CN114965774B - 一种检测水产品中208种农药及其代谢物残留的方法 - Google Patents
一种检测水产品中208种农药及其代谢物残留的方法 Download PDFInfo
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Abstract
本发明提供一种检测水产品中208种农药及其代谢物残留的方法,采用ASE快速溶剂萃取,通过对萃取温度、萃取溶剂种类和在萃取池中吸附剂的优化选择,优化前处理过程,从而达到对多种农药残留同时检测的目的。该方法一方面对水产类产品具有通用性,尤其是对河蟹类高脂肪、高蛋白、基质复杂的产品,能够达到很好的在线萃取净化效果,实现批处理样品。另外一方面解决了不同种类农药检测需要不同前处理、不同检测仪器的技术瓶颈,实现了多残留农药同时检测。本方法实现了水产品中208种农药及其代谢物残留的检测方法,为科学合理使用农药,控制水产品农药残留起到积极作用,同时也为水产品质量安全综合评价提供数据支撑。
Description
技术领域
本发明涉及农药检测分析领域,具体涉及一种检测水产品中208种农药及其代谢物残留的方法。
背景技术
随着食品安全意识的提高,多种农药残留检测的需求已从单纯的植物源性食品延伸到了动物源性食品,日益成为人们关注的焦点。农药残留是指使用农药防治病虫害后一个时期内没有分解而残存于收获物、土壤、水源、大气中的那部分农药及其有毒衍生物。农药以养殖环境(养殖水、池塘底泥、投入品等)为媒介,通过食物链富集在水生动物体内,最终食用受污染的水产品在人体积累后,对机体进而产生明显的毒害作用。近年来,农药新种类越来越多,针对农药多残留检测的种类和标准越来越多,由于农药种类性质不同,水产品样品的基质复杂干扰因素较多,特别是脂类物质严重影响分离效果,因此需要对应多个标准、多种前处理过程和多种检测仪器才能完成,建立不同种类农药多残留检测技术成为农药残留检测的瓶颈。尽可能检测出较多的农药种类,对水产品质量安全也具有重要意义。
目前常用的前处理方法有超声波提取,索氏抽提,加速溶剂萃取/凝胶渗透色谱净化,固相萃取,QuEChERS,方法各有利弊,如凝胶渗透色谱净化法,虽然在分离分子大小上有优势,但受柱容量有限,尤其针对脂肪含量高的河蟹样品,并不能有效去除脂肪以达到净化的效果,且设备昂贵,耗时长,溶剂消耗较多。QuEChERS净化包在前处理上具有便捷性,但是水产品批量检测中经常面临样品基质不同(如河蟹成熟度不同,脂肪含量差异性大),QuEChERS的净化填料也需要不同,增加了批量检测复杂度;另外提取需要进行溶剂置换,也增加了操作难度及工作量。实验室通用的固相萃取法,SPE小柱选取合适的话,其净化效果和回收率也较为理想,但操作效率较低,需要手动操作。
发明内容
为解决现有技术存在的缺陷,本发明拟通过优化水产品样品前处理,利用自动萃取技术,对萃取温度、萃取溶剂种类和在萃取池中吸附剂的优化,以达到在短时间内完成复杂基质样品多种农药残留同时萃取的目的。本发明以富集、净化效果好和通用性强为特点,同时具有时间短,省溶剂,省劳力优点,通过对水产品多种农药残留的监测,为科学合理使用农药,控制水产品农药残留起到积极作用,同时也为水产品质量安全综合评价提供数据支撑。为达到上述目的,本发明提供的技术方案是:一种检测水产品中208种农药及其代谢物残留的方法,其包括:
(1):将水产品可食用部分与硅藻土混合均匀,粉碎机打成匀浆,得到样品与硅藻土混合填料,备用;所述水产品可食用部分与硅藻土混合比例为5:(3-5),所述水产品可食用部分的脂肪含量为0.5%-15%;
(2):在萃取池中依次加入氧化铝AL2O3、石墨化炭黑GCB、十八烷基硅烷键合硅胶C18、乙二胺-N-丙基硅烷化硅胶PSA填料,再加入样品与硅藻土混合填料,最后用硅藻土填满萃取池;
(3):Dionex ASE 350加速溶剂萃取仪萃取,得到萃取液40mL,其中萃取条件如下:
系统压力:10Mpa(1500psi)
温度:60℃-100℃
加热时间:5min
静态时间:5min
溶剂:乙腈和二氯甲烷;
冲洗体积:60%
N2吹扫:1Mpa(150psi),60s;
(4):萃取液于40℃水浴下氮气吹至近干,加入50μL 10mg/L环氧七氯内标液,用乙酸乙酯定容至1mL,得到样品溶液;
(5):将所述样品溶液采用气相色谱/串联三重四级杆质谱GC-MS/MS进行分析,得到残留量。
