CN112067727A - 一种直接测定罐装茶饮料中七种痕量卤乙酸的气相色谱法 - Google Patents
一种直接测定罐装茶饮料中七种痕量卤乙酸的气相色谱法 Download PDFInfo
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Abstract
本发明涉及痕量物质分析检测方法,具体涉及到一种直接测定罐装茶饮料中七种痕量卤乙酸的气相色谱法,卤乙酸种类包括二氯乙酸、三氯乙酸、一溴一氯乙酸、二溴乙酸、一溴二氯乙酸、二溴一氯乙酸和三溴乙酸。方法步骤包括以叔丁醇与甲基叔丁基醚混合液萃取茶饮料中的卤乙酸,不经过衍生化处理,以配备强极性毛细管柱的气相色谱仪对其测定,采用基质曲线进行校正,外标法定量。本发明开发了针对罐装茶饮料中痕量卤乙酸的检测方法,弥补检测基质上缺失的不足;未对卤乙酸进行衍生化处理,有效简化了前处理方法;仅适用少量的有机溶剂作为目标物的萃取溶剂,具有显著的安全、快捷高效的优势。
Description
技术领域
本发明涉及痕量物质分析检测的方法,具体涉及到一种直接测定罐装茶饮料中痕量二氯乙酸(DCAA)、三氯乙酸(TCAA)、一溴一氯乙酸(BCAA)、二溴乙酸(DBAA)、一溴二氯乙酸(BDCAA)、二溴一氯乙酸(DBCAA)和三溴乙酸(TBAA)等七种卤乙酸化合物的气相色谱法。
背景技术
卤乙酸类化合物(Haloacetic acids,HAAs)是氯化消毒制备饮用水的主要消毒副产物(Disinfection by-products,DBPs)之一。研究表明,部分卤乙酸类化合物对动物具有生殖和发育毒性,具有在极低的暴露水平下引发癌症的风险,从而引起人们对其危害的高度重视。
人们主要关注水质中卤乙酸的残留分析检测研究,但对消费量巨大的罐装饮料类中HAAs的残留关注度低。当前对于罐装食品中卤乙酸的检测研究报道较少,已有方法对罐装茶饮料中HAAs的检测适用性和借鉴性不强,亟待开发适用罐装饮料中HAAs残留的快速检测方法。
由于HAAs分子结构中存在的卤素元素使得其可以在微电子检测器(μECD)上获得很高的检测灵敏度,因此采用配备微电子检测器的气相色谱法仍是检测HAAs的常见分析方法。同时,由于HAAs室温下具有极性强、易溶于水、难挥发的特点,在采用气相色谱法分析时常需要将其进行衍生化处理,以增强其挥发性。
当前尚未见不经过衍生化前处理而直接采用GC或GC-MS法对其分析的研究报道。衍生化处理存在过程复杂、操作繁琐耗时、方法重现性较差的缺点。因此“使用气相色谱法分析HAAs且避免采用衍生化前处理”仍是亟待解决的技术难题。
为了满足罐装茶饮料中HAAs残留检测的需求,同时解决采用气相色谱法需要衍生化处理的技术难题,本发明利用HAAs在高温下可挥发的特点,采用强极性的INNOWAX毛细管柱为分析色谱柱,优化前处理方法,建立了一种可不经衍生化而采用气相色谱直接测定罐装茶饮料中七种痕量HAAs残留的快速分析方法。
发明内容
为了克服当前罐装茶饮料中痕量卤乙酸同时检测方法缺乏以及前处理中需要进行衍生化的不足,本发明要解决的技术问题在于提供一种直接测定罐装茶饮料中七种痕量卤乙酸的气相色谱法。
本发明是通过以下技术方案来实现上述目标的。
一种直接测定罐装茶饮料中七种痕量卤乙酸的气相色谱法,包括如下步骤:
步骤1:向50mL具塞螺口离心管中添加20mL罐装茶水样品和1mL浓硫酸,添加8.0g的无水硫酸钠,并向其中添加2.00mL的叔丁醇与甲基叔丁基醚混合液,密封,以2500rpm涡旋15min,以4500rpm转速离心3min;全取上层液至10mL具塞螺口离心管中,向其中添加1.0mL的洗涤液,涡旋1min,吸取上层液体并经0.45μm滤膜过滤,待分析;
步骤2化合物的分析测试:将上述溶液应用气相色谱法按照下列条件进行分析测试:
