CN104777110B - 一种痕量镉和铅的检测方法 - Google Patents
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Abstract
本发明公开一种痕量镉和铅的检测方法,属于食品安全检测技术领域;本发明涉及镉、铅与吡咯烷二硫代氨基甲酸铵形成的络合物能均匀分散在含表面活性剂的溶液中,利用Fe3O4纳米粒子进行分散固相微萃取,外加磁场分离,用洗脱剂进行洗脱,结合原子吸收光度法测定痕量镉和铅;本方法应用到农产品中痕量镉和铅测定中,本发明方法具有检测灵敏度高、时间短、有机溶剂用量少等特点,可以实现农副产品重金属镉和铅高灵敏、快速、简便的检测。
Description
技术领域
本发明涉及一种痕量镉和铅的检测方法,属于食品安全检测技术领域。
背景技术
重金属元素会对生态环境和人体健康产生影响。重金属一般以天然浓度广泛存在于自然界中,但由于人类对重金属的开采、冶炼、加工及商品制造活动日益增多,造成不少重金属如铅、镉、钴等进入大气、水及土壤中,引起严重的环境污染和人体危害,因此准确检测环境样品中的重金属元素变得日趋重要。重金属铅(Pb)是一种重要的重金属元素,其本身和化合物对人体各组织均有毒性,铅中毒的危害主要表现在对神经系统、血液系统、心血管系统、骨骼系统等终身性的伤害上。由于铅是不可降解的,它在环境中持久性存在,并且产生在动物和植物的毒性作用,铅中毒的危害之严重,使得预防和检测工作变得非常之重要。镉(Cd)作为联合国粮农组织和世界卫生组织公布的人体毒性最强的重金属之一,是环境中常见的化学毒物,人体摄入一定量的镉会损伤肾脏和肝肺等。原子吸收光谱法是测定环境样品中镉的常用方法。石墨炉原子吸收法检测成本相对较高,火焰原子吸收法快捷、简易,但灵敏度不够高。由于镉的含量往往较低,采用火焰原子吸收法时需进行预富集,实现食品特别是农副产品重金属高灵敏检测具有十分重要的意义。
纳米材料由于比表面积大,对许多重金属离子的吸附能力强、吸附容量大。在较短时间内即可达到吸附平衡,是一种较为理想的固相萃取吸附材料。特别是磁性纳米材料,因具有超顺磁性,借助于外加磁场,可大大缩短富集时间。农副产品的重金属的浓度通常非常低且基体干扰不能消除,因而测定前分离富集的样品前处理技术显得非常重要。传统的对金属离子的样品前处理技术主要采用液液萃取(LLE)、固相萃取(SPE)、双水相萃取(ATPS)、浊点萃取(CPE)及分散液液微萃取(DLLME)。磁性纳米材料用于重金属的吸附已有研究,主要集中在磁性纳米材料上健合相应的金属络合剂或离子液体,以达到分离富集的目的。
本发明对于含重金属的样品溶液,一是加入络合剂使重金属形成疏水性的络合物;二是在形成的重金属络合物溶液中加入非离子表面活性剂,升高温度形成混浊溶液;三是由于非离子表面活性剂的浊点形成,改变了样品溶液的性质,使磁性纳米材料均匀分散且较好吸附重金属络合物,实现农副产品重金属铅高灵敏、简便的检测方法,对食品安全、人体健康有重要的意义。
发明内容
本发明的目的在于针对现有技术的不足,提供一种痕量镉和铅的检测方法,在保证检测准确度和灵敏度的同时,降低检测成本,缩短检测时间;本发明所述痕量镉和铅的检测方法,具体包括以下步骤:
(1)按每10mL添加0.1~0.5mL吡咯烷二硫代氨基甲酸铵溶液的比例,在含有Pb2+、Cd2+的水溶液中加入吡咯烷二硫代氨基甲酸铵溶液,混合均匀;
(2)将步骤(1)得到的溶液调节pH为2.5~4.5,按每10mL添加0.2~0.5mL非离子表面活性剂的比例加入非离子表面活性剂,涡旋混合1~3min,加热,得到混浊乳液;
(3)在步骤(2)得到的混浊乳液中加入制备好的四氧化三铁磁性纳米材料,涡旋混合1~3min,用外磁场收集磁性纳米产物,倒出溶液,用洗脱剂洗脱磁性纳米产物,收集洗脱剂,进原子吸收分光光度计进行含量测定,其中四氧化三铁磁性纳米材料的添加量为每10mL混浊乳液中添加0.25~0.4g。
