电喷雾串联质谱模拟天然单质铀的形成
|
摘要
采用三重四级杆质谱模拟并分析微观含铀分子化学键断裂形成新的物质的过程以探讨单质铀的产生机理。结果表明,含铀分子在质谱中离子化后经碰撞诱导解离可生成U~+。研究还发现,硝酸铀酰溶液通过电喷雾可形成UO~+_2(m/z 270)、UO_2OH~+(m/z 287)、UO_2H_2OOH~+(m/z 305)、UO_2NO~+_3(m/z 332)、UO_2(H_2O)_3NO~+_3(m/z 386)及双聚铀酰离子[(UO_2NO_3H_2O)_2NO_3]~+(m/z 762),在具有一定动能N_2的碰撞下它们均可产生游离的U~+。通过模拟实验推测,天然单质铀形成的微观机理为:在漫长地质年代中放射性核素持续衰变产生的能量粒子撞击含铀分子使其化学键断裂生成游离铀离子,在封闭或强还原性等特殊地质条件下形成单质铀并被保存下来。
To explore the formation mechanism of uranium, electrospray ionization tandem mass spectrometry was used to simulate and analyze the chemical bond breaking of uranium-containing molecules. The results show that U~+ is generated in collision-induced dissociation mode after uranium-containing molecules were ionized in mass spectrometry. By further study it is found that there are UO~+_2(m/z 270), UO_2OH~+(m/z 287), UO_2H_2OOH~+(m/z 305), UO_2NO~+_3(m/z 332), UO_2(H_2O)_3NO~+_3(m/z 386) and bis-uranyl ion [(UO_2NO_3H_2O)_2NO_3]~+(m/z 762) in the solution, all of which could form U~+ under the collision of N_2 with kinetic energy. The formation mechanism of natural native uranium deducted from simulation experiment is the following: Free uranium cations are generated from the breaking of uranium-containing molecules by collision of neutral particles which are the decay products of radioactive substance, and further, uranium cations form natural native uranium and is preserved in closed or strong reduction geological conditions in a long geological period.
To explore the formation mechanism of uranium, electrospray ionization tandem mass spectrometry was used to simulate and analyze the chemical bond breaking of uranium-containing molecules. The results show that U~+ is generated in collision-induced dissociation mode after uranium-containing molecules were ionized in mass spectrometry. By further study it is found that there are UO~+_2(m/z 270), UO_2OH~+(m/z 287), UO_2H_2OOH~+(m/z 305), UO_2NO~+_3(m/z 332), UO_2(H_2O)_3NO~+_3(m/z 386) and bis-uranyl ion [(UO_2NO_3H_2O)_2NO_3]~+(m/z 762) in the solution, all of which could form U~+ under the collision of N_2 with kinetic energy. The formation mechanism of natural native uranium deducted from simulation experiment is the following: Free uranium cations are generated from the breaking of uranium-containing molecules by collision of neutral particles which are the decay products of radioactive substance, and further, uranium cations form natural native uranium and is preserved in closed or strong reduction geological conditions in a long geological period.
引文
[1] KOK D K. Nuclear engineering handbook[M]. Boca Raton, USA: CRC Press, 2009.
[2] 宋金如. 铀矿石的化学分析[M]. 北京:原子能出版社,2006.
[3] LI Ziying, HUANG Zhizhang, LI Xiuzhen, et al. The discovery of natural native uranium and its significance[J]. Acta Geologica Sinica, 2015, 89(5): 1 561-1 567.
[4] 刘成龙,王兆周. 一种超显微自然铅与自然锡的混合物的研究[J]. 岩石矿物学杂质,1986,5(1):75-79. LIU Chenglong, WANG Zhaozhou. Study on a mixture of ultra-microscopic natural lead and natural tin[J]. Acta Petrologica et Mineralogica, 1986, 5(1): 75-79(in Chinese).
[5] 徐夕生,刘昌实,楚雪君. 滇西花岗岩中自然铅的发现及成因讨论[J]. 地质与勘探,1989(1):23-25. XU Xisheng, LIU Changshi, CHU Xuejun. Discussion on the discovery and genesis of natural lead in western Yunnan granite[J]. Geology and Exploration, 1989(1): 23-25(in Chinese).
[6] BERNHARD M. Capillary electrophoresis-inductively coupled plasma-mass spectrometry: A report on technical principles and problem solutions, potential, and limitations of this technology as well as on examples of application[J]. Electrophoresis, 2005, 26: 1 584-1 597.
[7] 施章宏,黄鹤翔,罗文华,等. ICP-MS技术快速测定尿样中的铀同位素[J]. 化学通报,2015,78(5):464-466. SHI Zhanghong, HUANG Hexiang, LUO Wenhua, et al. Rapid determination of uranium isotope in urine by ICP-MS[J]. Chemistry, 2015, 78(5): 464-466(in Chinese).
[8] TSERKEZOS N G, ROITHOVA J, SCHRODER D, et al. Can electrospray mass spectrometry quantitatively probe speciation hydrolysis of uranyl nitrate studied by gas-phase methods[J]. Inorganic Chemistry, 2009, 48(13): 6 287-6 296.
[9] 陈焕文,胡斌,张燮. 复杂样品质谱分析技术的原理与应用[J]. 分析化学,2010,38(8):1 069-1 088. CHEN Huanwen, HU Bin, ZHANG Xie. Fundamental principles and practical applications of ambient ionization mass spectrometry for direct analysis of complex samples[J]. Chinese Journal of Analytical Chemistry, 2010, 38(8): 1 069-1 088(in Chinese).
