|
|
|
|
|
|
Study on Methods of Detection Limit in XRF Spectrometry |
YUAN Liang-jing1, JIA Yun-hai1, 2, CHENG Da-wei1, 2* |
1. NCS Testing Technology Co., Ltd., Beijing 100094, China
2. Central Iron & Steel Research Institute, Beijing 100081, China
|
|
|
Abstract X-ray fluorescence (XRF) spectrometers have been developed rapidly and applied widely. They are quick and accurate without complicated pretreatment or consumables. In some industries, XRF has partially replaced traditional AAS, ICP and ICP-MS. The limit of detection (LOD) is one important evaluation indicator for its application performance. There are various LOD calculating methods, generally equal to 3 times standard deviation (SD) of blank samples. Analyte cannot be detected when it is lower than the LOD, could be qualitatively analyzed when higher than LOD and lower than the limit of quantification (LOQ), and could be accurately analyzed when higher than LOQ. XRF LOD calculation method is different from other common methods because measured values of traditional analysis are continuous distribution in accord with Gaussian distribution, however, XRF measured values conform to Poisson distribution, which is a discrete distribution and could approach Gaussian distribution only with high enough counts. In practical analysis, accumulating countsis not worth taking too long. This paper introduces seven methods for calculating LOD, including X-ray Poisson distribution method, K times SD method, linear calibration method, RSD method, SD method, environmental monitoring analysis method, marine monitoring specification and analysis method. Taking the detection data of XRF heavy metal instruments as an example, Pb, As and Cd elements were tested in six kinds of rice powder reference samples, and each method’s calculation processes and consideration factors were compared in detail. On account of the difficulty off inding the completely blank sample, the approximate blank sample was used this paper instead. The poisson distribution methods are quick and accurate, requiring only two measurements at the fastest. The linear calibration method, which considers comprehensive factors, is generally considered the most accurate method of LOD calculations and can be used as a reference value compared with others. RSD method and SD straight line extrapolation method need more test times, which can be used without blank samples or spectrum intensity. The RSD method can be used as a necessary condition for determining LOD. When RSD>43%, the analyte cannot be qualitatively detected.
|
Received: 2021-11-11
Accepted: 2022-05-25
|
|
Corresponding Authors:
CHENG Da-wei
E-mail: chengdawei@ncschina.com
|
|
[1] Suda Y, Grebennikov A V, Kuzmin Y V, et al. Journal of Archaeological Science: Reports, 2018, 17: 379.
[2] BAO Xi-bo, ZHAO Liang, LI Cai-hong, et al(鲍希波, 赵 亮, 李才红, 等). Metallurgical Analysis(冶金分析), 2019, 39(2):51.
[3] GUO Jin-ke, LU Ji-long, YIN Ye-chang, et al(郭金珂, 陆继龙, 尹业长, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2020, 40(5): 1461.
[4] LUO Li-qiang, ZHAN Xiu-chun, LI Guo-hui(罗立强, 詹秀春, 李国会). X-Ray Fluorescence Spectrometry 2(X射线荧光光谱法2). Beijing: Chemical Industry Press(北京: 化学工业出版社), 2015.
[5] JIA Yun-hai, SUN Xiao-fei, ZHANG Fan(贾云海, 孙晓飞, 张 帆). Metallurgical Analysis(冶金分析), 2021, 41(1): 1.
[6] Ministry of Ecology and Environment of the People’s Republic of China(中华人民共和国生态环境部). HJ 168—2020 Technical Guideline for the Development of Environmental Monitoring Analytical Method Standards(环境监测分析方法标准制定技术导则). Beijing: China Environmental Science Press, 2020.
[7] General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China & Standardization Administration(中华人民共和国国家质量监督检验检疫总局,中国国国家标准化管理委员会). GB 17378.2—2007 The Specification for Marine Monitoring-Part 2:Data Processing and Quality Control of Analysis(GB 17378.2—2007 海洋监测规范第2部分:数据处理与分析质量控制). Beijing: Standards Press of China, 2007.
[8] State Administration for Market Regulation & Standardization Administration,the People’s Republic of China(国家市场监督管理总局,中国国家标准化管理委员会). GB/T 33260.2—2018 Capability of Detection-Part 2: Methodology in the Linear Calibration Case(GB/T 33260.2—2018检出能力+第2部分:线性校准情形检出限的确定方法). Beijing, 2018.
[9] General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China & Standardization Administration(中华人民共和国国家质量监督检验检疫总局,中国国国家标准化管理委员会). GB/T 22554—2010 Linear Calibration Using Reference Materials(GB/T 22554—2010基于标准样品的线性校准). Beijing, 2010.
