CN111257461A - 一种海水中三嗪类除草剂及其降解产物的检测方法 - Google Patents
一种海水中三嗪类除草剂及其降解产物的检测方法 Download PDFInfo
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Abstract
本发明公开了一种海水中三嗪类除草剂及其降解产物的检测方法，属于水环境检测技术领域。本发明海水中三嗪类除草剂及其降解产物的检测方法，是对待检测海水样品进行高效前处理；再引入内标法并结合高效液相色谱‑‑四级杆串联质谱和高分辨质谱，对海水样品中三嗪类除草剂及其降解产物快速定量和准确定性分析。本发明采用样品高效前处理的方法，方法操作简单，易于重现。内标法并结合高效液相色谱‑‑四级杆串联质谱和高分辨质谱，对海水样品中三嗪类除草剂及其降解产物的快速定量和准确定性分析。
Description
技术领域
本发明属于水环境检测技术领域，具体涉及一种内标法并结合高效液相色谱-四级杆串联质谱和高分辨质谱定性定量检测海水中三嗪类除草剂及其降解产物的方法。
背景技术
三嗪类除草剂是一类含有3个氮原子的六元杂环化合物。因其高效的除草效果，在农业生产和水产养殖过程中广泛用于控制杂草和藻类的生长。该类除草剂通过地表径流和排放进入海洋系统，成为海洋环境污染的主要来源。由于三嗪类除草剂化学性质稳定、半衰期长、难降解、毒性大，对水生生态系统和水生生物的安全造成严重威胁，美国和欧盟等已将其列入内分泌干扰物名单。研究表明，环境中三嗪类除草剂经降解形成脱烷基、羟基化等极性更高的弱碱性化合物，地下水中脱乙基莠去津(Desethyl Atrazine,DEA)和脱异丙基莠去津 (Desisopropyl Atrazine,DIA)的含量是莠去津浓度的6-10倍。因此，需要建立高通量、高灵敏的分析方法来测定海水等环境基质中三嗪类除草剂及其降解产物的残留量。
对于水样中有机污染物的检测，高效前处理技术是提高检测灵敏度和准确度的关键。液液萃取(LLE)和固相萃取(SPE)是水体基质中常用可靠的检测手段，SPE由于高富集效果和可重复性好被最广泛使用。目前，三嗪类除草剂常用检测方法主要有气相色谱法(GC)、高效液相色谱法(HPLC)、气相色谱－质谱法(GC-MS)和液相色谱－质谱法(LC-MS)。其中，GC和HPLC仅以保留时间定性，容易出现假阳性结果；相比较而言，色谱与质谱联用技术具有可靠性强、灵敏度高、基质干扰小等优势。与LC-MS相比，GC-MS主要用于检测热稳定性高且具有一定挥发性的化合物，检测范围大大缩小。目前，国内外基本通过LC-MS 外标法对海水中三嗪类除草剂进行定量。外标法不能消除前处理过程对分析结果的影响，回收率难以保证，准确度不高。
发明内容
针对现有技术中存在的不足，本发明的目的在于提供一种海水中三嗪类除草剂及其降解产物的检测方法。采用HLB固相萃取柱富集净化，完成了海水中三嗪类除草剂及其降解产物的高效前处理。同时选用多个内标对海水中三嗪类除草剂及其降解产物的含量进行校正，通过高效液相色谱--四级杆串联质谱(HPLC-MS/MS)准确定量，结合高分辨质谱(QExactive Orbitrap MS)的结构解析和精准识别能力，实现了海水基质中三嗪类除草剂及其降解产物的高通量定性筛查和高灵敏准确定量。
为了达到上述目的，本发明采用如下技术方案：
一种海水中三嗪类除草剂及其降解产物的检测方法，是对待检测海水样品进行高效前处理；再引入内标法并结合高效液相色谱--四级杆串联质谱和高分辨质谱，对海水样品中三嗪类除草剂及其降解产物快速定量和准确定性分析；
所述样品的高效前处理是将海水样品抽滤后，加入内标，混合均匀后加到活化后的HLB 萃取柱中净化，洗脱液干燥后复溶，过膜，待测。