[10] MCDONALD L W, CAMPBELL J A, VERCOUNTER T, et al. Characterization of actinides complexed to nuclear fuel constituents using ESI-MS[J]. Analytical Chemistry, 2016, 88: 2 614-2 621.
[11] DAU P D, DAU P V, LINFENG R, et al. A uranyl peroxide dimer in the gas phase[J]. Inorganic Chemistry, 2017, 56: 4 186-4 196.
[12] 花榕,李毅,钟达财,等. 铀胁迫凤眼莲根部代谢产物内部萃取电喷雾电离质谱分析[J]. 原子能科学技术,2018,52(9):1 576-1 581. HUA Rong, LI Yi, ZHONG Dacai, et al. Analysis of metabolitein root of Eichhornia crassipes exposed to uranium using iEESI-MS[J]. Atomic Energy Science and Technology, 2018, 52(9): 1 576-1 581(in Chinese).
[13] LUO Mingbiao, HU Bin, ZHANG Xie, et al. Extractive electrospray ionization mass spectrometry for sensitive detection of uranyl species in natural water samples[J]. Analytical Chemistry, 2010, 82(1): 282-289.
[14] 胡斌,陈焕文,张燮,等. 新化合物五氧化铀的电喷雾串联质谱法制备与表征[J]. 化学学报,2009,67(12):1 331-1 335. HU Bin, CHEN Huanwen, ZHANG Xie, et al. Preparation and characterization of UO5 by using electrospray ionization tandem mass spectrometry[J]. Acta Chimica Sinica, 2009, 67(12): 1 331-1 335(in Chinese).
[2] 宋金如. 铀矿石的化学分析[M]. 北京:原子能出版社,2006.
[3] LI Ziying, HUANG Zhizhang, LI Xiuzhen, et al. The discovery of natural native uranium and its significance[J]. Acta Geologica Sinica, 2015, 89(5): 1 561-1 567.
[4] 刘成龙,王兆周. 一种超显微自然铅与自然锡的混合物的研究[J]. 岩石矿物学杂质,1986,5(1):75-79. LIU Chenglong, WANG Zhaozhou. Study on a mixture of ultra-microscopic natural lead and natural tin[J]. Acta Petrologica et Mineralogica, 1986, 5(1): 75-79(in Chinese).
[5] 徐夕生,刘昌实,楚雪君. 滇西花岗岩中自然铅的发现及成因讨论[J]. 地质与勘探,1989(1):23-25. XU Xisheng, LIU Changshi, CHU Xuejun. Discussion on the discovery and genesis of natural lead in western Yunnan granite[J]. Geology and Exploration, 1989(1): 23-25(in Chinese).
[6] BERNHARD M. Capillary electrophoresis-inductively coupled plasma-mass spectrometry: A report on technical principles and problem solutions, potential, and limitations of this technology as well as on examples of application[J]. Electrophoresis, 2005, 26: 1 584-1 597.
[7] 施章宏,黄鹤翔,罗文华,等. ICP-MS技术快速测定尿样中的铀同位素[J]. 化学通报,2015,78(5):464-466. SHI Zhanghong, HUANG Hexiang, LUO Wenhua, et al. Rapid determination of uranium isotope in urine by ICP-MS[J]. Chemistry, 2015, 78(5): 464-466(in Chinese).
[8] TSERKEZOS N G, ROITHOVA J, SCHRODER D, et al. Can electrospray mass spectrometry quantitatively probe speciation hydrolysis of uranyl nitrate studied by gas-phase methods[J]. Inorganic Chemistry, 2009, 48(13): 6 287-6 296.
[9] 陈焕文,胡斌,张燮. 复杂样品质谱分析技术的原理与应用[J]. 分析化学,2010,38(8):1 069-1 088. CHEN Huanwen, HU Bin, ZHANG Xie. Fundamental principles and practical applications of ambient ionization mass spectrometry for direct analysis of complex samples[J]. Chinese Journal of Analytical Chemistry, 2010, 38(8): 1 069-1 088(in Chinese).
[10] MCDONALD L W, CAMPBELL J A, VERCOUNTER T, et al. Characterization of actinides complexed to nuclear fuel constituents using ESI-MS[J]. Analytical Chemistry, 2016, 88: 2 614-2 621.
[11] DAU P D, DAU P V, LINFENG R, et al. A uranyl peroxide dimer in the gas phase[J]. Inorganic Chemistry, 2017, 56: 4 186-4 196.
[12] 花榕,李毅,钟达财,等. 铀胁迫凤眼莲根部代谢产物内部萃取电喷雾电离质谱分析[J]. 原子能科学技术,2018,52(9):1 576-1 581. HUA Rong, LI Yi, ZHONG Dacai, et al. Analysis of metabolitein root of Eichhornia crassipes exposed to uranium using iEESI-MS[J]. Atomic Energy Science and Technology, 2018, 52(9): 1 576-1 581(in Chinese).
[13] LUO Mingbiao, HU Bin, ZHANG Xie, et al. Extractive electrospray ionization mass spectrometry for sensitive detection of uranyl species in natural water samples[J]. Analytical Chemistry, 2010, 82(1): 282-289.
[14] 胡斌,陈焕文,张燮,等. 新化合物五氧化铀的电喷雾串联质谱法制备与表征[J]. 化学学报,2009,67(12):1 331-1 335. HU Bin, CHEN Huanwen, ZHANG Xie, et al. Preparation and characterization of UO5 by using electrospray ionization tandem mass spectrometry[J]. Acta Chimica Sinica, 2009, 67(12): 1 331-1 335(in Chinese).