电感耦合等离子体串联质谱法测定高纯稀土中铁的含量
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摘要
针对四极杆ICP-MS法无法测定高纯稀土中的痕量杂质铁元素的问题,建立了电感耦合等离子体串联质谱(ICP-MS/MS)分析方法。采用氧气反应池的串联质谱技术,经优化仪器参数,确定O_2流量为2.0 mL/min,基体进样浓度为3.00 g/L,以内标In校正;同时,选择丰度为91.68%的同位素~(56)Fe~+离子为分析目标,并计算出八级杆偏置负压V_(oct)=-10 eV时产生的质心碰撞能量E_(cm)高于~(56)Fe~(16)O~+反应焓ΔHr的3倍,提供的动能可确保利用O_2碰撞反应与~(56)Fe~+生成目标产物~(56)Fe~(16)O~+;再设置Q_1=56/Q_2=72,有效克服~(40)Ar~(16)O~+、~(40)Ca~(16)O~+、~(37)Cl~(18)OH~+等多原子离子的质谱干扰,并准确测定了15种高纯稀土氧化物以及Ce、Nd、Y、Pr-Nd 4种高纯稀土中痕量杂质Fe的含量。在选定的分析条件下,校准曲线的线性相关系数大于0.9999,方法检出限(L_0)为68μg/g,精密度(RSD,n=11)为2.1%～4.3%,回收率为95%～105%。本方法操作简便、环保,适合高纯稀土及其氧化物中痕量铁的快速测定。
Because inductively coupled plasma mass spectrometry (ICP-MS) could not be used for determination of trace Fe in high purity rare earths,an inductively coupled plasma-tandem mass spectrometry(ICP-MS/MS) method was proposed. The mass spectral technique based on the oxygen reaction cell was used to optimize the instrument parameters,the flow rate of O_2 was adjusted to 2. 0 mL/min,and the matrix injection concentration was determined to be 3. 00 g/L,as well as the internal standard In was used for the calibration. Then,the isotope ~(56)Fe~+ ion with abundance of 91.68% was selected as the analysis target. With Q_1= 56/Q_2= 72,the collision reaction of O_2 with ~(56)Fe~+ was carried out to generate the target product of ~(56)Fe~(16)O~+,which performed effectively to eliminate the mass spectrum interference of polyatomic ion of ~(40)Ar~(16)O~+,~(40)Ca~(16)O~+ and ~(37)Cl~(18)OH~+. So that it could accurately determine the trace impurities of Fe content in 15 kinds of high purity rare earth oxide and 4 kinds of high purity rare earth metals of cerium,neodymium,yttrium,and praseodymium-neodymium. According to the selected analysis conditions,the linear correlation coefficient of the calibration curve was greater than 0. 9999,the detection limit was 68 μg/g,the relative standard deviations (RSD,n = 11) were 2.1%-4.3%,and the recoveries were 95%-105%. This method is simple and environmentally friendly,and suitable for the rapid determination of trace of Fe in high purity rare earth metals and their oxides.
Because inductively coupled plasma mass spectrometry (ICP-MS) could not be used for determination of trace Fe in high purity rare earths,an inductively coupled plasma-tandem mass spectrometry(ICP-MS/MS) method was proposed. The mass spectral technique based on the oxygen reaction cell was used to optimize the instrument parameters,the flow rate of O_2 was adjusted to 2. 0 mL/min,and the matrix injection concentration was determined to be 3. 00 g/L,as well as the internal standard In was used for the calibration. Then,the isotope ~(56)Fe~+ ion with abundance of 91.68% was selected as the analysis target. With Q_1= 56/Q_2= 72,the collision reaction of O_2 with ~(56)Fe~+ was carried out to generate the target product of ~(56)Fe~(16)O~+,which performed effectively to eliminate the mass spectrum interference of polyatomic ion of ~(40)Ar~(16)O~+,~(40)Ca~(16)O~+ and ~(37)Cl~(18)OH~+. So that it could accurately determine the trace impurities of Fe content in 15 kinds of high purity rare earth oxide and 4 kinds of high purity rare earth metals of cerium,neodymium,yttrium,and praseodymium-neodymium. According to the selected analysis conditions,the linear correlation coefficient of the calibration curve was greater than 0. 9999,the detection limit was 68 μg/g,the relative standard deviations (RSD,n = 11) were 2.1%-4.3%,and the recoveries were 95%-105%. This method is simple and environmentally friendly,and suitable for the rapid determination of trace of Fe in high purity rare earth metals and their oxides.
