CN113960197A - 一种测定土壤或沉积物中39种农药残留的方法 - Google Patents
一种测定土壤或沉积物中39种农药残留的方法 Download PDFInfo
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Abstract
本发明公开一种测定土壤或沉积物中39种农药残留的方法,该方法中,首先对粉末土壤或沉积物样品进行提取、净化、浓缩,得到待测上机样品;将样品待测溶液进行气相色谱质谱测定;然后建立基质标准曲线,将待测上机样品与每种农药的标准曲线进行对比,得到每种农药的定量结果。本方法基于QuEChERS前处理和气质联用,可以实现土壤或沉积物中39种农药残留的同时测定且准确度高、检测速度快、重现性好,具有较强的实用价值。
Description
技术领域
本发明涉及环境监测领域,尤其涉及一种测定土壤或沉积物中39种农药残留的方法。
背景技术
种植业是我国的重要产业。农药在种植业中担任着无比重要的角色,农药在农作物种植过程中用于防治疾病、害虫以及杂草等,贡献巨大,是不可或少的生产资料,对促进农作物增产方面起着非常关键的作用。尽管如此,我们不能不正视农药给人们带来巨大帮助的同时也带来了不可忽视的负面影响。基于农药有效除虫害、草害作用的同时农药的使用量也在大量增加,田间所施的农药大部分都会进入到水、土壤和大气中去,人们平常喷洒的农药,大部分会在土壤中形成农药残留,而且有些农药的残留量比较大并且较难分解,如此日积月累最终危害的是人类自身的安全,尤其是高毒性、难于降解农药的使用已经到了威胁到生态环境和危害人类身体健康的地步。喷洒在农作物上的农药,其中一部分附着在作物上,另一部分汇集于土壤、大气和水等环境中,上述环境中的农药中的一部分又会被植物吸收,这些途径都会带来农药残留。人类作为食物链中的最高级,会最终吸收残留在植物果实或水及大气中的农药。因此对土壤和沉积物中的农药检测也是人们在种植完作物后所必须做的检查。
目前土壤及沉积物样品中常用的前处理方法包括萃取和净化,比如液液萃取、索氏提取法、固相微萃取、快速溶剂萃取等,虽然这些方法成熟、稳定,但是耗精力、耗时间,同时消耗大量有毒有害有机试剂,比如索氏提取虽然成本低,但是耗费时间长,快速溶剂萃取虽然操作时间短、萃取效率高,但是仪器设备非常昂贵。力求易操作、快速、简便、溶剂使用少的前处理方法是土壤样品前处理所探讨的方向。
发明内容
本发明的目的在于针对现有前处理技术的不足,提供一种测定土壤或沉积物中39种农药残留的方法,具体技术方案如下:
一种测定土壤或沉积物中39种农药残留的方法,包括以下步骤:
(1)提取:取粉末土壤或沉积物样品,加入乙腈和水的混合溶液,均质提取,再加入无水乙酸钠、无水硫酸镁,涡旋混匀,离心,取上清液备用;
(2)净化:将上清液加入净化剂,涡旋混匀,离心,取上清液氮吹至近干,加入正己烷定容,涡旋,过滤膜,得到用于上机测定的溶液样品;
(3)将39种农药的混合标准物质用正己烷稀释,配制1.0~10μg/mL农药混标溶液;采用气质联用仪对农药混标溶液进行全扫,全扫描范围为m/z45~500,通过控制升温程序将39种农药完全分离,确认39种农药的保留时间并得到混标溶液的总离子流图;
(4)扫描结果用特征离子挑选,对挑选结果进行NIST谱库比对,每种农药选择3~4个特征离子,选择一个丰度高、荷质比较大的离子作为定量离子,剩余的特征离子作为定性离子;
(5)建立基质标准曲线
将空白土壤或沉积物经过步骤(1)和(2)处理,得到空白基质提取溶剂,用空白基质提取溶剂将39种农药的混标溶液稀释,配制成0.01~1.0μg/mL的系列混标溶液;按选定的色谱条件和质谱条件,并根据步骤(4)确定的每种农药的定性和定量离子,采用选择离子监测模式,以定量离子峰面积为纵坐标、混标溶液的浓度为横坐标,进行测定,得到39种农药的线性方程和相关系数;
(6)按照选定的色谱条件和质谱条件,采用选择离子监测模式,将步骤(2)得到的样品进行上机测定,并与步骤(5)得到的由每种农药的线性方程和相关系数形成的标准曲线进行对比,得到每种农药的定量结果。
