马拉硫磷在莴笋中的残留行为及膳食摄入风险评估

2016年于湖南、山东等六地进行了马拉硫磷在莴笋中的规范性残留试验,建立了气相色谱-火焰光度检测器(GC-FPD)测定马拉硫磷在莴笋样品中的残留分析方法,并对我国各类人群的膳食摄入风险进行了评估。样品采用乙腈提取,丙酮置换净化、GC-FPD检测,结果表明:当马拉硫磷在莴笋全株、茎和叶中的添加浓度为0.02~8.0mg/kg时,其回收率在83%~108%之间,相对标准偏差(RSD)在1%~6%之间;马拉硫磷的最小检出量(LOD)为1.0×10~(-11)g,定量限(LOQ)均为0.02mg/kg。湖南和山东莴笋全株中马拉硫磷的消解动态试验结果显示,马拉硫磷的半衰期为1.75~2.27d,属于易降解农药;六地的最终残留试验结果表明,最后一次施用马拉硫磷5、7、10d后,莴笋茎中的最终残留量≤0.509mg/kg,莴笋叶中的最终残留量≤5.670mg/kg。莴笋的膳食风险评估结果显示,我国各类人群对马拉硫磷在莴笋茎和莴笋叶中的国家估计每日摄入量(NEDI)分别为0.115~0.445μg/(kg·d)和1.042~5.583μg/(kg·d),风险商值(RQ)分别为0.000 4~0.001 5和0.003 5~0.018 6,证明马拉硫磷在莴笋中的长期膳食摄入风险较低。推荐我国马拉硫磷在莴笋茎和莴笋叶上的最大残留限量值(MRL)分别为1 mg/kg和10mg/kg。     

Harmonised pesticide risk trend indicator for food (HAPERITIF): The methodological approach

To provide a harmonised European approach for pesticide risk indicators, the Sixth EU Framework Programme recently financed the HAIR (HArmonised environmental Indicators for pesticide Risk) project. This paper illustrates the methodology underlying a new indicator-HAPERITIF (HArmonised PEsticide RIsk Trend Indicator for Food), developed in HAIR, for tracking acute and chronic pesticide risk trends for consumers. The acute indicator, HAPERITIF(ac), is based on the ratio between an estimated short-term intake (ESTI), calculated as recommended by the World Health Organisation (WHO), and the acute reference dose (ARfD); the chronic indicator HAPERITIF(chr) is based on the ratio between an estimated daily intake (EDI) and the admissible daily intake (ADI). HAPERITIF can be applied at different levels of aggregation. Each level gives information for proper risk management of pesticides to reduce the risk associated with food consumption. An example of application using realistic scenarios of pesticide treatments on a potato crop in central-northern Italy is reported to illustrate the different steps of HAPERITIF.     

山东主产区苹果和梨中农药残留风险因子排序

风险排序是风险评估或管理中的重要一环,是对风险因子进行排序从而确定管控优先顺序的重要手段。2014-2015年连续两年对山东省主产区苹果、梨进行102种农药残留风险监测。利用农产品质量安全风险排序系统对苹果和梨中检出的农药残留进行风险得分计算和排序。结果显示:苹果中检出27种农药,风险得分较高的有三唑磷、毒死蜱、氰戊菊酯、联苯菊酯、吡虫啉、戊唑醇、唑螨酯7种农药;梨中检出37种农药,风险得分从高到低分别有氧乐果、克百威、水胺硫磷、苯醚甲环唑、毒死蜱、唑螨酯、灭多威、氟硅唑8种农药。建议对上述风险得分较高的农药予以优先管控。     

