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摘要:
将标准样品和一定数量已知浓度水平的实际样品，在特定的实验室进行比对测试，从而获得某一项目分析测试方法的精密度控制水平，是当前技术规范或标准方法制定过程的常用手段。本文选取来自中国31个省（区、市）的大批量（871个）、不同浓度梯度、不同类型（34种）、具有地域代表性的实际土壤样品，开展了土壤中Zn元素含量测定的精密度控制研究，全部以盲样方式分发至76家不同的实验室，每个样品由2~4家不同实验室进行室内和室间平行比对测试，旨在提出更具有效性、代表性和普适性的精密度控制评价标准建议值。实验中选用当前国家土壤生态环境监测工作中最常用的两种标准方法——火焰原子吸收光谱法（AAS）和波长色散X射线荧光光谱法（XRF）测试土壤中Zn含量。数据分析结果表明，两种不同的测试方法下其精密度控制结果无显著差异；不同土壤类型可能会对精密度控制水平产生影响，主要原因在于不同土壤类型存在基质组成的差异，可能会导致消解程度或压片密实度不同。因此，在实际监测工作中，还需考虑不同类型土壤的分析测试条件需求差异和测试结果的可比性。
Abstract:BACKGROUND The current technical specification, or standard method, to obtain the precision control level of a certain test item is to send the standard sample and a certain number of actual samples, with a known concentration level, to specific laboratories for comparison testing.
OBJECTIVES To provide a more effective, representative and universal precision control evaluation standard.
METHODS 871 actual soil samples with different concentration gradients, types (34 kinds) and geographical representation from 31 provinces (autonomous regions and municipalities) were selected and distributed blind to 76 different laboratories. Each sample was subjected to indoor and inter-laboratory parallel comparison tests by 2 to 4 different laboratories. Two standard methods, flame atomic absorption spectrometry (AAS) and wavelength dispersive X-ray fluorescence spectrometry (WD-XRF), which are commonly used in soil ecological environment monitoring in China, were selected.
RESULTS When the concentration of Zn is less than 50mg/kg, it is proposed to control RD ≤ 15% in laboratory and RD' ≤ 20% inter laboratories for the open code test samples and standard samples, while RD ≤ 20% in laboratory and RD' ≤ 30% inter laboratories for the blind test samples. In the case of the concentration of Zn is 50-90mg/kg, it is proposed to control RD ≤ 10% in laboratory and RD' ≤ 20% inter laboratories for the open code test samples and standard samples, while RD ≤ 15% in laboratory and RD' ≤ 25% inter laboratories for the blind test samples. When the concentration of Zn is higher than 90mg/kg, it is proposed to control RD ≤ 10% in laboratory and RD' ≤ 15% inter laboratories for the open code test samples and standard samples, while RD ≤ 10% in laboratory and RD' ≤ 20% inter laboratories for the blind test samples.
CONCLUSIONS There is no significant difference in the precision control results under AAS and XRF analysis methods. Different soil types may affect the precision control level. The main reason is that different matrix compositions of different soil types lead to different levels of digestion or compaction. Therefore, in actual monitoring work, it is also necessary to consider the difference in requirements of analysis and test conditions for different types of soil and the comparability of test results.
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表 1 不同置信度下不同浓度梯度的RD和RD’值统计
Table 1. Statistics of RD and RD' values of different concentration ranges under different levels of confidence
精密度指标 置信度
(%)Zn含量 < 50mg/kg Zn含量在50~90mg/kg之间 Zn含量>90mg/kg 平均值
(%)中位值
(%)标准偏差
(%)平均值
(%)中位值
(%)标准偏差
(%)平均值
(%)中位值
(%)标准偏差
(%)RD 80 2.48 1.69 2.34 2.05 1.70 1.53 1.69 1.23 1.42 90 3.72 2.13 4.11 2.70 2.08 2.40 2.35 1.48 2.30 95 4.49 2.38 5.27 3.36 2.29 3.62 3.05 1.66 3.85 RD’ 80 6.64 5.78 4.73 4.75 4.37 3.24 4.52 3.78 3.15 90 8.26 6.28 6.45 5.23 4.99 4.54 5.79 4.89 4.82 95 10.03 6.38 9.57 6.92 5.32 6.33 7.13 5.04 7.14 
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表 2 不同浓度下不同测试方法的RD和RD’值统计
Table 2. Statistics of RD and RD'values of different methods under different concentration ranges
Zn含量
(mg/kg)XRF法RD值 AAS法RD值 AAS法RD’值 平均值
(%)中位值
(%)标准偏差
(%)平均值
(%)中位值
(%)标准偏差
(%)平均值
(%)中位值
(%)标准偏差
(%)< 50 2.67 1.35 3.91 6.14 3.55 7.60 9.40 5.60 10.92 50~90 3.48 1.70 7.61 6.27 3.53 8.19 6.88 4.63 7.06 >90 2.42 1.03 6.73 8.50 4.48 12.19 14.42 8.07 18.95
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表 3 土壤环境质量监测中Zn元素平行测定精密度控制指标汇总
Table 3. Precision evaluation standard of Zn in soil environmental monitoring
Zn含量
(mg/kg)相对偏差(%) 数据来源 适用分析测定方法 RD RD’ ＜50
50~90
＞90±25 ±30
±20 ±30
±15 ±25《土壤环境监测技术规范》
(HJ/T 166—2004)
(相对标准偏差)AAS ＜50
50~90
＞90±10 ±15
±10 ±15
±5 ±10《农田土壤环境监测技术规范》
(NY/T 395—2012)AAS，ICP-MS，ICP-OES 56.2
88.4
68.1±2.8 ±7.3
±1.6 ±5.0
±3.2 ±4.1《土壤质量铜、锌的测定火焰原子吸收分光光度法》
(GB/T 17138—1997)
(标准样品的精密度控制结果)AAS < 0.1
0.1 ~1.0
1.0~10
10~100
>100±30 -
±25 -
±20 -
±10 -
±5 -《土壤和沉积物无机元素的测定波长色散X射线
荧光光谱法》
(HJ 780—2015)XRF < 50
50~90
>90±20 ±30
±15 ±25
±10 ±20本文建议值
(明码样品和标准样品可适度严格)AAS，XRF
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