Bing-bing Liu; Lin Zhang; Ke Li

doi:10.26599/JGSE.2026.9280071

doi: 10.26599/JGSE.2026.9280071

^{1, 2},
^1, ,,
¹

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出版历程
- 收稿日期: 2025-02-26
- 录用日期: 2025-10-10
- 网络出版日期: 2025-11-20
- 刊出日期: 2026-03-15

Precision and trueness of a method for determing antimony content in groundwater using hydride generation-atomic fluorescence spectrometry

Bing-bing Liu^{1, 2},
Lin Zhang^{1
, ,},
Ke Li¹

1.
Institute of Hydrogeology and Environmental Gelogy, Chinese Academy of Geological Science, Shijiazhuang 050001, China
2.
Key Laboratory of Groundwater Remediation of Hebei Province and China Geological Survey, Zhengding 050803, Hebei, China

More Information

Corresponding author: zhl5369@163.com

摘要

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Abstract: At present, there is currently a lack of unified standard methods for the determination of antimony content in groundwater in China. The precision and trueness of related detection technologies have not yet been systematically and quantitatively evaluated, which limits the effective implementation of environmental monitoring. In response to this key technical gap, this study aimed to establish a standardized method for determining antimony in groundwater using Hydride Generation–Atomic Fluorescence Spectrometry (HG-AFS). Ten laboratories participated in inter-laboratory collaborative tests, and the statistical analysis of the test data was carried out in strict accordance with the technical specifications of GB/T 6379.2—2004 and GB/T 6379.4—2006. The consistency and outliers of the data were tested by Mandel's h and k statistics, the Grubbs test and the Cochran test, and the outliers were removed to optimize the data, thereby significantly improving the reliability and accuracy. Based on the optimized data, parameters such as the repeatability limit (r), reproducibility limit (R), and method bias value (δ) were determined, and the trueness of the method was statistically evaluated. At the same time, precision-function relationships were established, and all results met the requirements. The results show that the lower the antimony content, the lower the repeatability limit (r) and reproducibility limit (R), indicating that the measurement error mainly originates from the detection limit of the method and instrument sensitivity. Therefore, improving the instrument sensitivity and reducing the detection limit are the keys to controlling the analytical error and improving precision. This study provides reliable data support and a solid technical foundation for the establishment and evaluation of standardized methods for the determination of antimony content in groundwater.
- Mandel's h and k statistics /
- Grubbs test /
- Cochran test /
- Repeatability limit /
- Reproducibility limit /
- Method bias value

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Figure 1. Mandel's h statistics grouped by laboratory

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Figure 2. Mandel's k statistic grouped by laboratory

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Figure 3. Data fitting relationship between r and m

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Figure 4. Data fitting relationship between R and m

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Table 1. Sample information

Sample number	YP-1	YP-2	YP-3	YP-4	YP-5
pH	8.37	8.38	7.35	7.95	7.86
Hydrochemical type	HCO₃+Cl-Na	HCO₃-Na	HCO₃+SO₄-Ca+Mg	HCO₃-Ca	HCO₃-Ca
Antimony content (μg/L)	0.10–0.30	0.50–1.00	1.20–1.80	2.00–3.00	3.00–5.00

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Table 2. Method trueness test

Sample number	Background value (μg/L)	Added value (μg/L)	Measured value (μg/L)	Recovery rate (%)
1#	N.D	0.30	0.3021, 0.3104, 0.3068, 0.3113, 0.3124, 0.2943,	98.10%–104.7%
		0.30	0.3081, 0.3108, 0.3056, 0.3099, 0.3011, 0.3142	98.10%–104.7%
		1.00	0.9874, 1.0196, 1.0296, 0.9851, 0.9644, 0.9661	96.20%–105.7%
		1.00	1.0281, 1.0574, 0.9996, 1.0471, 1.0056, 0.9620	96.20%–105.7%
		3.00	2.9761, 2.9914, 2.9414, 3.0499, 3.0309, 3.0354	98.05%–103.8%
		3.00	3.0980, 3.0695, 3.0662, 3.1142, 2.9856, 3.0304	98.05%–103.8%
2#	N.D	0.30	0.3072, 0.3121, 0.3078, 0.2906, 0.2964, 0.2933	95.77%–104.3%
		0.30	0.3110, 0.2873, 0.3024, 0.3018, 0.3128, 0.3115	95.77%–104.3%
		1.00	0.9654, 0.9511, 0.9758, 0.9882, 1.0274, 1.0447	95.11%–104.5%
		1.00	1.0115, 1.0083, 1.0356, 1.0298, 1.0059, 0.9627	95.11%–104.5%
		3.00	3.1055, 3.0631, 2.9652, 3.0321, 3.0615, 3.0629	97.18%–103.5%
		3.00	2.9881, 3.0054, 3.0015, 3.0445, 2.9653, 2.9155	97.18%–103.5%

