Determination of heavy metal elements in soil and sediment by energy dispersive X-ray fluorescence spectrometer with simplified matrix effect correction model
YIN Hui-min1, DU Zhen-yu1, LI Yu-wu1, LI Guo-hui*2
1. National Research Center for Environmental Analysis and Measurements, Beijing 100029, China; 2. Institute of Geophysical and Geochemical Exploration, Chinese Academy of Geological Sciences, Langfang 065000, China
Abstract：During the determination of inorganic elements in soil and sediment samples by wavelength dispersive X-ray fluorescence spectrometry (WD-XRF), the determination results of macro elements such as Mg, Al, Si, Ti, K, Fe and Ca are usually required in empirical model for the correction of matrix effect. According to the application scheme of energy dispersive X-ray fluorescence spectrometry (ED-XRF), if the number of elements which participates in the correction of matrix effect can be reduced, the analysis cost and time can be significantly optimized when the light elements such as Mg, Al and Si are not considered. The feasibility of simplified model for correction of matrix effect was discussed. Based on Compton scattering and simplified model for correction of matrix effect, the determination method of heavy metal elements in soil and sediment samples (As, Cr, Cu, Ni, Pb, Zn, Mn and V) by ED-XRF was established. The accuracy and precision of method was evaluated according to the quality control requirements in HJ 780-2015. The certified values of five soil samples and nine sediment samples and the determination results of three soil examining samples by wavelength dispersion X-ray fluorescence spectrometry (WD-XRF) were used as the benchmarks. The pass rate of accuracy for analysis results of target elements were between 94.1% and 100%, and the pass rate of precision was 100%. The detection limit was evaluated based on classical background counting method and replicate experiments method. The experimental results indicated that ED-XRF could be used for the laboratory quality control of heavy metal pollution in soil samples.
殷惠民, 杜祯宇, 李玉武, 李国会. 能量色散X射线荧光光谱仪和简化的基体效应校正模型测定土壤、沉积物中重金属元素[J]. 冶金分析, 2018, 38(4): 1-10.
YIN Hui-min, DU Zhen-yu, LI Yu-wu, LI Guo-hui. Determination of heavy metal elements in soil and sediment by energy dispersive X-ray fluorescence spectrometer with simplified matrix effect correction model. , 2018, 38(4): 1-10.
辛文彩,夏宁,徐磊,等.长江三角洲沉积物标准物质研制[J].岩矿测试,2017,36(4):388-395.XIN Wen-cai,XIA Ning,XU Lei,et al.Preparation of Yangtze river delta sediment reference materials[J].Rock and Mineral Analysis,2017,36(4):388-395.
[4]
程志中,刘妹,张勤,等.水系沉积物标准物质研制[J].岩矿测试,2011,30(6):714-722.CHENG Zhi-zhong,LIU Mei,ZHANG Qin,et al.Preparation of geochemical reference materials of stream sediments[J].Rock and Mineral Analysis,2011,30(6):714-722.
Byers Harris L,McHenry Lindsay J,Grundl Timothy J.Forty-nine major and trace element concentrations measured in soil reference materials NIST SRM 2586,2587,2709a,2710a and 2711a using ICP-MS and wavelength dispersive-XRF[J].Geostandards and Geoanalytical Research,2016,40(3):433-445.
[9]
张勤,樊守忠,潘宴山,等.X射线荧光光谱法测定多目标地球化学调查样品中主次痕量组分[J].岩矿测试,2004,23(1):19-24.ZHANG Qin,FAN Shou-zhong,PAN Yan-shan,et al.Determination of 25 major,minor and trace elements in geochemical exploration samples by X-ray fluorescence spectrometry[J].Rock and Mineral Analysis,2004,23(1):19-24.
[10]
于波,严志远,杨乐山,等. X射线荧光光谱法测定土壤和水系沉积物中碳和氮等36个主次痕量元素[J].岩矿测试,2006,25(1):74-78.YU Bo,YAN Zhi-yuan,YANG Le-shan,et al.Determination of 36 major, minor and trace elements in soil and stream sediment samples by X-ray fluorescence spectrometry[J].Rock and Mineral Analysis,2006,25(1):74-78.
[11]
陈素兰,胡冠九,周春宏,等.X射线荧光光谱法测定土壤及底泥中多种元素[J].环境监测管理与技术,2006,18(4):15-18.CHEN Su-lan,HU Guan-jiu,ZHOU Chun-hong,et al.To measure variety elements in the soil and mud by X-ray fluorescence spectrographic[J].Environmental Monitoring Management and Technology,2006,18(4):15-18.
