Improved Carrier Buffer for AC Arc Direct Reading Atomic Emission Spectrometry Based on the SEM Technique
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摘要: 原子发射光谱粉末固体进样法由于样品处理方法简单，检出限低，环境污染小，被大量应用于痕量Ag、B、Sn等多种元素的同时测定，但显著的基体效应制约了方法的适用性。本文基于扫描电镜微区检测技术，对比分析了特定配方与不同样品、在不同时段反应产物的组成差异，结合蒸发曲线反推反应过程，研制了适用于不同基体类型地球化学样品的载体缓冲剂。在实现前人致力改善弧烧过程的基础上，研制的载体缓冲剂是以K2S2O7、NaF作为助熔剂，“催化”基体分解，与聚四氟乙烯、沉降S等协同促进待测元素以多种形式快速蒸发；缓冲剂在与样品基体作用过程中形成的Al2O3-SiO2-CaO-BaO互熔体降低了Tammann温度，能够原位吸收CaO、SiO等基体氧化物，抑制了其干扰。相比已有方法，灵敏度提高1.2倍以上，精密度、准确度、检出限等优于各类地球化学调查规范要求。Abstract: Powder solid sampling atomic emission spectrometry is a simple sample pretreatment method with high sensitivity, low detection limit, and little environmental pollution. This method has been applied to the simultaneous analysis of trace Ag, B and Sn in geochemical samples. However, the serious matrix effect limits the application of this method. Based on the Scanning Electron Microscopy (SEM) technique, the differences in the composition of the reaction products at different times for specific formulations and different samples was compared. Combined with the evaporation curve to reverse the reaction process, a carrier buffer suitable for different types of geochemical samples was developed. In order to realize the improvement of the arc burning process, K2S2O7 and NaF were used as flux during preparing carrier buffer to catalytically decompose the matrix. Synergizing with PTFE and sedimentation S promotes rapid evaporation of analyzed elements in various forms. The formation of Al2O3-SiO2-CaO-BaO mutual melt lowers the Tammann temperature and can absorb matrix oxides in-situ, suppressing the interferences. Compared with the available method, the sensitivity increased by 1.2 times, and the precision, accuracy and detection limit are superior to a number of geochemical survey specifications.
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表 1 GBW07108与新载体缓冲剂不同反应时段熔渣组分对比
Table 1. A comparison of fusing beads components in GBW07108 at different reaction times with new carrier buffer by SEM
元素 反应30 s时的表面成分(%) 反应30 s时熔渣内部成分(%) 反应60 s时熔渣内部成分(%) 原子比 换算成氧化物含量 原子比 换算成氧化物含量 原子比 换算成氧化物含量 O 56.65 - 56.96 - 57.22 - Na 1.01 1.27 1.65 2.16 1.21 1.57 Mg 0.85 1.4 2.55 4.33 2.6 4.4 Al 15.33 31.7 16.03 34.48 15.87 33.97 Si 4.36 10.65 6.54 16.58 6.42 16.2 S 1.07~0.46 3.48~1.53 0.37 1.26 0.54 1.82 K 0.72 1.62 1.09 2.17 0.79 1.57 Ca 18.23 41.5 13.1 30.98 13.56 31.92 Fe 0.72 2.11 0.86 2.62 0.85 2.55 Ba 1.06 6.57 0.84 5.41 0.93 5.99 合计 100 100.3 99.99 99.99 99.99 99.99 
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表 2 GBW07407与新载体缓冲剂不同预反应时间对谱线强度及背景的影响
Table 2. Effect of different prereaction time with the new carrier buffer on spectral line intensity and background for GBW07407
平行测定次数 4.5 A电弧加热预反应2 s 4.5 A电弧加热预反应4 s 271线 背景 327线 背景 271线 背景 327线 背景 1 1292 175 511 198 2004 518 837 369 2 629 70 244 81 2170 514 906 343 3 1160 148 421 118 1924 586 874 426 4 1016 157 437 186 1710 293 664 239 5 871 177 378 163 2168 375 863 321 6 1880 309 635 285 2110 477 867 353 7 827 146 347 79 2072 350 791 279 8 1472 372 551 216 1804 209 585 146 9 2803 296 904 412 2209 293 782 240 10 867 111 316 109 1671 293 621 210 11 615 87 245 106 1893 744 957 519 12 1241 502 566 292 1973 392 795 267 RSD(%) 50.37 61.03 40.39 54.01 9.16 36.19 14.59 32.69
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表 3 GBW07706与新载体缓冲剂反应15 s时熔体残渣表面与内部组分扫描电镜分析结果
Table 3. The SEM data of surface residue and inner compositions on GBW07706 rereacted with the new carrier buffer at 15 s
元素 熔渣上表面成分(%) 熔渣内部成分(%) 原子比 换算成氧化物含量 原子比 换算成氧化物含量 O 63.04 - 64.56 - Na 4.12 7.48 0.88 1.34 Al 4.34 13.09 19.76~11.43 49.9~26.11 Si 17.3 61.65 9.05~21.39 27.03~50.48 K 3.08 10.07 1.14 3.12 Ca 未检出 未检出 0.51 1.42~4.0 F 6.55 - 未检出 未检出 S 1.4 6.08 未检出 未检出 Fe 未检出 未检出 0.34~2.75 1~15.3 Ba 0.18 1.63 0.69 5.22 Ti 未检出 未检出 0.53 2.1 合计 100 100 100 100
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