中国西南岩溶区天然矿泉水痕量级溴酸盐测定中的基质干扰研究

Discussion on Matrix Interference in Trace-Level Bromate Detection of Natural Mineral Water in Southwest China Karst Area

  • 摘要: 溴酸盐作为天然矿泉水界限指标,具有潜在致癌风险,世界卫生组织与中国国家标准设置了严格浓度限值,仅为0.01mg/L。中国西南贵州岩溶区天然矿泉水中溴酸盐浓度通常为痕量级,但水化学环境背景复杂,使用离子色谱检测时极易因基质干扰导致无法准确定性、定量。本文通过逐一排除干扰离子的方法确定了硫酸盐为基质干扰主要因素,高浓度硫酸盐更易占据色谱柱中固定相点位,造成离子峰向前漂移及信号减弱。为实现痕量级溴酸盐准确检测提出三种检测方法:离子色谱-电导检测器法Ⅰ(IC-CDⅠ)采用可消除基质干扰的标准加入法;离子色谱-电导检测器法Ⅱ(IC-CDⅡ)创新使用Ba柱去除硫酸盐基质干扰;离子色谱-电感耦合等离子体质谱法(IC-ICP-MS)使用抗干扰性更强的质谱作检测器。结果表明,三种方法均能有效地消除高浓度硫酸盐基质干扰,IC-CDⅠ方法的相关系数为0.9993;IC-CDⅡ方法精密度(RSD)为0.42%~0.76%,加标回收率为94.5%~102.7%;IC-ICP-MS方法精密度(RSD)为0.31%~0.48%,加标回收率为95.9%~97.7%。并且,IC-CDⅡ与IC-ICP-MS方法定量限均低于《食品安全国家标准 饮用天然矿泉水检验方法》(GB 8538—2022)。当溴酸盐浓度低于10.0μg/L时,采用IC-CDⅡ与IC-ICP-MS方法;当溴酸盐浓度高于10.0μg/L时,三种方法均可采用。三种方法为存在高浓度硫酸盐基质干扰的天然矿泉水中痕量级溴酸盐的测定提供了思路和依据。

     

    Abstract: As a limitation of natural mineral water, bromate has potential carcinogenic risk. The World Health Organization and China National Standard have set a strict concentration limit of 0.01mg/L. The bromate in natural mineral water in the Guizhou karst area of southwest China is usually at trace levels while the chemical background of water is complex, which causes great difficulties using ion chromatography to detect the bromate due to matrix interference. Sulfate was determined as the factor of matrix interference by screening interference factors. High concentration sulfate readily occupied the stationary phase points of the chromatographic column, thus the peak of bromate was drifted and the signal response was reduced. In order to detect the trace-level bromate accurately, three detection methods were proposed: ion chromatography-conductivity detector method Ⅰ(IC-CDⅠ) used a standard addition method to eliminate matrix interference; ion chromatography-conductivity detector method Ⅱ (IC-CDⅡ) innovatively adopted Ba column to remove sulfate matrix interference; ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) employed the anti-interference mass spectrometer as a detector. The results showed that the three methods could be used to effectively eliminate the matrix interference of high concentration sulfate. The correlation coefficient of method IC-CDⅠ was 0.9993. The RSD of method IC-CDⅡ was 0.42%−0.76% and the recovery rate was 94.5%−102.7%. The RSD of method IC-ICP-MS was 0.31%−0.48% and the recovery rate was 95.9%−97.7%. Moreover, the quantitative limits of method IC-CDⅡ and method IC-ICP-MS were lower than the China National Standard. When the concentration of bromate in water was lower than 10.0μg/L, method IC-CDⅡ and method IC-ICP-MS were preferred. When the concentration was higher than 10.0μg/L, the three methods could be optionally used. The three methods provide ideas and basis for the determination of trace-level bromate in natural mineral water with high concentration sulfate matrix interference.

     

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