食品中农药残留风险评估述评

综合分析近5年文献报道和2021—2022年各省 (市、区) 市场监督管理部门蔬菜水果中农药残留监测检出情况,发现文献报道和各级市场监督管理部门发布情况大致相符：蔬菜中农药残留总的超标率为5.09%,其中豆类蔬菜超标率最高 (24.93%),其余依次是鳞茎类 (22.39%)、根茎类和薯芋类 (8.53%)、叶菜类 (6.91%)、瓜果类 (4.29%) 及茄果类蔬菜 (3.00%)。农药残留超标率较高的蔬菜有豇豆、韭菜、芹菜、普通白菜及辣椒等;豇豆中主要超标农药是灭蝇胺,超标样品占检测豇豆样品的8.27%;韭菜中腐霉利残留量超标率最高,按GB 2763―2021标准[残留限量(MRL) 0.2 mg/kg],超标率为15.97% [按最新标准GB 2763.1―2022 (MRL5.0 mg/kg)则为2.21%],韭菜中其他残留超标农药包括毒死蜱、甲胺磷、氯氟氰菊酯/高效氯氟氰菊酯、甲拌磷、多菌灵、啶虫脒等,基本涵盖了蔬菜中残留超标的农药品种;芹菜和普通白菜中残留超标的农药主要是毒死蜱,超标样品分别占检测芹菜和普通白菜样品的4.26%和1.79%;姜和辣椒中主要超标农药是噻虫胺,超标样品分别占检测辣椒和姜样品的15.42%和3.81%。水果中农药残留总的超标率为6.33%,其中超标率最高的是热带和亚热带水果类 (31.50%),其余依次是柑橘类 (3.15%)、浆果和其他小型水果类 (2.19%)、核果类 (1.58%) 和仁果类 (0.78%)。分析造成我国蔬菜水果中农药残留超标的直接原因主要有两个：一是未登记农药品种违规使用的情形较多,二是不合理用药,超出使用剂量、多频次使用及未遵守安全间隔期等原因造成。此外,未及时评估修订不合理的标准也可能对农药残留超标统计产生明显影响,如韭菜中腐霉利残留的评价即属于此种情况。     

三唑磷残留的膳食摄入与风险评估

以FAO/WHO农药残留专家联席会议(JMPR)提出的农药残留膳食摄入和风险评估原理及方法为基础,引入食物摄入量调整系数、急性风险安全界限和消费者保护水平,建立了适用于我国现阶段技术及数据积累水平的膳食摄入风险和消费者保护水平评估方法。基于现有的三唑磷残留试验数据,计算得到国家估计每日摄入量(NEDI)、国家估计短期摄入量(NESTI)及风险商(RQ)。结果表明,我国各类人群的三唑磷慢性膳食摄入风险均属于不可接受水平,RQ值达2.1~6.2;其在苹果、甘蓝、稻米和小麦粉中的残留还具有不可接受的急性膳食摄入风险,RQ值分别为14.2~34.3、8.2~17.0、2.9~4.7和2.8~4.0。通过计算理论最大每日摄入量(TMDI)和理论最大短期摄入量(TMSTI)评估了现有最大残留限量(MRL)标准对消费者的保护水平。结果显示,我国现有的7项三唑磷 MRL 标准对2~10岁人群慢性膳食摄入风险的保护均未达到可接受水平,消费者保护水平(CPL)只有0.6~0.8;甘蓝、节瓜、柑橘和苹果中的 MRL 标准对儿童(4~6岁)和成人(30~44岁)以及荔枝中的 MRL 标准对儿童的急性风险保护也未达到可接受水平, CPL 分别只有0.2~0.4、0.3、0.1~0.2、0.1~0.2和0.6。建议:将柑橘(果肉)和荔枝(果肉)的 MRL 值分别修订为0.02和0.05 mg/kg;调整三唑磷在水稻上使用的良好农业规范(GAP),延长其安全间隔期至60 d;撤销三唑磷在十字花科蔬菜、节瓜及苹果上的使用登记,并将其在蔬菜、苹果及其他未登记使用的动植物产品中的 MRL 标准设定为0.01 mg/kg或其检出限附近;同时对三唑磷的违规使用应进行重点监管。     

Pesticide residues in food--acute dietary exposure

Consumer risk assessment is a crucial step in the regulatory approval of pesticide use on food crops. Recently, an additional hurdle has been added to the formal consumer risk assessment process with the introduction of short-term intake or exposure assessment and a comparable short-term toxicity reference, the acute reference dose. Exposure to residues during one meal or over one day is important for short-term or acute intake. Exposure in the short term can be substantially higher than average because the consumption of a food on a single occasion can be very large compared with typical long-term or mean consumption and the food may have a much larger residue than average. Furthermore, the residue level in a single unit of a fruit or vegetable may be higher by a factor (defined as the variability factor, which we have shown to be typically x3 for the 97.5th percentile unit) than the average residue in the lot. Available marketplace data and supervised residue trial data are examined in an investigation of the variability of residues in units of fruit and vegetables. A method is described for estimating the 97.5th percentile value from sets of unit residue data. Variability appears to be generally independent of the pesticide, the crop, crop unit size and the residue level. The deposition of pesticide on the individual unit during application is probably the most significant factor. The diets used in the calculations ideally come from individual and household surveys with enough consumers of each specific food to determine large portion sizes. The diets should distinguish the different forms of a food consumed, eg canned, frozen or fresh, because the residue levels associated with the different forms may be quite different. Dietary intakes may be calculated by a deterministic method or a probabilistic method. In the deterministic method the intake is estimated with the assumptions of large portion consumption of a 'high residue' food (high residue in the sense that the pesticide was used at the highest recommended label rate, the crop was harvested at the smallest interval after treatment and the residue in the edible portion was the highest found in any of the supervised trials in line with these use conditions). The deterministic calculation also includes a variability factor for those foods consumed as units (eg apples, carrots) to allow for the elevated residue in some single units which may not be seen in composited samples. In the probabilistic method the distribution of dietary consumption and the distribution of possible residues are combined in repeated probabilistic calculations to yield a distribution of possible residue intakes. Additional information such as percentage commodity treated and combination of residues from multiple commodities may be incorporated into probabilistic calculations. The IUPAC Advisory Committee on Crop Protection Chemistry has made 11 recommendations relating to acute dietary exposure.     

