(LC-MS/MS)建立桃胶中44种农药残留的定量分析方法,并对全国173份桃胶样品进行农药残留检测和风险评估分析。结果:基于LC-MS/MS农药残留检测方法的检出限(LOD)为0.05～1.80μg/kg,定量下限(LOQ)为0.20～2.42μg/kg,加标回收率为61.77%～119.48%。桃胶样品中共检出22种农药,农药总检出率为98.8%,平均每个样品检出农药次数为2.8次,苯醚甲环唑检出率最高(95%),其次是毒死蜱(54%)、多菌灵(34%)、呋虫胺(32%)、吡唑醚菌酯(19%)等。不同桃胶样品中苯醚甲环唑平均残留量最高为0.332 mg/kg,其次是呋虫胺(0.093 mg/kg)、多菌灵(0.061 mg/kg)、毒死蜱(0.033 mg/kg)。结论:桃胶中农药的残留与桃生产用药有关,其残留量总体处于低风险水平,推荐8—10月份采摘桃胶。     

Organophosphorus pesticide residues in market foods in Shaanxi area,China

The aim of this study was to investigate the organophosphorus (OP) pesticide residues in market foods (cereals, vegetables, and fruits) in the Shaanxi area of China. The concentrations of eight OP pesticides were determined by gas chromatography with flame photometric detection (GC-FPD). In 18 of 200 samples, five OP pesticides, including dichlorvos, dimethoate, parathion-methyl, pirimiphos-methyl and parathion, were found in concentrations ranging from 0.004 to 0.257 mg/kg. The mean levels of dimethoate in fruits and parathion in vegetables exceeded the maximum residue limits (MRLs) allowed by the Ministry of Health, of China. Other detectable OP pesticide residues levels were below their MRLs. Demeton, diazinon and sumithion were not found in any sample. The results provide important information on the current contamination status of a key agricultural area in China, and point to the need for urgent action to control the use of some excessively applied and potentially persistent OP pesticides, such as dimethoate and parathion.     

Characterisation of virgin olive oil of Italian olive cultivars: `Frantoio' and `Leccino', grown in Andalusia

Work was carried out on the characterisation of virgin olive oils from the main Italian cultivars, `Frantoio' and `Leccino', grown in two different locations in Andalusia: Mengibar (Jaén) and Cabra (Córdoba), with important differences in altitude. The study was carried out during the crop years 1999/2000 and 2001/2002. There were significant differences between the oils from both cultivars when grown in the different environments, Cabra close to the hills and Mengibar in the open at 280 m height. At higher altitude, the oils showed a greater content of oleic acid and higher stability, while in the open the oils had higher tocopherol and linoleic acid contents. For the phenolic compounds, the environment influenced each cultivar in different ways. Sensorial characteristics, showed significant differences between the oils from each cultivar and location. In general, the oils from Andalusia had higher levels of natural antioxidants, greater oxidative stability and more marked sensorial characters.     

Estimation of the dietary intake of pesticide residues, lead, cadmium, arsenic and radionuclides in France

Estimation of the dietary exposure of French consumers to 10 pesticides (omethoate, oxydemeton, phosalon, phosphamidon, triazophos, dicofol (op'+pp'), parathion ethyl, dichlorvos, procymidon and vinchlozolin), three heavy metals (lead, cadmium and arsenic) and three radionuclides (¹³⁴caesium, ¹³⁷caesium and ¹³¹iodine) from collected duplicate portion in mass catering establishments in 1998/1999 are reported, and compared with those from previous French studies as well as those from other countries. Dietary exposure estimates appear to be reassuring, in that Estimated Daily Intake (EDI) estimates are generally low, representing at maximum only 4% of the Acceptable Daily Intake (ADI) for pesticide residues and 28% of the Provisional Tolerable Weekly Intake (PTWI) for heavy metals. Moreover, none of the three radionuclides has been found in duplicate meals. When comparisons are possible, estimated dietary exposures for heavy metals are lower than those from previous French studies and similar or above those from other countries.     

农药残留加工因子及其在膳食暴露评估中的应用

从初级农产品到入口的食品通常需要各种加工处理,而加工过程会影响食品中的农药残留水平,从而影响来源于初级农产品检测数据的风险评估结果的准确性,因此在风险评估模型中纳入农药残留加工因子有助于真实反映农药残留膳食暴露风险。本文以常用的食品加工技术如清洗、去皮、烹调、榨汁、杀菌及其他相关技术为出发点,综述了典型的加工方式对食品中农药残留的影响以及目前相应的加工因子在农药残留暴露评估中的应用情况,为掌握食品中农药在加工过程中的残留动态、改进食品加工技术提供参考,也为农药残留膳食暴露评估提供依据,进而真实反映人群中农药残留的暴露风险。