本发明步骤(1)中所述的所述吡咯烷二硫代氨基甲酸铵溶液为质量体积比浓度为2%(w/v)的水溶液。
本发明步骤(2)中所述的非离子表面活性剂为聚乙二醇辛基苯基醚Triton X-114、支链仲醇聚氧乙烯醚Tergitol TMN 6两种之一种;所述加热温度为40~50℃,加热时间为10~20min。
本发明步骤(3)中所述的四氧化三铁磁性纳米材料的制备如下:按照三价铁盐与二价铁盐的摩尔比为2.0~1.6:1的比例将三价铁盐溶液与二价铁盐溶液加入5~10倍的三价铁盐和二价铁盐溶液体积的去离子水中溶解,在氮气保护下,滴加氨水使溶液体系pH为9~12,在60~80℃、搅拌速度400~800 rpm下,水浴加热,恒温搅拌反应1~3h后,用去离子水洗涤至中性,40~80℃真空干燥6~12h,制得四氧化三铁磁性纳米材料。
本发明中所述三价铁盐为FeCl3·7H2O或Fe2(SO4)3·9H2O,二价铁盐为FeCl2·4H2O或FeSO4·7H2O。
本发明步骤(3)中所述的洗脱剂为乙腈、四氢呋喃、甲醇中之一种,用量为1~3mL。
本发明方法应用于农副产品重金属镉和铅的测定中,农副产品样品中镉和铅的提取分离方法按常规方法操作。
本发明的有益效果:
(1)利用磁性纳米材料大的比表面,对金属离子的络合物的吸附能力强、吸附容量大的特点,将其分散在含有非离子表面活性剂的样品溶液中,利用非离子表面活性剂的浊点现象,磁性纳米材料得到了更好的分散,有利于与目标重金属接触,对复杂基体的痕量重金属有更好的吸附效果。
(2)利用磁性纳米材料具有的超顺磁性,借助于外加磁场进行分离,可大大缩短及简化分离时间。
(3)磁性纳米材料可以重复使用,降低使用成本。
具体实施方式
下面结合实施例对本发明作进一步地说明,但本发明的保护范围并不限于此。
实施例1:茶叶中镉和铅的测定
1、样品处理:将干燥茶叶粉碎、过1 mm 筛,准确称0.1g(精确到0.0001 g),加入2mol L-1硝酸10mL,放入超声浴中,40℃超声15min,2000r/min离心10min,取上清液,用蒸馏水定容10mL,备用,同时做试剂空白测定;
2、四氧化三铁磁性纳米材料的制备:将2mol/L FeCl3·7H2O 12mL与1mol/LFeCl2·4H2O 12mL混合于120mL去离子水中,在氮气保护下,滴加50mL氨水使溶液体系pH为9,在60℃下水浴加热,搅拌速度为400 rpm下,恒温搅拌反应3h后,用去离子水洗涤至中性,70℃真空干燥8h,制得四氧化三铁磁性纳米材料;
3、在步骤1中得到的10mL茶叶处理溶液中,加入2%(2g吡咯烷二硫代氨基甲酸铵溶于100mL蒸馏水中)吡咯烷二硫代氨基甲酸铵水溶液0.3mL,用1mol/L盐酸和1mol/L氢氧化钠调节pH为2.5,加入非离子表面活性剂Triton X114 0.2mL,涡旋混合2min,在水浴50℃加热15min,得到混浊乳液;再加入制备好的四氧化三铁磁性纳米材料0.3g,涡旋混合1min,用磁铁收集磁性纳米材料,倒出溶液,然后加入四氢呋喃3mL洗脱磁性纳米材料,进原子吸收分光光度计检测,得到镉含量为18μg/kg,铅含量为123μg/kg。
实施例2:饲料中镉和铅的测定
1、样品处理:将饲料样品粉碎,过1 mm 筛,称取约0.1 g(精确到0.0001 g),加入6mol L-1硝酸10mL,放入超声浴中,40℃超声15min,2000r/min离心10min,取上清液,用蒸馏水定容10mL,备用,同时做试剂空白测定;
2、四氧化三铁磁性纳米材料的制备:将2mol/L FeCl3·7H2O 12mL与1mol/LFeSO4·7H2O 15mL混合于150mL去离子水中,在氮气保护下,滴加50mL氨水使溶液体系pH为10,在70℃下水浴加热,搅拌速度为600 rpm下,恒温搅拌反应1.5h后,用去离子水洗涤至中性,40℃真空干燥12h,制得四氧化三铁磁性纳米材料;