进一步地,所述步骤(1)的提取具体为:称取粉末状土壤或沉积物样品,加入纯水,涡旋混匀,样品和水的质量体积比为1:2,加入乙腈,乙腈和纯水的体积比为1:1,超声提取20~30min,加入无水乙酸钠和无水硫酸镁,涡旋混匀,使乙腈和纯水充分进行盐析分层;在转速为6000-9000r/min的条件下离心5-10min,取上清液备用。
进一步地,所述步骤(2)的净化具体为:上清液中加入净化剂,上清液和净化剂的体积质量比为(1.4~1.5):(5~10);在转速为6000-8000r/min的条件下离心5-10min,再取上清液于35-45℃的水浴中氮吹近干,加入正己烷定容至1mL,涡旋混匀,过滤膜,涡旋,过滤膜,得到用于上机测定的样品。
进一步地,所述净化剂是由石墨化炭黑、N-丙基乙二胺混合而成,所述石墨化炭黑、N-丙基乙二胺的重量比为1:2.5。
进一步地,所述选定的色谱条件和质谱条件为:
气相色谱:
色谱柱:Thermo TG-5SiLMS毛细管色谱柱;
进样口温度:250~270℃;
载气:氦气,纯度≥99.999%,流速1mL/min;
进样量:1.0μL;
进样方式:不分流进样;
色谱柱温度:60℃保持2min,然后以25℃/min的速度升温至180℃,再以5℃/min的速度升温至280℃,最后以10℃/min的速度升温至300℃,保持5min;
质谱:
传输线温度:280℃;
电离方式:EI;
电离能量:70eV;
离子源温度:280℃;
溶剂延迟时间4min。
进一步地,所述39种农药为异丙威、α-六六六、莠去通、扑灭通、西玛津、莠去津、扑灭津、β-六六六、特丁津、γ-六六六、二嗪磷、仲丁通、δ-六六六、异稻瘟净、甲基对硫磷、西草净、莠灭净、扑草净、特丁草净、杀螟硫磷、马拉硫磷、反式丙烯菊酯、稻丰散、喹硫磷p,p'-DDE、噻嗪酮、p,p'-DDD、o,p'-DDT、三唑磷、p,p'-DDT、胺菊酯、联苯菊酯、甲氰菊酯、伏杀硫磷、高效氯氟氰菊酯、氯菊酯、氯氰菊酯、氰戊菊酯、溴氰菊酯。
本发明的有益效果如下:
本发明方法基于QuEChERS前处理和气质联用,前处理操作简便、快速,检测过程可以实现土壤和沉积物中39种农药残留的同时测定,且准确度高、检测速度快、重现性好,具有较强的实用价值。
附图说明
图1为实施例中39种农药的总离子流图。
图2为部分土壤和沉积物样品中测得的农药的种类和浓度示意图。
具体实施方式
下面根据附图和优选实施例详细描述本发明,本发明的目的和效果将变得更加明白,应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
一、主要仪器及试剂
气相色谱-质谱联用仪(TRACE GC1300 ISQ,赛默飞公司);台式冷冻离心机(德国Eppendorf公司);涡旋混合器(海门市其林贝尔仪器制造有限公司);超声波清洗器(昆山市超声仪器有限公司);实验室超纯水仪(费尔德北京科学仪器有限公司);冷冻混合球磨仪(上海一韦科技有限责任公司);氮气吹干仪(天津市旗美科技有限公司);真空冷冻干燥机(宁波市双嘉仪器有限公司)。
试剂:乙腈、正己烷均为色谱纯级别;39种农药混合标准溶液、乙二胺-N-丙基硅烷(PSA)、石墨化炭黑(GCB)、QuEChERS萃取盐包(6g无水硫酸镁1.5g无水乙酸钠)均购自上海安谱实验科技股份有限公司。
二、实施步骤
1.样品采集
从江苏省苏州市太湖流域采集湖泊、河流沉积物样品81份,采集果园土壤样品27份。样品置于洁净的磨口棕色玻璃瓶中保存。在运输过程中进行了密封、避光、冷藏(4℃以下)。
2.样品预处理和测定
除去土壤和沉积物样品中的动植物残骸、石头等异物后,将其进行冷冻干燥并通过四分法制备出均相干燥样品,将干燥样品放于冷冻混合球磨仪进行粉碎。
称取5g(精确到0.01g)土壤样品于50mL离心管,加入乙腈/水混合溶液(1:1,V:V)后进行涡旋超声萃取,萃取条件为涡旋1min,超声30min;然后加入QuEChERS萃取盐包(6g无水硫酸镁1.5g无水乙酸钠)离心,收集上清液并进行净化(净化条件为上清液中加入100mgPSA,40mgGCB),收集净化洗脱液,将所得净化洗脱液氮吹浓缩,即上清液于45℃的水浴中缓慢地吹至近干,加入正己烷定容至1mL,上GC/MS分析。
