密闭酸溶-电感耦合等离子体原子发射光谱法测定地球化学调查样品中硼
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摘要
采用酸溶法处理地质样品时,无论敞开或密闭体系,硼均会在最后蒸发赶除HF时形成三氟化硼或三氯化硼挥发损失,从而造成硼测定时结果精密度差。为了消除此种挥发损失,实验提出采用1mL HCl、1mL HNO3、2mL HF混合酸,在控温电热板上,于140℃恒温2h以密闭方式消解样品,不需赶除HF,直接定容后采用配置了耐HF进样系统的电感耦合等离子体原子发射光谱仪进行测定,从而建立了地球化学调查样品中硼的测定方法。确定了硼的最佳分析谱线为B 249.678nm,采用干扰方程校正计算消除了样品中钴对硼测定结果的影响,当样品中铁与硼的质量比大于14 000时,用氨水除铁以消除Fe的干扰。实验表明,硼的质量浓度为0.10~2.00μg/mL时与其发射强度成线性关系,相关系数为0.999 93;方法检出限为0.8μg/g。按照实验方法测定土壤、水系沉积物及岩石系列国家标准物质中硼,测定结果的相对标准偏差(RSD,n=12)为3.5%~9.9%,相对误差为-13%~8.4%。
During the pretreatment of geological sample by acid dissolution method,there were volatilization loss of boron because boron would form boron trifluoride or boron trichloride in final removal of HF by evaporation either in open or in closed system.As a result,the determination of boron had poor precision.In order to eliminate this kind of volatilization loss,the sample was digested on electric hot plate at 140℃for 2 h in closed system by 1 mL of HCl,1 mL of HNO3 and 2 mL of HF.The removal of HF was not required.The sample solution was diluted to constant volume and directly determined by inductively coupled plasma atomic emission spectrometer which was equipped with HF-resistant injection system.Consequently,a determination method of boron in geochemical survey sample was established.The optimal analysis spectral line for boron was B 249.678 nm.The influence of cobalt in sample on the determination results of boron was eliminated by correction with interference equation.When the mass ratio of iron to boron in sample was higher than 14 000,the interference of iron could be eliminated by removal of iron with ammonium hydroxide.The experimental results showed that the mass concentration of boron in range of 0.10-2.00μg/mL was linear to the corresponding emission intensity.The correlation coefficient was 0.999 93.The detection limit of method was 0.8μg/g.The proposed method was applied for determination of boron in national certified reference materials of soil,stream sediment and rock.The relative standard deviations(RSD,n=12)were 3.5%-9.9%.The relative errors were-13%-8.4%.
During the pretreatment of geological sample by acid dissolution method,there were volatilization loss of boron because boron would form boron trifluoride or boron trichloride in final removal of HF by evaporation either in open or in closed system.As a result,the determination of boron had poor precision.In order to eliminate this kind of volatilization loss,the sample was digested on electric hot plate at 140℃for 2 h in closed system by 1 mL of HCl,1 mL of HNO3 and 2 mL of HF.The removal of HF was not required.The sample solution was diluted to constant volume and directly determined by inductively coupled plasma atomic emission spectrometer which was equipped with HF-resistant injection system.Consequently,a determination method of boron in geochemical survey sample was established.The optimal analysis spectral line for boron was B 249.678 nm.The influence of cobalt in sample on the determination results of boron was eliminated by correction with interference equation.When the mass ratio of iron to boron in sample was higher than 14 000,the interference of iron could be eliminated by removal of iron with ammonium hydroxide.The experimental results showed that the mass concentration of boron in range of 0.10-2.00μg/mL was linear to the corresponding emission intensity.The correlation coefficient was 0.999 93.The detection limit of method was 0.8μg/g.The proposed method was applied for determination of boron in national certified reference materials of soil,stream sediment and rock.The relative standard deviations(RSD,n=12)were 3.5%-9.9%.The relative errors were-13%-8.4%.
引文
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[9]邵鑫,李小丹,何启生.ICP-AES测定地质样品中铍、硼和镓[J].光谱实验室,2006,23(5):1012-1014.SHAO Xin,LI Xiao-dan,HE Qi-sheng.Determination of beryllium,boron and gallium in geological samples by ICP-AES[J].Chinese Journal of Spectroscopy Laboratory,2006,23(5):1012-1014.
