波长与能量色散复合式X射线荧光光谱技术测定海洋沉积物元素
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摘要
波长与能量色散复合式X射线荧光光谱仪(WD-EDXRF)是一种先进的双核X射线分析技术,可对样品进行波长色散和能量色散同时测定。本研究优化了各元素波谱和能谱的条件,采用粉末压片法制样,使用α经验系数法及Rh靶Kα线的康普顿散射内标法校正基体效应,部分元素用多元回归进行谱线重叠干扰校正,建立了WD-EDXRF对海洋沉积物进行多元素同时定量分析的方法。本方法对稀土元素La、Ce、Nd、Y及其它微量元素的检出限均小于18μg/g,轻元素Na、Mg的检出限小于15μg/g,适用于绝大多数海洋地质样品的分析;对沉积物标样GBW07309进行精密度考察,除Cl和含量接近检出限的Mo元素外,其它元素的精密度(RSD,n=10)都低于9.4%;利用测量不确定度的评定方法,比较了标准样品的分析数据的扩展不确定度,大部分元素|E_n|≤1。对不同类型深海沉积物样品进行测定,测定结果与实验室电感耦合等离子体原子发射光谱仪(ICP-OES)和电感耦合等离子体质谱仪(ICP-MS)分析结果基本一致。结果表明,本方法能充分发挥波谱与能谱各自的优势,快速、准确分析海洋沉积物中多种元素,可满足大批量海洋沉积物样品测试的需求。
A total of 38 kinds of major, minor and trace elements in marine sediment were analyzed by a combination technique of wavelength dispersive and energy dispersion X-ray fluorescence spectrometer(WD-EDXRF). The sample was prepared by powder pressing, and the stream sediments, soil, rock and marine sediment certified reference materials(CRMs) were used to establish calibration curves. The light and trace elements with heavy overlapped spectral lines were analyzed by WDXRF, and the other major and minor elements that without heavy overlapped spectral lines were analyzed by EDXRF. The matrix effect was corrected by Alpha empirical coefficient method and scattered rays internal standard method. The spectral overlapping interference of elements was accurately deducted by multiple regression. With the proposed methodology, the detection limits of minor elements were mostly below 18 μg/g, and those of light elements(Na, Mg) were lower than 15 μg/g, which were suitable for element determination in most marine sediments. Precision of the proposed method was checked by analyzing the stream sediment CRMs(GBW07309), and the relative standard deviations(RSD, n=10) of the determination results were lower than 9.41% except for individual elements. The quality of the analytical procedure was demonstrated at a 95% confidence level, in which the estimated analytical uncertainties agreed with those from the RM's certificates of analysis. The WD-EDXRF method was applied to the determination of major and minor elements in different types of marine sediments collected from the Indian Ocean, and the relative error of some elements were less than 10%, between the values analyzed by ICP-OES, ICP-MS and WD-EDXRF. In a word, WD-EDXRF is a well-established analytical technique for multi-element determination in various sample types, especially for marine sediment, and it will be a new technical support to investigate the marine resource and ecology.
A total of 38 kinds of major, minor and trace elements in marine sediment were analyzed by a combination technique of wavelength dispersive and energy dispersion X-ray fluorescence spectrometer(WD-EDXRF). The sample was prepared by powder pressing, and the stream sediments, soil, rock and marine sediment certified reference materials(CRMs) were used to establish calibration curves. The light and trace elements with heavy overlapped spectral lines were analyzed by WDXRF, and the other major and minor elements that without heavy overlapped spectral lines were analyzed by EDXRF. The matrix effect was corrected by Alpha empirical coefficient method and scattered rays internal standard method. The spectral overlapping interference of elements was accurately deducted by multiple regression. With the proposed methodology, the detection limits of minor elements were mostly below 18 μg/g, and those of light elements(Na, Mg) were lower than 15 μg/g, which were suitable for element determination in most marine sediments. Precision of the proposed method was checked by analyzing the stream sediment CRMs(GBW07309), and the relative standard deviations(RSD, n=10) of the determination results were lower than 9.41% except for individual elements. The quality of the analytical procedure was demonstrated at a 95% confidence level, in which the estimated analytical uncertainties agreed with those from the RM's certificates of analysis. The WD-EDXRF method was applied to the determination of major and minor elements in different types of marine sediments collected from the Indian Ocean, and the relative error of some elements were less than 10%, between the values analyzed by ICP-OES, ICP-MS and WD-EDXRF. In a word, WD-EDXRF is a well-established analytical technique for multi-element determination in various sample types, especially for marine sediment, and it will be a new technical support to investigate the marine resource and ecology.