在上述方案的基础上，所述的三嗪类除草剂为西草净、西玛津、莠灭净、莠去津、扑草净、特丁净、特丁津中的至少一种；所述三嗪类降解产物为：2-羟基去双异丙基扑草净、去双异丙基扑草净、去异丙基扑草净、2-羟基扑草净、去乙基去异丙基莠去津、去异丙基莠去津中的至少一种。
在上述方案的基础上，所述内标物为D5-莠去津、D6-扑草净、D5-特丁津中的至少一种。
在上述方案的基础上，所述检测过程中，
液相条件：Kinetex XB C18色谱柱(4μm，2.1mm×150mm)；进样量:10μL；流速0.25mL/min；流动相：A为0.1％甲酸水溶液，B为乙腈；洗脱梯度：0min＝5％B,3.01min＝95％ B，6.31min＝5％B，8.00min＝5％B；
质谱条件：
四级杆串联质谱：电子轰击源，多反应监测扫描；正离子模式，喷雾电压为3500V；
其他相关四级杆串联质谱条件如下：
注：*定量离子。
高分辨质谱：加热电喷雾离子源，Full MS-DDMS2扫描；正离子模式；喷雾电压为3.0kV；毛细管温度320℃；采集范围m/z 80～1000；一级全扫描分辨率为70000FWHM，二级子离子扫描分辨率为17500FWHM。
本发明技术方案的优点：
1)本发明引进内标法，通过多个内标校正定量，并结合高效液相色谱-串联质谱(HPLC-MS/MS，ESI)和高分辨质谱(Q Exactive Orbitrap MS)，实现了海水样品中三嗪类除草剂及其降解产物的准确定性和定量分析。
2)本发明方法不仅适用于海水中三嗪类除草剂的检测，同样适用于三嗪类降解产物的检测。
3)本发明通过优化确定HLB固相萃取方法，可快速富集海水中痕量三嗪类除草剂及其降解产物，操作简单，易于重现。
附图说明
图1为HLB固相萃取和乙酸乙酯液液萃取对三嗪类除草剂回收率的影响比较(100ng/L)；
图2为外标法和内标校正方法对三嗪类除草剂的回收率比较(100ng/L)；
图3为三嗪类除草剂及其降解产物标准溶液的多反应监测扫描图(100μg/L)；
图4为海水阳性样品中2-OHDDIP-扑草净的高分辨质谱一级和二级谱图，其中A为2-OHDDIP-扑草净的FULL-MS一级图谱，B为2-OHDDIP-扑草净的FULL-MS-DDMS2二级图谱；
图5为海水阳性样品中DIP-扑草净的高分辨质谱一级和二级谱图，其中A为DIP-扑草净的FULL-MS一级图谱，B为DIP-扑草净的FULL-MS-DDMS2二级图谱；
图6为海水阳性样品中2-OH扑草净的高分辨质谱一级和二级谱图，其中A为2-OH扑草净的FULL-MS一级图谱，B为2-OH扑草净的FULL-MS-DDMS2二级图谱。
具体实施方式
在本发明中所使用的术语，除非有另外说明，一般具有本领域普通技术人员通常理解的含义。
下面结合具体实施例，并参照数据进一步详细的描述本发明。以下实施例只是为了举例说明本发明，而非以任何方式限制本发明的范围。
本发明所述技术方案中的仪器和试材如下：
Q-Exactive四极杆-静电场轨道阱高分辨质谱系统及Dionex UltiMate 3000超高效液相色谱系统(美国Thermo Fisher Scientific公司)，Thermo TSQ Endura液相色谱－串联质谱仪(美国 Thermo Fisher Scientific公司)。BT224S分析天平(法国Sartorius公司)，EVAPTM112型氮气吹扫仪(美国Organomation公司)，Talboys型涡旋混合器(上海安谱科学仪器有限公司)，N-Milli-Q 型超纯水仪(美国Millipore公司)。
