Determination of Volatile and Nonvolatile Trace Elements in Geochemical Samples by Fluoride Solid Buffer-AC Arc Direct Reading Emission Spectrometry
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摘要: 应用电弧直读发射光谱法测定化探样品，样品无需消解，采用固体进样的方式可以同时测定多个元素。但目前化探分析中常采用的固体缓冲剂（如焦硫酸钾、氟化钠）的电弧温度较低，只能分析银、硼、锡、铅、钼、铜等易挥发元素，而不能分析铬、锰、钛等沸点较高的难挥发性元素。本文通过碱金属控制较低的电弧温度，并利用难挥发元素能在高温条件下与氟离子发生化学反应降低其激发温度，配制了一种以氟化铝、聚三氟氯乙烯等氟化效率较高的化合物为主要成分的固体缓冲剂，通过优化分析线对的选择、曝光时间、电极形状等分析条件，实现了一次制样可同时分析地球化学样品中14种易挥发和难挥发元素。方法检出限为0.016~46.93 μg/g，相对标准偏差为4.1%~12.3%，通过国家标准物质验证了准确度，测定值与标准值相符，各项参数都能满足地球化学普查规范要求。本方法分析效率高，在化探分析中具有一定的实用性。Abstract: It is not necessary to digest a sample if it is determined by Arc Direct Reading Emission Spectrometry, and multiple elements can be simultaneously determined by solid injection. Currently used geochemical solid buffers, such as potassium persulfate and sodium fluoride have a low temperature arc flame, and can only analyze silver, boron, tin, molybdenum, lead, copper and other volatile elements but cannot analyze chromium, manganese, titanium and other high boiling point elements. Alkali metal was used to control the low arc temperature, and a solid buffer composed of aluminum fluoride, PCTFE and other high efficiency fluorination compounds was prepared based on the fact that the reaction between difficult volatile elements and fluorine ion under high temperature would have lower excitation energy. By optimizing the choice of line pairs, exposure time, electrode shape and other analysis conditions, 14 volatile and non-volatile elements in the geochemical samples can be simultaneously analyzed. The detection limit of the method ranges from 0.016 to 46.93 μg/g, and the relative standard deviation is 4.1% to 12.3%. The accuracy was verified by national standard material. The results were in accordance with the standard values, and the parameters meet the requirements of geochemical census. The method has high analysis efficiency and is practical in geochemical analysis.
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表 1 线性方程和方法检出限
Table 1. Linear equation and the detection limits of elements
元素 分析线
(nm)内标线
(nm)线性方程 相关系数
(R2)检出限
(μg/g)1：5万规范要求
