DETERMINATION OF TRACE MERCURY IN SILICATES BY CATALYTIC PYROLYSIS-COLD ATOMIC ABSORPTION SPECTROPHOTOMETRY
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摘要:
硅酸盐中痕量汞测定对确定岩石中汞含量以及理论地球化学、勘查地球化学、生态和环境地球化学研究具有重要意义. 但汞在硅酸盐中分布是痕量级, 对分析方法检出限指标要求很高, 且硅酸盐中二氧化硅质量分数变化大、岩性分类多、干扰基体成分复杂和元素挥发损失等特性使得硅酸盐中痕量汞的准确测试面临挑战. 直接进样测汞仪无需化学试剂消解(防止汞元素挥发损失), 采用催化管(消除复杂基体干扰)和配置汞捕集装置(元素富集降低检出限)可提供符合绿色化学技术发展趋势的解决方案. 本文通过试验探究, 优化直接进样测汞仪的参数, 其方法检出限(0.5×10-9)、测定下限(2.0×10-9)、准确度(ΔlogC < 0.05)、精密度(RSD < 10%, n=12)等指标满足DZ/T 0130-2006中《多目标地球化学调查规范》要求, 达到或优于硅酸盐化学分析方法GB/T 14506.33-2019(汞量测定: 氢化物发生-原子荧光光谱法)的检出限(2×10-9)和定量下限(5×10-9), 可为硅酸盐样品中痕量汞的原子荧光测试和绿色化学技术更新提供参考.
Abstract:The measurement of trace mercury in silicates is of great significance to the determination of mercury content in rocks and study of theoretical geochemistry, exploration geochemistry, and ecological and environmental geochemistry. However, the distribution of mercury in silicates is in trace level, which demands high criterion to the detection limits of analytical methods. The accurate measurement of trace mercury in silicates also faces challenges such as the great variation of silicon dioxide contents in silicates, multiple lithology classification, complex interference matrix composition, and element volatilization loss. The direct sampling mercury analyzer, without chemical digestion process (to prevent mercury volatilization loss), using catalytic tubes (to eliminate complex matrix interference) and mercury trapping devices (to reduce the detection limit by enriched element), can provide a solution in line with the development trend of green chemistry technology. In this study, the parameters of direct sampling mercury analyzer are optimized through experiments. The method indicators, including detection limit (0.5×10-9), determination lower limit (2.0×10-9), accuracy (ΔlogC < 0.05) and precision (RSD < 10%, n=12), meet the requirements of Specification of Multi-Target Geochemical Survey in DZ/T 0130-2006, and reach or excel the detection limit (2×10-9) and quantitative lower limit(5×10-9) in GB/T 14506.33-2019 Methods for Petrochemical Analysis of Silicates(Determination of Mercury Content: Hydride Generation-Atomic Fluorescence Spectrometry), which can provide references for determination of trace mercury in silicate samples by atomic fluorescence spectrometry and improvement of green chemistry technology.
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Key words:
- catalytic pyrolysis /
- cold atomic absorption /
- silicate /
- trace mercury /
- direct mercury analyzer /
- green chemistry
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表 1 直接测汞仪工作参数
Table 1. Specification of direct mercury analyzer
序号 过程 温度/℃ 时间/s 1 裂解 760 65 2 催化 450 保持 3 捕集 100 10 4 释放 800 保持 5 吸收 130 保持 注: 测试时间4~5 min; 读数方式为峰高. 
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表 2 方法准确度和精密度试验
Table 2. Test results of method accuracy and precision
标准样品 标准值Hg/10-9 测试值Hg/10-9 测试平均值Hg/10-9 对数差△logC 相对标准偏差RSD/% T值/T表值 显著性 GBW07103 0.0041 0.0039 0.0046 0.0042 0.0048 0.00413 0.003 9.30 0.29/2.20 无 0.0043 0.0042 0.0037 0.0038 0.0045 0.0042 0.0038 0.0036 GBW07107 0.0100 0.0101 0.0113 0.0098 0.0115 0.0103 0.014 9.24 1.29/2.20 无 0.0095 0.0093 0.0108 0.0099 0.0102 0.0091 0.0114 0.0111 GBW07122 0.0033 0.0031 0.0031 0.0032 0.0035 0.0032 -0.004 5.48 0.62/2.20 无 0.0036 0.0033 0.0035 0.0032 0.0031 0.0032 0.0031 0.0033 GBW07728 0.0035 0.0037 0.0031 0.0032 0.0034 0.0034 -0.008 8.44 0.77/2.20 无 0.0036 0.0037 0.0039 0.0032 0.0031 0.0031 0.0037 0.0035 测试次数: n=12.
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表 3 方法比对试验
Table 3. Comparison test results of methods
标准样品 测试值Hg/10-9 S最大2 S最小2 f最小 f最大 F值/F表值 显著性 GBW07103 0.0038 0.0043 0.0039 0.0041 0.0040 1.44E-07 3.70E-08 4 11 3.89/5.93 无 GBW07107 0.0093 0.0096 0.0121 0.0115 0.1040 7.33E-07 1.45E-06 11 4 1.97/3.16 无 GBW07122 0.0036 0.0033 0.0035 0.0032 0.0034 5.70E-08 3.15E-08 11 4 1.80/3.16 无 GBW07728 0.0036 0.0037 0.0039 0.0032 0.0031 8.24E-08 4.3oE-08 4 11 1.92/5.93 无
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表 4 样品比对试验
Table 4. Comparison test results of samples
样品 方法 测试值Hg/10-9 平均值 平均偏差 标准偏差 相对标准偏差/% SYBH01 1 0.0032 0.0033 0.0033 0.0032 0.0032 0.0032 4.80E-05 5.48E-05 1.69 2 0.0034 0.0031 0.0032 0.0030 0.0035 0.0032 1.68E-04 2.07E-04 6.40 SYBH02 1 0.0083 0.0082 0.0084 0.0083 0.0084 0.0083 6.40E-05 8.37E-05 1.01 2 0.0081 0.0086 0.0083 0.0082 0.0083 0.0083 1.20E-04 1.87E-04 2.25 SYBH03 1 0.0041 0.0042 0.0041 0.0042 0.0041 0.0041 4.80E-05 5.48E-05 1.32 2 0.0048 0.0045 0.0040 0.0040 0.0042 0.0043 2.80E-04 3.46E-04 8.06
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