三嗪类除草剂：莠去津、扑草净、西草净、西玛津、莠灭净、特丁净、特丁津。三嗪类降解产物：2-羟基去双异丙基扑草净(2-OHDDIP-扑草净)、去双异丙基扑草净(DDIP-扑草净)、去异丙基扑草净(DIP-扑草净)、2-羟基扑草净(2-OH-扑草净)、去乙基去异丙基莠去津(DEDIP-莠去津)、去异丙基莠去津(DIP-莠去津)。内标物：D6-扑草净、D5-莠去津、D5- 特丁津。以上药品均购于德国Dr.Ehrenstorfer GmbH公司。
甲醇、二氯甲烷(色谱纯，Merk公司)，其他试剂皆为分析纯。
实施例1
(1)工作液的制备
称取适量的三嗪类除草剂、降解产物和内标标准品，用甲醇稀释定容，分别配制成1.0 mg/mL的标准储备液，-18℃避光保存。然后分别准确吸取一定量标准储备溶液，用甲醇稀释分别配成1μg/mL的混合标准外标工作液和内标工作液，4℃冷藏保存。
(2)高效前处理
将海水样品过滤后待用，HLB小柱(200mg/6mL)提前用3mL甲醇和3mL超纯水活化，速度控制在2-3s/滴。取过滤后的海水100mL，加入50μL内标(1ppm)，混匀后加到HLB小柱，然后用3mL 3％的甲醇水溶液淋洗，挤干淋洗液，最后用6mL甲醇分两次洗脱，收集洗脱液，于40℃氮气流下吹干，用1mL初始流动相进行复溶，过膜，供液相色谱-质谱仪测定。
分别采用HLB固相萃取和乙酸乙酯液液萃取对海水样品进行前处理，两不同方法测得的三嗪类除草剂回收率如图1所示。同时，在HLB固相萃取过程中采用3％甲醇水淋洗比纯水淋洗回收率好，以及采用甲醇作为洗脱溶剂比乙腈作为洗脱溶剂杂质干扰小，另外，HLB固相萃取中采用6mL洗脱用量优于3mL洗脱用量；因而采用HLB固相萃取，3mL 3％的甲醇水溶液淋洗，6mL甲醇洗脱可以实现海水样品的高效前处理。
(3)高效液相色谱--四级杆串联质谱和高分辨质谱检测
具体参数条件如下：
液相条件：Kinetex XB C18色谱柱(美国phenomenex公司，4μm，2.1mm×150mm)；进样量:10μL；流速0.25mL/min；流动相：A为0.1％甲酸水溶液，B为乙腈；洗脱梯度：0min＝5％B,3.01min＝95％B，6.31min＝5％B，8.00min＝5％B。
四级杆串联质谱条件：电子轰击源(ESI)，多反应监测扫描(MRM)；正离子模式，喷雾电压为3500V。其他相关质谱条件见表1。
高分辨质谱(Q Exactive Orbitrap MS)条件：加热电喷雾离子源(HESI)，FullMS-DDMS2扫描；正离子模式；喷雾电压为3.0kV；毛细管温度320℃；采集范围m/z 80～1000；一级全扫描分辨率为70000FWHM，二级子离子扫描分辨率为17500FWHM。
内标物需要选择与对应目标物的响应相当，同时消除操作过程对分析结果的影响，保证目标物的回收率结果在70％～120％。通常选择每个目标物对应的氘代试剂作为内标，而试验过程中出于成本和操作需要，针对多个目标物在满足回收率条件下，可以选择同一内标物定量。本发明通过试验筛选出满足条件的三个内标物。在优化过程中发现用D6-扑草净和D5-莠去津作为内标校正特丁津时，其回收率皆低于50％，说明二者的响应均高于特丁津，不适合作其内标，而用D5-特丁津校正可以将回收率做到70％以上。
其中西草净、西玛津、莠去津、去乙基去异丙基莠去津(DEDIP-莠去津)以及去异丙基莠去津(DIP-莠去津)以D5-莠去津为内标，莠灭净、扑草净、特丁净、2-羟基去双异丙基扑草净(2-OHDDIP-扑草净)、去双异丙基扑草净(DDIP-扑草净)、去异丙基扑草净(DIP-扑草净)和2-羟基扑草净(2-OH-扑草净)以D6-扑草净为内标，特丁津以D5-特丁津为内标。
其他相关质谱条件如下：
表1三嗪类除草剂及其降解产物的相关四级杆串联质谱参数
注：*定量离子。
(4)检出限、回收率和精密度