3、在步骤1中得到的10mL饲料处理溶液中,加入3%(2g吡咯烷二硫代氨基甲酸铵溶于100mL蒸馏水中)吡咯烷二硫代氨基甲酸铵水溶液0.5mL,用1mol/L盐酸和1mol/L氢氧化钠调节溶液pH为3.5,加入非离子表面活性剂Triton X114 0.4mL,涡旋混合2min,在水浴50℃加热15min,得到混浊乳液;再加入制备好的四氧化三铁磁性纳米材料0.4g,涡旋混合3min,用磁铁收集磁性纳米材料,倒出溶液,然后加入乙腈2mL洗脱磁性纳米材料,进原子吸收分光光度计检测,得到镉含量为219μg/kg,铅含量为28μg/kg。
实施例3:白菜中镉和铅的测定
1、样品处理:将白菜样品清洗、干燥、粉碎,过1 mm 筛,准确称取2.5000g样品于微波消解罐中,加入消解试剂HNO3-H2O2(5:1,V/V)12.5mL,放入密闭微波消解系统,调节温度l80℃升温10min,并在该温度下恒温15min,微波输出功率l000w ;消解结束后,用水少量多次洗涤并转移消解液于聚四氟乙烯烧杯中,在可调式电热板上加热赶酸30min,然后用蒸馏水定容至10 mL,备用,同时做试剂空白测定;
2、将2mol/L Fe2(SO4)3·9H2O 10mL与1mol/L FeSO4·7H2O 12mL混合于150mL去离子水中,在氮气保护下,滴加50mL氨水使溶液体系pH为11,在80℃下水浴加热,搅拌速度为500 rpm下,恒温搅拌反应2h后,用去离子水洗涤至中性,50℃真空干燥10h,制得四氧化三铁磁性纳米材料;
3、在步骤1中得到的10mL白菜处理溶液中,加入2%(2g吡咯烷二硫代氨基甲酸铵溶于100mL蒸馏水中)吡咯烷二硫代氨基甲酸铵水溶液0.2mL,用1mol/L盐酸和1mol/L氢氧化钠调节溶液pH为3.0,加入非离子表面活性剂Tergitol TMN 6 0.5mL,涡旋混合2min,在水浴40℃加热20min,得到混浊乳液;再加入制备好的四氧化三铁磁性纳米材料0.25g,涡旋混合1min,用磁铁收集磁性纳米材料,倒出溶液,然后加入甲醇1mL洗脱磁性纳米材料,进原子吸收分光光度计检测,得到镉含量为5μg/kg,铅含量为77μg/kg。
实施例4:苹果中镉和铅的测定
1、样品处理:将苹果样品清洗、干燥、粉碎,过1 mm 筛,准确称取2.5000g样品于微波消解罐中,加入消解试剂HNO3-H2O2(5:1,V/V)12.5mL,放入密闭微波消解系统,调节温度l80℃升温10min, 并在该温度下恒温15min,微波输出功率l000w 。消解结束后,用水少量多次洗涤并转移消解液于聚四氟乙烯烧杯中,在可调式电热板上加热赶酸30min,然后用蒸馏水定容至10 mL,备用,同时做试剂空白测定;
2、四氧化三铁磁性纳米材料的制备:将2mol/L FeCl3·7H2O 10mL与1mol/LFeSO4·7H2O 11mL混合于160mL去离子水中,在氮气保护下,滴加50mL氨水使溶液体系pH12,在60℃下水浴加热,搅拌速度为800 rpm下,恒温搅拌反应1h后,用去离子水洗涤至中性,60℃真空干燥8h,制得四氧化三铁磁性纳米材料;
3、在步骤1中得到的10mL苹果处理溶液中,加入2%(2g吡咯烷二硫代氨基甲酸铵溶于100mL蒸馏水中)吡咯烷二硫代氨基甲酸铵水溶液0.1mL,用1mol/L盐酸和1mol/L氢氧化钠调节溶液pH为4.0,加入非离子表面活性剂Tergitol TMN 6 0.4mL,涡旋混合1min,在水浴45℃加热15min,得到混浊乳液;再加入制备好的四氧化三铁磁性纳米材料0.3g,涡旋混合2min,用磁铁收集磁性纳米材料,倒出溶液,然后加入甲醇1.5mL洗脱磁性纳米材料,进原子吸收分光光度计检测,得到镉含量为0.35μg/kg,铅含量为5.02μg/kg。
实施例5:大米中镉和铅的测定