优选的,按质量份数计,氧化铝AL2O3为0.5份、石墨化炭黑GCB为2份、十八烷基硅烷键合硅胶C18为1份,乙二胺-N-丙基硅烷化硅胶PSA为1份。
优选的,所述乙腈和二氯甲烷的体积比为(0.5-2):(0.5-2),所述水产品选自鱼、小龙虾或河蟹中的一种或几种。
优选的,所述乙腈和二氯甲烷的体积比为(1:1)或(2:1)或(1:2)。
优选的,所述河蟹,其作为样品的脂肪含量为10%-15%;所述小龙虾,其作为样品的脂肪含量为1%-2%;
所述草鱼,其作为样品的脂肪含量为0.5%-1%;
优选的,所述农药包括乙酰甲胺磷、乙草胺、苯草醚、氟丙菊酯、甲草胺、艾氏剂、烯丙菊酯、莠灭净、莎稗磷、阿特拉通、莠去津、脱乙基莠去津、益棉磷、氟丁酰草胺、苯霜灵、乙丁氟灵、α-六六六、β-六六六、δ-六六六、γ-六六六、甲羧除草醚、联苯菊酯、联苯、啶酰菌胺、除草定、溴苯烯磷、乙基溴硫磷、溴硫磷、溴螨酯、乙嘧酚磺酸酯、丁草胺、抑草磷、克百威、三硫磷、氯丹-反式、杀螨酯、毒虫畏-反式、毒虫畏-顺式、乙酯杀螨醇、氯苯甲醚、氯苯胺灵、毒死蜱、甲基毒死蜱、虫螨磷-1、虫螨磷-2、异噁草酮、蝇毒磷、环草敌、环氟菌胺、氟氯氰菊酯-1、氟氯氰菊酯-2、氟氯氰菊酯-3、氟氯氰菊酯-4、高效氯氟氰菊酯-1、高效氯氟氰菊酯-2、氯氰菊酯-1、氯氰菊酯-2、氯氰菊酯-3、氯氰菊酯-4、环丙唑醇-1、环丙唑醇-2、嘧菌环胺、4,4'-滴滴滴、2,4'-滴滴滴、2,4'-滴滴伊、4,4'-滴滴伊、2,4'-滴滴涕、4,4'-滴滴涕、溴氰菊酯-1、溴氰菊酯-2、敌草净、二嗪磷、敌草腈、除线磷、敌敌畏、禾草灵、氯硝胺、三氯杀螨醇、百治磷、狄氏剂、苯醚甲环唑-1、苯醚甲环唑-2、乐果、烯唑醇、敌噁磷、二苯胺、异丙净、灭菌磷、敌瘟磷、α-硫丹、β-硫丹、异狄氏剂、苯硫膦、氟环唑-1、氟环唑-2、乙丁烯氟灵、硫草敌、乙硫磷、乙氧呋草黄、灭线磷、乙螨唑、土菌灵、乙嘧硫磷、伐灭磷、咪唑菌酮、氯苯嘧啶醇、腈苯唑、皮蝇磷、杀螟硫磷、仲丁威、苯硫威、甲氰菊酯、丰索磷、倍硫磷、倍硫磷砜、倍硫磷亚砜、氰戊菊酯-1、氰戊菊酯-2、氟虫腈、吡氟禾草灵、氟氰戊菊酯-1、氟氰戊菊酯-2、咯菌腈、三氟硝草醚、氟喹唑、氟酰胺、氟胺氰菊酯-1、氟胺氰菊酯-2、地虫硫膦、安硫磷、噻唑膦-1、噻唑膦-2、六氯苯、己唑醇、环嗪酮、环氧七氯B、抑霉唑、异稻瘟净、异菌脲、氯唑磷、水胺硫磷、氧异柳磷、异柳磷、甲基异柳磷、异丙威、稻瘟灵、噁唑啉、醚菌酯、溴苯膦、马拉氧磷、马拉硫磷、苯噻酰草胺、嘧菌胺、地胺磷、甲霜灵、虫螨畏、甲胺磷、杀扑磷、烯虫酯、甲氧滴滴涕、异丙甲草胺、嗪草酮、速灭磷、禾草敌、久效磷、绿谷隆、腈菌唑、二溴磷、敌草胺、除草醚、氧乐果、噁草酮、噁霜灵、乙氧氟草醚、多效唑、对氧磷、甲基对氧磷、对硫磷、甲基对硫磷、戊菌唑、二甲戊灵、五氯苯胺、氯菊酯-1、氯菊酯-2、甲拌磷、甲拌磷砜、甲拌磷亚砜、伏杀硫磷、硫环磷、亚胺硫磷、磷胺-1、磷胺-2、增效醚、哌草磷、抗蚜威、嘧啶磷、甲基嘧啶磷、丙草胺、腐霉利、丙溴磷、环丙氟灵、扑草净、炔苯酰草胺、敌稗、扑灭津、胺丙畏、丙环唑-1、丙环唑-2、残杀威、丙硫磷、吡菌磷、哒螨灵、哒嗪硫磷、嘧霉胺、吡丙醚、喹硫磷、喹氧灵、五氯硝基苯、西玛津、治螟磷、戊唑醇、吡螨胺、丁基嘧啶磷、四氯硝基苯、特丁硫磷、特丁硫磷砜、特丁津、特丁净、杀虫畏、四氟醚唑、三氯杀螨砜、胺菊酯-1、胺菊酯-2、禾草丹、虫线磷、甲基立枯磷、三唑酮、三唑醇、野麦畏、三唑磷、脱叶磷、毒壤膦、肟菌酯、乙烯菌核利中的一种或几种。
优选的,步骤5中,色谱条件如下:色谱柱DB35-MS 30m×0.25mm×0.25μm;进样口温度280℃;载气为99.999%高纯氦气;不分流进样,进样量1μL;流量1.2mL/min;柱升温程序:初始温度40℃,保持1.5min,以25℃/min升至90℃,保持1.5min,25℃/min升至180℃,5℃/min升至280℃,10℃/min升至300℃保持5min。
优选的,步骤5中,质谱条件如下:质谱条件:EI源;离子源温度:300℃;传输线温度280℃;采集方式:Time-SRM;
本发明的有益效果如下:
1.本发明填料中使用硅藻土混合。常规操作手段中,在前处理过程中加入烘过的无水硫酸钠或者硫酸镁去除水产品中的水分,一方面是因为水会阻碍非极性有机溶剂与目标萃取物的充分接触;另一方面是因为,气相色谱有避免引入样品水分的要求。本发明填料中使用硅藻土混合,它具有吸收水分的功能,一个步骤既去除了样品中的水分,样品与硅藻土充分混合又增大了样品的表面积,使得溶剂与样品接触面增大,提高高温高压下样品具有更高的萃取效率。
