熔融制样-能量色散X射线荧光光谱仪分析硅酸盐中32种组分
|
摘要
为充分发挥小型实验室设备的功能,实验采用熔融制样,使用台式能量色散X射线荧光光谱仪(10W,Rh靶)定量分析了硅酸盐样品中的Na_2O、MgO、Al_2O_3、SiO_2、P_2O_5、SO_3、Cl、K_2O、CaO、TiO_2、V、Cr、MnO、Fe_2O_3、Co、Ni、Cu、Zn、Ga、Rb、Sr、Y、Zr、Nb、As、Ba、La、Ce、Th、U、Hf、Pb等32种主、次、痕量组分。对3种不同的解谱方法进行比较,确定Na、Mg、Al、Si、P、As、Ce、Cr、Cu、Ga、La、Nb、Ni、Pb、Th、U、V、Y选择感兴趣区解谱,其余元素用高斯或经改进的高斯函数的最小二乘法拟合解谱。选用有代表性的多个硅酸盐类样品,比较了理论检出限及10次重复测定计算3倍标准偏差得出的检出限,发现以3倍标准偏差作为检出限再取它们的平均值则更具代表性和使用意义。各组分的检出限为0.2～1 740μg/g。精密度试验表明,各组分测定结果的相对标准偏差(RSD)为0.12%～10.5%(Na为轻元素,由于含量低,小能谱测定的精密度稍差);对两个土壤标准样品进行正确度验证,测定值与标准值一致。
In order to give full play to the functions of small laboratory instrument,32 major,minor,trace components in silicate sample(including Na_2 O,MgO,Al_2 O_3,SiO_2,P_2 O_5,SO_3,Cl,K_2 O,CaO,TiO_2,V,Cr,MnO,Fe_2 O_3,Co,Ni,Cu,Zn,Ga,Rb,Sr,Y,Zr,Nb,As,Ba,La,Ce,Th,U,Hf and Pb)were quantitatively analyzed using energy dispersive X-ray fluorescence spectrometer(EDXRF).The sample was prepared by fusion sample preparation.The optimization of analysis conditions for elements was focused.Moreover,three different spectrum unfolding methods were compared.The region of interest was selected for spectrum unfolding for Na,Mg,Al,Si,P,As,Ce,Cr,Cu,Ga,La,Nb,Ni,Pb,Th,U,V and Y,while the least squares fitting of Gaussian function or modified Gaussian function was selected for other elements.Several representative silicate samples were used to compare the theoretical detection limit and the detection limit calculated using three times of standard deviation(n=10).It was found that the average of detection limits calculated using three times of standard deviation was more representative and meaningful for use.The detection limits of components ranged from 0.2μg/g to 1 740μg/g.The precision tests indicated that the relative standard deviations(RSD)were between 0.12% and 10.5%(Na belonged to light element.The determination precision of small energy spectrometry was poor due to low content).Two certified reference materials of soil were used for accuracy verification,and the found results were consistent with the certified values.
In order to give full play to the functions of small laboratory instrument,32 major,minor,trace components in silicate sample(including Na_2 O,MgO,Al_2 O_3,SiO_2,P_2 O_5,SO_3,Cl,K_2 O,CaO,TiO_2,V,Cr,MnO,Fe_2 O_3,Co,Ni,Cu,Zn,Ga,Rb,Sr,Y,Zr,Nb,As,Ba,La,Ce,Th,U,Hf and Pb)were quantitatively analyzed using energy dispersive X-ray fluorescence spectrometer(EDXRF).The sample was prepared by fusion sample preparation.The optimization of analysis conditions for elements was focused.Moreover,three different spectrum unfolding methods were compared.The region of interest was selected for spectrum unfolding for Na,Mg,Al,Si,P,As,Ce,Cr,Cu,Ga,La,Nb,Ni,Pb,Th,U,V and Y,while the least squares fitting of Gaussian function or modified Gaussian function was selected for other elements.Several representative silicate samples were used to compare the theoretical detection limit and the detection limit calculated using three times of standard deviation(n=10).It was found that the average of detection limits calculated using three times of standard deviation was more representative and meaningful for use.The detection limits of components ranged from 0.2μg/g to 1 740μg/g.The precision tests indicated that the relative standard deviations(RSD)were between 0.12% and 10.5%(Na belonged to light element.The determination precision of small energy spectrometry was poor due to low content).Two certified reference materials of soil were used for accuracy verification,and the found results were consistent with the certified values.
引文
[1]吉昂,李国会,张华.高能偏振能量色散X射线荧光光谱仪应用现状和进展[J].岩矿测试,2008,27(6):451-462.JI Ang,LI Guo-hui,ZHANG Hua.Application and development of high energy polarized energy-dispersive Xray fluorescence spectrometry[J].Rock and Mineral Analysis,2008,27(6):451-462.
[2]杨明太,唐慧.能量色散X射线荧光光谱仪现状及其发展趋势[J].核电子学与探测技术,2011,31(12):1307-1311.YANG Ming-tai,TANG Hui.The actualities and trend of energy dispersive X-ray fluorescence spectrometry[J].Nuclear Electronics &Detection Technology,2011,31(12):1307-1311.
[3]王祎亚,詹秀春,刘以建,等.偏振能量色散X射线荧光光谱法测定地质样品中18种元素[J].分析试验室,2009,28(9):90-94.WANG Yi-ya,ZHAN Xiu-chun,LIU Yi-jian,et al.Determination of 18elements in geological samples by polarized energy-dispersive X-ray fluorescence spectrometry[J].Chinese Journal of Analysis Laboratory,2009,28(9):90-94.