a)色谱柱:HP-Innowax石英毛细管柱,30m×0.32mm,膜厚0.50μm;
b)进样口温度:240℃;
c)进样体积:1μL;进样方式:不分流进样;
d)载气:高纯氮气,纯度≥99.999%;载气流速:2.0min/L,恒流模式;尾吹气流速:60min/L;
e)升温程序:初始温度40℃(保持1min),以10℃/min速率升温至85℃,以10℃/min速率升温至180℃(保持1min),后运行250℃(保持3min);
f)检测器温度:300℃;
步骤3基质校正工作曲线的建立:取适量的七种卤乙酸标准使用液对空白的罐装绿茶样品进行加标,混合后得到阳性样品,按照上述步骤(1)“卤乙酸的萃取”规定进行操作得到系列浓度的基质校正工作曲线,最终用于仪器分析的的卤乙酸浓度分别为:10μg/L、20μg/L、50μg/L、100μg/L和200μg/L;
步骤4定量方法:以上述基质匹配标准溶液的测试峰面积和浓度绘制基质校正工作曲线,外标法定量分析溶液中的七种卤乙酸的含量。
其中,
步骤1中所述的叔丁醇与甲基叔丁基醚混合液中叔丁醇的体积占比为1%-5%。
步骤2中所述的洗涤液为饱和无水硫酸钠-碳酸氢钠混合物。
本发明的优点在于:
(1)本发明开发了针对罐装茶饮料中痕量卤乙酸的检测方法,弥补检测基质上缺失的不足;
(2)本发明未对卤乙酸进行衍生化处理,有效简化了前处理方法,具有快捷高效的特点;
(3)本发明仅适用少量的有机溶剂作为目标物的萃取溶剂,具有显著的安全、环保优点和经济优势。
附图说明
1.图1是具体实施方式中七种卤乙酸的基质标准溶液色谱图,其中二氯乙酸;2.三氯乙酸;3.一溴一氯乙酸;4.一溴二氯乙酸;5.二溴乙酸;6.二溴一氯乙酸;7.三溴乙酸;A是绿茶基质空白样;B是绿茶基质阳性样;C是溶剂标准溶液(10ng/mL)。
具体实施方式
为进一步公开而不是限制本发明,以下结合实例对本发明作进一步的详细说明。
1.本发明实施例中所涉及到的试剂药品如下:
二氯乙酸(DCAA)、三氯乙酸(TCAA)、一溴一氯乙酸(BCAA)、二溴乙酸(DBAA)、一溴二氯乙酸(BDCAA)、二溴一氯乙酸(DBCAA)和三溴乙酸(TBAA)等七种卤乙酸化合物,纯度≥98.5%(德国dr.ehrenstorfe公司)。
5%叔丁醇-甲基叔丁基醚混合液:将5mL叔丁醇与95mL甲基叔丁基醚混合。
无水硫酸钠-碳酸氢钠混合物:取等量的无水硫酸钠和碳酸氢钠研磨混合,添加至蒸馏水中溶解并保留底部留有未溶解盐。
七种卤乙酸标准储备液:准确称取适量标准品,用甲醇溶解并配置成浓度为1000.0mg/L的标准储备液,冷藏保存于-4℃的冰箱中,使用前根据检测要求以基质提取液稀释成相应浓度的标准工作溶液。
2.本发明实施例中所涉及到的仪器如下:
气相色谱仪,配备微电子检测器(μECD)和7683B液体自动进样器(美国安捷伦科技有限公司);HP-Innowax石英毛细管柱(30m×0.32mm×0.50μm)(美国安捷伦科技有限公司)。
3.分析步骤如下:
(1)卤乙酸的萃取:向50mL具塞螺口离心管中添加20mL罐装茶水样品和1mL浓硫酸,添加8.0g的无水硫酸钠,并向其中添加2.00mL的叔丁醇与甲基叔丁基醚混合液,密封,以2500rpm涡旋15min,以4500rpm转速离心3min;全取上层液至10mL具塞螺口离心管中,向其中添加1.0mL的洗涤液,涡旋1min,吸取上层液体并经0.45μm滤膜过滤,待分析;
(2)化合物的分析测试:将上述溶液应用气相色谱法按照下列条件进行分析测试:
a)色谱柱:HP-Innowax石英毛细管柱,30m×0.32mm,膜厚0.50μm;
b)进样口温度:240℃;
c)进样体积:1μL;进样方式:不分流进样;
d)载气:高纯氮气,纯度≥99.999%;载气流速:2.0min/L,恒流模式;尾吹气流速:60min/L;