引文
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8 Yasukawa K,Nakamura K,Fujinaga K,Machida S,Ohta J,Takaya Y,Kato Y.Geochem.J.,2015,49:621-635
9 Iijima K,Yasukawa K,Fujinaga K,Nakamura K,Machida S,Takaya Y,Ohta J,Haraguchi S,Nishio Y,Usui Y,Nozaki T,Yamazaki T,Ichiyama Y,Ijiri A,Inagaki F,Machiyama H,Suzuki K,Kato Y,KR13-02 Cruise Members.Geochem.J.,2016,50(6):557-573
10 Krzysztof L,Danuta W.Microchim.Acta,2006,154(3-4):235-240
11 Hung J J,Yeh H Y,Peng S H,Chen C T A.Mar.Chem.,2018,198:88-96
12 MarguíE,Queralt I,Carvalho M L,Hidalgo M.Anal.Chim.Acta,2005,549:197-204
13 Kazi T G,Jamali M K,Arain M B,Afridi H I,Jalbani N,Sarfraz R A,Ansari R.J.Hazard.Mater.,2009,161:1391-1398
14 Fernández Z H,dos Santos J A,Amaral R D,Alvarez J R E,da Silva E B,de Fran9a E J,Menezes R S C,de Farias EE G,Santos J M D.Environ.Monit.Assess.,2017,189(9):447
15 McComb J Q,Rogers C,Han F X,Tchounwou P B.Water Air Soil Poll.,2014,225(12):1-10
16 ZHANG Qin,LI Guo-Hui,FAN Shou-Zhong,PAN Yan-Shan.Chinese Journal of Analysis Laboratory,2008,27(11):51-57张勤,李国会,樊守忠,潘宴山.分析试验室,2008,27(11):51-57
17 Tiwari M,Sahu S K,Bhangare R C,Ajmal P Y,Pandit G G.Appl.Radiat.Isotopes,2013,80:78-83
18 RAN Jing,WANG De-Jian,WANG Chan,BO Lu-Ji,ZHENG Ji-Cheng,YAO Li-Peng.Spectroscopy and Spectral Analysis,2014,34(11):3113-3118冉景,王德建,王灿,薄录吉,郑继成,姚利鹏.光谱学与光谱分析,2014,34(11):3113-3118
19 HAN Ping,WANG Ji-Hua,LU An-Xiang,MA Zhi-Hong,PAN Li-Gang.Spectroscopy and Spectral Analysis,2012,32(3):826-829韩平,王纪华,陆安祥,马智宏,潘立刚.光谱学与光谱分析,2012,32(3):826-829
20 Ryan J G,Shervais J W,Li Y,Reagan M K,Li H Y,Heaton D,Godard M,Kirchenbaur M,Whattam S A,Pearce J A,Chapman T,Nelson W,Prytulak J,Shimizu K,Petronotis K,the IODP Expedition 352 Scientific Team.Chem.Geol.,2017,451:55-66
21 Ravisanka R,Sivakumar S,Chandrasekaran A,Kanagasabapathy K V,Prasad M V R,Satapathy K K.Appl.Radiat.Isotopes,2015,102:42-47
22 Wien K,Wissmann D,K9lling M,Schulz H D.Geo.Mar.Lett.,2005,25(4):248-264
23 Zaaboub N,Oueslati W,Helali M A,Abdeljaouad S,Huertas F J,Galindo A L.Chem.Spec.Bioavailab.,2014,26(1):1-12
24 ZHAN Xiu-Chun,LUO Li-Qiang.Spectrosc.Spect.Anal.,2003,23(4):804-807詹秀春,罗立强.光谱学与光谱分析,2003,23(4):804-807
25 Zhan X C.X-Ray Spectrom.,2005,34(3):207-212
