原子荧光光谱测定土壤和水系沉积物中硒的干扰来源及消除方法
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摘要
原子荧光光谱法(AFS)具有灵敏度高、结构简单、容易操作等优点,但目前测定土壤和沉积物中的硒等元素的标准方法所采用的消解过程繁琐,易产生干扰。沸水浴可以把土壤和水系沉积物中硒提取完全,本文根据样品中元素丰度和仪器性能,将AFS测定Se的干扰分为Cu和Pb两大类,根据实验提出在水浴消解液加入浓盐酸(不宜加入硫脲-抗坏血酸),通过增加溶液酸度和Cl~-浓度,即保持样品中盐酸浓度高于23%,可抑制Cu~(2+)还原为Cu~0和Pb~(4+)生成PbH_4,有效降低了Cu的负干扰和Pb的正干扰,提高了AFS测定Se的精密度和准确度。本方法测定Se的检出限为0.008mg/kg,测试标准物质的相对标准偏差为0.5%～11%,相对误差为-16.3%～9.5%;比行业标准HJ 680—2013的检出限(0.01mg/kg)、精密度(0.79%～23.1%)和准确度等技术指标更佳。
BACKGROUND: Atomic Fluorescence Spectrometry(AFS) has advantages of high sensitivity, simple structure and easy operation, but the digestion process of the standard analysis method for determination of Se in soil is cumbersome and readily produces interference.OBJECTIVES: To evaluate the applicability of Se determination in soil and sediment by water bath digestion/AFS, and uncover the main interference and elimination methods.METHODS: Based on the standard method of GB/T 22105—2008, boiling water bath of aqua regina was used to digest Se in soil and sediment. Four treatments, including Fe~(3+), concentrated hydrochloric acid, Fe~(3+)with concentrated hydrochloric acid, and water bath solution, were used to eliminate the interference of Cu~(2+) and Pb~(4+).RESULTS: The detection limit of Se by this method was 0.008 mg/kg, the relative standard deviation of the test reference materials was 0.5%-11%, and the relative error was-16.3%-9.5%, better than the detection limit(0.01 mg/kg), precision(0.79%-23.1%) and accuracy of the industry standard HJ 680—2013.CONCLUSIONS: According to the experiment, it is proposed to add concentrated hydrochloric acid to the water bath digestion solution without adding thiourea-ascorbic acid. By increasing the acidity and Cl~- concentration of the solution and keeping the concentration of hydrochloric acid in the sample higher than 23%, the reduction of Cu~(2+) to Cu~0 and Pb~(4+) to form PbH_4 can be inhibited. The negative interference of Cu and the positive interference of Pb are effectively reduced, and the precision and accuracy of Se measured by AFS are improved.
BACKGROUND: Atomic Fluorescence Spectrometry(AFS) has advantages of high sensitivity, simple structure and easy operation, but the digestion process of the standard analysis method for determination of Se in soil is cumbersome and readily produces interference.OBJECTIVES: To evaluate the applicability of Se determination in soil and sediment by water bath digestion/AFS, and uncover the main interference and elimination methods.METHODS: Based on the standard method of GB/T 22105—2008, boiling water bath of aqua regina was used to digest Se in soil and sediment. Four treatments, including Fe~(3+), concentrated hydrochloric acid, Fe~(3+)with concentrated hydrochloric acid, and water bath solution, were used to eliminate the interference of Cu~(2+) and Pb~(4+).RESULTS: The detection limit of Se by this method was 0.008 mg/kg, the relative standard deviation of the test reference materials was 0.5%-11%, and the relative error was-16.3%-9.5%, better than the detection limit(0.01 mg/kg), precision(0.79%-23.1%) and accuracy of the industry standard HJ 680—2013.CONCLUSIONS: According to the experiment, it is proposed to add concentrated hydrochloric acid to the water bath digestion solution without adding thiourea-ascorbic acid. By increasing the acidity and Cl~- concentration of the solution and keeping the concentration of hydrochloric acid in the sample higher than 23%, the reduction of Cu~(2+) to Cu~0 and Pb~(4+) to form PbH_4 can be inhibited. The negative interference of Cu and the positive interference of Pb are effectively reduced, and the precision and accuracy of Se measured by AFS are improved.
引文
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[21] 张洁,阳国运.树脂交换分离-电感耦合等离子体质谱法测定铅锌矿中钨钼锡锗硒碲[J].岩矿测试,2018,37(6):657-663.Zhang J,Yang G Y.Determination of tungsten,molybdenum,tin,germanium,selenium and tellurium in lead-zinc ore by ICP-MS with resin exchange separation[J].Rock and Mineral Analysis,2018,37(6):657-663.
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