Determination of Three Benzalkonium Chloride Homologues in Environmental Water by Ultra High Performance Liquid Chromatography- Quadrupole/Electrostatic Field Orbitrap High Resolution Mass Spectrometry
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摘要:
苯扎氯铵具有非氧化性杀菌作用，被大量应用于医疗卫生系统，随着污水排放到环境中，已被确定为可能严重影响生态系统中敏感生物的有害化合物，准确检测环境水体中苯扎氯铵的含量对于维护人体和生态环境健康具有重要意义。由于环境水体中残留苯扎氯铵的浓度低，且检测时容易受到复杂污染组分的干扰，结果出现假阳性，因此要求检测方法具有更低的检出限和更准确的定性能力。本文利用超高效液相色谱-四极杆-静电场轨道阱高分辨质谱技术(UPLC-Q-Orbitrap HRMS)，建立了准确定性定量检测环境水体中苯扎氯铵三种同系物(十二烷基二甲基苄基氯化铵、十四烷基二甲基苄基氯化铵、十六烷基二甲基苄基氯化铵)的方法。样品经0.22μm孔径滤膜过滤，加入同等体积的甲醇混匀，流动相为含1%(V/V)三乙胺的10mmol/L乙酸铵-水溶液和甲醇，梯度洗脱，采用Accucore C18色谱柱(150mm×2.1mm，2.6μm)进行分离，6min内三种苯扎氯铵同系物实现基线分离，静电场轨道离子阱质谱在60000分辨率条件下以SIM模式进行数据采集。结果表明：三种苯扎氯铵在0.10~10.0μg/L浓度范围内线性关系良好(R＞0.999)，检出限为0.03~0.06μg/L，加标回收率为86.7%~111.2%。经实际样品验证，该方法在检出限和抗干扰能力上能够满足地表水和浅层地下水等环境水体中三种苯扎氯胺同系物的检测，并识别出十六烷基二甲基苄基氯化铵的疑似干扰物为质量数m/z 360.323的丙二醇脂肪酸酯。
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关键词:
- 环境水体 /
- 苯扎氯铵 /
- 超高效液相色谱 /
- 四极杆-静电场轨道阱高分辨质谱法 /
- SIM模式
Abstract:BACKGROUND Benzalkonium chloride has a non-oxidizing bactericidal effect and is widely used in medical and health service. With the discharge of sewage into the environment, benzalkonium chloride has been identified as a harmful compound that may seriously inspect susceptible organisms in the ecosystem. Exact quantitative analysis of benzalkonium chloride in environmental water is of great significance for human and ecological environmental health. However, low content of benzalkonium chloride exist in environmental water. The interference of a complex matrix causes false positive results to occur easily. Therefore, the detection method is required to have lower detection limits and more accurate qualitative analysis ability.
OBJECTIVES To establish a method for the determination of three benzalkonium chloride homologues (n-C12H25-C9H13NCl, n-C14H29-C9H13NCl, n-C16H33-C9H13NCl) in environmental water.
METHODS Ultra-high performance liquid chromatography quadrupole/electrostatic field orbitrap high resolution mass spectrometry (UPLC-Q-Orbitrap HRMS) was used. The sample was filtered through a 0.22μm membrane, and then mixed with the same volume of methanol. The mobile phase consisted of 10mmol/L ammonium acetate aqueous solution which contained 1% (V/V) triethylamine as mobile phase B and methanol as phase A, with gradient elution. Accucore C18 column (150mm×2.1mm, 2.6μm) was used to separate the baseline of three benzalkonium chloride within 6 minutes, and the data were collected by electrostatic field orbitrap mass spectrometry in SIM mode at 60, 000 resolution.
RESULTS The contents of three benzalkonium chloride within the range of 0.10-10.0μg/L had a linear relationship (r>0.999). The detection limits ranged from 0.03 to 0.06μg/L. The recoveries of three kinds of benzalkonium chloride were 86.7%-111.2%.
CONCLUSIONS Verified by samples, this method meets the detection limits and has anti-interference abilities of three benzalkonium chloride homologues in surface water and shallow groundwater. Moreover, it was identified that the suspected disrupting chemical of cetyl dimethyl benzyl ammonium chloride is propylene glycol fatty acid ester at m/z 360.323.
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表 1 苯扎氯铵同系物的母离子、产物离子及其强度
Table 1. Parent ions, product ions of benzalkonium chloride homologues and their response intensity
苯扎氯铵同系物 母离子 产物离子 质量数(m/z) 响应强度 质量数(m/z) 响应强度 C12-BAC 304.2988 4.10×107 91.0537(定量)
212.2354(定性)9.89×105
-C14-BAC 332.3300 4.56×107 91.0536(定量)
240.2673(定性)7.10×105
-C16-BAC 360.3613 3.27×107 91.0537(定量)
268.2991(定性)3.48×105
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表 2 三种苯扎氯铵同系物的方法特性指标
Table 2. Linear regression equations, correlation coefficients and detection limits of three benzalkonium chloride homologues
苯扎氯铵同系物 线性方程 线性范围(μg/L) 相关系数 检出限(μg/L) C12-BAC y=1.12×106+3.77×107x 0.10~10.0 0.9998 0.03 C14-BAC y=2.48×106+5.35×107x 0.10~10.0 0.9998 0.03 C16-BAC y=-3.21×106+5.26×107x 0.10~10.0 0.9998 0.06
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表 3 三种苯扎氯铵同系物的加标回收率和精密度(n=6)
Table 3. Recoveries and RSD for three benzalkonium chloride homologues in spiked samples (n=6)
水样 苯扎氯铵同系物 加标量0.20μg/L 加标量1.00μg/L 加标量5.00μg/L 平均加标回收率(%) RSD (%) 平均加标回收率(%) RSD (%) 平均加标回收率(%) RSD (%) C12-BAC - - 94.2 5.5 92.3 3.9 地表水 C14-BAC - - 92.5 5.9 89.7 6.4 C16-BAC - - 90.7 7.7 89.6 5.6 C12-BAC 99.7 4.1 111.2 3.7 86.7 9.3 地下水 C14-BAC 88.6 6.5 91.2 4.2 89.3 7.1 C16-BAC 103.0 7.0 101.3 6.7 96.5 10.2
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