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中文题名:

 三七中农药残留的检测及健康风险评价    

姓名:

 李慧君    

保密级别:

 公开    

论文语种:

 中文    

学科代码:

 100800    

学科专业:

 中药学    

学生类型:

 硕士    

学位:

 医学硕士    

学位类型:

 学术学位    

学位年度:

 2019    

校区:

 北京校区培养    

学院:

 地理科学学部    

研究方向:

 中药安全    

第一导师姓名:

 张文生    

第一导师单位:

 北京师范大学地理科学学部自然资源学院    

提交日期:

 2019-06-14    

答辩日期:

 2019-06-14    

外文题名:

 DETECTION OF PESTICIDE RESIDUES AND HEALTH RISK ASSESSMENT IN PANAX NOTOGINSENG    

中文关键词:

 三七 ; 农药残留 ; 检测 ; 现状 ; 健康风险评价    

中文摘要:
三七(Panax notoginseng (Burk.) F.H. Chen)为五加科人参属多年生草本植物,是我国传统名贵中药材。然而,由于三七生长周期长、对环境条件的要求较为苛刻等特性,其在栽培过程中很容易遭受多种病虫的侵害。为了提高三七产量,种植者往往会施用大量农药,导致三七农药残留现象普遍。 与食品相比,三七基质更加复杂,其农药残留的检测也相对复杂。目前,我国尚无专门针对三七的农药多残留的检测标准。因此,本研究参考食品中农药残留的检测方法,建立了三七药材农药多残留检测方法。之后,通过文献调研、收集我国出入境检验检疫部门送检三七样品农药残留检测结果以及在我国三七药材交易市场随机抽样检测的方式,初步了解了我国三七农药残留现状。最后,对三七药材中农药残留的健康风险进行了评价。主要研究内容及结果如下所述: (1)QuEChERS-GC-MS/MS法同时测定三七药材中92种农药残留。 取三七药材粉末2g,加入10mL水浸润,再加入10mL乙腈和4g NaCl提取,在提取液中加入无水MgSO4 100mg,PSA 100mg,C18 100mg净化,并通过GC-MS/MS的MRM模式进行确证和分析,采用基质匹配标准曲线结合外标法定量。结果92种农药在10~500ng/mL范围内均呈现出良好的线性关系,相关系数(R2)均大于0.98;在高(200μg/kg)、中(50μg/kg)、低(25μg/kg)三个水平添加条件下,92种农药的加标回收率大多数在70%~120%之间,并且所有农药的相对标准偏差(RSD)均小于10%;92种农药检出限(LODs)与定量限(LOQs)范围则分别为0.28~5.77μg/kg、0.94~19.23μg/kg,满足相关要求。 (2)三七农药残留现状。 首先,统计近20年我国文献报道三七中农药残留情况。结果检出农药27种,超标农药15种。其中狄氏剂和苯醚甲环唑的检出率最高,均为100%;腐霉利的超标率最高,83.87%的样品腐霉利残留量超过欧盟限量。有机氯类农药是三七中农药残留研究的热点,尤其是五氯硝基苯,样本量最大,统计结果最具代表性,其检出率为61.48%,残留量超过欧盟限量的样品数占总样品数的23.77%。之后,分析2016~2017年珠海出入境检验检疫技术中心送检三七样品中五氯硝基苯的残留情况。参照欧盟限量,五氯硝基苯的检出率和超标率分别为24.11%、17.79%。最后,利用本研究建立的三七药材农药多残留检测方法,测定在我国中药材市场随机抽取的26批三七药材中92种农药残留水平。结果26批三七药材均检出不同程度的农药残留。检测的92种农药中检出32种,其中18种农药残留量超标。三七药材中腐霉利的残留最严重,参照欧盟限量,其检出率和超标率分别为100%、96.15%。此外,五氯硝基苯也是三七药材中检出率最高(100%)的农药品种之一,参照2015版《中国药典》、欧盟和我国 《地理标志产品“文山三七”GB/T 19086-2008》限量标准,其超标率分别为15.38%、30.77%和84.62%。 (3)三七药材中农药残留健康风险评价。 对在我国中药材市场抽检的26批三七药材中检出的32种农药残留的健康风险进行评价。结果六氯苯和p,p’-DDD 2种农药为致癌物,其致癌风险分别为4.75×10-7和5.72×10-7,均小于1.0×10-6,即为可接受致癌风险水平。对其余30种非致癌农药的健康效应进行评价,最终获得了28种农药的慢性膳食暴露风险和16种农药的急性膳食暴露风险,均为可接受风险。其中,28种农药的慢性膳食暴露风险在3.04×10-5~3.00×10-1之间,16种农药的急性膳食暴露风险在8.37×10-5~9.22×10-1之间。对三七药材中上述非致癌农药的累积暴露风险进行评价,结果28种农药的慢性累积暴露和16种农药的急性累积暴露均存在一定的风险,其风险值分别为1.0017和1. 4614。其中,慢性风险和急性风险最高的农药均为吡唑醚菌酯。 综上所述,本研究建立了QuEChERS-GC-MS/MS法同时测定92种农药残留,适于三七药材中农药多残留的检测,为我国三七药材中农药多残留检测标准的建立提供了依据。过去20年,有机氯类农药,尤其是五氯硝基苯一直是我国三七中农药残留研究的热点。我国出入境检验检疫部门也将五氯硝基苯作为三七样品农药残留监测的重点项目。目前我国三七药材中五氯硝基苯的残留依然严重,在今后的研究中应进一步加强对三七药材中五氯硝基苯的监测。同时,三七药材中腐霉利的残留也十分严重,同样应引起重视。我国三七药材中虽然存在一定的农药残留,但健康风险评估的结果显示获得的2种农药的致癌风险、28种农药的慢性膳食暴露风险和16种农药的急性膳食暴露风险均在可接受的范围内,而三七药材中非致癌农药的累积暴露存在一定的健康风险,今后应引起重视。
外文摘要:
Panax notoginseng (Burk.) F.H. Chen, a kind of perennial herb which belongs to Panax Linn. of Araliaceae, is a precious traditional Chinese medicine. However, because of the characteristics of long growth cycle and harsh requirements on environmental conditions, it is easy to suffer from a variety of diseases and pests in the cultivation process. In order to increase the yield of Panax notoginseng, growers tend to apply a lot of pesticides, leading to the widespread pesticide residues in Panax notoginseng. Compared with food, the substrate of Panax notoginseng is more complex, and the detection of its pesticide residues is relatively complex. At present, there is no specific standard for the detection of