Determination of Sulfur in Soil by Inductively Coupled Plasma-Optical Emission Spectrometry with Four Acids Open Dissolution
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摘要: 当前土壤中硫元素的测定方法主要是X射线荧光光谱法和燃烧法，上述两种方法分析速度慢，对高、低含量样品的分析精度较差，难以满足大批量样品快速、准确分析的要求。为提高分析速度和结果的准确度，本文建立了用盐酸-硝酸-氢氟酸-高氯酸（四酸）溶解土壤样品，电感耦合离子体发射光谱法测定硫的方法。通过考察王水消解、王水水浴消解和四酸消解的溶样效果，测定结果表明采用四酸能更好地溶解土壤样品中的硫。方法检出限为10 μg/g，测量范围为33.3~50000 μg/g，相对标准偏差为0.47%~4.05%。本方法简单快速，准确度高，已经过数千件实际样品验证，在不增加分析成本的情况下，一份溶液还可以同时测定钾钠钙镁铁锰铍锂镧铈钪钒钴镍钛等元素，适合在地质行业推广应用。
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关键词:
- 电感耦合等离子体发射光谱法 /
- 土壤 /
- 硫 /
- 敞口酸溶
Abstract: At present, sulfur in soil is mainly determined by X-ray Fluorescence Spectrometry and tube furnace combustion iodine methods. The analysis speed of these two methods is slow, and the analysis accuracy is poor for both high and low content samples, difficult to meet the requirements of accurate and rapid determination of many samples. In order to improve the speed and accuracy of analysis, a new method for the determination of sulfur in soil samples by Inductively Coupled Plasma-Optical Emission Spectrometry combined with four acids digestion was developed. In this paper the digestion effect of aqua regia, aqua hot water bath and HCl-HNO3-HF-HClO4 is compared. The four acids digestion method was proven to better dissolve sulfur in soil samples. The method is simple, rapid and accurate with a low detection limit of 10 μg/g, analysis range between 33.3 μg/g and 50000 μg/g, and relative standard deviation between 0.47% and 4.05%. Many elements such as potassium, sodium, calcium, magnesium, iron, manganese, beryllium, lithium, lanthanum, cerium, scandium, vanadium, cobalt, nickel, and titanium can be determined simultaneously in a solution without increasing analysis cost. The method, which has been verified with actual samples, is suitable for application in the geological industry. -
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表 1 四酸、王水、王水水浴溶解结果
Table 1. Analytical results of samples disoluted with four acids, aqua regia and aqua waterbath methods
标准物质编号 硫含量(μg/g) 三种溶解方法测定值与标准值的相对误差(%) 标准值 四酸溶解测定值 王水溶解测定值 王水水浴溶解测定值 四酸溶解 王水溶解 王水水浴溶解 GBW07446 108±14 112 99 103 3.70 -8.33 -4.63 GBW07451 440±42 436 390 410 -0.91 -11.36 -6.82 GBW07456 254±12 257 238 246 1.18 -6.30 -3.15 GBW07457 281±26 279 203 214 -0.71 -27.76 -23.84 
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表 2 电热板温度的影响
Table 2. Effect of electric heating plate temperature
电热板表面温度(℃) GBW07446 GBW07453 硫标准值(μg/g) 硫测定值(μg/g) 硫溶出率(%) 硫标准值(μg/g) 硫测定值(μg/g) 硫溶出率(%) 130 108±14 74 68.52 2000±300 1632 81.60 140 108±14 98 90.74 2000±300 1730 86.50 150 108±14 113 104.63 2000±300 1977 98.85 160 108±14 107 99.07 2000±300 1993 99.65 170 108±14 110 101.85 2000±300 1998 99.90 180 108±14 116 107.41 2000±300 2013 100.65 190 108±14 112 103.70 2000±300 2007 100.35 200 108±14 110 101.85 2000±300 1987 99.35 210 108±14 104 96.30 2000±300 1965 98.25 220 108±14 87 80.56 2000±300 1891 94.55 230 108±14 76 70.37 2000±300 1874 93.70
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表 3 浸泡时间的选择
Table 3. Choice of soaking time
标准物质编号 粗粒级主要矿物 不同浸泡时间下溶解情况 0 h 4 h 8 h 12 h GBW07401 石英、长石 反应，冒泡 有少量固体 有极少量固体 基本清亮 GBW07403 石英、长石 无明显反应 有少量固体 基本清亮 基本清亮 GBW07407 褐铁矿、石英、高岭土 无明显反应 有少量固体 基本清亮 基本清亮 GBW07408 碳酸盐物质、长石、石英、黑云母、白云母、褐铁矿、贝壳 反应剧烈，大量冒泡 有少量白色、黑色固体 有极少量固体 基本清亮
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表 4 国家标准物质中硫含量的分析结果
Table 4. Analytical results of sulfur in national standard references
标准物质编号 硫含量(μg/g) 相对误差(%) RSD (%) 标准值 本法测定平均值(n=12) GBW07446 108±14 108.4 0.37 4.05 GBW07447 (7000) 7041.94 0.60 0.50 GBW07448 (816) 820.06 0.50 2.00 GBW07449 27000±2900 26995.59 -0.02 0.47 GBW07450 (167) 171.17 2.50 3.66 GBW07451 440±42 442.96 0.67 1.12 GBW07452 (420) 422.02 0.48 1.46 GBW07453 2000±300 2000.51 0.03 1.63 GBW07454 170±22 170 0.00 3.02 GBW07455 162±10 157.25 -2.93 3.59 GBW07456 254±12 254.93 0.37 2.58 GBW07457 281±21 281.36 0.13 2.04 注：括号内数据为参考值。
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表 5 三种分析方法的结果比较
Table 5. A comparison of the three analytical methods
样品编号 XRF法 管式炉碘量法 本法(四酸溶样ICP-OES法) 硫含量三次测定平均值(μg/g) RSD(%) 硫含量三次测定平均值(μg/g) RSD(%) 硫含量三次测定平均值(μg/g) RSD(%) 1 112* 5.63 83.1 11.46 78.3 6.42 2 143 2.42 124 8.97 136.7 3.82 3 266 2.41 270 5.43 274.2 2.33 4 355 1.62 349 4.32 343.1 2.67 5 527 1.74 534 3.66 536.3 1.82 6 832 0.86 827 4.22 816.4 0.69 7 966 2.42 933 5.21 946.6 1.11 8 1386 1.57 1276 4.14 1233 0.68 9 5233 2.44 4320 3.12 4362 2.43 10 5604* 1.87 7465 4.17 7654 3.26 11 28335* 1.52 21364 3.13 21362 2.03 12 55027* 1.62 42187 1.86 43227 2.74 13 176 2.87 188 7.33 182.4 3.11 14 256 2.11 263 4.87 261.2 2.46 15 687 1.14 693 3.22 684.2 2.03 16 778 1.06 786 4.16 781.4 1.06 17 1125 1.68 1139 3.55 1132 0.97 18 7864* 1.93 8546 3.68 8574 1.33 19 29365* 1.44 24652 4.15 24468 2.36 20 43225* 1.67 40271 2.87 40298 1.93
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