Towards the construction of a resistance risk evaluation scheme

Pesticide resistance management needs an indication of the risk of resistance developing in pests against pesticide applications. This paper describes an evaluation system for the ranking of these risks. The term pests includes all organisms which are causing economic damage in agriculture, including weeds and plant pathogens. The system distinguishes six broad risk categories. It is based on expert judgement of answers to a maximum of ten questions on crop husbandry, pest biology and pest control. The system has been developed for registration purposes in The Netherlands, and is currently being discussed within the European and Mediterranean Plant Protection Organisation (EPPO). ©1997 SCI     

中国食品中农药MRL标准对急性膳食暴露评估需求的研究

为了评估当前国内相关农药最大残留限量(MRL)标准及我国居民的急性膳食暴露风险水平,采用FAO/WHO农药残留专家联席会议(JMPR)推荐的农药残留急性膳食暴露评估方法,利用我国居民大份额膳食消费数据、国内登记农药的规范残留试验数据和JMPR推荐的农药毒理学数据,对我国普通人群、0~6岁儿童和育龄妇女的农药残留摄入情况进行了急性膳食暴露评估。结果表明:白菜中的虫螨腈和丙森锌、甘蓝中的高效氯氰菊酯和灭多威对三类人群的国家估算急性暴露水平(NESTI)均大于急性参考剂量(ARf D);香蕉中的氟硅唑对0~6岁儿童和普通人群的NESTI分别为ARf D值的300%和160%;苹果中的二氰蒽醌、甘蓝中的高效氯氟氰菊酯、花椰菜中的阿维菌素及番茄中的丙森锌仅对0~6岁儿童有较高的急性膳食暴露风险;儿童相比其他人群摄入农药残留的急性膳食暴露风险更高、概率更大。建议我国采取相应的风险管理措施,降低农药残留摄入的急性膳食风险,同时尽快完善短期膳食消费数据库和农药残留数据库,在制定农药MRL标准时进行相应的急性膳食暴露评估,以保障消费者的农药急性膳食暴露风险在可接受水平。     

Variability of pesticide residues in crop units

The results of 89 new field trials and 11 supervised trials were considered, together with 91 sets of residue data evaluated earlier. The datasets consisted of 22,643 valid residue data. As all variability factors calculated from individual sample sets are affected by the uncertainties of sampling and analysis, the average of the P(0.975)/R(ave) (97.5th percentile of the residue population divided by the average residues in the lot) values gives the best estimate for the variability factor. The Harrell-Davis (H-D) method gave an average value of 2.89 for the variability factor for all samples, while the average variability factors obtained from samples derived from the new field and supervised trials were 2.8 and 2.7 with the IUPAC and H-D methods respectively. The number of residue values below the LOQ in a sample set significantly affects the observed variability factors. It was found that datasets containing over 20% non-quantifiable residues might not reflect the true variability of the residues. Mixing of treated and non-treated commodities may significantly increase the apparent variability. Consequently, only datasets of known origin and consisting of well-quantifiable residues should be used for estimation of the variability factor. Samples taken from marketed lots may not represent a single lot, and thus they have limited value in estimating the variability factor. The large number of residue data confirms the applicability of the default variability factor of 3 adopted by the FAO/WHO for deterministic estimation of the acute intake of pesticide residues.     