pesticide residues in Panax notoginseng in China. Therefore, this study first established a exclusive method for the multi-residue determination in Panax notoginseng with reference to that in food. After that, we studied the current status of pesticide residue in Panax notoginseng by means of literature research, collecting the results of pesticide residue detection in Panax notoginseng from Chinese entry-exit inspection and quarantine department and analyzing the multi-residue of Panax notoginseng randomly sampled from Chinese Panax notoginseng medicinal materials trading market. Finally, the health risks of pesticide residues in Panax notoginseng were assessed. The main research contents and results of this study were as follows: (1) Simultaneous determination of 92 pesticide residues in Panax notoginseng by QuEChERS combined with GC-MS/MS. 2g Panax notoginseng sample, immersed by 10mL water, was extracted with 10mL acetonitrile and 4g NaCl, cleaned up with 100mg Anhydrous MgSO4, 100mg primary–secondary amine (PSA) and 100mg octadecyl-modified silica (C18) and determined by GC-MS/MS under multiple reactions monitoring (MRM) mode, and quantified by matrix-match calibration. The results of all the 92 pesticides showed good linearity in the range of 10~500ng/mL with correlation coefficients (R2) > 0.98. The recoveries of most pesticides were between 70% and 120% excepting for chlordimeform, dimethoate, prochloraz, triadimenol and tebuconazole and relative standard deviations (RSDs) were all less than 10% at three spiked levels of 25, 50 and 200μg/kg. The low limits of detection (LODs) were between 0.28μg/kg and 5.77μg/kg, while the method limits of quantification (LOQs) were between 0.94μg/kg and 19.23μg/kg. They all met the relevant standards. (2) Current status of pesticide residues in Panax notoginseng. First of all, China's literature on pesticide residues of Panax notoginseng in the past 20 years showed that 27 kinds of pesticides were detected and 15 of that exceeded the standard. The detection rates of dieldrin and difenoconazole were the highest, both were 100%. The excess rate of procymidone was the highest, 83.87% of the samples exceeded the standard of European Union maximum residue level for herbs. Organochlorine pesticides were the focus of pesticide residues research in Panax notoginseng, especially quintozene, whose statistical results were most representative for its largest sample size. According to European Union maximum residue level for herbs, the detection and excess rate of quintozene were 61.48% and 23.77%, respectively. .After that, the residue of quintozene in Panax notoginseng sent by Zhuhai entry-exit inspection and quarantine technology center from 2016 to 2017 was analyzed. As a result, the detection rate of quintozene were 24.11%, and the excess rate of quintozene were 17.79% with reference to the standard of European Union maximum residue level for herbs. Finally, the method established exclusively for the detection of 92 pesticide residues in Panax notoginseng in this study was applied on 26 Panax notoginseng samples randomly selected from the Chinese herbal medicine market. Thirty-two of the 92 pesticides tested were detected, and 18 of which exceeded the standard. The residue of