2.通过对萃取温度、萃取溶剂种类和在萃取池中吸附剂的优化选择,本发明在ASE的控制模式,,不同批次或种类样品都以相同的条件进行萃取,不必专人调试程序,也避免了人工前处理操作的差异,实现了流程标准化流程和多种类样品批处理,处理效果重现性好,大大提高了工作效率,具有很好的推广前景。
3.本发明中,各种填料经过实验优化,按一定顺序填在萃取池的出口端以吸附脂肪类等非目标共萃物。通过对水产类鱼虾蟹产品前处理对比,确定了填料的通用性布置方式,尤其是河蟹类等高脂肪、高蛋白、基质复杂的产品中,能够达到很好的在线萃取净化效果。比起传统萃取技术先全萃取脂类物质再使用分离技术如(GPC、SPE等)的方法,本发明具有更高的回收率和每种组分更干净的优点。
4.本方法涉及对水产品样品前处理的优化,实行该程序,每个样品仅需15min,溶剂消耗小于40mL,相较于传统处理方法,无需溶剂置换,离心等前处理,明显节省时间、人力及溶剂的消耗。在后续仪器分析前不需要进行任何其他后处理过程,使实验操作简单、快捷。
5.本发明通过对工作液进行GC-MS/MS上样测定,开展线性回归分析,获得了208种农药及代谢物的线性曲线,针对样品油脂含量筛选出最佳色谱条件(见步骤四),控制基质标准曲线浓度在0.01-0.50mg/L范围内,R2范围0.93-0.99之间,其中R2大于0.99的化合物占化合物总数的94.2%。方法检出限以3倍信噪比计算得到检出限(LOD),以10倍为定量限(LOQ),定量限范围为0.23-9.88μg/kg;以样品(草鱼、克原氏螯虾、中华绒螯蟹)作为样本进行添加实验,添加水平在0.010-0.05mg/kg,回收率在51.7-129.1%之间,相对标准偏差在0.39-14.12%之间,超过81.73%化合物回收率在60-120%之间,验证了同时进行定量多农药检测方法的有效性。
6.通过本申请的实验方法处理样品,随后再进行农药残留检测,能够有效分离待检物,减少基质效应的影响,对于提高检测精度有显著的作用。
附图说明
图1为ASE萃取池类填料及含量的示意图,即在纤维素滤膜上从下到上依次平铺AL2O3、GCB、C18、PSA填料;
图2为河蟹样品前处理萃取液对比图,从左到右依次为1、2、3号管,其中试管1号为填料只有硅藻土;试管2号为填料(PSA:C18:GCB:AL2O3)用量为(0.5:0.5:0.5:0.5),处理结果图;试管3号为填料顺序(PSA:C18:GCB:AL2O3)用量为(1:1:2:0.5)结果图;
图3为河蟹样品前处理萃取液对比图,从左到右依次为1、2、3、4、5、6号管;
图4为试剂不同体积比下208种化合物回收率范围占比结果图;
图5为不同温度下208种化合物回收率范围占比结果图;
图6为河蟹基质中208种农药及代谢物MRM色谱图,从图中可知其具有高准确性、高效性及基质干扰小的优点,能够满足检测条件的要求;
图7为鱼、小龙虾、螃蟹基质中208种农药定量限(LOQ)分布图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合说明书附图对本发明的具体实施方式做详细的说明。
实施例1
(1)采集选取200g代表性中华绒螯蟹样品,取可食部分,在高速均质器内充分粉碎、均质备用;测得样品脂肪含量12.6%,称取5g样品,与5g Hydromatrix硅藻土混合并研磨,得到样品与硅藻土混合填料,备用;
(2)在萃取池(34mL)中依次加入一片纤维素过滤片、0.5g氧化铝AL2O3、2g石墨化炭黑GCB、1g十八烷基硅烷键合硅胶C18和1g乙二胺-N-丙基硅烷化硅胶PSA填料,再加入样品与硅藻土混合填料,最后用硅藻土填满萃取池;如图1;
(3)用Dionex ASE 350加速溶剂萃取仪萃取,得到萃取液40mL,萃取条件如下:
系统压力:10Mpa(1500psi)
温度:100℃
加热时间:5min
静态时间:5min
溶剂:乙腈/二氯甲烷(1:2),(V/V)
冲洗体积:60%
N2吹扫:1Mpa(150psi),60s
(4)萃取液于40℃水浴下氮气吹至近干,加入50μL环氧七氯内标液(10mg/L),用乙酸乙酯定容至1mL,用于后续上机测定;
(5)使用赛默飞三重四级杆气质联用仪型号(TSQ 9000MS and TRACE 1300),色谱条件和质谱条件如下,
