Determination of 15 Rare Earth Elements in Phosphate Ores by Inductively Coupled Plasma-Mass Spectrometry with Atmospheric Pressure Closed Microwave Digestion
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摘要:
磷矿石中的稀土元素测定方法主要使用电感耦合等离子体质谱法（ICP-MS），样品处理方式主要采用敞口混合酸溶和碱熔。传统的酸溶和碱熔处理矿石样品时间较长，试剂加入量大，操作过程较为繁琐，且易造成环境污染。微波消解直接向样品释放能量，工作效率高，且易挥发元素被保留在消化溶液中，防止挥发造成结果偏差及环境污染。本文采用微波消解对磷矿石进行处理，并在二次消解过程中加入饱和硼酸络合溶矿过程中产生的不溶物氟化钙，在线加入铑和铼双内标的方式，建立了ICP-MS测定磷矿石中15种稀土元素的方法。结果表明：二次消解过程中加入饱和硼酸能有效地络合沉淀，彻底溶解样品，经上机测定后15种稀土元素的相对标准偏差（RSD）在0.68%～4.52%之间，回收率在93.1%～106.6%之间，方法检出限为0.003～0.029μg/g。选取两个磷矿石样品，用本方法与混合酸（盐酸-硝酸-氢氟酸-硫酸）酸溶方法进行对比试验，相对标准偏差在−5.82%～5.99%之间，表明本方法测定稀土元素是有效可行的。对于样品的前处理方法，酸溶、碱熔和微波消解都有各自的特点，微波密封消解能避免一些能形成易挥发组分的损失并且外源性污染少。本方法拓展了测定磷矿石中稀土元素的样品前处理方法，操作性强，是对现行方法的有益补充。
Abstract:It takes a long time to treat ore samples by traditional alkali fusion and acid dissolution, and it is easy to cause environmental pollution. Microwave digestion directly releases energy to the sample with high efficiency, and volatile elements are retained in the digestion solution to prevent volatilization from causing deviation of results and environmental pollution. In this experiment, 0.2g of phosphate rock sample was taken and placed in a microwave digestion tank. 3mL hydrochloric acid, 3mL nitric acid, and 2mL hydrofluoric acid were added and then dissolved in the microwave digestion instrument. Then, 2mL of saturated boric acid solution was added for a further microwave digestion. After cooling, the sample was diluted in a 100mL volumetric flask with deionized water. Online addition of rhodium and rhenium as dual internal standards for inductively coupled plasma-mass spectrometry (ICP-MS) determination of rare earth elements in phosphate rock was performed. The relative standard deviation (RSD) of 15 rare earth elements was between 0.68% and 4.52%, the recovery was between 93.1% and 106.6%, and detection limit was between 0.003-0.029μg/g. Two phosphate ore samples were selected and compared with the mixed acid dissolution method. The relative standard deviation was −5.82%-5.99%.
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表 1 电感耦合等离子体质谱仪工作参数
Table 1. Working parameters for ICP-MS instrument
工作参数 实验条件 工作参数 实验条件 射频功率 1350W 采样锥（镍锥）孔径 1.0mm 反射功率 2.0W 截取锥（镍锥）孔径 0.8mm 冷却气（氩气）流速 15.2L/min 采样深度 110mm 辅助气（氩气）流速 0.8L/min 数据采集时间 36mm 雾化气（氩气）流速 0.85L/min 扫描方式 跳峰 
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表 2 微波消解升温程序
Table 2. Temperature program of microwave digestion
消解步骤 升温时间
（min）保持时间
（min）目标温度
（℃）功率
（W）1 5 2 100 1400 2 5 5 150 1400 3 5 30 180 1400 4 5 10 120 1400 注：第4步为加入饱和硼酸后二次消解步骤。
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表 3 方法检出限
Table 3. Detection limit of the method
稀土
元素内标 本文方法检出限
（μg/g）文献［28］方法检出限
（μg/g）稀土
元素内标 本文方法检出限
（μg/g）文献［28］方法检出限
（μg/g）89Y 103Rh 0.016 0.016 159Tb 185Re 0.007 0.015 139La 103Rh 0.015 0.013 163Dy 185Re 0.007 0.006 140Ce 103Rh 0.029 0.021 165Ho 185Re 0.003 0.001 141Pr 103Rh 0.009 0.012 166Er 185Re 0.006 0.039 146Nd 103Rh 0.003 0.010 169Tm 185Re 0.006 0.002 147Sm 103Rh 0.009 0.008 172Yb 185Re 0.007 0.005 151Eu 103Rh 0.004 0.002 175Lu 185Re 0.004 0.001 157Gd 185Re 0.008 0.005