引文
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3 ZHANG Xin-Quan,LIU Jing-Lei,YI Yong,JIANG Yu-Mei,LIN Ping,TONG Ying-Dong.Journal of Instrumental Analysis,2004,23(6):73-76章新泉,刘晶磊,易永,姜玉梅,林平,童迎东.分析测试学报,2004,23(6):73-76
4 Jackson S L,Spence J,Janssen D J,Ross A R S and Cullen J T.J.Anal.At.Spectrom.,2018,33:304-313
5 HAN Jian-Hua,SUN Chuan-Qiang,WANG Yan,ZHAO Xue-Hong,CAI Biao.Metallurgical Analysis.,2014,34(9):1-7韩建华,孙传强,汪曣,赵学玒,蔡彪.冶金分析,2014,34(9):1-7
6 GB/T 12690.5-2003.Chemical Analysis of Non-rare Earth Impurities in Rare Earth Metals and Oxides-Determination of Cobalt,Manganese,Lead,Nickel,Copper,Zinc,Aluminum and Chromium by Inductively Coupled Plasma Mass Spectrometry(method 2).National Standards of the People's Republic of China稀土金属及其氧化物中非稀土杂质化学分析方法-钴、锰、铅、镍、铜、锌、铝、铬的测定电感藕合等离子体质谱法(方法2).中华人民共和国国家标准.GB/T 12690.5-2003
7 LIU Jing-Lei,LI Xiang,LIU Yong-Lin,LIN Ping,YI Yong,SU Ya-Qin,ZHANG Xin-Quan.Physical Testing and Chemical Analysis Part B:Chemical Analysis,2007,43(6):457-462刘晶磊,李翔,刘永林,林平,易永,苏亚勤,章新泉.理化检验(化学分册),2007,43(6):457-462
8 GB/T 12690.5-2003.Chemical Analysis of Non-Rare Earth Impurities in Rare Earth Metals and Oxides-Determination of Aluminum,Chromium,Manganese,Iron,Drilling,Nickel,Copper,Zinc,Lead by Inductively Coupled Plasma Emission Spectrometry(method 1).National Standards of the People's Republic of China稀土金属及其氧化物中非稀土杂质化学分析方法-铝、铬、锰、铁、钻、镍、铜、锌、铅的测定电感藕合等离子体发射光谱法(方法1).中华人民共和国国家标准.GB/T 12690.5-2003
9 GB/T 12690.6-2003.Methods for the Determination of Iron Content in Non-Rare Earth Impurities of Rare Earth Metals and their Oxides by Potassium Thiocyanate and 1,10-diazafine Spectrophotometry.National Standards of the People's Republic of China稀土金属及其氧化物中非稀土杂质化学分析方法铁量的测定硫氰酸钾、1,10-二氮杂菲分光光度法.中华人民共和国国家标准.GB/T 12690.6-2003
10 ZHAO Jin-Wei,FENG Ya-Hui,CHENG Wei,LYU Bao-Yuan.Spectrosc.Spect.Anal.,2003,23(5):972-975赵金伟,封亚辉,程薇,吕宝源.光谱学与光谱分析,2003,23(5):972-975
11 Fari1as J C,Rucandio I,Pomares-Alfonso M S,Villanueva-Tagle M E,Larrea M T.Talanta,2016,154:53-62
12 He M,Hu B,Chen B B,Jiang Z C.Phys.Sci.Rev.,2017,2(1):1-37
13 DU Mei,LIU Xiao-Jie.Rock and Mineral Analysis,2014,33(2):218-223杜梅,刘晓杰.岩矿测试,2014,33(2):218-223
14 He Q,Xing Z,Wei C,Fang X,Zhang S C,Zhang X R.Chem.Commun.,2016,52(69):10501-10504
15 Lieve Balcaen,Eduardo Bolea-Fernandez,Martín Resano,Frank Vanhaecke.Anal.Chim.Acta,2015,894:7-19
16 Meyer S,Markova M,Pohl G,Marschall T A,Pivovarova O,Pfeiffer A F H,Schwerdtle T.J.Trace Elements Med.Biol.,2018,49:157-163
17 FU Liang,SHI Shu-Yun.Chinese J.Anal.Chem.,2017,45(8):1222-1226符靓,施树云.分析化学,2017,45(8):1222-1226
18 Wu S C,Zeng X C,Dai X F,Hu Y P,Li G,Zheng C J.Spectrochim.Acta B,2016,123:129-133
19 Fu L,Shi S Y,Chen X Q,Xie H L.Microchem.J.,2018,139:236-241
20 FU Liang,SHI Shu-Yun,TANG You-Gen,WANG Hai-Yan.Spectrosc.Spect.Anal.,2018,38(8):2588-2594符靓,施树云,唐有根,王海燕.光谱学与光谱分析,2018,38(8):2588-2594
21 Clases D,Fingerhut S,Jeibmann A,Sperling M,Doble P,Kars U.J.Trace Elements Med.Biol.,2019,51:212-218
22 FU Liang,SHI Shu-Yun,CHEN Xiao-Qing.Chinese J.Anal.Chem.,2018,46(1):107-112符靓,施树云,陈晓青.分析化学,2018,46(1):107-112