用甲醇配置成系列浓度的标准溶液。同时含有混合标准外标和内标的溶液，每个溶液中内标浓度相同，外标浓度成梯度浓度分别为0.50μg/L、1.00μg/L、5.00μg/L、10.0μg/L、20.0 μg/L、50.0μg/L、100μg/L。按照步骤(2)和步骤(3)的方法通过高效液相色谱-四级杆串联质谱(HPLC-MS/MS)内标法准确定量，以目标物定量离子与内标物定量离子峰面积比为纵坐标，质量浓度为横坐标，制作标准曲线。
通过向空白海水样品中添加7种三嗪类除草剂和6种降解产物标准溶液按照步骤(2)和步骤(3)的方法得到相应的回收率和精密度。
同时对比了外标法和本发明内标校正方法的准确性。其中外标法是通过标准曲线对样品中待测物定量，内标法是向样品中添加内标物，通过相对响应值对待测物进行定量。外标法和内标校正方法对三嗪类除草剂的回收率比较见图2。
选用三个不同浓度的海水加标实验(20ng/L，100ng/L和200ng/L)(表2，n＝6)，回收率都在70.0％～120％之间，相对标准偏差皆小于15％。同时本发明方法具有较高的灵敏度，7 种三嗪类除草剂和6种降解产物的最低检出限(LOD)为5.0ng/L(S/N>3)，定量限(LOQ)为20ng/L(S/N>10)。
表2海水样品中三嗪类除草剂及其降解产物的添加回收实验(n＝6)
三嗪类除草剂和降解产物标准溶液的多反应监测扫描(MRM)和海水加标样品的高分辨质谱一级二级谱图分别见图3、图4、图5和图6。结果表明，结合四级杆串联质谱的精准定量优势和Q Exactive质谱的Full MS-DDMS2一级和二级扫描，进一步增强了目标物的准确定性能力，方法的准确性和灵敏度高，重现性好，且操作简便、高效。实现了海水样品中三嗪类除草剂及降解产物的高通量定性筛查和高灵敏准确定量。
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。
Claims (4)
1.一种海水中三嗪类除草剂及其降解产物的检测方法，其特征在于，对待检测海水样品进行高效前处理；再引入内标法并结合高效液相色谱--四级杆串联质谱和高分辨质谱，对海水样品中三嗪类除草剂及其降解产物快速定量和准确定性分析；
所述样品的高效前处理是将海水样品过滤后，加入内标，混合均匀后加到活化后的HLB萃取柱中净化，洗脱液干燥后复溶，过膜，待测。
2.根据权利要求1所述海水中三嗪类除草剂及其降解产物的检测方法，其特征在于，所述的三嗪类除草剂为西草净、西玛津、莠灭净、莠去津、扑草净、特丁净、特丁津中的至少一种；所述三嗪类降解产物为：2-羟基去双异丙基扑草净、去双异丙基扑草净、去异丙基扑草净、2-羟基扑草净、去乙基去异丙基莠去津、去异丙基莠去津中的至少一种。
3.根据权利要求1或2所述海水中三嗪类除草剂及其降解产物的检测方法，其特征在于，所述内标物为D5-莠去津、D6-扑草净、D5-特丁津中的至少一种。
4.根据权利要求3所述海水中三嗪类除草剂及其降解产物的检测方法，其特征在于，所述检测过程中，
液相条件：Kinetex XB C18色谱柱(4μm，2.1mm×150mm)；进样量:10μL；流速0.25mL/min；流动相：A为0.1％甲酸水溶液，B为乙腈；洗脱梯度：0min＝5％B,3.01min＝95％B，6.31min＝5％B，8.00min＝5％B；
质谱条件：
四级杆串联质谱：电子轰击源，多反应监测扫描；正离子模式，喷雾电压为3500V；
其他相关四级杆串联质谱条件如下：
注：*定量离子
高分辨质谱：加热电喷雾离子源，Full MS-DDMS2扫描；正离子模式；喷雾电压为3.0kV；毛细管温度320℃；采集范围m/z 80～1000；一级全扫描分辨率为70000FWHM，二级子离子扫描分辨率为17500FWHM。
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