[4]樊守忠,张勤,李国会,等.偏振能量色散X射线荧光光谱法测定水系沉积物和土壤样品中多种组分[J].冶金分析,2006,26(6):27-31.FAN Shou-zhong,ZHANG Qin,LI Guo-hui,et al.Determination of multi-element in sediment and soil samples by polarized energy-dispersive X-ray fluorescence spectrometry[J].Metallurgical Analysis,2006,26(6):27-31.
[5]戴礼洪,刘潇威,王迪,等.偏振能量色散X射线荧光光谱法在土壤环境监测中的应用[J].光谱实验室,2011,28(2):836-841.DAI LI-hong,LIU Xiao-wei,WANG Di,et al.Application of polarized energy dispersive X-ray fluorescence spectrometry in soil environmental determination[J].Chinese Journal of Spectroscopy Laboratory,2011,28(2):836-841.
[6]龙昌玉,李小莉,张勤,等.能量色散X射线荧光光谱仪现场快速测定多金属矿中17种组分[J].岩矿测试,2010(3):313-315.LONG Chang-yu,LI Xiao-li,ZHANG Qin,et al.Onsite determination of 17components in polymetallic ore by energy X-ray fluorescence spectrometry[J].Rock and Mineral Analysis,2010(3):313-315.
[7]詹秀春,樊兴涛,李迎春,等.直接粉末制样-小型偏振激发能量色散X射线荧光光谱法分析地质样品中多元素[J].岩矿测试,2009,28(6):501-506.ZHAN Xiu-chun,FAN Xing-tao,LI Ying-chun,et al.Multi-element determination in geological materials by bench-top polarized energy dispersive X-ray fluorescence spectrometry coupled with directly pressed powder sample preparation technique[J].Rock and Mineral Analysis,2009,28(6):501-506.
[8]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.
[9]詹秀春,罗立强.偏振激发-能量色散X-射线荧光光谱法快速分析地质样品中34种元素[J].光谱学与光谱分析,2003,34(4):804-807.ZHAN Xiu-chun,LUO Li-qiang.Rapid multi-element analysis of geological samples by energy X-ray fluorescence spectrometry[J].Spectroscopy and Spectral Analysis,2003,34(4):804-807.
[10]吉昂,卓尚君,李国会.能量色散X射线荧光光谱[M].北京:科学出版社,2011:120.
[2]杨明太,唐慧.能量色散X射线荧光光谱仪现状及其发展趋势[J].核电子学与探测技术,2011,31(12):1307-1311.YANG Ming-tai,TANG Hui.The actualities and trend of energy dispersive X-ray fluorescence spectrometry[J].Nuclear Electronics &Detection Technology,2011,31(12):1307-1311.
[3]王祎亚,詹秀春,刘以建,等.偏振能量色散X射线荧光光谱法测定地质样品中18种元素[J].分析试验室,2009,28(9):90-94.WANG Yi-ya,ZHAN Xiu-chun,LIU Yi-jian,et al.Determination of 18elements in geological samples by polarized energy-dispersive X-ray fluorescence spectrometry[J].Chinese Journal of Analysis Laboratory,2009,28(9):90-94.
[4]樊守忠,张勤,李国会,等.偏振能量色散X射线荧光光谱法测定水系沉积物和土壤样品中多种组分[J].冶金分析,2006,26(6):27-31.FAN Shou-zhong,ZHANG Qin,LI Guo-hui,et al.Determination of multi-element in sediment and soil samples by polarized energy-dispersive X-ray fluorescence spectrometry[J].Metallurgical Analysis,2006,26(6):27-31.
[5]戴礼洪,刘潇威,王迪,等.偏振能量色散X射线荧光光谱法在土壤环境监测中的应用[J].光谱实验室,2011,28(2):836-841.DAI LI-hong,LIU Xiao-wei,WANG Di,et al.Application of polarized energy dispersive X-ray fluorescence spectrometry in soil environmental determination[J].Chinese Journal of Spectroscopy Laboratory,2011,28(2):836-841.
[6]龙昌玉,李小莉,张勤,等.能量色散X射线荧光光谱仪现场快速测定多金属矿中17种组分[J].岩矿测试,2010(3):313-315.LONG Chang-yu,LI Xiao-li,ZHANG Qin,et al.Onsite determination of 17components in polymetallic ore by energy X-ray fluorescence spectrometry[J].Rock and Mineral Analysis,2010(3):313-315.
[7]詹秀春,樊兴涛,李迎春,等.直接粉末制样-小型偏振激发能量色散X射线荧光光谱法分析地质样品中多元素[J].岩矿测试,2009,28(6):501-506.ZHAN Xiu-chun,FAN Xing-tao,LI Ying-chun,et al.Multi-element determination in geological materials by bench-top polarized energy dispersive X-ray fluorescence spectrometry coupled with directly pressed powder sample preparation technique[J].Rock and Mineral Analysis,2009,28(6):501-506.
[8]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.
[9]詹秀春,罗立强.偏振激发-能量色散X-射线荧光光谱法快速分析地质样品中34种元素[J].光谱学与光谱分析,2003,34(4):804-807.ZHAN Xiu-chun,LUO Li-qiang.Rapid multi-element analysis of geological samples by energy X-ray fluorescence spectrometry[J].Spectroscopy and Spectral Analysis,2003,34(4):804-807.
[10]吉昂,卓尚君,李国会.能量色散X射线荧光光谱[M].北京:科学出版社,2011:120.