• 百种中国杰出学术期刊
  • 中国精品科技期刊
  • 中国高校百佳科技期刊
  • 中国高校精品科技期刊
  • 中国国际影响力优秀学术期刊
  • 中国科技核心期刊

留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

阿维菌素4种剂型中NPEOs与NP含量分布及其在外包装中的迁移分析

罗惠莉 贺晓美 周静如 张舸帆

罗惠莉, 贺晓美, 周静如, 张舸帆. 阿维菌素4种剂型中NPEOs与NP含量分布及其在外包装中的迁移分析[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2021.0062
引用本文: 罗惠莉, 贺晓美, 周静如, 张舸帆. 阿维菌素4种剂型中NPEOs与NP含量分布及其在外包装中的迁移分析[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2021.0062
Huili LUO, Xiaomei HE, Jingru ZHOU, Gefan ZHANG. Distribution of NPEOs and NP in 4 formulations of abamectin and their migration from packing[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2021.0062
Citation: Huili LUO, Xiaomei HE, Jingru ZHOU, Gefan ZHANG. Distribution of NPEOs and NP in 4 formulations of abamectin and their migration from packing[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2021.0062

阿维菌素4种剂型中NPEOs与NP含量分布及其在外包装中的迁移分析

doi: 10.16801/j.issn.1008-7303.2021.0062
基金项目: 第二次全国污染源普查专项项目 (CLPSP18GZ02ZC95),湖南省重点研发计划项目 (2016SK2061)
详细信息
    通讯作者:

    罗惠莉,通信作者 (Author for correspondence) 女,博士,副教授,研究方向为环境检测与农业污染防控,E-mail:luohuili770121@126.com

  • 中图分类号: S482.3; S482.92; TQ450.263;

Distribution of NPEOs and NP in 4 formulations of abamectin and their migration from packing

  • 摘要: 通过高效液相色谱-荧光法对阿维菌素类农药中壬基酚聚氧乙烯醚 (NPEOs) 及壬基酚 (NP) 进行检测,分析乳油 (EC)、水乳剂 (EW)、悬浮剂 (SC) 和微乳剂 (ME) 4种剂型中NPEOs和NP含量的分布特征。以甲醇为油基模拟物浸泡样品外包装材料 (塑料),对其中NPEOs和NP的溶出迁移进行检测,并对制剂中NPEOs和NP进行源解析。结果表明:在4种类型制剂中,NPEOs检出率为60.47%,NP检出率为62.79%,两者均检出的占51.16%。复配制剂中NPEOs及NP检出率高于单剂。4种剂型中NPEOs和NP的检出量均值及中位数从高到低依次为:EC > EW > ME > SC。NPEOs和NP最高含量均出现在EC中,分别为6.83%和8.41%。EC制剂中NPEOs多于NP,而EW制剂中两者使用相当。2 h NPEOs和NP的迁移量分别为0.16~49.34和0.19~18.05 µg/cm2,30 d的迁移量分别为0.76~66.48和2.84~137.79 µg/cm2。试验初期,NPEOs溶出迁移相对NP更易趋于稳定,而至15 d时NPEOs和NP的迁移量接近,分别占30 d迁移量的46.64%~100.82%和46.89%~102.03%。外包装塑料中NP贡献率高达2.43%,而NPEOs贡献率最大为0.241%,30d NP贡献率是NPEOs的1.66~107.51倍,并且塑料袋中NP贡献率比塑料瓶大。农药外包装塑料中NP使用相对NPEOs多,生产过程中添加仍是制剂中NPEOs和NP主要来源。
  • 图  1  添加样品色谱图 (NPEOs和NP: 5 mg/g)

    a.空白;b.标准品;c.乳油;d.水乳剂;e.微乳剂;f.悬浮剂。

    Figure  1.  Chromatogram of addition samples (NPEOs and NP: 5 mg/g)

    a. Blank; b. Standard sample; c. EC; d. EW; e.ME; f. SC.

