6 7 Vol. 6 No. 7 2015 7 Journal of Food Safety and Quality Jul., 2015 兰丰, 刘传德 *, 周先学, 王志新, 鹿泽启, 姚杰, 柳璇, 姜蔚 (, ( ), 265500) 摘要 : 目的, 方法 110 102, (acute reference dose, ARfD) (international estimated short-term intake, IESTI) 结果 26, (2 ) 78%, ; ; (%ARfD ) 37.7% 7.37% 0.28% 1.53% 结论,,, 关键词 : ; ; ; Residue levels and cumulative acute risk assessment of pesticides in apples of main fruits area in Shandong province LAN Feng, LIU Chuan-De *, ZHOU Xian-Xue, WANG Zhi-Xin, LU Ze-Qi, YAO Jie, LIU Xuan, JIANG Wei (Laboratory of Quality & Safety Risk Assessment for Fruit (Yantai), Ministry of Agricultural, Yantai Academy of Agricultural Science in Shandong Province, Yantai 265500, China) ABSTRACT: Objective To assess the levels of pesticide residues and provide scientific basis for regulation of pesticide residues in major apple producing areas in Shandong province. Methods Residues of 102 pesticides in 110 apples from main fruits areas were detected by standard methods The method of cumulative acute risk assessment of pesticide in apple was established by acute reference dose (ARfD) and international estimated short-term intake (IESTI). Results Many types of pesticide residues (26 kinds) were detected in apples. Multiple residues (2 kinds of pesticides and above) accounted for a higher sample proportion of the total number of samples (78%). All pesticide residues detected in the samples did not exceed the maximum residue limit (MRL). Banned methomyl and unregistered buprofezin, spirodiclofen, and triflumuron pesticides were detected. The values of accumulation acute risk of organophosphate, pyrethroid, triazoles and neonicotinoid 基金项目 : (GJFP2015002) (2014NC111) Fund: Supported by National Program of Fruit Product Quality and Safety Risk Assessment and Evaluation(GJFP2015002) and Yantai Science and Technology Project(2014NC111) * 通讯作者 :,, E-mail: ytncpjc888@sina.com *Corresponding author: LIU Chuan-De, Professor, Yantai Academy of Agricultural Science in Shandong Province, Yantai 265500, China. E-mail: ytncpjc888@sina.com
2596 6 pesticides were 37.7%, 7.37%, 0.28% and 1.53%. Conclusion Many types of pesticides residue were detected, but the levels were not high. Organophosphate and pyrethroid, triazoles and neonicotinoid pesticides accumulate less risk of acute dietary intake of apples in Shandong, and the likelihood of harm is unlikely. The banned pesticides and unregistered pesticides are needed to focus on. KEY WORDS: apple; pesticide; residue level; cumulative acute risk assessment 1 引言,,,,,, [1,2],, [3-5], [6,7],,,, [8],,, 2 材料与方法 2.1 样品来源, 2013 2014 ( )( )( )( )( )( )( )7 12 110 2.2 农药残留检测方法 [9,10] 102, 1 2.3 累积性膳食摄入风险评估方法, ( ) 2.3.1 相对强度系数 (relative potency factors, RPF) [11], 4, [11-13] (acute reference dose, ARfD), RPF 1.0, ARfD, RPF [14] ARfD RPF 2 2.3.2 参照农药累积当量浓度计算 (RPF), [16], : n i i i 1 HR C RPF (1) (1) HR, mg/kg; C i i, mg/kg; RPF i i RPF 2.3.3 累积急性膳食风险评估 JMPR (IESTI) ( 2) [17,18] U HR v ( LP-U) HR IESTI (2) bw IESTI % ARfD 100 (3) ARfD
