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摘要:
锂是绿色能源和轻质合金的理想原料，作为一种重要的战略性资源而备受各国重视。热泉水中富含锂，储量可观，然而热泉水主要分布在西藏、云南等偏远地区，样品运输与实验室测试成本高、效率低，锂资源勘查急需现场分析技术的支持。热泉水一般含有较高浓度的钠、钾等元素，基体效应显著。本文利用自主研发的便携式锂钾分析仪，搭配负性滤光片，选择锂的分析谱线波长670.78nm，通过优化测量条件，建立了标准曲线法与标准加入法现场测定热泉水中锂元素的分析方法。实验结果表明，当电解质是体积分数为1.5%的盐酸，工作电流为70mA，进样流速为3.0mL/min时，锂检出限为4.07μg/L，相对标准偏差(RSD)为1.03%。对热泉水样品进行加标测试，加标回收率为81.6%～115.9%。当热泉水样品基体组成较简单时，直接采用标准曲线法即可获得较准确的分析结果；当样品基体组成较复杂或者基体浓度高时，采用标准加入法可有效地减小基体效应，获得的分析结果相对更准确。本方法适用于不同类型基体的热泉水中锂含量的分析测试。
Abstract:Lithium is an ideal material for green energy and lightweight alloys, and has been valued by many countries as an important strategic resource. Many hot springs, are rich in Li. However, hot springs are mainly distributed in remote areas such as Xizang and Yunnan, where the cost of sample transportation and laboratory testing is high and the efficiency is low, so the exploration of lithium resources urgently needs the support of on-site analysis technology. Hot spring water generally contains high concentrations of sodium, potassium and other elements, and the matrix effect is significant. In this study, the wavelength of the characteristic Li spectral line was set at 670.78nm. The analytical method for on-site determination of Li in hot spring water samples was established by a self-developed portable Li-K analyzer with a negative filter using the standard curve and standard addition methods. The experimental results show that when the electrolyte is 1.5% hydrochloric acid, the working current is 70mA and the sample flow rate is 3.0mL/min, the detection limit of Li is 4.07μg/L, and the measured precision (RSD) is better than 2%. The hot spring water samples were tested by standard addition, and the spiked recoveries were 81.6% to 115.9%. When the matrix composition of hot spring water samples is simple, accurate analysis results can be obtained by directly using the standard curve method. When the matrix composition of the sample is complex or the matrix concentration is high, the matrix effect can be effectively reduced by the standard addition method, and the analysis results obtained are relatively more accurate, which is suitable for the analysis of lithium content in hot spring water with different matrix types.
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Key words:
- portable /
- Li-K analyzer /
- hot spring water /
- field analysis /
- lithium /
- electrolyte acidity /
- working current /
- sample flow rate
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表 1 热泉水样品Li元素加标回收率测试结果
Table 1. Spiked recovery of Li in hot spring water
样品编号 Li含量测定值*
(mg/L)加标量
(mg/L)加标后Li含量
测定值(mg/L)加标回收率
(%)W1 0.40 0.50 0.90 101.0 W2 0.32 0.30 0.61 98.1 W3 0.07 0.10 0.15 81.6 W4 0.90 1.00 1.96 106.6 W5 1.85 1.50 3.59 115.9 W6 1.51 1.00 2.60 109.0 W7 0.18 0.20 0.39 102.6 W8 1.38 1.00 2.48 110.1 W9 0.32 0.30 0.61 97.6 W10 0.43 0.50 0.95 102.4 注：“*”表示结果为样品溶液中的Li含量测定值，没有乘以稀释倍数。 
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表 2 热泉水样品中Li含量的锂钾分析仪测定值与ICP-OES测定值对比
Table 2. Comparison of analytical results of Li content in hot spring samples by Li-K analyzer and ICP-OES
样品编号 Li含量
ICP-OES
测定值
(mg/L)锂钾分析仪(标准曲线法) 锂钾分析仪(标准加入法) Li含量测定值
(mg/L)与ICP-OES测定值
相对偏差(%)Li含量测定值
(mg/L)与ICP-OES测定值
相对偏差(%)W1 2.00 2.00 −0.20 1.96 −2.12 W2 1.64 1.59 −3.21 1.55 −5.41 W3 0.38 0.36 −4.04 0.35 −9.13 W4 4.45 4.48 0.78 4.42 −0.66 W5 8.40 9.26 10.3 9.16 9.03 W6 6.97 7.55 8.38 7.47 7.15 W7 0.94 0.92 −2.18 0.89 −5.01 W8 6.62 6.89 4.08 6.81 2.93 W9 1.56 1.60 2.78 1.57 0.54 W10 2.24 2.18 −2.78 2.14 −4.61 注：相对偏差=(锂钾分析仪测定值−ICP-OES测定值)/ICP-OES测定值×100%。
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