(μg/g)Ag 328.0683 Ge (326.94) y=0.01991x+2.6824 0.9980 0.016 0.03 B 249.7733 Pd (311.40) y=0.01465x-0.87846 0.9869 0.57 5 Sn 283.9989 Ge (270.96) y=41.84187x-59.60691 0.9981 0.67 1 Cu 282.4281 Ge (270.96) y=45.70798x-141.53336 0.9981 27.23 1.5 327.4047 Ge (270.96) y=37.0919x-11.0803 0.9931 1.02 - Pb 283.3160 Pd (311.40) y=49.90404x-125.23204 0.9985 1.12 5 266.3160 Pd (311.40) y=38.8363x-61.44835 0.9988 12.65 - Zn 328.2422 Pd (325.88) y=40.3932x-113.90369 0.9893 9.12 15 Mo 313.2318 Pd (311.40) y=39.90176x-22.15677 0.9943 0.13 0.5 Co 324.351 Ge (270.96) y=45.24665x-117.73741 0.9962 0.81 1 Ni 305.0748 Pd (311.40) y=34.75742x-38.14033 0.9846 1.09 3 Ga 294.3800 Ge (270.96) y=48.51972x-146.11944 0.9889 0.39 - Cr 297.110 Pd (325.88) y=0.7352x+0.7152 0.9930 8.37 15 Mn 304.4300 Pd (325.88) y=1.0439x-0.5983 0.9961 17.65 30 Ti 318.6168 Pd (325.88) y=0.9747x-0.3757 0.9861 46.93 100 V 319.801 Pd (325.88) y=0.9356x+1.6726 0.9970 8.91 20 
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表 2 方法准确度和精密度
Table 2. Accuracy and precision tests of the method
元素 GBW07317 GBW07307a GBW07401 标准值
(μg/g)测定值
(μg/g)相对误差
(%)RSD
(%)标准值
(μg/g)测定值
(μg/g)相对误差
(%)RSD
(%)标准值
(μg/g)测定值
(μg/g)相对误差
(%)RSD
(%)Ag 0.027 0.026 3.7 9.6 1.25 1.32 -5.6 4.5 0.35 0.36 -2.9 6.0 B 5.30 5.84 -10.2 11.2 195 182 6.7 4.6 50 51 -2.0 5.0 Sn 0.97 0.92 5.2 5.3 2.5 2.6 -4.0 7.8 6.1 6.5 -6.6 5.0 Cu 11 12 -9.1 9.7 22.5 24.1 -7.1 7.7 21 25 -19.0 6.5 Pb 13 13 0.0 6.1 555 576 -3.8 5.4 98 91 7.1 5.7 Zn 16 19 -18.8 12.3 780 758 2.8 9.7 680 704 -3.5 6.4 Mo 0.500 0.392 21.6 9.2 0.82 0.97 -18.3 6.3 1.4 1.3 7.1 4.3 Co 3.60 3.75 -4.2 6.6 15.2 14.5 4.6 8.8 14.2 16.3 -14.8 8.5 Ni 3.00 2.86 4.7 5.9 22 20 9.1 8.1 20.4 18.5 9.3 8.7 Ga 11.2 10.4 7.1 8.0 14.4 16.5 -14.6 5.5 19.3 16.9 12.4 8.7 Cr 12.0 13.5 -12.5 8.0 43 42 2.3 5.4 62 60 3.2 9.2 Mn 218 241 -10.6 6.9 886 991 -11.9 8.7 1760 1700 3.4 4.3 Ti 1370 1299 5.2 6.3 4100 4612 -12.5 7.4 4830 5300 -9.7 5.4 V 20 23 -15.0 6.2 77 81 -5.2 4.1 86 78 9.3 6.2 元素 GBW07408 GBW07103 GBW07104 标准值
(μg/g)测定值
(μg/g)相对误差
(%)RSD
(%)标准值
(μg/g)测定值
(μg/g)相对误差
(%)RSD
(%)标准值
(μg/g)测定值
(μg/g)相对误差
(%)RSD
(%)Ag 0.06 0.067 -11.7 9.4 0.033 0.031 6.1 9.3 0.072 0.075 -4.2 6.3 B 54 56 -3.7 6.8 24 22 8.3 5.1 4.7 5.5 -17.0 9.3 Sn 2.8 3.0 -7.1 4.5 12.5 12.0 4.0 7.0 0.79 0.87 -10.1 9.8 Cu 24.3 22.63 6.9 8.5 3.2 4.0 -25.0 10.6 55 60 -9.1 9.0 Pb 21 21 0.0 9.3 31 28 9.7 8.5 11.3 10.1 10.6 9.8 Zn 68 75 -10.3 8.6 167 183 -9.6 9.4 99 88 11.1 8.0 Mo 1.16 1.22 -5.2 5.9 3.5 3.2 8.6 8.6 0.54 0.46 14.8 8.7 Co 12.7 13.7 -7.9 5.3 3.4 3.0 11.8 9.0 13.2 11.9 9.8 8.8 Ni 31.5 36.6 -16.2 9.2 2.3 2.6 -13.0 9.3 17 16 5.9 7.7 Ga 14.8 13.7 7.4 8.7 19 17 10.5 9.4 18.1 15.8 12.7 7.7 Cr 68 77 -13.2 6.4 - - - - 32 37 -15.6 5.8 Mn 650 710 -9.2 6.9 463 500 -8.0 8.1 604 579 4.1 7.4 Ti 3800 3612 4.9 7.6 1720 1902 -10.6 4.2 3090 3241 -4.9 7.0 V 81 94 -16.0 5.1 24 25 -4.2 7.5 94 111 -18.1 6.9
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