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针对传统铂金坩埚在土壤全硅测定中存在的熔融物难溶出、实验成本高昂及分析效率低下等问题，本研究基于石墨粉的耐高温特性，开展了石墨粉坩埚的制作及其对土壤样品处理技术的研究。通过精密度和准确度、实验室间比对、不同砂粒含量和不同混合熔剂用量对全硅熔融的影响实验，分析了石墨粉坩埚-碱熔法的精准性、适用性、可操作性和可移植性。研究结果表明，石墨粉坩埚-碱熔法测定土壤全硅的测定值与标准物质认定值吻合，且RSD<5%。处理0.1 g左右土壤样品，分别使用混合熔剂0.8、0.6、0.4 g熔融黏土、黏壤土、壤土、砂土及壤质砂土，0.4 g熔剂对砂土及壤质砂土熔融影响较大，相比0.6 g和0.8 g的结果偏低，甚至超过5%，呈现显著性差异，熔剂用量在0.6 g以上，可以完全熔融不同质地土壤样品，对测定结果无影响，由此，推荐0.6 g熔剂作为土壤全硅含量测定的熔剂使用量，同时减少基体干扰。实验室间比对结果相关性好、没有显著性差异。此外，通过优化操作步骤，石墨粉坩埚碱熔法具有可操作性强、成本低、精准度高的优点，而且适用于大批量土壤全硅的测定。
Abstract：To address the issues of difficult fusion dissolution,high experimental costs,and low analytical efficiency associated with traditional platinum crucibles in total soil silicon determination,this study explored the fabrication of graphite powder crucibles and their application in soil sample processing techniques,leveraging the high-temperature resistance properties of graphite powder. Through experiments evaluating precision and accuracy,inter-laboratory comparisons,and investigations into the effects of varying sand content and mixed flux amounts on total silicon fusion,the precision,applicability,operability,and transferability of the graphite powder crucible-alkali fusion method were comprehensively analyzed. The results demonstrated that the measured values of total silicon in soil obtained by the graphite powder crucible-alkali fusion method were consistent with the certified values of standard reference materials,with a relative standard deviation(RSD) of less than 5%. For soil samples weighing approximately 0. 1 g,different amounts of mixed flux(0. 8,0. 6,and 0. 4 g) were tested on various soil types,including clay,silty clay,loam,sandy soil,and loamy sand. The study found that a flux amount of 0. 4 g had a significant impact on the fusion of sandy soil and loamy sand,resulting in lower measured values compared to those obtained with 0. 6 g and 0. 8 g of flux. In some cases,the deviation exceeded 5%,indicating a statistically significant difference. However,when the flux dosage exceeds 0. 6 g,it can completely fuse soil samples of varying textures without affecting the determination results. Therefore,a 0. 6 g flux dosage is recommended for total silicon determination in soils,as it ensures complete fusion while minimizing matrix interference. Inter-laboratory comparison tests further confirmed the method's reliability,showing strong correlation and no significant differences between laboratories. Furthermore,by optimizing operational procedures,the graphite powder crucible-alkali fusion method demonstrates significant advantages in terms of enhanced operability,reduced cost,and improved accuracy,making it particularly suitable for high-throughput determination of total silicon in soil samples.
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基本信息:
DOI：10.20236/j.CJIAC.2025.12.006
中图分类号:S153.6;O657.31
引用信息:
[1]陈勇,陈烨文,卢瑛,等.石墨粉坩埚碱熔-电感耦合等离子体发射光谱(ICP-OES)法测定土壤中全硅[J].中国无机分析化学,2025,15(12):1951-1958.DOI:10.20236/j.CJIAC.2025.12.006.
基金信息:
国家自然科学基金资助项目(42277290); 广东省农业科学院农业质量标准与监测技术研究所所长基金资助项目(202205)