    图  2  阿维菌素类制剂样品中NPEOs和NP检出分布

    EC: 乳油; ME: 微乳剂; EW: 水乳剂; SC: 悬浮剂。

    Figure  2.  Content distribution of NPEOs and NP in abamectin samples

    EC: Emulsifiable concentrate; ME: Microemulsion; EW: Emulsion in water; SC: Suspension concentrate.

    图  3  外包装材料中NPEOs和NP的迁移量

    P:塑料瓶;S:塑料袋。

    Figure  3.  Migration of NPEOs and NP from packaging materials

    P: Plastic bottle; S: Plastic bag.

    表  1  阿维菌素类制剂样品信息

    Table  1.   Information of abamectin samples

    有效成分
    Pesticide
    样品编号
    Sample
    含量
    Content/%
    剂型1)
    Formul-ation1)
    包装类型2)
    Packing type2)
    有效成分
    Pesticide
    样品编号
    Sample
    含量
    Content/%
    剂型1)
    Formul-ation1)
    包装类型2)
    Packing type2)
    阿维菌素
    abamectin
    A1 1 EC P 甲氨基阿维菌素苯甲酸盐
    emamectin benzoate
    A25 0.5 EC P
    A2-A7 1.8 EC P A26 2 EC P
    A8 1.8 EC G A27 2 EC S
    A9-A11 1.8 EC P A28 1 EW P
    A12 2 EC P A29, A30 1 ME P
    A13,A14 3.2 EC P A31 3.4 ME S
    A15-A17 5 EC P 阿维 • 二嗪磷
    abamectin + diazinon
    A32, A33 0.1 EC P
    A18 1.8 EW P 阿维 • 矿物油
    abamectin + mineral oil
    A34 0.2 EC P
    A19 3 EW P 阿维 • 哒螨灵
    abamectin + pyridaben
    A35, A36 0.2 EC S
    A20 1.8 ME P A37, A38 0.3 EC P
    A21 3 ME P 阿维 • 高氯
    abamectin + beta-cypermethrin
    A39 0.3 EC G
    A22 2 SC P 阿维 • 啶虫脒
    abamectin + acetamiprid
    A40 1 EC S
    A23 3 SC P 阿维 • 炔螨特
    abamectin + Propargite
    A41 0.5 EW S
    A24 5 SC P 阿维 • 螺螨酯
    abamectin + Spirodiclofen
    A42 2 SC P
    阿维 • 氟酰胺
    abamectin + Flutolanil
    A43 6.7 SC P
    注:1) EC: 乳油; ME: 微乳剂; EW: 水乳剂; SC: 悬浮剂。2) P: 塑料瓶; G: 玻璃瓶; S: 塑料袋。Note: 1) EC: Emulsifiable concentrate; ME: Microemulsion; EW: Emulsion in water; SC: Suspension concentrate; 2) P: Plastic bottle; G: Glass bottle; S: Plastic bag.
    下载: 导出CSV

    表  2  制剂外包装信息

    Table  2.   Information of out packing samples

    样品编号
    Sample
    剂型1)
    Formulation1)
    包装类型2)
    Packing type2)
    直径 (或长)
    Diameter or length/cm
    高 (或宽)
    High or width/cm
    接触面积
    Contact area/cm2
    规格
    Specifications/mL
    A9ECP3.629.73120.89100
    A15ECP4.586.07103.76100
    A18EWP4.416.58106.38100
    A21MEP4.227.16108.86100
    A26ECP4.406.58106.11100
    A27ECS10.817.44160.8515
    A36ECS8.025.6290.1410
    A41EWS15.410.60326.4830
    注:1) EC: 乳油; ME: 微乳剂; EW: 水乳剂。2) P: 塑料瓶; S: 塑料袋。Note: 1) EC: Emulsifiable concentrate; ME: Microemulsion; EW: Emulsion in water. 2) P: Plastic bottle; S: Plastic bag.
    下载: 导出CSV

    表  3  NPEOs和NP的添加回收率及相对标准偏差 (n = 3)

    Table  3.   Mean recoveries and relative standard deviation (RSD) for NP and NPEOs (n = 3)