色谱条件:色谱柱DB35-MS(30m×0.25mm×0.25μm);进样口温度280℃;载气为99.999%高纯氦气;不分流进样,进样量1μL;流量1.2mL/min;柱升温程序:初始温度40℃,保持1.5min,以25℃/min升至90℃,保持1.5min,25℃/min升至180℃,5℃/min升至280℃,10℃/min升至300℃保持5min;
质谱条件:EI源;离子源温度:300℃;传输线温度280℃;采集方式:Time-SRM;各种农药名称及内标物的定性、定量离子见表3。
(6)建立基质标准曲线(内标法定量),分别吸取适量的农药标准储备液及内标储备液(天津阿尔塔科技有限公司,1ST27671-100E,100ug/mL,1ST27672-100E,100ug/mL,化合物名称见表3,共208种),用乙酸乙酯稀释,配置成浓度为5,10,25,100,250,500ng/mL的标准工作液。空白基质溶液氮气吹近干,加入50μL环氧七氯内标液(10mg/L),分别加入1mL上述标准工作溶液复溶,过微孔滤膜配置成系列基质混合标准溶液,供上机测定。以农药定量离子峰面积和内标物定量离子峰面积的比值为纵坐标、农药标准溶液质量浓度和内标物质浓度的比值为横坐标,绘制标准曲线,相关系数R2范围0.93-0.99之间,其中R2大于0.99的化合物占化合物总数的95.2%。
本发明方法的检出限与定量限:通过混标溶液经过前处理和进样分析,以3倍信噪比计算得到检出限(LOD),以10倍为定量限(LOQ),检测限范围为0.14~2.44μg/kg,定量限范围在0.48~2.97ug/kg之间,具体统计如图6。
本发明方法的重复性和加标回收率:
在蟹样品中加入混合农药的标准溶液,按照蟹样品前处理方法进行前处理(步骤1)、GC-MS/MS分析(步骤2-5),并按照加标量和测定值计算其回收率208种农药及代谢物在三个浓度水平10、25、50μg/kg,添加回收率范围在51.7-126.9%,平均相对标准偏差(RSD)小于14.9%,超过81.7%的化合物回收率在60-120%。
实施例2
(1)采集选取500g代表性草鱼样品,取可食部分,在高速均质器内充分粉碎、均质备用;样品的脂肪含量为0.53%;称取5g样品,与3g Hydromatrix硅藻土混合并研磨,得到样品与硅藻土混合填料备用;
(2)在萃取池(34mL)中依次加入一片纤维素过滤片、0.2g氧化铝AL2O3、0.3g石墨化炭黑GCB、0.2g十八烷基硅烷键合硅胶C18、0.4g乙二胺-N-丙基硅烷化硅胶PSA填料,再加入样品与硅藻土混合填料,最后用硅藻土填满萃取池;
(3)用Dionex ASE 350加速溶剂萃取仪萃取,得到萃取液40mL,
萃取条件如下:
系统压力:10Mpa(1500psi)
温度:100℃
加热时间:5min
静态时间:5min
溶剂:乙腈/二氯甲烷(1:2),(V/V)
冲洗体积:60%
N2吹扫:1Mpa(150psi),60s
(4)萃取液于40℃水浴下氮气吹至近干,加入100μL环氧七氯内标液(10mg/L),用乙酸乙酯定容至1mL,用于后续上机测定;
(5)使用赛默飞三重四级杆气质联用仪型号(TSQ 9000MS and TRACE 1300),色谱条件和质谱条件如下,
色谱条件:色谱柱DB35-MS(30m×0.25mm×0.25μm);进样口温度280℃;载气为99.999%高纯氦气;不分流进样,进样量1μL;流量1.2mL/min;柱升温程序:初始温度40℃,保持1.5min,以25℃/min升至90℃,保持1.5min,25℃/min升至180℃,5℃/min升至280℃,10℃/min升至300℃保持5min
质谱条件:EI源;离子源温度:300℃;传输线温度280℃;采集方式:Time-SRM;各种农药名称及内标物的定性、定量离子见表3。
(6)建立基质标准曲线(内标法定量),分别吸取适量的农药标准储备液及内标储备液(天津阿尔塔科技有限公司,1ST27671-100E,100ug/mL,1ST27672-100E,100ug/mL,化合物名称见表3),用乙酸乙酯稀释,配置成浓度为5,10,25,100,250,500ng/mL的标准工作液。空白基质溶液氮气吹近干,加入50μL环氧七氯内标液(10mg/L),分别加入1mL上述标准工作溶液复溶,过微孔滤膜配置成系列基质混合标准溶液,供上机测定。以农药定量离子峰面积和内标物定量离子峰面积的比值为纵坐标、农药标准溶液质量浓度和内标物质浓度的比值为横坐标,绘制标准曲线,相关系数R2范围0.95-0.99之间,其中R2大于0.99的化合物占化合物总数的95.7%。