1、样品处理:将大米样品粉碎,过1 mm 筛,称取约0.1 g(精确到0.0001 g) 样品于微波消解罐中,加入消解试剂HNO3-H2O2(5:1,V/V)5mL,放置预消解2h,放入微波炉中消解,微波消解程序:第一步,50% 功率,3min内自室温加热至120℃,保持3min;第二步,100%功率,3min内120℃加热至160℃,保持5min;第三步,100% 功率,3min内160℃加热至185℃,保持15min。微波消解完毕后将消解液冷却,将消解液转入10 mL量瓶中,用蒸馏水定容,备用,同时做试剂空白测定;
2、四氧化三铁磁性纳米材料的制备:将2mol/L Fe2(SO4)3·9H2O 6mL与1mol/LFeSO4·7H2O 12mL混合于150mL去离子水中,在氮气保护下,滴加50mL氨水使溶液体系pH为12,在80℃下水浴加热,搅拌速度为500 rpm下,恒温搅拌反应2h后,用去离子水洗涤至中性,70℃真空干燥6h,制得四氧化三铁磁性纳米材料;
3、在步骤1中得到的10mL大米处理溶液中,加入2%(2g吡咯烷二硫代氨基甲酸铵溶于100mL蒸馏水中)吡咯烷二硫代氨基甲酸铵水溶液0.3mL,用1mol/L盐酸和1mol/L氢氧化钠调节pH4.5,加入非离子表面活性剂Tergitol TMN 6 0.3mL,涡旋混合2min,在水浴40℃加热20min,得到混浊乳液;再加入制备好的四氧化三铁磁性纳米材料0.25g,涡旋混合1min,用磁铁收集磁性纳米材料,倒出溶液,然后加入乙腈2mL洗脱磁性纳米材料,进原子吸收分光光度计检测,得到镉含量为82μg/kg,铅含量为71μg/kg。
实施例1~5与电感耦合等离子体质谱比较结果见表1。
表1检测结果比较
由表1结果可知:用本发明测定的农副产品铅、镉含量与国家标准采用的微波消解结合ICP-MS法测定的铅、镉含量结果较吻合,说明方法具有可靠性。
Claims (7)
1.一种痕量镉和铅的检测方法,其特征在于包括以下步骤:
(1)按每10mL添加0.1~0.5mL吡咯烷二硫代氨基甲酸铵溶液的比例,在含有Pb2+、Cd2+的水溶液中加入吡咯烷二硫代氨基甲酸铵溶液,混合均匀;
(2)将步骤(1)得到的溶液调节pH为2.5~4.5,按每10mL添加0.2~0.5mL非离子表面活性剂的比例加入非离子表面活性剂,涡旋混合1~3min,加热,得到混浊乳液;
(3)在步骤(2)得到的混浊乳液中加入制备好的四氧化三铁磁性纳米材料,涡旋混合1~3min,用外磁场收集磁性纳米产物,倒出溶液,用洗脱剂洗脱磁性纳米产物,收集洗脱剂,洗脱剂进原子吸收分光光度计进行含量测定,其中四氧化三铁磁性纳米材料的添加量为每10mL混浊乳液中添加0.25~0.4g。
2.根据权利要求1所述的痕量镉和铅的检测方法,其特征在于:所述吡咯烷二硫代氨基甲酸铵溶液为质量体积比浓度为2%的水溶液。
3.根据权利要求1或2所述的痕量镉和铅的检测方法,其特征在于:所述非离子表面活性剂为聚乙二醇辛基苯基醚Triton X-114或支链仲醇聚氧乙烯醚Tergitol TMN 6。
4.根据权利要求3所述的痕量镉和铅的检测方法,其特征在于:所述步骤(2)加热温度为40~50℃,加热时间为10~20min。
5.根据权利要求4所述的痕量镉和铅的检测方法,其特征在于四氧化三铁磁性纳米材料的制备方法为:按照三价铁盐与二价铁盐的摩尔比为2.0~1.6:1的比例将三价铁盐溶液与二价铁盐溶液加入5~10倍的三价铁盐和二价铁盐溶液体积的去离子水中溶解,在氮气保护下,滴加氨水使溶液体系pH为9~12,在60~80℃、搅拌速度400~800 rpm下,水浴加热,恒温搅拌反应1~3h后,用去离子水洗涤至中性,40~80℃真空干燥6~12h制得。
6.根据权利要求5所述的痕量镉和铅的检测方法,其特征在于:三价铁盐为FeCl3·7H2O或Fe2(SO4)3·9H2O,二价铁盐为FeCl2·4H2O或FeSO4·7H2O。
7.根据权利要求5所述的痕量镉和铅的检测方法,其特征在于:所述的洗脱剂为乙腈、四氢呋喃、甲醇中的一种。
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