Evaluation of Data Quality on the Detection of Heavy Metals in Soils by Atomic Absorption Spectrometry or Atomic Fluorescence Spectrometry and X-ray Fluorescence Spectrometry in Ecological Environment Monitoring
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摘要: 当前我国生态环境监测工作中，测定土壤重金属等无机元素全量所采用的标准方法主要为原子吸收光谱法（AAS）、原子荧光光谱法（AFS）和波长色散X射线荧光光谱法（WDXRF）等。为掌握AAS、AFS和WDXRF等方法测试结果的有效性和可比性，本文选取了20个来自全国不同区域、不同类型的实际土壤样品，通过盲样方式插入国家土壤环境监测任务样品批次中，分发至3~5个实验室，采用AAS/AFS、WDXRF和便携式X射线荧光光谱法（p-XRF）平行测定Cr、Ni、Cu、Zn、As、Hg、Cd、Pb、V和Mn十个元素全量。结果表明：元素含量水平分布均匀（在≤ 1.0、1.0~2.0、2.0~10.0及>10.0水平均有分布）；85%以上样品Cr、Ni、Cu、Zn和Pb元素WDXRF方法的实验室间相对偏差（RD）更理想，60%样品As元素AFS方法的RD更优，元素含量对WDXRF方法的RD有更明显影响。总体上，AAS/AFS和WDXRF两类方法实验室间精密度控制水平均较高，WDXRF法更理想。进一步分析AAS/AFS和WDXRF方法间平行性（以这两类方法测试结果的相对偏差RD'进行评价），Cr、Ni、Cu和Zn元素的RD'基本低于20%，As和Pb元素80%以上的RD'低于20%，Pearson相关性和线性关系分析表明这两类方法有较高的可比性；另外，Cr、Ni、Cu、Zn、Pb和As元素的p-XRF与AAS/AFS方法测试结果也有较理想的可比性。本研究认为，AAS/AFS和WDXRF两类方法具有等同测试效果，实际监测工作中Cd、Hg等含量较低元素宜选择检出限较低的AAS/AFS法；因WDXRF方法的前处理过程简单易控，大批量土壤分析中使用该方法更加高效，在特定实验条件下p-XRF方法也有可接受的定量效果。
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关键词:
- 土壤 /
- 重金属元素 /
- 原子吸收光谱法 /
- 原子荧光光谱法 /
- 波长色散X射线荧光光谱法 /
- 便携式X射线荧光光谱法 /
- 相对偏差
Abstract:BACKGROUNDIn current ecological environmental monitoring, the standard methods used to determine the total contents of inorganic elements, such as heavy metals in soil, include atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS) and wavelength dispersive X-ray fluorescence spectrometry (WDXRF). OBJECTIVESTo evaluate the quality, validity and mutual comparability of the results obtained by different analytical methods. METHODSTwenty actual soil samples of different types from different regions in China were selected and inserted into the national soil environmental monitoring sample batch blind, and sent to 3-5 laboratories. AAS/AFS, WDXRF and portable X-ray fluorescence spectrometry (p-XRF) were used to determine the total amount of Cr, Ni, Cu, Zn, As, Hg, Cd, Pb, V and Mn in parallel. RESULTSThe content of these elements was equally distributed at levels of ≤ 1.0, 1.0-2.0, 2.0-10.0, and 10.0. The results show that 85% samples had better inter-laboratory relative deviation (RD) of the WDXRF method in terms of Cr, Ni, Cu, Zn and Pb. On the other hand, 60% samples had better RD using AFS method for the As determination. Element content had more obvious effect on RD for WDXRF method. Generally, the inter-laboratory precision control was good for both AAS/AFS and WDXRF methods, and the WDXRF method was more desirable. Through further analysis of the parallelism between AAS/AFS and WDXRF methods (evaluated as the relative deviation RD' of the analytical results of these two methods), it showed that almost all the RD' of Cr, Ni, Cu and Zn was less than 20%, and more than eighty percent RD' of As and Pb was less than 20%. The results of Pearson correlation and linear relationship analysis also show that the analytical results of two methods were highly comparable. Additionally, there was also good comparability between the results of AAS/AFS and p-XRF methods for determination of Cr, Ni, Cu, Zn, Pb and As. CONCLUSIONSAAS/AFS method and WDXRF method have equivalent test results. In actual monitoring task, the determination of Cd and Hg with lower contents should be determined by AAS/AFS which have lower detection limits. WDXRF should be chosen for the analysis large quantities of soil. Under specific experimental conditions, the p-XRF method also can obtain an acceptable quantitative results. -