选定的色谱条件和质谱条件为:
气相色谱:
色谱柱:Thermo TG-5SiLMS毛细管色谱柱;
进样口温度:250℃;
载气:氦气,纯度≥99.999%,流速1mL/min;
进样量:1.0μL;
进样方式:不分流进样;
色谱柱升温程序:60℃保持2min,然后以25℃/min程序升温至180℃,再以5℃/min程序升温至280℃,最后以10℃/min升温至300℃,保持5min;
质谱:
传输线温度:280℃;
电离方式:EI;
电离能量:70eV;
离子源温度:280℃;
溶剂延迟时间4min。
3.绘制总离子流示意图
将39种农药的混合标准物质用正己烷稀释,配制1.0mL农药混标溶液;通过全扫描模式(SCAN),质量扫描范围:45amu~500amu,得到总离子流示意图,见图1所示。从图中可以看出,各峰之间分离明显,峰型好。
每种农药选择3~4个特征离子,以离子响应强度作为选取原则确立各物质的定性、定量离子,按照农药出峰顺序确定保留时间,进行监测,在某一时间段监测特征离子,使得特征离子在单位时间内被扫描的次数增多,提高特征离子的灵敏度,避免其他离子的干扰。39种农药的特征离子和保留时间如表1所示。除六六六,DDT和部分菊酯存在同分异构体(定量和定性离子相同),其余各待测农药的特征定性、定量离子均没有重复,可以很好地进行定性识别及定量测试。而同分异构体的保留时间不同,分离效果好,因此并不影响物质的定量定性分析。
表1 39种农药的特征离子和保留时间
4.本发明的方法的线性范围、相关系数和检出限
将土壤或沉积物样品按相同的样品前处理方法进行样品提取、净化及浓缩,采用相同的仪器分析条件分析测定,未有目标物检出,则将土壤或沉积物样品作为空白样品。
将空白样品经过提取和净化处理,得到提取溶剂,用提取溶剂将39种农药混标溶液稀释,配制成浓度范围在0.01~1.0μg/mL的系列标准溶液。将混合标准溶液进样分析,结果以目标化合物浓度为横坐标,以目标化合物峰面积为纵坐标,各待测物在0.01~1μg/mL范围内呈良好的线性关系,相关系数(r)大于0.99。按照三倍信噪比计算检出限。39种农药检出限范围在0.02~5.56μg/kg之间,结果见表2,具有很好的灵敏度。
表2 39种农药标准曲线的回归方程、相关系数和检出限
5.精密度、准确度
对空白样品进行低、中、高浓度分别为0.02,0.1和0.4mg/kg(称样量为5.0g)的加标测定,计算相对标准偏差(RSD)及加标回收率,分析数据可得39种农药的回收率在65.6%~117.4%之间,4个平行样品的相对标准偏差(RSD)1.4%~10.0%之间,结果见表3,具有很好的准确度。
表3方法的精密度和加标回收率结果(n=4)
6.实际样品测定
采用相同的提取和净化、浓缩的方法预处理样品,采用已优化的色谱、质谱条件对39种目标农药残留进行检测。检测结果见图2,共检出11种农药包括p,p'DDE、p,p'DDD、o,p'DDT、噻嗪酮、联苯菊酯、高效氯氟氰菊酯、氯菊酯、溴氰菊酯、氯氰菊酯、氰戊菊酯、扑草净,其中3种有机氯农药,6种拟除虫菊酯类农药,1种三嗪类农药,1种噻二嗪类农药。检出率最高的农药是p,p'DDE、噻嗪酮、联苯菊酯,均大于40%。其他农药检出率较低,某果园土壤中氯氰菊酯的检出浓度最高,为1462.69ng·g-1。
本领域普通技术人员可以理解,以上所述仅为发明的优选实例而已,并不用于限制发明,尽管参照前述实例对发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实例记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在发明的精神和原则之内,所做的修改、等同替换等均应包含在发明的保护范围之内。
Claims (6)