26 ZHAN Xiu-Chun,CHEN Shui-Jun,ZHENG Miao-Zi,WANG Jian,LI Ying-Chun,LI Bing,ZHANG Qin.Rock and Mineral Analysis,2002,21(1):12-18詹秀春,陈水君,郑妙子,王健,李迎春,李冰,张勤.岩矿测试,2002,21(1):12-18
27 SHEN Ya-Ting,LI Ying-Chun,SUN Meng-He,HE Yu-Jun,WANG Yan-Fei,LIN Ya-Jie.Spectrosc.Spect.Anal.,2017,37(7):2216-2224沈亚婷,李迎春,孙梦荷,何玉君,王艳飞,蔺雅洁.光谱学与光谱分析,2017,37(7):2216-2224
28 LIU Ju-Qin,LI Xiao-Li.Metallurgical Analysis,2018,38(5):7-12刘菊琴,李小莉.冶金分析,2018,38(5):7-12
29 LI Xiao-Li,ZHANG Qin.Metallurgical Analysis,2013,33(7):35-40李小莉,张勤.冶金分析,2013,33(7):35-40
30 LUO Li-Qiang,ZHAN Xiu-Chun,LI Guo-Hui.X-Ray Fluorescence Spectrometry.Beijing:Chemical Industry Press,2015:117-119罗立强,詹秀春,李国会.X射线荧光光谱分析.北京:化学工业出版社,2015:117-119
31 SUN Xuan,SONG Jin-Ming,WEN Ting-Yu,LIU Yao.Marine Sciences,2018,42(4):79-88孙萱,宋金明,温廷宇,刘瑶.海洋科学,2018,42(4):79-88
32 ZHAN Xiu-Chun,LUO Li-Qiang.Spectrosc.Spect.Anal.,2003,23(4):804-807詹秀春,罗立强.光谱学与光谱分析,2003,23(4):804-807
33 JI Ang,ZHUO Shang-Jun,LI Guo-Hui.Energy Dispersive X-ray Fluorescence Spectrometer.Beijing:Science Press,2011:9吉昂,卓尚军,李国会.能量色散X射线荧光光谱.北京:科学出版社,2011:9
34 Kato Y,Fujinaga K,Nakamura K,Takaya Y,Kitamura K,Ohta J,Toda R,Nakashima T,Iwamori H.Nat.Geosci.,2011,4:535-539
35 Yasukawa K,Liu H J,Fujinaga K,Machida S,Haraguchi S,Ishii T,Nakamura K,Kato Y.J.Asian Earth Sci.,2014,93:25-36
36 GB/T 27418-2017.Guide to the Evaluation and Expression of Uncertainty in Measurement.National Standards of the People's Republic of China测量不确定度评定与表示.中华人民共和国国家标准.GB/T 27418-2017
37 GB/T 28043-2011/ISO 13528:2005.Statistical Method for Use in Proficiency Testing by Interlaboratory Comparisons.National Standards of the People's Republic of China利用实验室间比对进行能力验证的统计方法.中华人民共和国国家标准.GB/T 28043-2011/ISO 13528:2005
38 HJ 780-2015.Soil and Sediment-Determination of Inorganic Element-Wavelength Dispersive X-ray Fluorescence Spectrometry.The People's Republic of China State Environmental Protection Standards土壤和沉积物无机元素的测定波长色散X射线荧光光谱法.中华人民共和国国家环境保护标准.HJ 780-2015
39 Zuzaan P,Gansukh N,Bolortuya D.X-Ray Spectrom.,2010,39(1):52-56
2 Li J R,Liu S F,Feng X L,Sun X Q,Shi X F.Acta Oceanol.Sin.,2017,36(3):82-90
3 Um I K,Choi M S,Bahk J J,Chun J H.Quatern.Int.,2017,459:153-164
4 Pham D T,Gouramanis C,Switzer A D,Rubin C M,Jones B G,Jankaew K,Carr P F.Mar.Geol.,2018,396:79-99