    样品编号
    Sample
    剂型1)
    Formulation1)
    添加水平
    Spiked
    level/
    (mg/g)
    平均回收率
    Mean recovery/%
    相对标准偏差
    RSD/%
    NPEOsNP NPEOsNP
    A16 EC 0.5 102 105 3.3 6.0
    5 102 103 2.3 2.1
    20 79 104 3.5 3.1
    A28 EW 0.5 104 106 4.9 1.1
    5 92 101 7.3 8.1
    20 85 82 11 14
    A20 ME 0.5 102 103 3.4 5.1
    5 103 105 5.6 3.6
    20 108 100 1.4 3.6
    A22 SC 0.5 91 106 7.9 3.4
    5 93 106 4.6 1.4
    20 94 91 7.2 7.7
    注:1) EC: 乳油; ME: 微乳剂; EW: 水乳剂; SC: 悬浮剂。
    下载: 导出CSV

    表  4  外包装材料中NPEOs和NP贡献率

    Table  4.   Contribution rate of NPEOs and NP from outer packing materials

    样品编号
    No of samples
    2 h贡献率 2 h Cn/% 30 d贡献率 30 d Cn/%
    NPEOsNPNP/NPEOs NPEOsNPNP/NPEOs
    A9 0.023 0.011 0.48 0.054 0.198 3.69
    A15 0.003 0.000 0.14 0.004 0.007 1.66
    A18 0.001 0.071 62.63 0.080 0.234 2.92
    A21 0.015 0.126 8.19 0.235 0.470 2.00
    A26 0.000 0.003 10.81 0.006 0.020 3.17
    A27 0.179 1.347 7.52 0.241 2.430 10.07
    A36 0.104 0.101 0.97 0.144 1.602 11.15
    A41 0.001 0.145 97.94 0.024 2.568 107.51
    下载: 导出CSV
  • 卜元卿, 王昝畅, 智勇, 等. 农药制剂中助剂使用状况调研及风险分析[J]. 农药, 2014, 53(12): 932-936.

    BU Y Q, WANG Z C, ZHI Y, et al. Investigation and risk analysis of pesticide inert ingredients in pesticide products[J]. Agrochemicals, 2014, 53(12): 932-936.
    HUANG S L, TUAN N N, LEE K. Occurrence, human intake and biodegradation of estrogen-like nonylphenols and octylphenols[J]. Curr Drug Metab, 2016, 17(3): 293-302. doi: 10.2174/1389200217666151210124821
    孔祥吉, 韦笑, 王娜, 等. 聚氧乙烯型非离子表面活性剂类农药助剂的环境行为特性综述[J]. 农业资源与环境学报, 2017, 34(3): 197-206.

    KONG X J, WEI X, WANG N, et al. A review on the environmental behavior of the polyoxyethylene type nonionic surfactants adjuvants in pesticides[J]. J Agric Resour Environ, 2017, 34(3): 197-206.
    EU (European Union). Directive 2003/53/EC of the European parliament and of the council of 18 June 2003 amending for the 26th time council directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations (nonylphenol, nonylphenol ethoxylate and cement)[EB/OL]. (2003-06-18) [2020-09-02]. http://eur-lex.europa.eu/legal-content/en/txt/?qid=1489201055422&uri=celex: 32003l0053.
    农药检定所. 关于征求《农药助剂禁限用名单》(征求意见稿)意见的通知[EB/OL]. (2015-07-13) [2016-12-16]. http://www.chinapesticide.gov.cn/zwtz/755.jhtml.

    Institute for the Control of Agrochemicals. A consultation paper on prohibited and restricted lists of pesticide adjuvants [EB/OL]. (2015-07-13) [2020-09-02]. http://www.chinapesticide.gov.cn/zwtz/755.jhtml.
    林琴, 周利, 罗逢健, 等. 超高效液相色谱-串联质谱联法测定茶园用农药制剂中烷基酚聚氧乙烯醚含量[J]. 茶叶科学, 2019, 39(1): 105-113. doi: 10.3969/j.issn.1000-369X.2019.01.014

    LIN Q, ZHOU L, LUO F J, et al. Determination of alkylphenol ethoxylates in agrochemicals for tea garden by UPLC-MS/MS[J]. J Tea Sci, 2019, 39(1): 105-113. doi: 10.3969/j.issn.1000-369X.2019.01.014
    江泽军, 曹晓林, 李辉, 等. 液体农药制剂中烷基酚及其聚氧乙烯醚类助剂的高效液相色谱分析[J]. 农药学学报, 2017, 19(2): 245-253.