本发明方法的检出限与定量限:通过混标溶液经过前处理和进样分析,以3倍信噪比计算得到检出限(LOD),以10倍为定量限(LOQ),检测限范围为0.10~2.44μg/kg,定量限范围在0.32~8.06μg/kg之间,具体统计如下图6;
本发明方法的重复性和加标回收率:
以草鱼样品为例,在草鱼肉样品中加入混合农药的标准溶液,进行按照鱼肉样品的前处理方法进行处理,GC-MS/MS分析,并按照加标量和测定值计算其回收率208种农药及代谢物在三个浓度水平10、25、50μg/kg添加回收率范围在54.3-129.1%,平均相对标准偏差(RSD)小于14.8%,超过84.6%的化合物回收率在60-120%。
实施例3
(1)采集选取500g代表性克原氏螯虾取可食部分样品,在高速均质器内充分粉碎、均质备用;测得样品脂肪含量1.9%,称取5g样品,与3g Hydromatrix硅藻土混合并研磨,得到样品与硅藻土混合填料,备用;
(2)在萃取池(34mL)中依次加入一片纤维素过滤片、0.2g氧化铝AL2O3、0.25g石墨化炭黑GCB、0.2g十八烷基硅烷键合硅胶C18、0.2g乙二胺-N-丙基硅烷化硅胶PSA填料,再加入样品与硅藻土混合填料,最后用硅藻土填满萃取池;
(3)用Dionex ASE 350加速溶剂萃取仪萃取,得到萃取液40mL;
萃取条件如下:
系统压力:10Mpa(1500psi)
温度:100℃
加热时间:5min
静态时间:5min
溶剂:乙腈/二氯甲烷(1:2),(V/V)
冲洗体积:60%
N2吹扫:1Mpa(150psi),60s 100μL环氧七氯内标液(10mg/L),用乙酸乙酯定容至1mL,用于后续上机测定;
(5)使用赛默飞三重四级杆气质联用仪型号(TSQ 9000MS and TRACE 1300),色谱条件和质谱条件如下,
色谱条件:色谱柱DB35-MS(30m×0.25mm×0.25μm);进样口温度280℃;载气为99.999%高纯氦气;不分流进样,进样量1μL;流量1.2mL/min;柱升温程序:初始温度40℃,保持1.5min,以25℃/min升至90℃,保持1.5min,25℃/min升至180℃,5℃/min升至280℃,10℃/min升至300℃保持5min
质谱条件:EI源;离子源温度:300℃;传输线温度280℃;采集方式:Time-SRM;各种农药名称及内标物的定性、定量离子见表3。
(6)建立基质标准曲线(内标法定量),分别吸取适量的农药标准储备液及内标储备液(天津阿尔塔科技有限公司,1ST27671-100E,100ug/mL,1ST27672-100E,100ug/mL,化合物名称见表3),用乙酸乙酯稀释,配置成浓度为5,10,25,100,250,500ng/mL的标准工作液。空白基质溶液氮气吹近干,加入50μL环氧七氯内标液(10mg/L),分别加入1mL上述标准工作溶液复溶,过微孔滤膜配置成系列基质混合标准溶液,供上机测定。以农药定量离子峰面积和内标物定量离子峰面积的比值为纵坐标、农药标准溶液质量浓度和内标物质浓度的比值为横坐标,绘制标准曲线,相关系数R2范围0.94-0.99之间,其中R2大于0.99的化合物占化合物总数的94.2%。
本发明方法的检出限与定量限:通过混标溶液经过前处理和进样分析,以3倍信噪比计算得到检出限(LOD),以10倍为定量限(LOQ),检测限范围为0.07~2.94μg/kg,定量限范围在0.23~9.80ug/kg之间,具体统计如下图6;
本发明方法的重复性和加标回收率:
在小龙虾样品中加入混合农药的标准溶液,按照虾样品前处理方法进行前处理,GC-MS/MS分析,并按照加标量和测定值计算其回收率208种农药及代谢物在三个浓度水平10、25、50μg/kg,添加回收率范围在55.7-127.4%,平均相对标准偏差(RSD)小于14.4%,超过82.7%的化合物回收率在60-120%。
样品的脂肪含量对萃取效果有影响,进而影响农药检出效果,为了保证实验效果,实施例1-3中适用的水产品样品脂肪含量范围如下表1,且不同脂肪含量的水产品样品,填料各成分的用量也有差异。
表1适用的水产品样品脂肪含量范围
样品 | 脂肪含量(%) |
河蟹 | 10-15 |
小龙虾 | 1-2 |
草鱼 | 0.5-1 |
对比例1
