温度、质量浓度对富氟流体中Hf高温高压水解行为的影响
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摘要
Hf是一种高场强元素,在地壳中的丰度较低,往往以类质同象的形式进入锆石中。以氟铪酸钾(K_2HfF_6)络合物为研究对象,观察它们在富水热液中的水解程度,进而研究Hf元素在地质过程中的迁移行为。结果表明:K_2HfF_6络合物在热液条件下能发生一定程度的水解反应,总体趋势为络合物的初始质量浓度越低且反应的温度越高,其水解程度越剧烈,络合物的稳定性也就越低;获得了高温高压条件下K_2HfF_6络合物的累积水解平衡常数。同时运用实验模拟的方法,根据提取液中Hf元素含量来推测矿物结晶时富氟流体中Hf元素含量,若以K_2HfF_6络合物最高配位的离子团形迁移时,Hf与F元素之间的质量浓度比值为1.6,据此可以计算成矿流体所需的最小F元素含量。
Hf is a high field strength element(HFSE) with low abundance in the earth's crust, and often enters zircon in the form of isomorphism. The migration behavior of Hf in natural geological processes was studied by observing the hydrolysis degree of K_2HfF_6 complex in hydrothermal solution. The results show that K_2HfF_6 complex could undergo hydrolysis reaction to a certain extent under hydrothermal conditions, and the general trend is that the lower the initial mass concentration of the complex and the higher the reaction temperature, the more severe the hydrolysis degree and the lower the stability of the complex; the cumulative hydrolysis equilibrium constant of K_2HfF_6 complex under high temperature and high pressure is obtained. At the same time, according to the content of Hf in the extraction solution, the content of Hf in the fluoride-rich fluid can be estimated based on the method of experimental simulation; if the ion group migrates with the highest coordination of K_2HfF_6, the ratio of mass concentrations between Hf and F is 1.6, so the minimum content of F required for the mineralization fluid can be calculated.
Hf is a high field strength element(HFSE) with low abundance in the earth's crust, and often enters zircon in the form of isomorphism. The migration behavior of Hf in natural geological processes was studied by observing the hydrolysis degree of K_2HfF_6 complex in hydrothermal solution. The results show that K_2HfF_6 complex could undergo hydrolysis reaction to a certain extent under hydrothermal conditions, and the general trend is that the lower the initial mass concentration of the complex and the higher the reaction temperature, the more severe the hydrolysis degree and the lower the stability of the complex; the cumulative hydrolysis equilibrium constant of K_2HfF_6 complex under high temperature and high pressure is obtained. At the same time, according to the content of Hf in the extraction solution, the content of Hf in the fluoride-rich fluid can be estimated based on the method of experimental simulation; if the ion group migrates with the highest coordination of K_2HfF_6, the ratio of mass concentrations between Hf and F is 1.6, so the minimum content of F required for the mineralization fluid can be calculated.
引文
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[17] 郑永飞.深俯冲大陆板块折返过程中的流体活动[J].科学通报,2004,49(10):917-929.ZHENG Yong-fei.Fluid Activity During Exhumation of Deep-subducted Continental Plates[J].Chinese Science Bulletin,2004,49(10):917-929.第41卷第3期
[2] CLAOUELONG J C,KING R W,KERRICH R.Archean Hydrothermal Zircon in the Abitibi Greenstone Belt:Constraints on the Timing of Gold Mineralisation[J].Earth and Planetary Science Letters,1990,98(1):109-128.
[3] GIERE R.Zirconolite,Allanite and Hoegbomite in a Marble Skarn from the Bergell Contact Aureole:Implications for Mobility of Ti,Zr and REE[J].Contributions to Mineralogy and Petrology,1986,93(4):459-470.
[4] GIERE R.Transport and Deposition of REE in H2S-rich Fluids:Evidence from Accessory Mineral Assemblages[J].Chemical Geology,1993,110(1/2/3):251-268.
