CN110187028B - 一种用于西兰花中三唑类农药残留检测的方法 - Google Patents
一种用于西兰花中三唑类农药残留检测的方法 Download PDFInfo
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Abstract
本发明提供了一种海绵状多壁碳纳米管复合材料结合QuEChERS技术用于西兰花中三唑类农药残留检测的方法,本发明方法能够选择性地萃取、分离和富集样品中的分析物,既可对样品基质进行净化操作,又对目标物进行富集浓缩,为复杂基质的前处理方法提供了新思路;本发明采用QuEChERS净化技术结合分散固相萃取技术,前者用于基质西兰花的前处理,后者以制备的海绵状多壁碳纳米管复合材料作为吸附剂,建立了检测西兰花中三唑类农药残留的分析方法,对各个影响因素分别进行优化,在优化条件下对西兰花实际样品中的三唑类农药进行测定,为西兰花种植过程的安全监控以及保障西兰花食品安全提供科学依据,具有重要研究意义和实际应用价值。
Description
(一)技术领域
本发明涉及一种用于西兰花中三唑类农药残留检测的方法,具体涉及一种海绵状多壁碳纳米管复合材料结合QuEChERS技术用于西兰花中三唑类农药残留检测的方法。
(二)背景技术
目前,农产品种类日趋多样化,许多国家对农产品的质量要求越来越高,食品中农药残留的安全问题已经引起民众的广泛关注。三唑类农药通常是含氮杂环的化合物,包括三唑酮、丙环唑、腈菌唑、戊菌唑、苄氯三唑醇、氟环唑、苯醚甲环唑等二十多个品种,因为具有独特的生物活性,较高的内吸性和较低的毒性,被广泛用于农业生产中,以控制昆虫、真菌、杂草等对农业生产的影响。由于其半衰期长,具有毒性且在环境中浓度较低,它在农产品以及生态系统中的富集对人类健康潜在的威胁也引起了关注。西兰花是一种很受人们欢迎的蔬菜,因其味道鲜美,营养丰富(如蛋白质、碳水化合物、脂肪、矿物质、维生素C和胡萝卜素等),而被称为蔬菜之王。然而,由于花球表面紧密,易于青虫类生长繁殖,加上农药的不合理使用,难以清洗等问题,使得西兰花中农药残留问题相当严重。因此,研究开发准确且高效的样品前处理技术和检测西兰花中农药残留的分析方法显得日益重要。
分散固相萃取(d-SPE)是多种有效前处理分析三唑类杀菌剂的手段之一。d-SPE技术的关键在于吸附剂材料。当前已有多种新型纳米材料(如金属-有机骨架材料、氮化硼空心球和碳纳米管等)被作为分散固相萃取吸附剂,应用于多种基质中农药残留的分析。碳纳米管是1991年日本电气股份有限公司研究实验室物理学家Sumio Iijima在利用高分辨投射电子显微镜观察电弧法制备富勒烯结构时意外发现的,并首次在《Nature》杂志上发表论文。在过去几年中,碳纳米管作为一种新兴的吸附剂,在环境分析领域受到了极大关注。根据形成碳纳米管壁石墨烯片层的不同,可分为单壁碳纳米管和多壁碳纳米管。由于材料具有大的比表面积,中空和层状结构,使得其具有十分优异的吸附能力,并被作为固相萃取的吸附剂萃取诸如农药残留、抗生素、直链烷基苯磺酸盐、多环芳烃和金属离子等。
QuEChERS法是一种快速、简便、经济、高效、可靠和安全的萃取净化技术,它于2003年首次由美国农业部教授Anastassiades等人提出,随后由Lehotay等人改进。QuEChERS法的基本原理是将传统的液相萃取和分散固相萃取(d-SPE)相结合,选取单一溶剂乙腈作为基质中目标物的提取剂,并通过NaCl进行相分离,通过无水MgSO4除去提取液中的水分,最后采用PSA(N-丙基乙二胺)作为净化剂除去基质中的干扰物质(脂肪酸、有机酸和色素等)。QuEChERS法作为一种绿色、简便、经济的样品预处理方法,被广泛应用于蔬菜水果中农药残留的检测。