农药类化合物经常采用丙酮、乙腈多种有机溶剂提取,乙腈与丙酮能够与不同种类农药具有较好的溶解度,但是丙酮其提取液种基质多且复杂。本发明以河蟹为样品,参照实施例1,用Dionex ASE 350加速溶剂萃取仪萃取,得到萃取液40mL左右,其中萃取溶剂优选乙腈作为溶剂,并针对有机磷农药在乙腈溶剂提取下效率较低的问题,加入二氯甲烷以提高有机磷回收率,具体用量上如图4所示。
用Dionex ASE 350加速溶剂萃取仪萃取的萃取条件如下:
系统压力:10Mpa(1500psi)
温度:100℃
加热时间:5min
静态时间:5min
溶剂:乙腈/二氯甲烷,体积比分别为(0:1)、(1:1)、(2:1)、(1:2)、(1:0);
冲洗体积:60%
N2吹扫:1Mpa(150psi),60s
回收率占比结果见图4,根据试验结果,选用乙腈:二氯甲烷(1:2)为优化后的试验条件。
对比例2
PSA能够有效去除有机酸、糖苷类物质,Al2O3与C18能够去除脂类化合物,GCB能够去除色素,填料的布置次序和用量都会影响萃取效果。本发明以河蟹为样品,研究了不同种类填料的布置方式,其他实验步骤均参照实施例1。结合溶剂流出的方向,优选在纤维素滤膜上从下到上分别平铺Al2O3、GCB、C18、PSA填料(图1),用Dionex ASE 350加速溶剂萃取仪萃取,得到萃取液40mL左右。
萃取条件如下:
系统压力:10Mpa(1500psi)
温度:100℃
加热时间:5min
静态时间:5min
溶剂:乙腈/二氯甲烷(1:2),(V/V)
冲洗体积:60%
N2吹扫:1Mpa(150psi),60s
从本次实验结果(图2)来看,试管1号为填料只有硅藻土;试管2号为填料按照图1顺序添加(PSA:C18:GCB:AL2O3)用量为(0.5:0.5:0.5:0.5),处理结果图;试管3号为本方法填料顺序处理,(PSA:C18:GCB:AL2O3)用量为(1:1:2:0.5)结果图,3号试管萃取液澄清。从萃取后溶剂的色泽等外观初步分析,可以初步判断2、3号试管的填料顺序比较合适;但填料的含量是否足量是导致萃取是否完全充分的主要原因,其是否能满足检测需求就需要上机测试。
在3号试管基础上,为确定填料最佳含量,按照表2的填料用量进行实验,以河蟹为样品,按照表中添加相应的填料,参照实施例1,用Dionex ASE 350加速溶剂萃取仪萃取,得到萃取液40mL。
萃取条件如下:
系统压力:10Mpa(1500psi)
温度:100℃
加热时间:5min
静态时间:5min
溶剂:乙腈/二氯甲烷(1:2),(V/V)
冲洗体积:60%
N2吹扫:1Mpa(150psi),60s
前处理后结果如图3,以前处理后的试管是否澄清透明、去除油脂含量为判断标准,从外观辨别可见填料含量不同,试管1-6,填料用量依次减少,萃取后试剂颜色也越来越深,表示油脂含量越来越高,其中试管1号为本发明的填料方法,确定(PSA:C18:GCB:AL2O3)用量为(1:1:2:0.5)g。考虑经济成本与前处理净化效果的前提下,试管1号为最适宜添加量,不再做高于试管1号用量的实验。
表2试验不同填料表
填料种类 | PSA(g) | C18(g) | GCB(g) | AL2O3(g) |
试管1号 | 1 | 1 | 2 | 0.5 |
试管2号 | 1 | 1 | 1.5 | 0.5 |
试管3号 | 0.75 | 1 | 1 | 0.5 |
试管4号 | 0.5 | 0.75 | 0.75 | 0.5 |
试管5号 | 0.5 | 0.5 | 0.75 | 0.5 |
试管6号 | 0.5 | 0.5 | 0.50 | 0.25 |
对比例3
不同温度下,溶剂萃取效率不同。本方法设定从60~120℃下,加入25ug/kg的标准溶液(天津阿尔塔科技有限公司,1ST27671-100E,100ug/mL,1ST27672-100E,100ug/mL),以河蟹为样品,萃取条件其余参数与实施例1相同。
根据208种化合物回收率在一定范围内的个数(或占比),来判断条件是否更优化。总的回收率情况,如图5,发现在80℃、100℃,208种化合物中大约86%的化合物回收率都能达到60%-120%范围内,随着温度的升高,120℃,回收率60~120%范围内明显减少,分析发现,有机磷类物质减少明显,由于有机磷等农药随着温度的升高而分解,进一步分析发现,回收率在90%-110%范围内的化合物,100℃多于80℃,因此最终选用100℃。