7, : 2597 Table 1 表 1 102 种农药参数及采用的标准方法 Parameters of 102 kinds of pesticides and the standard methods NY/T 761-2008 [9] NY/T 761-2008 [9] 3- NY/T 761-2008 [9] GB/T 20769-2008 [10] (2) U, kg, 0.255 kg [19] ; HR, mg/kg; v, 3 [19] ; LP (97.5 ), mg/kg, 0.6931 kg [19] ; bw, 60 kg, HR, RPF (3) %ARfD 100%, ; %ARfD 100%, [20] 3 结果与分析 3.1 山东省苹果农药残留水平分析, 70, 110 26, 5, 20, 1 5% 10,, 59.1% 33.6% 28.2% ( 2 ) 78% () 26,, [21] ; 5, CAC 3 3.2 累积急性膳食摄入风险评估 [23,24],, [25], 2013 (EFSA) [12] 26 4,, (MRL), 3, RPF, (HRt) (2), ARfD, 4, RPF, %ARfD, 4, MRL 7.5% 32.0% 1.2% 3.0%,, %ARfD 37.7%
2598 6 Table 2 表 2 4 组农药 ( 有机磷 菊酯类 三唑类 烟碱类 ) 各自对应的 ARfD 和 RPF 值 The ARfDs and RPFs of organophosphorus, pyrethroids, trazophos and neonicotinoids pesticides (mg/kg bw) (RPF) organophosphorus pyrethroids triazophos neonicotinoids 0.1 WHO/2004 0.01 2.0 WHO/2003 0.0005 0.001 0.2 0.01 0.02 WHO/2002 WHO/2003 WHO/1997 WHO/2003 1.0 0.005 0.1 0.05 0.02 WHO/2007 1.0 0.04 WHO/2006 0.5 0.2 WHO/2012 0.1 0.3 WHO/2007 1.0 0.9 WHO/2003 0.33 0.1 WHO/2011 1.0 0.4 WHO/2001 0.25 1.0 WHO/2010 0.1 : 2 [15] 表 3 苹果中 26 种农药的残留水平 Table 3 Residue levels of 26 pesticides in apples (%) (mg/kg) (mg/kg) Carbendazim 65 59.1 0.0010-0.17 3.0 Acetamiprid 37 33.6 0.0050-0.063 0.8 Chlorpyrifos 31 28.2 0.0016-0.36 1.0 Fenpyroximate 22 20.0 0.0010-0.021 0.3 Pyridaben 13 11.8 0.0020-0.054 2.0 Imidacloprid 12 10.9 0.0028-0.076 0.5 Tebuconazole 10 9.1 0.0045-0.020 2.0 Iprodione 9 8.2 0.0011-0.024 5.0 Cyhalothrin 9 8.2 0.0011-0.043 0.2 Spirodiclofen 7 6.4 0.0010-0.033 0.8(CAC) Fenvalerate 5 4.5 0.0043-0.087 1.0 Cypermethrin 4 3.6 0.0024-0.087 2.0 Trifloxystrobin 2 1.8 0.0010 0.0062 0.7 Paclobutrazol 2 1.8 0.0035 0.011 0.5 Difenoconazole 2 1.8 0.0032 0.037 0.5 Buprofezin 2 1.8 0.0010 0.0035 3.0(CAC) Dimethoate 2 1.8 0.012 0.014 1.0 Triazophos 1 0.9 0.021 0.2 Thiamethoxam 1 0.9 0.004 0.2( ) Tebufenozide 1 0.9 0.0054 1.0 Phosmet 1 0.9 0.0035 3.0(CAC) Methomyl 1 0.9 0.001 2.0 Methidathion 1 0.9 0.0015 0.5(CAC) Malathion 1 0.9 0.06 2.0 Hexythiazox 1 0.9 0.0020 0.5 Triflumuron 1 0.9 0.0064 0.1 : 3 [22]
7, : 2599 表 4 苹果中有机磷 菊酯类 三唑类 烟碱类农药的累积急性摄入风险评估 Table 4 Cumulative acute risk assessment of organophosphorus, pyrethroids, triazophos, and neonicotinoids pesticides in apples / (mg/kg) (HRt) (mg/kg) (IESTI)(mg/kg bw) (ARfD)(mg/kg bw) %ARfD /0.015 /0.32 /0.012 /0.06 /0.043 /0.052 /0.045 /0.037 /0.015 /0.054 /0.063 0.0188 0.000377 0.001 37.7 0.0735 0.00147 0.02 7.37 0.0420 0.000842 0.3 0.28 0.0765 0.00153 0.1 1.53 : 4 [15] 4, (%ARfD ) 37.7% 7.37% 0.28% 1.53%, 100%,,,, 4, (ARfD), %ARfD 100%, 4 讨论 4.1 关于相对强度系数 (RPF) (RPF), RPF [5,14,26,27], (ARfD) RPF [11] 1995,, ( ARfD ),,, 4, ARfD 4 RPF, RPF, 4.2 累积急性膳食摄入风险评估, (hazard index, HI) (point of departure index, PODI) (magin of exposure, MOE) (cumulative risk index, CRI),, (physiologically based toxicokinetics, PBTK) (Monte Carlo risk assessment, MCRA) [28] HI PODI MOE CRI, HI, PBTK MCRA,, 2003 FAO Andréia [18]