[10]李冰,马新荣,杨红霞,等.封闭酸溶-电感耦合等离子体原子发射光谱法同时测定地质样品中硼砷硫[J].岩矿测试,2003,22(4):241-247.LI Bing,MA Xin-rong,YANG Hong-xia,et al.Determination of boron,arsenic and sulfur in geological samples by inductively coupled plasma atomic emission spectrometry with sample treatment by pressurized decomposition[J].Rock and Mineral Analysis,2003,22(4):241-247.
[11]谢小风,罗明标,施媛媛.ICP-AES法直接测定地热温泉水样中的钾、钠、钙、镁、硅、锂、硼的研究[J].光谱实验室,2000,17(6):701-706.XIE Xiao-feng,LUO Ming-biao,SHI Yuan-yuan.The research on the determination of K,Na,Ca,Mg,Si,Li,B in the samples of hot spring by ICP-AES method[J].Chinese Journal of Spectroscopy Laboratory,2000,17(6):701-706.
[12]Gregoire D C.Determination of boron isotope ratios in geological materials by inductively coupled plasma mass spectrometry[J].Anal.Chem.,1987,59(20):2479-2484.
[13]Zarcinas B A,Cartwright B.Acid dissolution of soils and rocks for the determination of born by inductively coupled plasma atomic emission spectrometry[J].Analyst,1987,112(8):1107-1112.
[14]曾宪津,缪秀珍,黄本立.土壤和沉积物中全硼量与其他微量及常量元素的ICP-AES同时测定[J].分析化学,1987,15(12):1106-1109.ZENG Xian-jin,MIAO Xiu-zhen,HUANG Ben-li.Simultaneous determination of total boron and other micro and major elements in soils and sediments by inductively coupled plasma atomic emission spectrometry[J].Chinese Journal of Analytical Chemistry,1987,15(12):1106-1109.
[15]Nakamura E,Ishikawa T,Birck J L,et al.Precise boron isotopic analysis of natural rock samples using a boronmannitol complex[J].Chem.Geo1.,1992,94(3):193-204.
[16]邵鑫,李小丹,朱园园,等.密闭溶样-电感耦合等离子体-质谱法测定地质样品中的微量硼[J].光谱实验室,2012,29(5):3256-3259.SHAO Xin,LI Xiao-dan,ZHU Yuan-yuan,et al.Determination of trace boron in geological samples by ICPAES with closed-digestion[J].Chinese Journal of Spectroscopy Laboratory,2012,29(5):3256-3259.
[17]王英滨,姜浩,龙梅,等.等离子体发射光谱法测定地质样品中的硼[J].光谱实验室,1998,15(6):72-73.WANG Ying-bin,JIANG Hao,LONG Mei,et al.Determination of boron in geological samples by ICP-AES[J].Chinese Journal of Spectroscopy Laboratory,1998,15(6):72-73.
[2]张晗,靳青文,黄仁龙,等.大宝山矿区农田土壤重金属污染及其植物累积特征[J].土壤,2017,49(1):141-149.ZHANG Han,JIN Qing-wen,HUANG Ren-long,et al.Characteristics of heavy metal pollution in agricultural soils and bioaccumulation in plants of dabaoshan mine[J].Soils,2017,49(1):141-149.
[3]闫春燕,伊文涛,马培华,等.微量硼的测定方法研究进展[J].理化检验:化学分册,2008,44(2):197-201.YAN Chun-yan,YI Wen-tao,MA Pei-hua,et al.Recent progress of methods for determination of microamounts of boron[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2008,44(2):197-201.
[4]王艳泽,施燕之,张学凯,等.土壤中有效硼的分析进展[J].冶金分析,2007,27(6):36-40.WANG Yan-ze,SHI Yan-zhi,ZHANG Xue-kai,et al.Recent advances in the analysis of available boron in soil[J].Metallurgical Analysis,2007,27(6):36-40.
[5]孙中华,章志仁,毛英,等.电弧蒸馏光谱法测定化探样品中痕量银锡铅硼镓[J].岩矿测试,2004,23(2):153-156.SUN Zhong-hua,ZHANG Zhi-ren,MAO Ying,et al.Determination of trace amount of silver,tin,lead,boron and gallium in geochemical exploration samples by electric arc distillation-emission spectrometry[J].Rock and Mineral Analysis,2004,23(2):153-156.