本发明采用QuEChERS净化技术结合分散固相萃取技术,前者用于基质西兰花的前处理,后者以制备的海绵状多壁碳纳米管材料作为吸附剂,建立了检测西兰花中三唑类农药残留检测的分析方法。在建立检测蔬菜等复杂基质中的农药残留方法方面提供了新思路,为西兰花种植过程的安全监控以及保障西兰花食品安全提供科学依据,具有重要研究意义和实际应用价值。
(三)发明内容
针对现有技术中存在的不足,本发明提供了一种海绵状多壁碳纳米管复合材料结合QuEChERS的前处理技术用于西兰花中三唑类农药残留的检测方法,本发明方法能够选择性地萃取、分离和富集样品中的分析物,既可对样品基质进行净化操作,又对目标物进行富集浓缩,为复杂基质的前处理方法提供了新思路。
本发明采用QuEChERS净化技术结合分散固相萃取技术,前者用于基质西兰花的前处理,后者以制备的海绵状多壁碳纳米管复合材料作为吸附剂,建立了检测西兰花中三唑类农药残留的分析方法。对各个影响因素分别进行优化,在优化条件下对西兰花实际样品中的三唑类农药进行测定,为西兰花种植过程的安全监控以及保障西兰花食品安全提供科学依据,具有重要研究意义和实际应用价值。
本发明的技术方案如下:
一种海绵状多壁碳纳米管复合材料结合QuEChERS技术用于西兰花中三唑类农药残留检测的方法,所述方法包括如下步骤:
(1)海绵状多壁碳纳米管复合材料的制备
将羧甲基纤维素钠于乙醇(体积用量以羧甲基纤维素钠的质量计为2~3mL/g)中超声(功率为250W,下同)分散均匀,然后加入多壁碳纳米管、氢氧化钠、水,搅拌并超声混匀,接着加入环氧氯丙烷(交联剂),混匀后得到混合物(粘稠液体状),于-18℃下冷冻后,再经冷冻干燥,清洗(用乙醇和水体积比4:1的混合液)至中性,室温(20~30℃)干燥,得到所述海绵状多壁碳纳米管复合材料;
所述羧甲基纤维素钠、多壁碳纳米管、氢氧化钠、水、环氧氯丙烷的质量比为1:0.08:2:50:4;
(2)样品处理及QuEChERS净化
将西兰花洗净晾干,取可食用部分切成碎末,搅拌混匀,得到西兰花样品,在所得西兰花样品中加入标准溶液和乙腈,超声(30s),接着加入无水硫酸镁和氯化钠,涡旋(30s),离心(6000rpm,3min),吸取上层乙腈层,加入N-丙基乙二胺和石墨化炭黑,涡旋(30s),离心(6000rpm,3min),取上清液,即为样品溶液;
所述标准溶液为三种三唑类农药化合物腈菌唑、戊唑醇、苯醚甲环唑的混合标准溶液,其中腈菌唑、戊唑醇、苯醚甲环唑的浓度均为10mg/L,所述标准溶液按如下方法配制:
分别准确称取腈菌唑、戊唑醇、苯醚甲环唑各0.1g于烧杯中,用甲醇溶解,玻璃棒转移至100mL棕色容量瓶,甲醇定容,胶带密封,超声30min,储存在4℃冰箱环境中;取上述溶液1mL,转移至100mL容量瓶中,甲醇定容,胶带密封,储存在4℃冰箱环境中;
所述标准溶液的体积用量以西兰花样品的质量计为1mL/g;
所述乙腈的体积用量以西兰花样品的质量计为2mL/g;
所述西兰花样品、无水硫酸镁、氯化钠、N-丙基乙二胺、石墨化炭黑的质量比为1:0.8:0.5:0.065:0.02;
(3)萃取及检测
将步骤(2)所得样品溶液与步骤(1)所得海绵状多壁碳纳米管复合材料混合,用蒸馏水(样品溶液体积的0~5倍)稀释,于30~60℃恒温反应5~20min,超声(10min),收集固体弃去液体,将收集的固体用洗脱剂洗脱(1~3min),收集洗脱液,氮吹吹干,再用洗脱剂复溶,静置后进行GC-MS分析;
所述海绵状多壁碳纳米管复合材料的质量用量以样品溶液的体积计为50~83mg/mL;
所述洗脱剂选自三氯甲烷、甲苯、甲醇或乙腈。