2600 6,,,,, 4 %ARfD 100,,, ( ),,,, 4.3 禁用和未登记使用农药 2014, 33, 17,,,,,,,, 5 结论 102, 96.7%,,,, %ARfD 37.7% 7.37% 0.28% 1.53%, 100%,,,,, 参考文献 [1],,,. [J]., 2007, 34(5): 1123 1128. Liang J, Zhao ZY, Fan MT, et al. Monitoring and evaluation of apple pesticide residues in Shanxi [J]. Acta Hortic Sinica, 2007, 34(5): 1123 1128. [2],,,. [J]., 2005, 21(10): 88 90. Nie JY, Cong PH, Yang ZF, et al. Primary report of apple pesticide residues in China [J]. Chin Agric Sci Bulletin, 2005, 21(10): 88 90. [3] Drouillet-Pinard P, Boisset M, Periquet A, et al. Realistic approach of pesticide residues and French consumer exposure within fruit & vegetable intake [J]. J Environ Sci Health part B, 2011, 46(1): 84 91. [4] Sohair AGA, Mohsen MA, Mohamed AA, et al. Dietary intake of pesticide residues in some Egyptian fruits [J]. J Appl Sci Res, 2013, 9(1): 965 973. [5] Boon PE, Van der Voet H, Van Raaij MT, et al. Cumulative risk assessment of the exposure to organophosphorus and carbamate insecticides in the Dutch diet [J]. Food Chem Toxicol, 2008, 46(9): 3090 3098. [6],,,. [J]., 2010,12(3): 335 343. Zhang ZH, Yuan YW, Wang Q, et al. On the long-tem dietary exposure and its risk assessment of lorpyrifos and cypermethrin for the residents in Zhejiang Province [J]. Chin J Pest Sci, 2010, 12(3): 335 343. [7],,,. [J]., 2011,13(5): 485 495. Zhang ZH, Yuan YW, Zheng WR, et al. Dietary intake and its risk assessment of triazophos residue [J]. Chin J Pest Sci, 2011,13(5): 485 495. [8],,. [J]., 2011, 23(4): 378 382.
7, : 2601 Zhang L, Li FQ, Liu ZP. Cumulative risk assessment of chemaicals in food [J]. Chin J Food Hyg, 2011, 23(4): 378 382. [9] NY/T 761-2008 [S]. NY/T 761-2008 Pesticide multiresidue screen methods for determination of organophosphorus pesticides, organochlorine pesticides, pyrethroid pesticides and carbamate pesticides in vegetables and fruits [S]. [10] GB/T 20769-2008 450 [S]. GB/T 20769-2008 Determination of 450 kinds of pesticides and related chemicals residues in fruits and vegetables LC-MS-MS method[s]. [11] Winfried RL, Lisette K, Geert FH. Complex mixtures: Relevance of combined exposure to substances at low dose levels [J]. Food Chem Toxicol, 2013, (58): 141 148. [12] European Food Safety Authority. Scientific Opinion: Scientific Opinion on the developmental neurotoxicity potential of acetamiprid and imidacloprid [J]. EFSA Journal, 2013, 11(12): 3471. [13] European Food Safety Authority. Scientific/Technical Report submitted to EFSA [EB/OL]. [2010-01-15]. http://www.efsa. europa. eu/ en/ supporting/ doc/ 40e.pdf, [2015-04-10]. [14] [14] Environmental Protection Agency. Environmental Protection Agency Office of Pesticide Programs [EB/OL]. [2011-10-04]. http://www.regulations.gov/#!documentdetail;d=epa-hq-opp- 2011-0746-0003, [2015-04-10]. [15] World Health Organization. Inventory of evaluations performed by the Joint Meeting on Pesticide Residues(JMPR) [DB/OL]. http://apps.who.int/pesticide-residues-jmpr-database. [2015-04-10] [16],,,. [J]., 2013, 5(42): 844 848. Zhao MX, Wang CN, Li TT, et al. Acute risk assessment of cumulative dietary exposure to organophosphorus pesticide among people in Jiangsu province [J]. J Hyg Res, 2013, 5(42): 844 848. [17] Food and Agriculture Organization of the United Nations(FAO). Report of the