    JIANG Z J, CAO X L, LI H, et al. Determination of alkylphenols and their ethoxylates in liquid pesticide formulations by high-performance liquid chromatography[J]. Chin J Pestic Sci, 2017, 19(2): 245-253.
    赵陈晨, 王超, 郭文建, 等. 超声萃取-高效液相色谱法测定土壤中8种烷基酚和烷基酚聚氧乙烯醚[J]. 分析化学, 2018, 46(8): 1306-1313. doi: 10.11895/j.issn.0253-3820.171283

    ZHAO C C, WANG C, GUO W J, et al. Determination of eight kinds of alkylphenols and alkylphenol ethoxylates in soil by ultrasonic-assisted extraction and high performance liquid chromatography[J]. Chin J Anal Chem, 2018, 46(8): 1306-1313. doi: 10.11895/j.issn.0253-3820.171283
    LUO L, YANG Y, WANG Q, et al. Determination of 4-n-octylphenol, 4-n-nonylphenol and bisphenol A in fish samples from lake and rivers within Hunan Province, China[J]. Microchem J, 2017, 132: 100-106. doi: 10.1016/j.microc.2017.01.012
    KORSMAN J C, SCHIPPER A M, DE VOS M G, et al. Modeling bioaccumulation and biomagnification of nonylphenol and its ethoxylates in estuarine-marine food chains[J]. Chemosphere, 2015, 138: 33-39. doi: 10.1016/j.chemosphere.2015.05.040
    SHE Y X, WANG J, ZHENG Y Q, et al. Determination of nonylphenol ethoxylate metabolites in vegetables and crops by high performance liquid chromatography-tandem mass spectrometry[J]. Food Chem, 2012, 132(1): 502-507. doi: 10.1016/j.foodchem.2011.09.131
    FANG K, JIANG Z J, WANG J, et al. Simulation of nonylphenol degradation in leafy vegetables using a deuterated tracer[J]. Environ Sci: Process Impacts, 2015, 17(7): 1323-1330. doi: 10.1039/C5EM00073D
    CAI Q Y, HUANG H J, LÜ H X, et al. Occurrence of nonylphenol and nonylphenol monoethoxylate in soil and vegetables from vegetable farms in the Pearl River Delta, South China[J]. Arch Environ Contam Toxicol, 2012, 63(1): 22-28. doi: 10.1007/s00244-011-9741-4
    吕岱竹, 林勇, 李建国, 等. 壬基酚聚氧乙烯醚及其降解产物壬基酚在香蕉和土壤中的消解动态及风险评估[J]. 农药学学报, 2011, 13(6): 627-631. doi: 10.3969/j.issn.1008-7303.2011.06.12

    LÜ D Z, LIN Y, LI J G, et al. Residue decline study and risk assessment of nonylphenol ethoxylates and its metabolites nonylphenol in banana and soil[J]. Chin J Pestic Sci, 2011, 13(6): 627-631. doi: 10.3969/j.issn.1008-7303.2011.06.12
    GUART A, BONO-BLAY F, BORRELL A, et al. Migration of plasticizers phthalates, bisphenol A and alkylphenols from plastic containers and evaluation of risk[J]. Food Addit Contam Part A Chem Anal Control Expo Risk Assess, 2011, 28(5): 676-685. doi: 10.1080/19440049.2011.555845
    陈旭明, 李婷. 食品用塑料包装中壬基酚迁移量的检测[J]. 包装与食品机械, 2019, 37(2): 66-69. doi: 10.3969/j.issn.1005-1295.2019.02.015

    CHEN X M, LI T. Determination of nonylphenol migration in plastic food packaging[J]. Packag Food Mach, 2019, 37(2): 66-69. doi: 10.3969/j.issn.1005-1295.2019.02.015
    马强, 白桦, 王超, 等. 液相色谱-串联质谱法同时测定纺织品和食品包装材料中的壬基酚、辛基酚和双酚A[J]. 分析化学, 2010, 38(2): 197-201.