[5] MCNAUGHTON N J,MUELLER A G,GROVES D I.The Age of the Giant Golden Mile Deposit,Kalgoorlie,Western Australia:Ion-microprobe Zircon and Monazite U-Pb Geochronology of a Syn-mineralization Lamprophyre Dike[J].Economic Geology,2005,100(7):1427-1440.
[6] KEBEDE T,HORIE K,HIDAKA H,et al.Zircon ‘Microvein’ in Peralkaline Granitic Gneiss,Western Ethiopia:Origin,SHRIMP U-Pb Geochronology and Trace Element Investigations[J].Chemical Geology,2007,242(1/2):76-102.
[7] COLLINS W J,BEAMS S D,WHITE A J R,et al.Nature and Origin of A-type Granites with Particular Reference to Southeastern Australia[J].Contributions to Mineralogy and Petrology,1982,80(2):189-200.
[8] GAO J,JOHN T,KLEMD R,et al.Mobilization of Ti-Nb-Ta During Subduction:Evidence from Rutile-bearing Dehydration Segregations and Veins Hosted in Eclogite,Tianshan,NW China[J].Geochimica et Cosmochimica Acta,2007,71(20):4974-4996.
[9] DING X,HU Y H,ZHANG H,et al.Major Nb/Ta Fractionation Recorded in Garnet Amphibolite Facies Metagabbro[J].The Journal of Geology,2013,121(3):255-274.
[10] LEE B G,CHOI J W,LEE S E,et al.Formation Behavior of Anodic TiO2 Nanotubes in Fluoride Containing Electrolytes[J].Transactions of Nonferrous Metals Society of China,2009,19(4):842-845.
[11] RAPP J F,KLEMME S,BUTLER I B,et al.Extremely High Solubility of Rutile in Chloride and Fluoride-bearing Metamorphic Fluids:An Experimental Investigation[J].Geology,2010,38(4):323-326.
[12] 何俊杰,丁兴,王玉荣,等.温度、浓度对流体中氟钛络合物水解的影响:对深部地质过程中钛元素活动的制约[J].岩石学报,2015,31(3):802-810.HE Jun-jie,DING Xing,WANG Yu-rong,et al.The Effect of Temperature and Concentration on Hydrolysis of Fluorine-rich Titanium Complexes in Hydrothermal Fluids:Constraints on Titanium Mobility in Deep Geological Processes[J].Acta Petrologica Sinica,2015,31(3):802-810.
[13] 何俊杰.热液体系中高场强元素富氟络合物的水解行为及活动性规律[D].广州:中国科学院广州地球化学研究所,2018.HE Jun-jie.The Hydrolysis and Mobility of HFSE-F Complexes in Hydrothermal Conditions[D].Guangzhou:Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,2018.
[14] 丁兴,何俊杰,刘灼瑜.热液条件下锐钛矿晶体生长的实验[J].地球科学,2018,43(5):1763-1772.DING Xing,HE Jun-jie,LIU Zhuo-yu.Experimental Studies on Crystal Growth of Anatase Under Hydrothermal Conditions[J].Earth Science,2018,43(5):1763-1772.
[15] PHILIPPOT P.高压流体(1～3 GPa)的化学组成:自然观察与实验对比[J].地学前缘,1996,3(3/4):39-52.PHILIPPOT P.The Chemistry of High-pressure Fluids(1 to 3 GPa) Natural Observations vs.Experimental Constraints[J].Earth Science Frontiers,1996,3(3/4):39-52.
[16] YARDLEY B W D,BODNAR R J.Fluids in the Continental Crust[J].Geochemical Perspectives,2014,3(1):1-123.
[17] 郑永飞.深俯冲大陆板块折返过程中的流体活动[J].科学通报,2004,49(10):917-929.ZHENG Yong-fei.Fluid Activity During Exhumation of Deep-subducted Continental Plates[J].Chinese Science Bulletin,2004,49(10):917-929.第41卷第3期
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