Joint Meeting of the FAO panel of experts on pesticide residues in food and the environment and the WHO expert group on pesticide redidues [DB/OL]. [2003-9-24]. http://www.fao.org/fileadmin/templates/agphome/documents/pests_p esticides/jmpr/reports_1991-2006/report_2003.pdf [2015-4-10]. [18] Andréia NOJ, Denise CM, Fernanda CSG, et al. Pesticide residues in cashew apple, guava, kaki and peach: GC-µECD, GC-FPD and LC-MS/MS multiresidue method validation, analysis and cumulative acute risk assessment [J]. Food Chem, 2014, (164): 195 204. [19],,,. [J]., 2014, 47(18): 3655 3667. Nie JY, Li ZX, Liu CD, et al. Risk assessment of pesticide residues in apples [J]. Sci Agric Sinica, 2014, 47(18): 3655 3667. [20] Łozowicka B, Jankowska M, Kaczyński P. Pesticide residues in Brassica vegetables and exposure assessment of consumers [J]. Food Control, 2012, 2(25): 561 575. [21]. [DB/OL]. http://www.chinapesticide.gov.cn/service/zhcx/yxcfxx.html. [2015-4-10] Institute for the Control of Agrochemicals, Ministry of Agriculture, People s Republic of China. China Pesticide Information Network [DB/OL]. http://www.chinapesticide.gov. cn/service/zhcx/yxcfxx.html. [2015-4-10]. [22]. [DB/OL]. http://202.127.42.84/tbt-sps/mrlsdb/mrlsdb.do. [2015-4-10] Institute for the Control of Agrochemicals, Ministry of Agriculture, People s Republic of China. The database of the maximum pesticide residue limits[db/ol]. http://202.127.42.84/ tbt-sps/mrlsdb/mrlsdb.do. [2015-4-10] [23] Food Standard Agency. Review of the Risk Assessment of Mixtures of Pesticides and Similar Substances [EB/OL]. [2002-9]. http://cot.food.gov.uk/sites/default/files/cot/reportindexed.pdf. [2015-4-10] [24] European Food Safety Authority. Cumulative Risk Assessment of Pesticides to Human Health: The Way Forward. European Food Safety Authority Scientific Colloquium 7, Summary report[eb/ol]. [2006-11-29]. http://www.efsa.europa.eu/en/ supporting/doc/colloquiapesticides.pdf. [2015-4-10] [25] European Food Safety Authority. Scientific services to support EFSA systematic reviews: Lot 5 Systematic literature review on the neonicotinoids (namely active substances clothianidin, thiamethoxam and imidacloprid) and the risks to bees[eb/ol]. [2013-3]. http://www.efsa.europa.eu/en/supporting/doc/756e.pdf [2015-4-10]. [26] Environmental Protection Agency. EPA's Points of Departure and Revised Relative Potency Factors for the Cumulative Risk Assessment of the Organophosphate Pesticides [EB/OL]. [2002-4-17]. http://www.epa.gov/pesticides/cumulative/pra-op/
2602 6 rpf_final.htm [2015-4-10]. [27] Environmental Protection Agency. Revised organophosphorous pesticides cumulative risk assessment. [EB/OL]. [2002-6-10]. http://www.epa.gov/pesticides/cumulative/rra-op/ [2015-4-10]. [28] Denis AS, Ute H. Considering the cumulative risk of mixtures of chemicals-a challenge for policy makers [J]. Sarig Hansen Environ Health, 2012, 11(suppl 1): s18. ( 责任编辑 : 杨翠娜 ) 作者简介 兰丰, 硕士, 助理农艺师, 主要研究方向为农药残留检测和果品质量安全风险评估 E-mail: lanfeng9527@163.com 刘传德, 本科, 研究员, 主要研究方向为植物保护和果品质量安全风险评估 E-mail: ytncpjc888@sina.com