本发明提供一种应用于水产品中208种农药及其代谢物残留检测方法。该方法采用ASE快速溶剂萃取,通过对萃取温度、萃取溶剂种类和在萃取池中吸附剂的优化选择,优化前处理过程,从而达到对多种农药残留同时检测的目的。方法采用乙腈/二氯甲烷(1:2)提取,在萃取池中按顺序添加一定数量的填料(氧化铝、石墨化炭黑、十八烷基硅烷键合硅胶、乙二胺-N-丙基硅烷化硅胶),比起使用传统萃取加后净化如GPC、SPE等方法,能明显节省时间、人力及溶剂的消耗。在后续仪器分析前不需要进行任何其他后处理过程。该方法一方面对水产类产品具有通用性,尤其是在河蟹类高脂肪、高蛋白、基质复杂的产品,能够达到很好的在线萃取净化效果,实现批处理样品。另外一方面解决了不同种类农药检测需要不同前处理、不同检测仪器的技术瓶颈,实现了多残留农药同时检测。本方法实现了水产品中208种农药及其代谢物残留的检测方法,为科学合理使用农药,控制水产品农药残留起到积极作用,同时也为水产品质量安全综合评价提供数据支撑。
表3化合物名称、出峰时间及定量、定性离子
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应说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (5)
1.一种检测水产品中208种农药及其代谢物残留的方法,其特征在于:包括
(1):将水产品可食用部分与硅藻土混合均匀,粉碎机打成匀浆,得到样品与硅藻土混合填料,备用;所述水产品可食用部分与硅藻土混合比例为5:(3-5),所述水产品可食用部分的脂肪含量为0.5%-15%;
(2):在萃取池中依次加入氧化铝AL2O3、石墨化炭黑GCB、十八烷基硅烷键合硅胶C18、乙二胺-N-丙基硅烷化硅胶PSA填料,按质量份数计,氧化铝AL2O3 为0.5 份,石墨化炭黑GCB为2份,十八烷基硅烷键合硅胶C18为1份,乙二胺-N-丙基硅烷化硅胶PSA为1份,再加入样品与硅藻土混合填料,最后用硅藻土填满萃取池;
(3):Dionex ASE 350加速溶剂萃取仪萃取,得到萃取液40 mL,其中萃取条件如下:
系统压力: 10 Mpa
温度: 60℃-100℃
加热时间: 5 min
静态时间: 5 min
溶剂:乙腈和二氯甲烷,所述乙腈和二氯甲烷的体积比为(0.5-2):(0.5-2);
冲洗体积: 60 %
N 2 吹扫: 1Mpa,60 s;
(4):萃取液于40 ℃水浴下氮气吹至近干,加入50μL 10 mg/L的环氧七氯内标液,用乙酸乙酯定容至1 mL,得到样品溶液;
(5):将所述样品溶液采用气相色谱/串联三重四级杆质谱 GC-MS/MS进行分析,得到残留量,其中,色谱柱DB35-MS 30 m×0.25 mm×0.25 μm;进样口温度280℃;载气为99.999%高纯氦气;不分流进样,进样量1 μL;流量1.2 mL/min;柱升温程序:初始温度40 ℃,保持1.5 min,以 25 ℃/min升至90 ℃,保持1.5 min,25 ℃/min升至180 ℃,5 ℃/min升至280℃,10℃/min升至300 ℃保持5 min;EI源;离子源温度:300 ℃;传输线温度280℃;采集方式:Time-SRM。
2.根据权利要求1所述的检测水产品中208种农药及其代谢物残留的方法,其特征在于:所述水产品可食用部分选自草鱼、小龙虾或河蟹中的一种或几种。
3.根据权利要求1所述的检测水产品中208种农药及其代谢物残留的方法,其特征在于:所述乙腈和二氯甲烷的体积比为1:1或2:1或1:2。
4.根据权利要求2所述的检测水产品中208种农药及其代谢物残留的方法,其特征在于:所述河蟹,其作为样品的脂肪含量为10%-15%;所述小龙虾,其作为样品的脂肪含量为1%-2%;所述草鱼,其作为样品的脂肪含量为0.5%-1%。
5.根据权利要求1所述的检测水产品中208种农药及其代谢物残留的方法,其特征在于:所述农药包括乙酰甲胺磷、乙草胺、苯草醚、氟丙菊酯、甲草胺、艾氏剂、烯丙菊酯、莠灭净、莎稗磷、阿特拉通、莠去津、脱乙基莠去津、益棉磷、氟丁酰草胺、苯霜灵、乙丁氟灵、α-六六六、β-六六六、δ-六六六、γ-六六六、甲羧除草醚、联苯菊酯、联苯、啶酰菌胺、除草定、溴苯烯磷、乙基溴硫磷、溴硫磷、溴螨酯、乙嘧酚磺酸酯、丁草胺、抑草磷、克百威、三硫磷、氯丹-反式、杀螨酯、毒虫畏-反式、毒虫畏-顺式、乙酯杀螨醇、氯苯甲醚、氯苯胺灵、毒死蜱、甲基毒死蜱、虫螨磷-1、虫螨磷-2、异噁草酮、蝇毒磷、环草敌、环氟菌胺、氟氯氰菊酯-1、氟氯氰菊酯-2、氟氯氰菊酯-3、氟氯氰菊酯-4、高效氯氟氰菊酯-1、高效氯氟氰菊