[10] State Administration for Market Regulation & Standardization Administration,the People’s Republic of China(国家市场监督管理总局,中国国家标准化管理委员会). GB/T 33260.5—2018 Capability of Detection-Part 5: Methodology in the Linear and Nonlinear Calibration Cases(GB/T 33260.5—2018检出能力第5部分:非线性校准情形检出限的确定方法). Beijing, 2018.
|
[1] |
WU Hu-lin1, DENG Xian-ming1*, ZHANG Tian-cai1, LI Zhong-sheng1, CEN Yi2, WANG Jia-hui1, XIONG Jie1, CHEN Zhi-hua1, LIN Mu-chun1. A Revised Target Detection Algorithm Based on Feature Separation Model of Target and Background for Hyperspectral Imagery[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2024, 44(01): 283-291. |
[2] |
FU Wan-lu1, 2, LU Hao3*, CHAI Jun4, SUN Zuo-yu1. Spectroscopic Characteristics of Longxi Nephrite From Sichuan and Its Color Genesis[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2023, 43(05): 1408-1412. |
[3] |
LIANG Jia-xiang1, WANG Tian1*, ZHANG Ya-xu2, WANG Fen1, LI Qiang3, LUO Hong-jie3, ZHAO Xi-chen2, ZHU Jian-feng1 . Study of the Painted Warrior Figurines Excavated in the Tomb of the
Sutong Family (Tang Dynasty) by Spectroscopic Techniques[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2023, 43(01): 175-182. |
[4] |
XIANG Xiong-zhi1, ZHONG Rong-qu1, GAO Shi-han1, SU Xiao-wei1, CHE Da2*. XRF Analysis of the Whole-Area Component of the Oil Painting “Lady in Evening Dress”[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(12): 3913-3916. |
[5] |
LU Hao1, FU Wan-lu2, 3*, CHAI Jun2, LIU Shuang2, SUN Zuo-yu2. Analysis of Sandstone in Leshan Giant Buhhda Based on Hand-Held
X-Ray Fluorescence Spectrometer[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(08): 2506-2512. |
[6] |
OUYANG Zhou-xuan, MA Ying-jie, LI Dou-dou, LIU Yi. The Research of Polarized Energy Dispersive X-Ray Fluorescence for Measurement Trace Cadmium by Geant4 Simulation[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(04): 1064-1069. |
[7] |
JIANG Ling-ling1, WANG Long-xiao1, 2 , WANG Lin2*, GAO Si-wen1, YUE Jian-quan1. Research on Remote Sensing Retrieval of Bohai Sea Transparency
Based on Sentinel-3 OLCI Image[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(04): 1209-1216. |
[8] |
YANG Jiong1, 2, QIU Zhi-li1, 4*, SUN Bo3, GU Xian-zi5, ZHANG Yue-feng1, GAO Ming-kui3, BAI Dong-zhou1, CHEN Ming-jia1. Nondestructive Testing and Origin Traceability of Serpentine Jade From Dawenkou Culture Based on p-FTIR and p-XRF[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(02): 446-453. |
[9] |
LIU Ming-bo1,2, LIAO Xue-liang2, CHENG Da-wei1,2, NI Zi-yue1,2, WANG Hai-zhou1,2*. An EDXRF Quantitative Algorithm Based on Fundamental Parameters and Spectrum Unfolding[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2021, 41(09): 2807-2811. |
[10] |
HUANG Ke-jia1, DU Jing2, ZHU Jian3*, LI Nai-sheng2, CHEN Yue2, WU Yuan-yuan4. Mapping Analysis by μ-X-Ray Fluorescence for Waterlogged Archaeological Wood From “Nanhai No.1” Shipwreck[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2021, 41(09): 2930-2933. |
[11] |
ZHAO Ting1,2,3, CHI Hai-tao1,2,3*, LIU Yi-ren1,2,3, GAO Xia1,2,3, HUANG Zhao1,2,3, ZHANG Mei1,2,3, LI Qin-mei1,2,3. Determination of Elements in Health Food by X-Ray Fluorescence Microanalysis Combined With Inductively Coupled Plasma Mass Spectrometry[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2021, 41(03): 750-754. |
[12] |
ZHAO Hong-kun1, 2, YU Tian3, XIAO Zhi-bo3, HAO Ya-bo4, LIU Ya-xuan1*. Homogeneity Test of Geochemical Certified Reference Materials by X-Ray Fluorescence Spectrometry With Pressed-Powder Pellets[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2021, 41(03): 755-762. |
[13] |
ZHENG Pei-chao, ZHONG Chao, WANG Jin-mei*, LUO Yuan-jiang, LAI Chun-hong, WANG Xiao-fa, MAO Xue-feng. Evaluation of Flow Injection-Solution Cathode Glow Discharge With an Interference Filter Wheel for Spectral Discrimination[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2021, 41(03): 842-847. |
[14] |
CAI Shun-yan1, 2, ZHOU Jian-bin1*, TUO Xian-guo1, YU Jie1. Optimized Filter Selection for Measuring Copper and Molybdenum Contents by EDXRF[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2020, 40(06): 1934-1939. |
[15] |
WANG Yi-ya1, WANG Yi-min1*, DENG Sai-wen1, GAO Xin-hua2, LIANG Guo-li1, ZHANG Zhong3. Review on the Application of Micro-X-Ray Fluorescence Analysis Technology in China[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2020, 40(06): 1728-1735. |
|
|
|
|