5 Santos I R,Favaro D I T,Schaefer C E G R,Silva-Filho E V.Mar.Chem.,2007,107:464-474
6 DOU Yan-Guang,LI Jun,LI Yan.Geochimica,2012,41(2):147-157窦衍光,李军,李炎.地球化学,2012,41(2):147-157
7 Xu F J,Hu B Q,Dou Y G,Liu X T,Wan S M,Xu Z K,Tian X,Liu Z Q,Yin X B,Li A C.Cont.Shelf Res.,2017,144:21-30
8 Yasukawa K,Nakamura K,Fujinaga K,Machida S,Ohta J,Takaya Y,Kato Y.Geochem.J.,2015,49:621-635
9 Iijima K,Yasukawa K,Fujinaga K,Nakamura K,Machida S,Takaya Y,Ohta J,Haraguchi S,Nishio Y,Usui Y,Nozaki T,Yamazaki T,Ichiyama Y,Ijiri A,Inagaki F,Machiyama H,Suzuki K,Kato Y,KR13-02 Cruise Members.Geochem.J.,2016,50(6):557-573
10 Krzysztof L,Danuta W.Microchim.Acta,2006,154(3-4):235-240
11 Hung J J,Yeh H Y,Peng S H,Chen C T A.Mar.Chem.,2018,198:88-96
12 MarguíE,Queralt I,Carvalho M L,Hidalgo M.Anal.Chim.Acta,2005,549:197-204
13 Kazi T G,Jamali M K,Arain M B,Afridi H I,Jalbani N,Sarfraz R A,Ansari R.J.Hazard.Mater.,2009,161:1391-1398
14 Fernández Z H,dos Santos J A,Amaral R D,Alvarez J R E,da Silva E B,de Fran9a E J,Menezes R S C,de Farias EE G,Santos J M D.Environ.Monit.Assess.,2017,189(9):447
15 McComb J Q,Rogers C,Han F X,Tchounwou P B.Water Air Soil Poll.,2014,225(12):1-10
16 ZHANG Qin,LI Guo-Hui,FAN Shou-Zhong,PAN Yan-Shan.Chinese Journal of Analysis Laboratory,2008,27(11):51-57张勤,李国会,樊守忠,潘宴山.分析试验室,2008,27(11):51-57
17 Tiwari M,Sahu S K,Bhangare R C,Ajmal P Y,Pandit G G.Appl.Radiat.Isotopes,2013,80:78-83
18 RAN Jing,WANG De-Jian,WANG Chan,BO Lu-Ji,ZHENG Ji-Cheng,YAO Li-Peng.Spectroscopy and Spectral Analysis,2014,34(11):3113-3118冉景,王德建,王灿,薄录吉,郑继成,姚利鹏.光谱学与光谱分析,2014,34(11):3113-3118
19 HAN Ping,WANG Ji-Hua,LU An-Xiang,MA Zhi-Hong,PAN Li-Gang.Spectroscopy and Spectral Analysis,2012,32(3):826-829韩平,王纪华,陆安祥,马智宏,潘立刚.光谱学与光谱分析,2012,32(3):826-829
20 Ryan J G,Shervais J W,Li Y,Reagan M K,Li H Y,Heaton D,Godard M,Kirchenbaur M,Whattam S A,Pearce J A,Chapman T,Nelson W,Prytulak J,Shimizu K,Petronotis K,the IODP Expedition 352 Scientific Team.Chem.Geol.,2017,451:55-66
21 Ravisanka R,Sivakumar S,Chandrasekaran A,Kanagasabapathy K V,Prasad M V R,Satapathy K K.Appl.Radiat.Isotopes,2015,102:42-47
22 Wien K,Wissmann D,K9lling M,Schulz H D.Geo.Mar.Lett.,2005,25(4):248-264