[6]张雪梅,张勤.发射光谱法测定勘查地球化学样品中银硼锡钼铅[J].岩矿测试,2006,25(4):323-326.ZHANG Xue-mei,ZHANG Qin.Determination of silver,boron,tin,molybdenum and lead in geochemical exploration samples by emission spectrometry[J].Rock and Mineral Analysis,2006,25(4):323-326.
[7]寇德凯,邱宏喜,冯俊,等.发射光谱单电极载体蒸馏法测定地球化学样品中的银硼锡[J].黄金,2014,35(6):80-84.KOU De-kai,QIU Hong-xi,FENG Jun,et al.Determination of Ag,B,Sn in geochemical samples by emission spectrometry with single electrode carrier distillation[J].Gold,2014,35(6):80-84.
[8]徐建平,谌文华.ICP-AES法测定硅铁中全硼[J].冶金分析,2001,21(4):59-60.XU Jian-ping,CHEN Wen-hua.ICP-AES determination of total boron in ferrosilicon[J].Metallurgical Analysis,2001,21(4):59-60.
[9]邵鑫,李小丹,何启生.ICP-AES测定地质样品中铍、硼和镓[J].光谱实验室,2006,23(5):1012-1014.SHAO Xin,LI Xiao-dan,HE Qi-sheng.Determination of beryllium,boron and gallium in geological samples by ICP-AES[J].Chinese Journal of Spectroscopy Laboratory,2006,23(5):1012-1014.
[10]李冰,马新荣,杨红霞,等.封闭酸溶-电感耦合等离子体原子发射光谱法同时测定地质样品中硼砷硫[J].岩矿测试,2003,22(4):241-247.LI Bing,MA Xin-rong,YANG Hong-xia,et al.Determination of boron,arsenic and sulfur in geological samples by inductively coupled plasma atomic emission spectrometry with sample treatment by pressurized decomposition[J].Rock and Mineral Analysis,2003,22(4):241-247.
[11]谢小风,罗明标,施媛媛.ICP-AES法直接测定地热温泉水样中的钾、钠、钙、镁、硅、锂、硼的研究[J].光谱实验室,2000,17(6):701-706.XIE Xiao-feng,LUO Ming-biao,SHI Yuan-yuan.The research on the determination of K,Na,Ca,Mg,Si,Li,B in the samples of hot spring by ICP-AES method[J].Chinese Journal of Spectroscopy Laboratory,2000,17(6):701-706.
[12]Gregoire D C.Determination of boron isotope ratios in geological materials by inductively coupled plasma mass spectrometry[J].Anal.Chem.,1987,59(20):2479-2484.
[13]Zarcinas B A,Cartwright B.Acid dissolution of soils and rocks for the determination of born by inductively coupled plasma atomic emission spectrometry[J].Analyst,1987,112(8):1107-1112.
[14]曾宪津,缪秀珍,黄本立.土壤和沉积物中全硼量与其他微量及常量元素的ICP-AES同时测定[J].分析化学,1987,15(12):1106-1109.ZENG Xian-jin,MIAO Xiu-zhen,HUANG Ben-li.Simultaneous determination of total boron and other micro and major elements in soils and sediments by inductively coupled plasma atomic emission spectrometry[J].Chinese Journal of Analytical Chemistry,1987,15(12):1106-1109.
[15]Nakamura E,Ishikawa T,Birck J L,et al.Precise boron isotopic analysis of natural rock samples using a boronmannitol complex[J].Chem.Geo1.,1992,94(3):193-204.
[16]邵鑫,李小丹,朱园园,等.密闭溶样-电感耦合等离子体-质谱法测定地质样品中的微量硼[J].光谱实验室,2012,29(5):3256-3259.SHAO Xin,LI Xiao-dan,ZHU Yuan-yuan,et al.Determination of trace boron in geological samples by ICPAES with closed-digestion[J].Chinese Journal of Spectroscopy Laboratory,2012,29(5):3256-3259.
[17]王英滨,姜浩,龙梅,等.等离子体发射光谱法测定地质样品中的硼[J].光谱实验室,1998,15(6):72-73.WANG Ying-bin,JIANG Hao,LONG Mei,et al.Determination of boron in geological samples by ICP-AES[J].Chinese Journal of Spectroscopy Laboratory,1998,15(6):72-73.