procymidone in Panax notoginseng was the most serious, whose detection rate and excess rate were 100% and 96.15%, respectively, according to the standard of European Union maximum residue level for herbs. In addition, quintozene was also one of the pesticides with the highest detection rate (100%) in Panax notoginseng. According to the 2015 edition of Chinese pharmacopoeia, GB/T 19086-2008- China's geographical indication product-wenshan Panax notoginseng and the European Union standard, the excess rate were 15.38%, 30.77% and 84.62%, respectively. (3) Health risk assessment of pesticide residues in Panax notoginseng The health risks of 32 pesticide residues in 26 batches of Panax notoginseng were assessed. As carcinogens, the carcinogenic risks of hexachlorobenzene and p,p'-DDD were 4.75×10-7 and 5.72×10-7, respectively, and both were acceptable carcinogenic risk levels for less than 1.0×10-6. The health risks of the other 30 non-carcinogenic pesticides were assessed. The chronic dietary exposure risk of 28 pesticides and the acute dietary exposure risk of 16 pesticides were finally obtained, and the risks were all acceptable. Among them, the chronic dietary exposure risks of 28 pesticides were between 3.04×10-5~3.00×10-1, and the acute dietary exposure risks of 16 pesticides were between 8.37×10-5~9.22×10-1. The cumulative exposure risk of the above non-carcinogenic pesticides in Panax notoginseng was assessed. The results showed that the chronic cumulative exposure of 28 pesticides and the acute cumulative exposure of 16 pesticides all had certain risks, with the risk values of 1.0017 and 1.4614 respectively. Pyraclostrobin had both the highest chronic and acute risk. In conclusion, a QuEChERS combined with GC-MS/MS method for simultaneous determination of 92 pesticide residues was established, which was suitable for the detection of multiple pesticide residues in Panax notoginseng. It provided a basis for the establishment of the detection standard for multiple pesticide residues of Panax notoginseng in China. Over the past 20 years, organochlorine pesticides, especially quintozene has been the hot topics in the study of pesticide residues of Panax notoginseng in China. Chinese entry-exit inspection and quarantine departments have also taken quintozene as a key project in the monitoring of pesticide residues in Panax notoginseng. At present, the residue of quintozene in Panax notoginseng was still serious in China. In the future study, the monitoring of quintozene in Panax notoginseng should be further strengthened. At the same time, we should also pay more attention to procymidone for its serious residue. Although there were some pesticide residues in Panax notoginseng, the results of health risk assessment showed that the carcinogenic risks of hexachlorobenzene and p,p'-DDD, the chronic dietary exposure risk of 28 pesticides and the acute dietary exposure risk of 16 pesticides were finally obtained, and the risks were all acceptable. However, the cumulative exposure of non-carcinogenic pesticides in Panax notoginseng had certain health risks, which should be paid more attention to in the future.
参考文献总数:

 195    

馆藏号:

 硕100800/19003    

开放日期:

 2020-07-09    

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