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表 1 研究样品中各元素含量
Table 1. Average concentrations of elements in research samples
样品编号 Cr
(mg/kg)Ni
(mg/kg)Cu
(mg/kg)Zn
(mg/kg)As
(mg/kg)Pb
mg/kg)Cd
(mg/kg)Hg
(mg/kg)V
(mg/kg)Mn
(mg/kg)土壤背景值中位值 57.3 24.9 20.7 68.0 9.60 23.5 0.079 0.038 76.8 540 1# 80.3 35.5 49.5 200.4 11.2 66.1 1.50 0.25 108 697 2# 76.3 32.3 28.6 89.4 9.8 30.3 0.14 0.03 93.8 599 3# 112.9 52.5 67.7 213.3 23.7 78.3 0.77 0.39 138 814 4# 63.5 30.1 19.3 94.2 3.0 32.4 0.19 0.02 107 718 5# 79.7 34.2 38.1 88.5 17.5 35.1 0.20 0.17 133 448 6# 81.8 35.2 23.6 87.1 6.0 22.7 0.10 0.05 107 736 7# 284.6 149.0 66.3 123 3.0 14.6 0.09 0.05 211 532 8# 75.7 33.2 37.5 101 64.1 22.5 0.20 0.05 153 730 9# 70.4 23.9 22.1 46.8 8.6 24.2 0.04 0.10 81.9 336 10# 58.7 26.4 29.6 182 15.4 101 0.31 0.03 160 3281 11# 47.0 24.0 17.7 49.1 8.5 19.8 0.10 0.03 83.3 604 12# 75.5 35.3 44.0 167.7 7.9 28.9 0.14 0.08 93.5 783 13# 66.3 28.0 26.4 64.7 11.5 23.3 / / 87.4 645 14# 69.9 34.1 31.6 87.5 10.9 26.9 0.17 0.08 99.2 762 15# 63.1 27.5 20.8 61.5 8.7 19.2 0.08 0.03 82.2 544 16# 51.5 17.3 15.9 44.2 6.7 22.3 / / 61.9 354 17# 95.8 50.9 44.0 139.8 12.5 39.7 0.97 0.21 247 673 18# 5587 4642 119 232 6.2 14.3 0.11 0.18 253 2495 19# 67.8 16.7 13.0 101.1 18.5 27.0 0.40 0.11 109 210 20# 65.5 30.4 23.8 74.2 8.6 22.5 0.05 0.03 85.9 564 
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表 2 AAS/AFS和WDXRF两种方法实验室间相对偏差
Table 2. RD values of AAS/AFS and WDXRF in different laboratories
测定方法 统计值 实验室间相对偏差(%) Cr Ni Cu Zn As Pb AAS/AFS 最小值 2.09 1.71 2.14 1.85 2.04 2.84 80% 11.83 8.87 10.54 9.06 15.08 23.17 85% 12.91 8.98 11.71 9.84 17.80 23.89 90% 13.07 9.06 12.77 13.45 21.03 27.69 95% 13.82 11.35 19.94 15.43 22.80 28.12 最大值 14.79 20.98 20.82 24.68 27.37 28.53 WDXRF 最小值 0.62 1.22 0.82 0.70 3.45 1.93 80% 3.39 3.34 4.76 4.47 11.19 7.82 85% 4.96 4.74 7.13 4.85 13.94 8.46 90% 5.18 4.76 8.43 5.95 18.63 10.16 95% 5.58 6.42 12.26 6.05 20.25 11.56 最大值 6.13 22.57 12.26 22.78 21.45 16.31
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表 3 实验室间相对偏差合格率结果统计
Table 3. Pass rate of RD control between the different laboratories
元素 测定方法合格率(%) WDXRF AAS/AFS Cr 100.0 95.0 Ni 95.0 90.0 Cu 95.0 90.0 Zn 95.0 90.0 As 90.0 85.0 Pb 100.0 85.0 Cd - 95.0 Hg - 95.0 V 55.0 - Mn 95.0 - 注：“-”表示该方法下无此元素的测定结果，故无统计结果。
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表 4 AAS/AFS与WDXRF方法测试结果Pearson相关性分析
Table 4. Pearson relevance analysis of AAS/AFS and WDXRF measured values
Cr Ni 测定方法 项目 WDXRF 测定方法 项目 WDXRF AAS/AFS Pearson相关性
显著性(双侧)
N1.000**
.000
18AAS/AFS Pearson相关性
显著性(双侧)
N1.000**
.000
18Cu Zn 测定方法 项目 WDXRF 测定方法 项目 WDXRF AAS/AFS Pearson相关性
显著性(双侧)
N0.945**
.000
18AAS/AFS Pearson相关性
显著性(双侧)
N0.911**
.000
18As Pb 测定方法 项目 WDXRF 测定方法 项目 WDXRF AAS/AFS Pearson相关性
显著性(双侧)
N0.967**
.000
18AAS/AFS Pearson相关性
显著性(双侧)
N0.929**
.000
18注：标注“**”表示在0.01水平(双侧)上显著相关。
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