    MA Q, BAI H, WANG C, et al. Simultaneous determination of nonylphenol, octylphenol and bisphenol A in textiles and food packaging materials by liquid chromatography tandem mass spectrometry[J]. Chin J Anal Chem, 2010, 38(2): 197-201.
    冷阳. 阿维菌素类农药制剂的存在问题和发展思路[J]. 世界农药, 2009, 31(z2): 5-8. doi: 10.3969/j.issn.1009-6485.2009.z2.003

    LENG Y. Problems and development trend of avermentics pesticide formulations[J]. World Pestic, 2009, 31(z2): 5-8. doi: 10.3969/j.issn.1009-6485.2009.z2.003
    DU P Q, WU X H, HE H R, et al. Evaluation of the safe use and dietary risk of beta-cypermethrin, pyriproxyfen, avermectin, diflubenzuron and chlorothalonil in button mushroom[J]. Sci Rep, 2017, 7(1): 8694. doi: 10.1038/s41598-017-07860-y
    ZHANG D L, WANG H Y, JI X X, et al. Effect of abamectin on the cereal cyst nematode (CCN, Heterodera avenae) and wheat yield[J]. Plant Dis, 2017, 101(6): 973-976. doi: 10.1094/PDIS-10-16-1441-RE
    食品安全国家标准 食品接触材料及制品迁移试验预处理方法通则: GB 5009.156—2016[S]. 北京: 中国标准出版社, 2017.

    National food safety standards—General rules for the preprocessing methods in migration tests of food contact materials and products: GB 5009.156—2016[S]. Beijing: Standards Press of China, 2017.
    食品安全国家标准 食品接触材料及制品迁移试验通则: GB 31604.1—2015[S]. 北京: 中国标准出版社, 2016.

    National food safety standards—General rules for the migration test of food contact materials and products: GB 31604.1—2015[S]. Beijing: Standards Press of China, 2016.
    FENG J G, CHEN Q C, WU X M, et al. Formulation of oil-in-water emulsions for pesticide applications: Impact of surfactant type and concentration on physical stability[J]. Environ Sci Pollut Res, 2018, 25(22): 21742-21751. doi: 10.1007/s11356-018-2183-z
    WANG P, KELLER A A. Particle-size dependent sorption and desorption of pesticides within a water-soil-nonionic surfactant system[J]. Environ Sci Technol, 2008, 42(9): 3381-3387. doi: 10.1021/es702732g
    HESSELSØE M, JENSEN D, SKALS K, et al. Degradation of 4-nonylphenol in homogeneous and nonhomogeneous mixtures of soil and sewage sludge[J]. Environ Sci Technol, 2001, 35(18): 3695-3700. doi: 10.1021/es010024l
    MANZANO M A, PERALES J A, SALES D, et al. The effect of temperature on the biodegradation of a nonylphenol polyethoxylate in river water[J]. Water Res, 1999, 33(11): 2593-2600. doi: 10.1016/S0043-1354(98)00480-1
    FRANSKA M, FRANSKI R, SZYMANSKI A, et al. A central fission pathway in alkylphenol ethoxylate biodegradation[J]. Water Res, 2003, 37(5): 1005-1014. doi: 10.1016/S0043-1354(02)00444-X
    JOHN D M, WHITE G F. Mechanism for biotransformation of nonylphenol polyethoxylates to xenoestrogens in Pseudomonas putida[J]. J Bacteriol, 1998, 180(17): 4332-4338. doi: 10.1128/JB.180.17.4332-4338.1998
  • 加载中
计量
  • 文章访问数:  171
  • HTML全文浏览量:  104
  • 被引次数: 0
出版历程
  • 收稿日期:  2020-09-11
  • 录用日期:  2020-11-08
  • 网络出版日期:  2021-01-27

目录

    /

    返回文章
    返回