e)升温程序:初始温度40℃(保持1min),以10℃/min速率升温至85℃,以10℃/min速率升温至180℃(保持1min),后运行250℃(保持3min);
f)检测器温度:300℃;
(3)基质校正工作曲线的建立:取适量的七种卤乙酸标准使用液对空白的罐装绿茶样品进行加标,混合后得到阳性样品,按照上述步骤(1)“卤乙酸的萃取”规定进行操作得到系列浓度的基质校正工作曲线,最终用于仪器分析的的卤乙酸浓度分别为:10μg/L、20μg/L、50μg/L、100μg/L和200μg/L;
(4)定量方法:以上述基质匹配标准溶液的测试峰面积和浓度绘制基质校正工作曲线,外标法定量分析溶液中的七种卤乙酸的含量。
以信噪比S/N的三倍值为方法的检测限(LOD,LOD=3S/N),以信噪比S/N的十倍为方法的定量限(LOQ,LOQ=10S/N),并结合添加基质的体积计算各个化合物在水中的检出限和定量限。
本发明所得的罐装绿茶样品基质的校正曲线相关参数见表1。
表1七种卤乙酸的回归方程、相关系数和线性范围
实施例1
本实施例1采用市售罐装冰绿茶为样品基质进行加标回收实验以验证本发明方法的可行性,样品购取自福州当地超市,并按照下列步骤进行处理:
(1)卤乙酸的萃取:向50mL具塞螺口离心管中添加20mL罐装茶水样品和1mL浓硫酸,添加8.0g的无水硫酸钠,并向其中添加2.00mL的1%叔丁醇与甲基叔丁基醚混合液,密封,以2500rpm涡旋15min,以4500rpm转速离心3min;全取上层液至10mL具塞螺口离心管中,向其中添加1.0mL的饱和无水硫酸钠-碳酸氢钠混合液,涡旋1min,吸取上层液体并经0.45μm滤膜过滤,待分析;
(2)化合物的分析测试:将上述溶液应用气相色谱法按照下列条件进行分析测试:
a)色谱柱:HP-Innowax石英毛细管柱,30m×0.32mm,膜厚0.50μm;
b)进样口温度:240℃;
c)进样体积:1μL;进样方式:不分流进样;
d)载气:高纯氮气,纯度≥99.999%;载气流速:2.0min/L,恒流模式;尾吹气流速:60min/L;
e)升温程序:初始温度40℃(保持1min),以10℃/min速率升温至85℃,以10℃/min速率升温至180℃(保持1min),后运行250℃(保持3min);
f)检测器温度:300℃;
(3)基质校正工作曲线的建立:取适量的七种卤乙酸标准使用液对空白的罐装绿茶样品进行加标,混合后得到阳性样品,按照上述步骤(1)“卤乙酸的萃取”规定进行操作得到系列浓度的基质校正工作曲线,最终用于仪器分析的的卤乙酸浓度分别为:10μg/L、20μg/L、50μg/L、100μg/L和200μg/L;
(4)定量方法:以上述基质匹配标准溶液的测试峰面积和浓度绘制基质校正工作曲线,外标法定量分析溶液中的七种卤乙酸的含量。
本实施例1的加标回收率实验相关参数见表2。
表2罐装冰绿茶样品的添加浓度及回收率实验数据(n=6)
实施例2
本实施例2采用市售罐装冰红茶为样品基质进行加标回收实验以验证本发明方法的可行性,样品购取自福州当地超市,并按照下列步骤进行处理:
(1)卤乙酸的萃取:向50mL具塞螺口离心管中添加20mL罐装茶水样品和1mL浓硫酸,添加8.0g的无水硫酸钠,并向其中添加2.00mL的5%叔丁醇与甲基叔丁基醚混合液,密封,以2500rpm涡旋15min,以4500rpm转速离心3min;全取上层液至10mL具塞螺口离心管中,向其中添加1.0mL的饱和无水硫酸钠-碳酸氢钠混合液,涡旋1min,吸取上层液体并经0.45μm滤膜过滤,待分析;
(2)化合物的分析测试:将上述溶液应用气相色谱法按照下列条件进行分析测试:
a)色谱柱:HP-Innowax石英毛细管柱,30m×0.32mm,膜厚0.50μm;