[12]
陈素兰,陈波,章勇.X射线荧光光谱法在土壤调查中的应用[J].中国环境监测,2007,23(1):19-22.CHEN Su-lan,CHEN Bo,ZHANG Yong.Determination of multi-elements in soils and sediments by X-ray fluorescence spectrometry[J].Environmental Monitoring in China,2007,23(1):19-22.
[13]
龚仓.直接粉末进样-能量色散X射线荧光光谱法测定地质样品中多种组分[J].冶金分析,2017,37(3):21-28.GONG Cang.Determination of multi-components in geological samples by energy dispersive X-ray fluorescence spectrometry coupled with direct powder introduction[J].Metallurgical Analysis,2017,37(3):21-28.
[14]
李玉莲,敖迎春,孙宁,等.能量色散X射线荧光光谱仪快速测定土壤中Cu、Pb、Zn、Rb、Nb和Th 6种元素[J].现代仪器,2012,18(6):81-84.LI Yu-lian,AO Ying-chun,SUN Ning,et al.Rapid determination of Cu,Pb,Zn,Rb,Nb and Th six elements in the clay sample using energy dispersive X-ray fluorescence spectrometer[J].Modern Instrument,2012,18(6):81-84.
[15]
李玉璞,于庆凯.X射线荧光光谱分析法在土壤样品多元素分析中的应用[J].环境科学与管理,2010,35(3):99-102.LI Yu-pu,YU Qing-kai.The application of X-ray fluorescence spectral analysis method in analyzing multielement of soil samples[J].Environmental Science and Management,2010,35(3):99-102.
[16]
Saini N K,Mukherjee P K,Rathi M S,et al.Trace element estimation in soils:an appraisal of ED-XRF technique using group analysis scheme[J].Journal of Trace and Microprobe Techniques,2002,20(4):539-551.
[17]
WEBB P C,POTTS P J,WATSON J S.Trace element analysis of geochemical reference samples by energy dispersive X-ray fluorescence spectrometry[J].Geostandards and Geoanalytical Research,1990,14(3):361-372.
[18]
Szalóki I,Somogyi A,Braun M,et al.Investigation of geochemical composition of lake sediments using ED-XRF and ICP-AES techniques[J].X-ray Spectrometry,1999,28(5):399-405.
[19]
Joanne Wai Ting Tung.Determination of metal components in marine sediments using energy-dispersive X-ray fluorescence (ED-XRF) spectrometry[J].Annali di Chimica,2004,94(11):837-846.
[20]
Ivona Janotkova,Lubomir Prokes,Tomas Vaculovic,et al.Comparison of inductively coupled plasma optical emission spectrometry,energy dispersive X-ray fluorescence spectrometry and laser ablation inductively coupled plasma mass spectrometry in the elemental analysis of agricultural soils[J].J.Anal.At.Spectrom.,2013,28:1940-1948.
[21]
Chris Vanhoof,Valere Corthouts,Kristof Tirez.Energy-dispersive X-ray fluorescence systems as analytical tool for assessment of contaminated soils[J].J.Environ.Monit.,2004,6(4):344-350.
[22]
田衎,杨珺,孙自杰,等.矿区污染场地土壤重金属元素分析标准样品的研制[J].岩矿测试,2017,36(1):82-88.TIAN Kan,YANG Jun,SUN Zi-jie,et al.Preparation of soil certified reference materials for heavy metals in contaminated sites[J].Rock and Mineral Analysis,2017,36(1):82-88.
[23]
彭杨,吴婧,巢静波,等.土壤/沉积物中14种金属元素的ICP-MS准确测定方法[J].环境化学,2017,36(1):175-182.PENG Yang,WU Jing,CHAO Jing-bo,et al.A method for the the accurate determination of 14 metal elements in soils/sediments by ICP-MS[J].Environmental Chemistry,2017,36(1):175-182.
[24]
田衎,吴忠祥,张萍,等.松花江哈尔滨段水系沉积物中无机元素环境标准样品的研制[J]. 岩矿测试,2012,31(2):338-341.TIAN Kan,WU Zhong-xiang,ZHANG Ping,et al.Determination of sediment environmental reference materials of the Songhuajiang river in Haerbin[J].Rock and Mineral Analysis,2012,31(2):338-341.
[25]
殷惠民,任立军,李玉武,等.基于方法验证数据用Top-down方法评估测量不确定度[J].中国环境监测,2016,32(3):42-52.YIN Hui-min,REN Li-jun,LI Yu-wu,et al.Estimation of measurement uncertainty based on validation data by top-down method[J].Environmental Monitoring in China,2016,32(3):42-52.