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Table 3. Comparison of HG-AFS, HG-AAS and ICP-MS methods

Performance indicators	This method (HG-AFS)	HG-AAS (Li et al. 2008)	ICP-MS (Zhang et al. 2016)
Detection limit (μg/L)	0.02	0.31	0.03
Precision (RSD,%)	1.34–2.46	2.2-4.2	0.36–1.15
Linear range (μg/L)	0–5.0	0–20.0	0–50.0
Matrix interference	Transition metals (Cu, Ni, etc.)	Transition metals, hydride-forming elements	Mass spectrometry interference
Analysis costs	Low	Intermediate	Very High

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Table 4. Mean and standard deviation of antimony content analysis results for each unit Unit: μg/L

Laboratory number	Level
	1		2		3		4		5
	Mean	Standard deviation	Mean	Standard deviation	Mean	Standard deviation	Mean	Standard deviation	Mean	Standard deviation
1	0.256	0.017	0.832	0.016	1.520	0.037	2.254	0.064	4.620	0.051
2	0.248	0.014	0.932	0.040	1.542	0.077	2.176	0.092	4.556	0.189
3	0.252	0.008	0.796	0.027	1.482	0.036	2.270	0.061	4.616	0.129
4	0.244	0.017	0.816	0.015	1.562	0.015	2.272	0.051	4.606	0.103
5	0.230	0.010	0.824	0.023	1.546	0.036	2.250	0.043	4.762	0.049
6	0.314	0.009	0.876	0.005	1.542	0.064	2.260	0.068	4.530	0.114
7	0.252	0.019	0.728	0.002	1.376	0.021	2.130	0.046	4.416	0.034
8	0.274	0.011	0.860	0.016	1.406	0.017	2.232	0.022	4.546	0.027
9	0.324	0.018	0.732	0.013	1.364	0.015	2.020	0.020	4.148	0.038
10	0.257	0.004	0.787	0.010	1.482	0.019	2.195	0.021	4.563	0.030

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Table 5. Grubbs and Cochran test results

	Collaborative sample number	YP-1	YP-2	YP-3	YP-4	YP-5
Grubbs test	Gp	1.928	1.375	1.138	0.926	1.829
	G1	1.149	1.517	1.47	1.964	1.694
	1% critical value	2.482	2.387	2.387	2.387	2.274
	5% critical value	2.29	2.215	2.215	2.215	2.126
Cochran test	C	0.197	0.316	0.424	0.298	0.348
	1% critical value	0.393	0.425	0.425	0.425	0.463
	5% critical value	0.331	0.358	0.358	0.358	0.391

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Table 6. Statistical analysis results of method precision and trueness parameters

Statistical parameters	Level
Statistical parameters	1	2	3	4	5
Number of accepted laboratories (p)	10	9	8	9	8
Number of test replicates (n)	5	5	5	5	5
Grand mean (m)/(μg/L)	0.265	0.806	1.47	2.23	4.58
Acceptable reference value (μ)/(μg/L)	0.26	0.80	1.50	2.20	4.55
Repeatability standard deviation (s_r)/(μg/L)	0.014	0.016	0.026	0.056	0.078
Repeatability coefficient of variation/%	5.09	1.99	1.79	2.52	1.69
Repeatability limit (r)/(μg/L)	0.038	0.045	0.074	0.159	0.219
Reproducibility standard deviation (s_R)/(μg/L)	0.033	0.053	0.080	0.070	0.120
Reproducibility coefficient of variation/%	12.41	6.59	5.47	3.16	2.62
Reproducibility limit (R)/(μg/L)	0.093	0.150	0.227	0.199	0.340
γ=s_R/s_r	2.429	3.311	3.048	1.250	1.551
Uncertainty coefficient (A)	0.630	0.625	0.626	0.658	0.645
Method bias value (δ)/(μg/L)	0.005	0.006	-0.033	0.027	0.032
δ − As*_R/(μg/L)	−0.016	−0.027	−0.083	−0.020	−0.045
δ + As*_R/(μg/L)	0.026	0.039	0.018	0.073	0.110

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Table 7. Inter-laboratory precision Unit: μg/L

Element	Mean level (m)	Repeatability limit (r)	Reproducibility limit (R)
Antimony	0.26–4.55	r = 0.0451 m + 0.0229	R = 0.1668 m^0.4357
Note: The precision was determined in accordance with GB/T 6379.2, based on statistical analysis of data from ten laboratories, each performing five replicate determinations for five concentration levels under repeatability conditions, after the elimination of outliers.

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