高效氯氰菊酯和吡丙醚在芥蓝中的残留消解及膳食暴露风险评估

为明确高效氯氰菊酯和吡丙醚在芥蓝上施用后的残留行为和膳食暴露风险, 研究基于规范田间残留试验、目标农药在芥蓝上残留分析方法, 得到芥蓝中2种农药的残留水平, 结合我国膳食结构不同性别/年龄组食物消费量及体重数据评估了高效氯氰菊酯和吡丙醚对各类消费人群的长期和短期膳食摄入风险。结果表明:高效氯氰菊酯和吡丙醚分别在0.01~1.0 mg/L和0.005~1.0 mg/L范围内线性关系良好, 决定系数(R2)≥0.996 7。在3个添加水平下, 芥蓝中2种农药的平均回收率为70.6%~113.4%, 相对标准偏差(RSD)为0.5%~8.5%, 定量限均为0.01 mg/kg。10%高氯·吡丙醚微乳剂以推荐高剂量施药, 高效氯氰菊酯和吡丙醚在芥蓝中的消解符合一级动力学, 半衰期分别为3.9~10.1 d和4.8~6.3 d。最终残留试验结果表明, 最后一次施药3、5、7、10 d后, 芥蓝中高效氯氰菊酯的最终残留量≤0.904 mg/kg, 吡丙醚的最终残留量≤0.202 mg/kg。膳食风险评估表明, 我国不同人群的长期慢性暴露风险最大值为27.26%;短期急性暴露风险最大值为67.17%, 表明对不同年龄段、不同性别人群健康不会产生不可接受的风险。     

草莓中吡虫啉和氟硅唑残留的膳食暴露风险

为明确吡虫啉和氟硅唑在草莓上施用后可能产生的膳食暴露风险,进行了规范的田间残留试验及对不同人群的膳食风险评估。结果表明:保护地栽培条件下,吡虫啉、氟硅唑在草莓上的消解速率符合一级动力学方程,半衰期分别为6.3 d和9.9~11.5 d。10%吡虫啉可湿性粉剂(WP)分别按有效成分37.5和56.25 g/hm2剂量于草莓果实为成熟个体一半大小时开始施药,共施2~3次,每次间隔7 d,于末次施药后3、5、7、10 d时分别采样测定,草莓中吡虫啉的残留量在0.022~0.16 mg/kg之间;400 g/L的氟硅唑乳油(EC)分别按有效成分45和67.5 g/hm2剂量于草莓果实为成熟个体一半大小时开始施药,共施2~3次,每次间隔7 d,于末次施药后3、5、7、10 d时分别采样测定,氟硅唑在草莓中的残留量为0.079~0.30 mg/kg。基于此残留试验数据、各类食物的日平均膳食摄入量及每日允许摄入量(ADI),计算得到中国各类人群中吡虫啉和氟硅唑暴露的风险商(RQ)。结果表明:草莓中吡虫啉和氟硅唑的急性风险商(ARQ)分别为其急性参考剂量(ARfD)的0.18%~1.0%和10%~37.7%,不存在不可接受的急性膳食暴露风险;草莓中吡虫啉和氟硅唑的慢性风险商(CRQ)分别为其ADI值的18.6%~85.3%和68.3%~316.4%,其中氟硅唑对2~4岁幼童的暴露风险超过100%,存在明显风险,但草莓中的氟硅唑对其全膳食暴露风险的贡献率不超过3.2%,并非其主要风险源;两种农药对其他暴露人群均不存在明显膳食风险。中国尚未制定草莓中吡虫啉和氟硅唑的最大残留限量(MRL)值,本研究推荐的吡虫啉和氟硅唑的MRL值对消费者长期慢性暴露风险的保护水平(CPLc)分别为18~109倍和2~13倍,短期急性暴露风险的保护水平(CPLa)分别为121~725倍及6~36倍,对消费者的保护水平均较高。建议:草莓中吡虫啉和氟硅唑的MRL值均可定为0.5 mg/kg,安全间隔期可分别为3 d和5 d;但对于2~4岁幼童,应充分关注氟硅唑对其的慢性膳食暴露风险。     

环氟菌胺在小麦生态系统中的残留消解及膳食风险评估

建立了环氟菌胺在小麦植株和麦田土壤中的残留检测方法, 并对其在小麦中的残留量进行了膳食摄入评估?样品中环氟菌胺经乙腈提取, 氨基固相萃取柱净化, 气相色谱检测, 外标法定量?结果表明:在0.02~10 mg/kg添加水平下, 环氟菌胺在小麦植株?小麦籽粒和土壤中的平均回收率在78%~119%之间, 相对标准偏差在0.63%~14%之间?小麦植株?小麦籽粒和土壤中环氟菌胺最低检测浓度(LOQ)均为0.02 mg/kg?环氟菌胺在小麦植株中的消解符合一级动力学方程, 半衰期为1.5~5.1 d?按推荐有效剂量132 g/hm2施药, 在30~50 d采收间隔期环氟菌胺的残留量均<0.2 mg/kg?环氟菌胺的普通人群国家估计每日摄入量(NEDI)是0.002 77 mg, 占日允许摄入量(ADI)的6.93%左右, 认为对一般人群健康不会产生不可接受的风险?     