b)进样口温度:240℃;
c)进样体积:1μL;进样方式:不分流进样;
d)载气:高纯氮气,纯度≥99.999%;载气流速:2.0min/L,恒流模式;尾吹气流速:60min/L;
e)升温程序:初始温度40℃(保持1min),以10℃/min速率升温至85℃,以10℃/min速率升温至180℃(保持1min),后运行250℃(保持3min);
f)检测器温度:300℃;
(3)基质校正工作曲线的建立:取适量的七种卤乙酸标准使用液对空白的罐装绿茶样品进行加标,混合后得到阳性样品,按照上述步骤(1)“卤乙酸的萃取”规定进行操作得到系列浓度的基质校正工作曲线,最终用于仪器分析的的卤乙酸浓度分别为:10μg/L、20μg/L、50μg/L、100μg/L和200μg/L;
(4)定量方法:以上述基质匹配标准溶液的测试峰面积和浓度绘制基质校正工作曲线,外标法定量分析溶液中的七种卤乙酸的含量。
本实施例2的加标回收率实验相关参数见表3。
表3罐装冰红茶样品的添加浓度及回收率实验数据(n=6)
以上所述实施例仅表达了本发明的实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员而言,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些均属于本发明的保护范围,因此本发明专利的保护范围应以所附权利要求为准。
Claims (3)
1.一种直接测定罐装茶饮料中七种痕量卤乙酸的气相色谱法,具体涉及到罐装茶饮料中痕量二氯乙酸、三氯乙酸、一溴一氯乙酸、二溴乙酸、一溴二氯乙酸、二溴一氯乙酸和三溴乙酸共七种卤乙酸化合物的同时测定方法,其特征在于,包括如下步骤:
(1)卤乙酸的萃取:向50mL具塞螺口离心管中添加20mL罐装茶水样品和1mL浓硫酸,添加8.0g的无水硫酸钠,并向其中添加2.00mL的叔丁醇与甲基叔丁基醚混合液,密封,以2500rpm涡旋15min,以4500rpm转速离心3min;全取上层液至10mL具塞螺口离心管中,向其中添加1.0mL的洗涤液,涡旋1min,吸取上层液体并经0.45μm滤膜过滤,待分析;
(2)化合物的分析测试:将上述溶液应用气相色谱法按照下列条件进行分析测试:
(a)色谱柱:HP-Innowax石英毛细管柱,30m×0.32mm,膜厚0.50μm;
(b)进样口温度:240℃;
(c)进样体积:1μL;进样方式:不分流进样;
(d)载气:高纯氮气,纯度≥99.999%;载气流速:2.0min/L,恒流模式;尾吹气流速:60min/L;
(e)升温程序:初始温度40℃(保持1min),以10℃/min速率升温至85℃,以10℃/min速率升温至180℃(保持1min),后运行250℃(保持3min);
(f)检测器温度:300℃;
(3)基质校正工作曲线的建立:取适量的七种卤乙酸标准使用液对空白的罐装绿茶样品进行加标,混合后得到阳性样品,按照上述步骤(1)“卤乙酸的萃取”规定进行操作得到系列浓度的基质校正工作曲线,最终用于仪器分析的的卤乙酸浓度分别为:10μg/L、20μg/L、50μg/L、100μg/L和200μg/L;
(4)定量方法:以上述基质匹配标准溶液的测试峰面积和浓度绘制基质校正工作曲线,外标法定量分析溶液中的七种卤乙酸的含量。
2.如权利要求1所述一种直接测定罐装茶饮料中七种痕量卤乙酸的气相色谱法,其特征在于步骤(1)中所述的叔丁醇与甲基叔丁基醚混合液中叔丁醇的体积占比为1%-5%。
3.如权利要求1所述一种直接测定罐装茶饮料中七种痕量卤乙酸的气相色谱法,其特征在于步骤(1)中所述的洗涤液为饱和无水硫酸钠-碳酸氢钠混合液。
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