旋转混匀-全自动凯氏定氮仪测定土壤阳离子交换量及在全国土壤普查中的应用

Determination of Soil Cation Exchange Capacity Using a Fully Automated Kjeldahl Nitrogen Analyzer with Rotary Mixing and Its Application in the National Soil Survey

  • 摘要: 测定土壤的阳离子交换量(CEC)常用乙酸铵、氯化铵-乙酸铵、氯化钡、乙酸钠作为浸提剂,以人工玻璃棒搅拌、磁力搅拌、超声、淋洗等进行浸提或清洗,存在操作繁琐、效率低、重现性差等问题,亟需建立一种兼具高精度、自动化与普适性的快速检测方法。本文以EDTA-乙酸铵作为浸提剂,仅需对土壤处理一次,浸提处理次数较传统方法减少67%~75%,采用旋转混匀浸提/清洗方式,提高了固-液接触效率,样品处理效率提升至192件/12h,与单台全自动凯氏定氮仪配套时可检测样品110件/12h。通过对旋转混匀仪转速、浸提剂EDTA浓度、浸提剂用量、浸提剂酸度、浸提时间、清洗剂及用量、称样量关键参数优化,确定了最佳实验条件。对不同地理分布、不同pH、不同黏性及不同研制单位的2种酸性、3种中性、5种碱性土壤有效态成分分析参比/标准物质进行测试,CEC测定值在不确定度范围内,方法精密度(RSD)为0.85%~2.05%,正确度(RE)为-3.47%~2.31%。采用本方法测定第三次全国土壤普查1642件林草地、耕园地表层及剖面土壤样品,质量控制满足要求。与传统人工搅拌方法相比,本方法自动化程度高、操作简便,适用于大批量酸性、中性、碱性土壤的快速测定。

     

    Abstract: To determine the cation exchange capacity (CEC) of soil, ammonium acetate, ammonium chloride-ammonium acetate, barium chloride, and sodium acetate are commonly used as extractants, while manual glass rod stirring, magnetic stirring, ultrasonication, or leaching are employed as extraction/washing methods. These methods suffer from cumbersome operation, low efficiency, and poor reproducibility. Establishing a rapid detection method with high precision, automation, and universality is therefore of great significance. In this work, EDTA-ammonium acetate was employed as the extractant, requiring only a single soil treatment step, thereby reducing the number of extraction treatments by 67%–75% compared with traditional methods. Rotary mixing during extraction/washing enhanced solid-liquid contact efficiency, increasing sample pretreatment throughput to 192 samples per 12h. When coupled with a single fully automated Kjeldahl nitrogen analyzer, the workflow enabled the detection of 110 samples per 12h. Through investigation and optimization of key parameters—rotary mixer speed, EDTA concentration in the extractant, extractant volume, extractant acidity, extraction time, rinsing agent and its volume, and sample weight—the optimal experimental conditions were determined. The method was tested on two acidic, three neutral and five alkaline soil reference/standard materials for available component analysis, sourced from different geographical distributions, pH levels, textures, and preparation institutions. All measured CEC values fell within the certified uncertainty intervals; precision (RSD) was 0.85%–2.05% and trueness (relative error) was −3.47% to 2.31%. The method was successfully applied to determine CEC in 1642 surface and profile soil samples from forest, grassland, cultivated, and garden land during China’s Third National Soil Survey, meeting quality control requirements. Compared to traditional manual stirring methods, this method offers a high degree of automation, simple operation, and is suitable for the rapid determination of large batches of samples, including acidic, neutral, and alkaline soils.

     

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