欧盟、美国和日本加工农产品中农药残留评估现状

本文介绍了欧盟、美国和日本评估加工农产品中农药残留的数据要求和试验准则,以及开展膳食摄入风险评估和推荐农药最大残留限量(MRL)的方法,汇总了用于农药残留评估的加工农产品及其分类,分析了加工农产品中农药MRL制定现状,为进一步提高我国相关领域技术提供借鉴。比较分析结果表明,欧盟和美国在农药登记资料要求中明确提出了加工试验数据要求并且制定了相应的试验准则,美国在试验准则中描述了加工农产品中农药MRL的推荐原则;美国和日本制定了一定数量的加工农产品中农药MRL,欧盟建立了适用于监管农药MRL的加工因子数据库;欧盟、美国和日本均在相关法规中规定了加工农产品中农药残留的合规性判定。     

苯醚甲环唑在三七中的残留及其膳食风险评估

通过田间试验和气相色谱(GC-ECD)检测,研究了苯醚甲环唑在三七中的残留消解动态以 及三七茎叶对其的吸收、转运与分布特性。结果表明:苯醚甲环唑在三七植株中的半衰期为12.3~12.8 d;叶面施药后,其可被三七茎叶吸收并迅速向下传导至根部,且主要集中在须根中。苯醚甲环唑在三七不同部位之间的最终残留量存在差异,依次为花>须根>块根。于三七病害发病初期 (通常在三七开花前的营养生长期)施用苯醚甲环唑10%水分散粒剂,用量为有效成分67.5 g/hm2, 施药4次,间隔期为7 d,距最后1次施药后间隔28 d收获的三七块根中苯醚甲环唑的残留量RQ)仅为0.21%,处于安全水 平。建议在使用苯醚甲环唑10%水分散粒剂防治三七上的病害时,用药量为有效成分67.5 g/hm2, 最多施用3次,安全间隔期为28 d。     

农药职业健康风险评估方法

农药职业健康风险评估是评价农药对使用者和再进入施药区域劳动者健康危害的方法体系。根据国际风险评估的原理和流程,主要介绍了农药职业健康风险评估的方法,即采用安全剂量与不同场景农药暴露量的比值来评估非遗传毒性农药的健康风险。并阐述了暴露模型、出发点和不确定因子等概念及其运用。最后,从建立符合中国国情的风险评估方法、基础数据库及加快农药毒理学良好实验室(GLP实验室)建设等几方面,就我国应该如何开展农药职业健康风险评估工作提出了可行性建议。     

化学计量学在农药残留分析中的应用与进展

本文对近几年来化学计量学方法在农药残留分析测试中的应用进行了评述．指出了化学计量学在农药残留分析中的重要性及应用前景。     

基于点评估方法的渤海湾产区苹果中农药残留膳食暴露风险研究

为评估渤海湾产区苹果中主要农药的残留情况及其产生的风险,在山东、辽宁及河北3个主要省份的150个生产基地进行了苹果样品采集与测定分析,并对我国不同人群的膳食暴露风险进行了评估。结果表明:93.3%的苹果样品检出有低浓度农药残留,经最大残留限量值(MRL)判定后100%合格,82.0%的样品中农药残留种类在3种及以下;共检出17种农药残留,大多为低毒或无毒农药,无禁用和高毒农药。采用点评估方法,选择检出率在20%以上的多菌灵、毒死蜱、啶虫脒和戊唑醇进行不同消费人群暴露点评估。结果显示:4种农药的急性和慢性摄入风险均为儿童高于成年人,绝大多数女性人群的摄入风险高于男性;4种农药急性摄入风险均高于慢性摄入风险,风险水平由高到低为多菌灵毒死蜱戊唑醇啶虫脒,但点评估结果均远低于100%,说明通过食用苹果摄入的农药残留极其微量,不会对人体产生急性或慢性风险。     

Risk assessment of dietary exposure to pesticides using a Bayesian method

Risk assessment of pesticides can be a statistically difficult problem because pesticides occur only occasionally, but they may occur on multiple components in the diet. A Bayesian statistical model is presented which incorporates multivariate modelling of food consumption and modelling of pesticide measurements which are for a large part below a measurement threshold. It is shown that Bayesian modelling is feasible for a limited number of food components, and that in a data-rich situation the model compares well with an empirical Monte Carlo modelling.