1.一种测定土壤或沉积物中39种农药残留的方法,其特征在于,包括以下步骤:
(1)提取:取粉末土壤或沉积物样品,加入乙腈和水的混合溶液,均质提取,再加入无水乙酸钠、无水硫酸镁,涡旋混匀,离心,取上清液备用;
(2)净化:将上清液加入净化剂,涡旋混匀,离心,取上清液氮吹至近干,加入正己烷定容,涡旋,过滤膜,得到用于上机测定的溶液样品;
(3)将39种农药的混合标准物质用正己烷稀释,配制1.0~10μg/mL农药混标溶液;采用气质联用仪对农药混标溶液进行全扫,全扫描范围为m/z45~500,通过控制升温程序将39种农药完全分离,确认39种农药的保留时间并得到混标溶液的总离子流图;
(4)扫描结果用特征离子挑选,对挑选结果进行NIST谱库比对,每种农药选择3~4个特征离子,选择一个丰度高、荷质比较大的离子作为定量离子,剩余的特征离子作为定性离子;
(5)建立基质标准曲线
将空白土壤或沉积物经过步骤(1)和(2)处理,得到空白基质提取溶剂,用空白基质提取溶剂将39种农药的混标溶液稀释,配制成0.01~1.0μg/mL的系列混标溶液;按选定的色谱条件和质谱条件,并根据步骤(4)确定的每种农药的定性和定量离子,采用选择离子监测模式,以定量离子峰面积为纵坐标、混标溶液的浓度为横坐标,进行测定,得到39种农药的线性方程和相关系数;
(6)按照选定的色谱条件和质谱条件,采用选择离子监测模式,将步骤(2)得到的溶液样品进行上机测定,并与步骤(5)得到的由每种农药的线性方程和相关系数形成的标准曲线进行对比,得到每种农药的定量结果。
2.根据权利要求1所述的测定土壤或沉积物中39种农药残留的方法,其特征在于,所述步骤(1)的提取具体为:称取粉末状土壤或沉积物样品,加入纯水,涡旋混匀,样品和水的质量体积比为1:2,加入乙腈,乙腈和纯水的体积比为1:1,超声提取20~30min,加入无水乙酸钠和无水硫酸镁,涡旋混匀,使乙腈和纯水充分进行盐析分层;在转速为6000-9000r/min的条件下离心5-10min,取上清液备用。
3.根据权利要求1所述的测定土壤或沉积物中39种农药残留的方法,其特征在于,所述步骤(2)的净化具体为:上清液中加入净化剂,上清液和净化剂的体积质量比为(1.4~1.5):(5~10);在转速为6000-8000r/min的条件下离心5-10min,再取上清液于35-45℃的水浴中氮吹近干,加入正己烷定容至1mL,涡旋混匀,过滤膜,涡旋,过滤膜,得到用于上机测定的样品。
4.根据权利要求1所述的测定土壤或沉积物中39种农药残留的方法,其特征在于,所述净化剂是由石墨化炭黑、N-丙基乙二胺混合而成,所述石墨化炭黑、N-丙基乙二胺的重量比为1:2.5。
5.根据权利要求1所述的测定土壤或沉积物中39种农药残留的方法,其特征在于,所述选定的色谱条件和质谱条件为:
气相色谱:
色谱柱:Thermo TG-5SiLMS毛细管色谱柱;
进样口温度:250~270℃;
载气:氦气,纯度≥99.999%,流速1mL/min;
进样量:1.0μL;
进样方式:不分流进样;
色谱柱温度:60℃保持2min,然后以25℃/min的速度升温至180℃,再以5℃/min的速度升温至280℃,最后以10℃/min的速度升温至300℃,保持5min;
质谱:
传输线温度:280℃;
电离方式:EI;
电离能量:70eV;
离子源温度:280℃;
溶剂延迟时间4min。
6.根据权利要求1所述的测定土壤或沉积物中39种农药残留的方法,其特征在于,所述39种农药为异丙威、α-六六六、莠去通、扑灭通、西玛津、莠去津、扑灭津、β-六六六、特丁津、γ-六六六、二嗪磷、仲丁通、δ-六六六、异稻瘟净、甲基对硫磷、西草净、莠灭净、扑草净、特丁草净、杀螟硫磷、马拉硫磷、反式丙烯菊酯、稻丰散、喹硫磷p,p'-DDE、噻嗪酮、p,p'-DDD、o,p'-DDT、三唑磷、p,p'-DDT、胺菊酯、联苯菊酯、甲氰菊酯、伏杀硫磷、高效氯氟氰菊酯、氯菊酯、氯氰菊酯、氰戊菊酯、溴氰菊酯。
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