酯-2、氯氰菊酯-1、氯氰菊酯-2、氯氰菊酯-3、氯氰菊酯-4、环丙唑醇-1、环丙唑醇-2、嘧菌环胺、4,4'-滴滴滴、2,4'-滴滴滴、2,4'-滴滴伊、4,4'-滴滴伊、2,4'-滴滴涕、4,4'-滴滴涕、溴氰菊酯-1、溴氰菊酯-2、敌草净、二嗪磷、敌草腈、除线磷、敌敌畏、禾草灵、氯硝胺、三氯杀螨醇、百治磷、狄氏剂、苯醚甲环唑-1、苯醚甲环唑-2、乐果、烯唑醇、敌噁磷、二苯胺、异丙净、灭菌磷、敌瘟磷、α-硫丹、β-硫丹、异狄氏剂、苯硫膦、氟环唑-1、氟环唑-2、乙丁烯氟灵、硫草敌、乙硫磷、乙氧呋草黄、灭线磷、乙螨唑、土菌灵、乙嘧硫磷、伐灭磷、咪唑菌酮、氯苯嘧啶醇、腈苯唑、皮蝇磷、杀螟硫磷、仲丁威、苯硫威、甲氰菊酯、丰索磷、倍硫磷、倍硫磷砜、倍硫磷亚砜、氰戊菊酯-1、氰戊菊酯-2、氟虫腈、吡氟禾草灵、氟氰戊菊酯-1、氟氰戊菊酯-2、咯菌腈、三氟硝草醚、氟喹唑、氟酰胺、氟胺氰菊酯-1、氟胺氰菊酯-2、地虫硫膦、安硫磷、噻唑膦-1、噻唑膦-2、六氯苯、己唑醇、环嗪酮、环氧七氯B、抑霉唑、异稻瘟净、异菌脲、氯唑磷、水胺硫磷、氧异柳磷、异柳磷、甲基异柳磷、异丙威、稻瘟灵、噁唑啉、醚菌酯、溴苯膦、马拉氧磷、马拉硫磷、苯噻酰草胺、嘧菌胺、地胺磷、甲霜灵、虫螨畏、甲胺磷、杀扑磷、烯虫酯、甲氧滴滴涕、异丙甲草胺、嗪草酮、速灭磷、禾草敌、久效磷、绿谷隆、腈菌唑、二溴磷、敌草胺、除草醚、氧乐果、噁草酮、噁霜灵、乙氧氟草醚、多效唑、对氧磷、甲基对氧磷、对硫磷、甲基对硫磷、戊菌唑、二甲戊灵、五氯苯胺、氯菊酯-1、氯菊酯-2、甲拌磷、甲拌磷砜、甲拌磷亚砜、伏杀硫磷、硫环磷、亚胺硫磷、磷胺-1、磷胺-2、增效醚、哌草磷、抗蚜威、嘧啶磷、甲基嘧啶磷、丙草胺、腐霉利、丙溴磷、环丙氟灵、扑草净、炔苯酰草胺、敌稗、扑灭津、胺丙畏、丙环唑-1、丙环唑-2、残杀威、丙硫磷、吡菌磷、哒螨灵、哒嗪硫磷、嘧霉胺、吡丙醚、喹硫磷、喹氧灵、五氯硝基苯、西玛津、治螟磷、戊唑醇、吡螨胺、丁基嘧啶磷、四氯硝基苯、特丁硫磷、特丁硫磷砜、特丁津、特丁净、杀虫畏、四氟醚唑、三氯杀螨砜、胺菊酯-1、胺菊酯-2、禾草丹、虫线磷、甲基立枯磷、三唑酮、三唑醇、野麦畏、三唑磷、脱叶磷、毒壤膦、肟菌酯、乙烯菌核利中的一种或几种。
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CN108680687A (zh) * | 2018-04-19 | 2018-10-19 | 浙江省海洋水产研究所 | 一种海产品中多氯联苯的检测方法 |
CN110161144A (zh) * | 2019-06-13 | 2019-08-23 | 中国水产科学研究院黄海水产研究所 | 一种食品中有机氯类和拟除虫菊酯类农药残留量的检测方法 |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108680687A (zh) * | 2018-04-19 | 2018-10-19 | 浙江省海洋水产研究所 | 一种海产品中多氯联苯的检测方法 |
CN108459112A (zh) * | 2018-05-18 | 2018-08-28 | 中国水产科学研究院淡水渔业研究中心 | 中华绒螯蟹蟹黄中有机氯农药含量的检测方法 |
CN110161144A (zh) * | 2019-06-13 | 2019-08-23 | 中国水产科学研究院黄海水产研究所 | 一种食品中有机氯类和拟除虫菊酯类农药残留量的检测方法 |
Non-Patent Citations (3)
Title |
---|
Rapid determination of organochlorine pesticides in fish using selective pressurized liquid extraction and gas chromatography-mass spectrometry;Minkyu Choi 等;《Food Chemistry》;1-31 * |
气相色谱法检测水产品中拟除虫菊酯类农药的基质效应研究;李丽春 等;《现代食品科技》;第34卷(第4期);270-280,220 * |
水产品中有机磷农药多残留的固相萃取-气相色谱串联质谱测定;叶茂盛 等;《浙江海洋大学学报(自然科学版)》;第38卷(第2期);174-179 * |
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