2 WU Wei-Ming,LIU He-Lian,ZHENG Teng-Fei.Chinese J.Anal.Chem.,2015,43(5):697-702吴伟明,刘和连,郑腾飞.分析化学,2015,43(5):697-702
3 ZHANG Xin-Quan,LIU Jing-Lei,YI Yong,JIANG Yu-Mei,LIN Ping,TONG Ying-Dong.Journal of Instrumental Analysis,2004,23(6):73-76章新泉,刘晶磊,易永,姜玉梅,林平,童迎东.分析测试学报,2004,23(6):73-76
4 Jackson S L,Spence J,Janssen D J,Ross A R S and Cullen J T.J.Anal.At.Spectrom.,2018,33:304-313
5 HAN Jian-Hua,SUN Chuan-Qiang,WANG Yan,ZHAO Xue-Hong,CAI Biao.Metallurgical Analysis.,2014,34(9):1-7韩建华,孙传强,汪曣,赵学玒,蔡彪.冶金分析,2014,34(9):1-7
6 GB/T 12690.5-2003.Chemical Analysis of Non-rare Earth Impurities in Rare Earth Metals and Oxides-Determination of Cobalt,Manganese,Lead,Nickel,Copper,Zinc,Aluminum and Chromium by Inductively Coupled Plasma Mass Spectrometry(method 2).National Standards of the People's Republic of China稀土金属及其氧化物中非稀土杂质化学分析方法-钴、锰、铅、镍、铜、锌、铝、铬的测定电感藕合等离子体质谱法(方法2).中华人民共和国国家标准.GB/T 12690.5-2003
7 LIU Jing-Lei,LI Xiang,LIU Yong-Lin,LIN Ping,YI Yong,SU Ya-Qin,ZHANG Xin-Quan.Physical Testing and Chemical Analysis Part B:Chemical Analysis,2007,43(6):457-462刘晶磊,李翔,刘永林,林平,易永,苏亚勤,章新泉.理化检验(化学分册),2007,43(6):457-462
8 GB/T 12690.5-2003.Chemical Analysis of Non-Rare Earth Impurities in Rare Earth Metals and Oxides-Determination of Aluminum,Chromium,Manganese,Iron,Drilling,Nickel,Copper,Zinc,Lead by Inductively Coupled Plasma Emission Spectrometry(method 1).National Standards of the People's Republic of China稀土金属及其氧化物中非稀土杂质化学分析方法-铝、铬、锰、铁、钻、镍、铜、锌、铅的测定电感藕合等离子体发射光谱法(方法1).中华人民共和国国家标准.GB/T 12690.5-2003
9 GB/T 12690.6-2003.Methods for the Determination of Iron Content in Non-Rare Earth Impurities of Rare Earth Metals and their Oxides by Potassium Thiocyanate and 1,10-diazafine Spectrophotometry.National Standards of the People's Republic of China稀土金属及其氧化物中非稀土杂质化学分析方法铁量的测定硫氰酸钾、1,10-二氮杂菲分光光度法.中华人民共和国国家标准.GB/T 12690.6-2003
10 ZHAO Jin-Wei,FENG Ya-Hui,CHENG Wei,LYU Bao-Yuan.Spectrosc.Spect.Anal.,2003,23(5):972-975赵金伟,封亚辉,程薇,吕宝源.光谱学与光谱分析,2003,23(5):972-975
11 Fari1as J C,Rucandio I,Pomares-Alfonso M S,Villanueva-Tagle M E,Larrea M T.Talanta,2016,154:53-62
12 He M,Hu B,Chen B B,Jiang Z C.Phys.Sci.Rev.,2017,2(1):1-37
13 DU Mei,LIU Xiao-Jie.Rock and Mineral Analysis,2014,33(2):218-223杜梅,刘晓杰.岩矿测试,2014,33(2):218-223
14 He Q,Xing Z,Wei C,Fang X,Zhang S C,Zhang X R.Chem.Commun.,2016,52(69):10501-10504
15 Lieve Balcaen,Eduardo Bolea-Fernandez,Martín Resano,Frank Vanhaecke.Anal.Chim.Acta,2015,894:7-19
16 Meyer S,Markova M,Pohl G,Marschall T A,Pivovarova O,Pfeiffer A F H,Schwerdtle T.J.Trace Elements Med.Biol.,2018,49:157-163
17 FU Liang,SHI Shu-Yun.Chinese J.Anal.Chem.,2017,45(8):1222-1226符靓,施树云.分析化学,2017,45(8):1222-1226
18 Wu S C,Zeng X C,Dai X F,Hu Y P,Li G,Zheng C J.Spectrochim.Acta B,2016,123:129-133
19 Fu L,Shi S Y,Chen X Q,Xie H L.Microchem.J.,2018,139:236-241
20 FU Liang,SHI Shu-Yun,TANG You-Gen,WANG Hai-Yan.Spectrosc.Spect.Anal.,2018,38(8):2588-2594符靓,施树云,唐有根,王海燕.光谱学与光谱分析,2018,38(8):2588-2594
21 Clases D,Fingerhut S,Jeibmann A,Sperling M,Doble P,Kars U.J.Trace Elements Med.Biol.,2019,51:212-218
22 FU Liang,SHI Shu-Yun,CHEN Xiao-Qing.Chinese J.Anal.Chem.,2018,46(1):107-112符靓,施树云,陈晓青.分析化学,2018,46(1):107-112