本发明中,所述三唑类农药具体为下列化合物中的至少一种:腈菌唑、戊唑醇、苯醚甲环唑。
本发明进行GC-MS分析的检测条件为:
气相色谱条件为:毛细管色谱柱:DB-5MS石英毛细管柱(30m×0.25mm×0.25μm);色谱柱升温程序:毛细管柱起始温度设置为180℃,在此温度下保持1min;然后以5℃·min-1升温至200℃,保持1min;之后以2℃·min-1升温至220℃,不保持;最后以10℃·min-1升至290℃,保持6.1min;高纯氦气(99.999%)为载气,流速为1.0mL·min-1;进样口温度:280℃;不分流进样;进样量:1.0μL;0.75min后以40mL·min-1进行载气吹扫;
质谱条件为:采用SIM模式,质量扫描m/z;电子轰击(EI)离子源;电子能量70eV;离子阱温度180℃;歧管温度为50℃;传输线温度250℃;扫描速度3scans·s-1,溶剂延迟12.2min。
与现有技术相比,本发明的有益效果为:
1、本发明提出了一种新型、高效检测西兰花中三唑类农药残留的分析方法;
2、将QuEChERS净化技术与分散固相萃取技术相结合,能够发挥这两种前处理技术各自的优势,提高萃取效率的同时有效降低了复杂样品基质对检测的干扰,具有重复性良好,回收率佳的优点;
3、采用改性修饰的海绵状碳纳米管作为分散固相萃取的吸附材料,具有很好的亲水性、十分优异的吸附能力和对目标分析物的良好的选择性;
4、既对样品基质进行净化操作,又对目标物进行富集浓缩,为复杂基质的前处理方法提供了新思路,为在西兰花种植过程中合理施用三唑类农药提供科学依据。
(四)附图说明
图1为海绵状多壁碳纳米管复合材料的制备原理图;
图2为本发明中的QuEChERS-d-SPE方法流程图;
图3为本发明所制备的海绵状多壁碳纳米管复合材料的实物图;
图4为实施例1中的海绵状多壁碳纳米管复合材料的扫描电镜图;
图5为实施例1中的海绵状多壁碳纳米管材料表面较为光滑区域的扫描电镜图;
图6为实施例1中的交联羧甲基纤维素钠(未添加碳纳米管)的扫面电镜图;
图7a、7b分别为实施例1中的羧甲基纤维素钠、海绵状多壁碳纳米管材料的红外光谱图;
图8为实施例1中的海绵状多壁碳纳米管复合材料的氮气吸脱附等温线(A)、孔径分布图(B);
图9a、9b、9c、9d分别为实施例1中的萃取过程中温度、时间、加水量、材料使用量对萃取效率的影响;
图10a、10b、10c分别为实施例1中的洗脱剂类型、体积、洗脱时间对萃取效率的影响;
图11为实施例1中的GC-MS的选择离子流图[(A)空白西兰花;(B)腈菌唑、戊唑醇、氟环唑加标浓度200μg·kg-1;(C)阳性西兰花样品。(标注:1:腈菌唑;2:戊唑醇;3:氟环唑)]。
(五)具体实施方式
下面通过具体实施例对本发明作进一步描述,但本发明的保护范围并不仅限于此。
实施例1:检测西兰花中三唑类农药残留(腈菌唑、戊唑醇、苯醚甲环唑)
(1)海绵状多壁碳纳米管复合材料的制备
称取1g的羧甲基纤维素钠于250mL的烧杯中,加入3mL乙醇,超声10分钟使其分散均匀。然后再称取0.08g多壁碳纳米管(购自深圳纳米港有限公司)、2g氢氧化钠,50mL水加入到上述混合物中,搅拌并超声10min。在室温下磁力搅拌10h以上,使混合物能够充分混匀。待混合物混合均匀后,加入4g环氧氯丙烷作为交联剂,继续在室温下搅拌24h。
反应结束后,将具有一定粘稠度的液体混合物置于培养皿中,放入冰箱中,-18℃下冷冻。待冷冻完成后,再用冷冻干燥机冷冻干燥24h,获得产物呈蓬松海绵状。将上述产物用乙醇和水(4:1,V:V)的混合液清洗至中性,室温下干燥。
将干燥后的产物裁切成不同质量的块状物,保存备用。
(2)西兰花实际样品处理
