Application of High Pressure Closed Digestion in Pretreatment of Effective Soil Samples
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摘要: 土壤样品经有机酸浸提后，浸提出的溶液中存在大量有机酸及有机质，如未进行破坏处理，进入电感耦合等离子体发射光谱仪（ICP-OES）进样系统后容易堵塞雾化器、中心管、矩管等，或有颗粒黏附于中心管壁和矩管壁上，造成测定结果精密度和准确度差、空白高等问题，进而影响土壤有效态的综合评价。本文将土壤样品用有机酸（DTPA、草酸-草酸铵、柠檬酸等）浸提后，过滤或离心，吸取上清液加入高压密闭消解罐中，经电热板上处理，再加2mL浓硝酸，于180℃烘箱中保温至少3h，采用ICP-OES测定有效态元素铜锌铁锰镉铅镍铬钼硅的含量。本方法采用高压密闭消解技术处理土壤样品，各元素测定结果的相对标准偏差（RSD）为2.5%~5.9%，相对误差为-2.1%~5.2%，回收率为90.1%~103.2%，方法检出限为0.32μg/kg~0.038mg/kg；而采用以往高温炉中灼烧法、硝酸-高氯酸（硫酸）敞开消解法等技术手段，回收率为89.2%~100.5%，方法检出限为0.50μg/kg~0.050mg/kg，两者相比，本方法的测定结果稳定、空白低，分析周期短，适合批量样品的连续分析。Abstract:
BACKGROUNDAfter the soil sample is extracted by organic acid, there are a lot of organic acids and organic matter in the solution. If these remaining materials are not destroyed, the central tube and rectangular tube of the atomizer are easily plugged after they have entered the inductively coupled plasma-optical emission spectrometry (ICP-OES) sampling system. Particles absorbed in the central tube wall and rectangular tube wall will result in poor analytical precision and accuracy, and further affect comprehensive evaluation of soil availability. OBJECTIVESTo make the determination of available state in soil sample more stable and accurate, reduce the detection limit of the method, and prevent the sample from contamination and volatilization loss in the pretreatment. METHODSSoil samples were extracted with organic acids (DTPA, oxalic acid-ammonium oxalate, citric acid, etc.), filtered or centrifuged, and the supernatant was absorbed into a high-pressure sealed digestion tank. The supernatant was treated by an electric heating plate and then added with 2mL concentrated nitric acid. The soil samples were heated for at least 3 hours in an oven at 180℃. The effective element contents of copper, zinc, iron, manganese, cadmium, lead, nickel, chromium, molybdenum and silicon were determined by ICP-OES. RESULTSThe relative standard deviations in this method were 2.5%-9.8%, the relative errors were -2.1%-5.2%, the recoveries were 90.1%-103.2%, and the detection limits were 0.32μg/kg-0.038mg/kg. Using the method of burning in the high temperature furnace and the open digestion by nitric acid-perchloric acid (sulfuric acid), the recoveries were 89.2%-100.5%, and the detection limits were 0.50μg/kg-0.050mg/kg. CONCLUSIONSThe method has stable measurement results, low blank and a short analysis period, and is especially suitable for continuous analysis of batch samples. -
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表 1 NY/T 1121/890与本法测定有效态精密度、准确度及加标回收率比对
Table 1. Precision, accuracy and recovery of the effective state treated with NY/T 1121/890 and this method
分析项目 RSD(%) 相对误差(%) 加标回收率(%) NY/T 1121/890 本法 NY/T 1121/890 本法 NY/T 1121/890 本法 有效铜锌铁
锰镉铅镍铬5.8%~9.2% 3.2%~5.5% -2.3%~5.2% -1.3%~4.1% 92.2%~100.5% 92.3%~103.2% 有效钼 6.1%~10.1% 4.6%~5.8% -3.2%~7.5% -2.1%~5.2% 89.2%~98.3% 90.1%~100.1% 有效硅 4.2%~7.9% 2.5%~5.9% -2.5%~4.8% -1.4%~2.5% 90.2%~99.1% 91.2%~99.3% 
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表 2 方法检出限
Table 2. Detection limit of the method
分析项目 方法检出限 《岩石矿物分析》(第四版) 本方法 有效铜锌铅 0.02mg/kg 0.015mg/kg 有效铁锰 0.02mg/kg 0.02mg/kg 有效镉 0.50μg/kg 0.32μg/kg 有效镍 0.05mg/kg 0.038mg/kg 有效铬 0.001mg/kg 0.001mg/kg 有效钼 0.05mg/kg 0.03mg/kg 有效硅 0.05mg/kg 0.03mg/kg
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