23 Zaaboub N,Oueslati W,Helali M A,Abdeljaouad S,Huertas F J,Galindo A L.Chem.Spec.Bioavailab.,2014,26(1):1-12
24 ZHAN Xiu-Chun,LUO Li-Qiang.Spectrosc.Spect.Anal.,2003,23(4):804-807詹秀春,罗立强.光谱学与光谱分析,2003,23(4):804-807
25 Zhan X C.X-Ray Spectrom.,2005,34(3):207-212
26 ZHAN Xiu-Chun,CHEN Shui-Jun,ZHENG Miao-Zi,WANG Jian,LI Ying-Chun,LI Bing,ZHANG Qin.Rock and Mineral Analysis,2002,21(1):12-18詹秀春,陈水君,郑妙子,王健,李迎春,李冰,张勤.岩矿测试,2002,21(1):12-18
27 SHEN Ya-Ting,LI Ying-Chun,SUN Meng-He,HE Yu-Jun,WANG Yan-Fei,LIN Ya-Jie.Spectrosc.Spect.Anal.,2017,37(7):2216-2224沈亚婷,李迎春,孙梦荷,何玉君,王艳飞,蔺雅洁.光谱学与光谱分析,2017,37(7):2216-2224
28 LIU Ju-Qin,LI Xiao-Li.Metallurgical Analysis,2018,38(5):7-12刘菊琴,李小莉.冶金分析,2018,38(5):7-12
29 LI Xiao-Li,ZHANG Qin.Metallurgical Analysis,2013,33(7):35-40李小莉,张勤.冶金分析,2013,33(7):35-40
30 LUO Li-Qiang,ZHAN Xiu-Chun,LI Guo-Hui.X-Ray Fluorescence Spectrometry.Beijing:Chemical Industry Press,2015:117-119罗立强,詹秀春,李国会.X射线荧光光谱分析.北京:化学工业出版社,2015:117-119
31 SUN Xuan,SONG Jin-Ming,WEN Ting-Yu,LIU Yao.Marine Sciences,2018,42(4):79-88孙萱,宋金明,温廷宇,刘瑶.海洋科学,2018,42(4):79-88
32 ZHAN Xiu-Chun,LUO Li-Qiang.Spectrosc.Spect.Anal.,2003,23(4):804-807詹秀春,罗立强.光谱学与光谱分析,2003,23(4):804-807
33 JI Ang,ZHUO Shang-Jun,LI Guo-Hui.Energy Dispersive X-ray Fluorescence Spectrometer.Beijing:Science Press,2011:9吉昂,卓尚军,李国会.能量色散X射线荧光光谱.北京:科学出版社,2011:9
34 Kato Y,Fujinaga K,Nakamura K,Takaya Y,Kitamura K,Ohta J,Toda R,Nakashima T,Iwamori H.Nat.Geosci.,2011,4:535-539
35 Yasukawa K,Liu H J,Fujinaga K,Machida S,Haraguchi S,Ishii T,Nakamura K,Kato Y.J.Asian Earth Sci.,2014,93:25-36
36 GB/T 27418-2017.Guide to the Evaluation and Expression of Uncertainty in Measurement.National Standards of the People's Republic of China测量不确定度评定与表示.中华人民共和国国家标准.GB/T 27418-2017
37 GB/T 28043-2011/ISO 13528:2005.Statistical Method for Use in Proficiency Testing by Interlaboratory Comparisons.National Standards of the People's Republic of China利用实验室间比对进行能力验证的统计方法.中华人民共和国国家标准.GB/T 28043-2011/ISO 13528:2005
38 HJ 780-2015.Soil and Sediment-Determination of Inorganic Element-Wavelength Dispersive X-ray Fluorescence Spectrometry.The People's Republic of China State Environmental Protection Standards土壤和沉积物无机元素的测定波长色散X射线荧光光谱法.中华人民共和国国家环境保护标准.HJ 780-2015
39 Zuzaan P,Gansukh N,Bolortuya D.X-Ray Spectrom.,2010,39(1):52-56