将西兰花样品洗净晾干,取可食用部分切成碎末,搅拌将其混匀,将混匀的西兰花样品储存于4℃环境中,备用。
(3)QuEChERS净化
准确称取1.0g西兰花样品于带盖离心管中,用移液枪移入1mL标准溶液,加入2mL乙腈,超声30s;加入0.8g无水硫酸镁和0.5g氯化钠,涡旋30s后于6000r·min-1转速下离心3min;用一次性塑料针管取上层乙腈层转移至事先装有65mg N-丙基乙二胺和20mg石墨化炭黑的离心管中,涡旋30s,在6000r·min-1转速下离心3min。
(4)萃取过程
取离心后的上清液(约1.5mL)于事先装有100mg海绵状多壁碳纳米管复合材料的50mL离心管中,再加入2mL蒸馏水。于45℃下恒温反应15min,然后将离心管超声10min,用镊子将材料夹取出后弃去液体。碳纳米管材料放回离心管,加入甲苯洗脱3次,每次使用甲苯1mL,将洗脱液收集至10mL带极少量无水Na2SO4的离心管中并用氮吹仪吹干。最后,加入50μL的甲苯复溶,静置片刻后取1μL进GC-MS分析。单因素条件优化实验时以上过程重复三次。
气相色谱条件为:毛细管色谱柱:DB-5MS石英毛细管柱(30m×0.25mm×0.25μm);色谱柱升温程序:毛细管柱起始温度设置为180℃,在此温度下保持1min;然后以5℃·min-1升温至200℃,保持1min;之后以2℃·min-1升温至220℃,不保持;最后以10℃·min-1升至290℃,保持6.1min。高纯氦气(99.999%)为载气,流速为1.0mL·min-1;进样口温度:280℃;不分流进样;进样量:1.0μL;0.75min后以40mL·min-1进行载气吹扫。
质谱条件为:电子轰击(EI)离子源;电子能量70eV;离子阱温度180℃;歧管温度为50℃;传输线温度250℃;扫描速度3scans·s-1,溶剂延迟12.2min;
采用SIM模式,质量扫描为(单位:m/z):(1)腈菌唑12.20-14.50min:152,179;(2)戊唑醇16.80-18.15min:250,308;(3)氟环唑:18.15-18.72min:192,330。
(5)方法评估
在最优化参数条件下分析5,10,20,50,100,200,500,1000μg·kg-1的空白加标样品,考察各目标分析物的线性范围、相关系数、检出限(S/N=3),定量限(S/N=10)和相对标准偏差,结果见表1。腈菌唑、戊唑醇和氟环唑的线性范围为5-1000μg·kg-1,相关系数均为0.999。检出限和定量限分别为0.62-1.32μg·kg-1,2.07-4.40μg·kg-1。为了测定该方法的相对标准偏差,选取腈菌唑、戊唑醇、氟环唑浓度为100μg·kg-1的标准溶液平行测定7次,最终得到的RSD%值为5.7-9.8%。
表1
真实样品分析:选用空白西兰花为基质,加入不同浓度水平的混合标准溶液,使腈菌唑、戊唑醇浓度为10,50,500μg·kg-1,按试验方法进行前处理后,平行测定5次,得到相应的回收率和精密度,结果见表2。结果表明,3种三唑的回收率在81.6%-111.1%之间,相对标准偏差在4.8%-12.1%之间。
表2
从浙江某农场得到2个空白大棚西兰花样品和13个阳性大棚西兰花样品(阳性大棚西兰花样品:西兰花种植在大棚中,定期施用2种三唑类农药,在施药后不同时间收集到的西兰花样品),将得到的所有样品用上述方法进行萃取富集进样并平行测定3次,检测结果如表3所示。实验结果表明本方法适用于实际西兰花样品的三唑类农药残留测定。
表3
Claims (8)
1.一种海绵状多壁碳纳米管复合材料结合QuEChERS技术用于西兰花中三唑类农药残留检测的方法,其特征在于,所述方法包括如下步骤:
(1)海绵状多壁碳纳米管复合材料的制备
称取1 g的羧甲基纤维素钠于250 mL的烧杯中,加入3 mL乙醇,超声10分钟使其分散均匀,然后再称取0.08 g多壁碳纳米管、2 g氢氧化钠,50 mL水加入到上述混合物中,搅拌并超声10 min,在室温下磁力搅拌10 h以上,使混合物能够充分混匀,待混合物混合均匀后,加入4 g环氧氯丙烷作为交联剂,继续在室温下搅拌24 h;
反应结束后,将具有一定粘稠度的液体混合物置于培养皿中,放入冰箱中,-18℃下冷冻,待冷冻完成后,再用冷冻干燥机冷冻干燥24 h,获得产物呈蓬松海绵状,将上述产物用乙醇和水体积比4:1的混合液清洗至中性,室温下干燥;
(2)样品处理及QuEChERS净化
将西兰花洗净晾干,取可食用部分切成碎末,搅拌混匀,得到西兰花样品,在所得西兰花样品中加入标准溶液和乙腈,超声,接着加入无水硫酸镁和氯化钠,涡旋,离心,吸取上层乙腈层,加入N-丙基乙二胺和石墨化炭黑,涡旋,离心,取上清液,即为样品溶液;
所述标准溶液为三种三唑类农药化合物腈菌唑、戊唑醇、苯醚甲环唑的混合标准溶液,其中腈菌唑、戊唑醇、苯醚甲环唑的浓度均为10 mg/L;
(3)萃取及检测
将步骤(2)所得样品溶液与步骤(1)所得海绵状多壁碳纳米管复合材料混合,用蒸馏水稀释,于30~60 ℃恒温反应5~20 min,超声,收集固体弃去液体,将收集的固体用洗脱剂洗脱,收集洗脱液,氮吹吹干,再用洗脱剂复溶,静置后进行GC-MS分析;
所述洗脱剂选自三氯甲烷、甲苯、甲醇或乙腈。
2.如权利要求1所述的方法,其特征在于,步骤(2)中,所述标准溶液按如下方法配制:
分别准确称取腈菌唑、戊唑醇、苯醚甲环唑各0.1 g于烧杯中,用甲醇溶解,玻璃棒转移至100 mL棕色容量瓶,甲醇定容,胶带密封,超声30 min,储存在4 ℃冰箱环境中;取上述溶液1 mL,转移至100 mL容量瓶中,甲醇定容,胶带密封,储存在4 ℃冰箱环境中。
3.如权利要求1所述的方法,其特征在于,步骤(2)中,所述标准溶液的体积用量以西兰花样品的质量计为1 mL/g。
4.如权利要求1所述的方法,其特征在于,步骤(2)中,所述乙腈的体积用量以西兰花样品的质量计为2 mL/g。
5.如权利要求1所述的方法,其特征在于,步骤(2)中,所述西兰花样品、无水硫酸镁、氯化钠、N-丙基乙二胺、石墨化炭黑的质量比为1:0.8:0.5:0.065:0.02。
6.如权利要求1所述的方法,其特征在于,步骤(3)中,所述蒸馏水的体积用量为样品溶液体积的0~5倍。
7.如权利要求1所述的方法,其特征在于,步骤(3)中,所述海绵状多壁碳纳米管复合材料的质量用量以样品溶液的体积计为50~83 mg/mL。
8.如权利要求1所述的方法,其特征在于,进行GC-MS分析的检测条件为:
气相色谱条件为:毛细管色谱柱:DB-5 MS石英毛细管柱;色谱柱升温程序:毛细管柱起始温度设置为180℃ ,在此温度下保持1 min;然后以5℃ ·min-1升温至200℃ ,保持1min;之后以2℃ ·min-1升温至220℃ ,不保持;最后以10℃ ·min-1升至290℃ ,保持6.1min;高纯氦气为载气,流速为1.0 mL·min-1;进样口温度:280℃ ;不分流进样;进样量:1.0µL;0.75 min后以40 mL·min-1进行载气吹扫;
质谱条件为:采用SIM模式,质量扫描m/z;电子轰击离子源;电子能量70 eV;离子阱温度180℃ ;歧管温度为50℃ ;传输线温度250℃ ;扫描速度 3 scans·s-1,溶剂延迟12.2min。
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