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表 4 磷矿石标准物质中稀土元素的测定值和精密度
Table 4. Determination values and precision of REEs in phosphate rock reference materials
稀土
元素GBW07210 GBW07211 平均值
（μg/g）加入量
（μg/g）加标后测定值
（μg/g）回收率
（%）RSD
（%）平均值
（μg/g）RSD
（%）La 11.51 10.00 22.21 103.3 2.28 30.25 3.22 Ce 21.73 20.00 42.56 102.0 1.36 27.64 1.98 Pr 2.86 2.00 4.97 102.3 1.83 6.31 1.53 Nd 12.33 10.00 22.46 100.6 1.97 25.42 2.66 Sm 2.95 2.00 4.86 98.2 2.08 5.20 4.52 Eu 0.82 1.00 1.76 96.7 2.16 1.12 1.28 Gd 3.05 5.00 7.89 98.0 1.57 5.26 3.55 Tb 0.60 1.00 1.51 94.4 1.36 0.96 1.13 Dy 4.11 5.00 8.87 97.4 2.65 7.32 2.78 Ho 0.86 1.00 1.97 105.9 2.41 1.41 2.32 Er 2.76 2.00 4.51 94.7 0.68 4.57 3.69 Tm 0.41 0.50 0.97 106.6 3.38 0.70 4.12 Yb 2.67 2.00 4.35 93.1 2.05 4.32 1.47 Lu 0.43 0.50 0.98 105.4 1.78 0.72 3.21 Y 38.57 40.00 80.42 102.4 1.38 71.31 1.12
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表 5 未加饱和硼酸和加入饱和硼酸条件下稀土元素的测定结果对比
Table 5. Comparison of determination results for REEs before and after adding saturated boric acid
稀土
元素GBW07210测定值（μg/g） GBW07211测定值（μg/g） 未加饱和硼酸 加饱和硼酸 未加饱和硼酸 加饱和硼酸 La 8.08 11.51 18.42 30.25 Ce 14.10 21.73 15.66 27.64 Pr 1.87 2.86 4.27 6.31 Nd 8.61 12.33 14.20 25.42 Sm 2.15 2.95 3.14 5.20 Eu 0.45 0.82 0.68 1.12 Gd 2.16 3.05 3.15 5.26 Tb 0.38 0.60 0.57 0.96 Dy 2.91 4.11 5.02 7.32 Ho 0.51 0.86 0.82 1.41 Er 1.91 2.76 2.71 4.57 Tm 0.23 0.41 0.40 0.70 Yb 1.82 2.67 3.02 4.32 Lu 0.28 0.43 0.36 0.72 Y 23.53 38.57 52.75 71.31
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表 6 二次消解保持时间不同条件下稀土元素测定结果对比
Table 6. Comparison of determination results for REEs under different conditions of secondary digestion holding time
稀土
元素GBW07210测定值（μg/g） GBW07211测定值（μg/g） 消解时间5min 消解时间10min 消解时间20min 消解时间5min 消解时间10min 消解时间20min La 10.23 11.51 11.31 26.55 30.25 30.53 Ce 19.4 21.73 21.35 23.71 27.64 27.16 Pr 2.43 2.86 2.91 5.34 6.31 6.15 Nd 10.52 12.33 12.54 22.78 25.42 24.82 Sm 2.36 2.95 2.87 4.52 5.20 5.26 Eu 0.69 0.82 0.84 0.93 1.12 1.08 Gd 2.57 3.05 3.07 4.37 5.26 5.31 Tb 0.55 0.60 0.58 0.82 0.96 0.98 Dy 3.76 4.11 4.07 6.58 7.32 7.47 Ho 0.73 0.86 0.88 1.37 1.41 1.42 Er 2.57 2.76 2.78 3.26 4.57 4.61 Tm 0.34 0.41 0.41 0.55 0.70 0.72 Yb 2.38 2.67 2.71 3.68 4.32 4.41 Lu 0.36 0.43 0.41 0.66 0.72 0.74 Y 32.71 38.57 37.62 63.72 71.31 73.56
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表 7 两种前处理方法条件下稀土元素的测定结果对比
Table 7. Comparison of determination results for REEs under two pretreatment methods
稀土
元素样品P1 样品P2 本文方法测定值
（μg/g）混合酸酸溶测定值
（μg/g）相对偏差
（%）本文方法测定值
（μg/g）混合酸酸溶测定值
（μg/g）相对偏差
（%）La 22.71 23.56 −3.74 16.51 15.88 3.82 Ce 35.63 34.85 2.19 28.34 28.01 1.16 Pr 5.87 6.01 −2.39 3.82 3.93 −2.88 Nd 26.03 25.12 3.50 14.45 13.98 3.25 Sm 6.62 6.48 2.11 3.39 3.58 −5.60 Eu 1.52 1.47 3.29 1.01 1.04 −2.97 Gd 5.97 5.85 2.01 3.56 3.68 −3.37 Tb 1.12 1.11 0.89 0.64 0.67 −4.69 Dy 6.64 6.46 2.71 4.05 3.87 4.44 Ho 1.33 1.27 4.51 0.87 0.86 1.15 Er 3.67 3.45 5.99 2.26 2.28 −0.88 Tm 0.59 0.56 5.08 0.35 0.37 −5.71 Yb 3.61 3.82 −5.82 2.48 2.55 −2.82 Lu 0.57 0.55 3.51 0.38 0.36 5.26 Y 35.88 37.24 −3.79 21.16 20.81 1.65
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