花岗岩浆结晶过程晚期铌、钽富集成矿的地球化学机理探讨

The mechanism of Nd.Ta-mineralixation is diseussed in the light of the properties of Nb-,Ta-complexes in different phases.Experiments show that Nb and Ta are essentially enriched in the melts when Nb-,Ta-bearing albite granites are completely melted(800-850℃）and in equilibrium with a HF-bearing vapor phase,It is also demonstrated from the experiments,that hydrolysis of Nb-,Ta-flourine complexes in aqueons solutions takes place with inereasing temperature,reaching a maximum value in the vicinity of critical temperature and becoming stable under supercritical conditions.Under this circumstance,Nb-,Ta-complexes can be trausported in the vapor phase,Ta exhibits a great,ability of transport in vapor phase as compared with Nb,while Nb is more soluble than Ta under hydrothermal conditions.The authors hold,on the basis of experiments and field observations,that Nb-,Ta-mineralixation is related to the proeess of crystllization-differentiation of lowmelting granitic magma which is rich in flourine.water and alkalis,as well as to the metasoatism during the late stage,pH ariation is also dealt with during Nb-.Ta-mineralization.     

Raman Spectroscopy of Nb,Ta-rich Cassiterite in Beauvoir and Montebras Granites,France

Cassiterites from both the Beauvoir and Montebras geanited of France are typically rich in trace elements such as Nb and Ta, and contain quite a number of inclusions of columbite (dominantly manganocolumbite).Two thin sections of cassiterite crystals have been prepared for Raman microprobe analysis).The spectra obtained from different parts of the cassiterites show that the vibra-tion frequency of the A1g peak decreases with increasing Nb ,Ta,Fe and Mn atomic contents.It is worthy to note that a new peak (named the “An peak”) has been reported for the first time in the part with oriented columbite inclusions.The vibration frequency varies from 827 to 830 cm^-1.The presence of th enew peak may be attributed to structural changes of cassiterite due to the excess of Nb and Ta in the lattice and the exsolution of columbite inclusions in cassiterite.     

南岭地区脉状黑钨矿床的地球化学类型

In accordance with the characteristics of associated minerals, trace elments in the altered rocks around the veins and the composition of wolframite and mica, the vein wolframite deposits in the Nanling Region can be divided into two geochemical types:the wolframite-beryl-molybdenite-bismutite (native bismuth) type and the wolframite.cassiterite-sulfide (copper, zine, lead) type. Vein wolframite deposits of these two geochemical types were formed under different conditions. The wolframite-beryl-molybdenite-bismutite (native bismuth) type may be connected with high pH-Eh conditions whereas the wolframite-eassiterite-sulfide (copper, zinc, lead) type with low pH-Eh conditions. It is concluded that the two geochemical types of vein wolframite deposits are genetically related with two different geochemical types of granites in the Nanling Region.     

Compositional Characteristics of Wolframite in Tin Dposits,Dupangling,Guangxi

Statistical data on major,trace and rare-earth elements in wolframite from the quartz vein-and greisen-type tin deposits in the Dupangling orefield reveal(1)The components in wolframite can be divided into two relatively independent groups:the WO3-Nb-Ta-Sc-REE group,in which WO3 is negatively correlated with the others and the FeO-MnO-Sn group,in which MnO is negatively corre-lated with the other two;(2)In general ,REE fractionation is not significant,reflected mainly by the separation of Eu from other REE‘s.LREE and HREE increase or decrease simultaneously ,with HREE being more variable;(3)Nb,Ta,Sc,REE substitute for W, and Sn may enter into wolframite lattice accompanied by Fe-Mn substitution;(4)In contrast to wolframite in quartz veins,which is poor in REE,Nb,Ta and has high δEu values and LREE/HREE and Nb/Ta ratios,wolframite in greisen is rich in REE, Nb,Ta,Sc and has low δEu values and LREE/HREE and Nb/Ta ratios ;and (5)The contents and ratios of trace elements and REE parti-tioning parameters of wolframite can be used as guide for prospecting.     

某蚀变花岗岩型铌钽矿床中钠长石化和天河石化

A Nb-, Ta-, rare metal deposit has been discovered in a albitization-, amazonitization-granite by using amazonite as an indicator. The ore-bearing dyke, early Yanshanian in age, occurs in a Late Jurassic metamorphic sandstone and breccia. Three stages of albite can be distinguished, showing regular variation in composition, optical property and structure with respective to different generations. Two generations of amazonite are noticed and studies are made on their composition and structure by using optical and X-ray diffraction methods. Amazonite is readily recognizable in the field by its colonr. Its occurrence with albitization can be used as a prospecting indicator for Nb, Ta and other rare metals.     

某钽铌钨铍矿化花岗岩岩石化学特征

During the magmatie evolution from biotite granite through two-mlca granite to mineralized muscovite granite it has been noted that Na^ , Mm^2 , Si^4 increase while K^ , Ca^2 , Mg^2 , Fe^2 , Fe^3 , Ti^4 , and P^5 decrease systematically in this district. Oreforming metals occur in higher abundance in biotite granite which is thought to be the representative of primary magma, and have been enriched rapidly with magmatic evolution R^ /R^2 Na^ /K^ , Rb/K, Mn/Fe and other petrochemical parameters increase whereas Ti^4 /Si^4 decreases in a sympathetic way with the enrichment of niobium and tantalum, providing good indicators of the degree of differentiation and metasematism of the magma ,Within the mineralized granite, there is a same trend of variation upward whioh is found closely related to the enrichment of tantalum. Fluorine is strongly concentrated in wall rocks above blind mineralized granite, and the eontente of tantalum and niobium in wolframite from quartz veins genetically related to the granite increase towards buried mineralization. The latter two phenomena are suggested by the author as clues to buried ore bodies.     

The mechanism of surface chemical kinetics of dissolution of minerals

This paper deals with the mechanism of dissolution reaction kinetics of minerals in aqueous solution based on the theory of surface chemistry.Surface chemical catalysis would lead to an obvous decrease in active energy of dissolution reaction of minerals.The dissolution rate of minerals is controlled by suface adsorption,surface exchange reaction and desorption,depending on pH of the solution and is directly proportional to δH^n0 ,When controlled by surface adsorption,i.e.,nθ=1,the dissolution rate will decrease with increasing pH;when controlled by surface exchane reaction,i.e.,nθ=0,the dissolution rate is independent of pH;when controlled by desorption,nθis a positive decimal between 0 and 1 in acidic solution and a negative decimal between-1 and 0 in alkaline solution.Dissolution of many minerals is controlled by surface adsorption and/or surface exchange reactions under acid conditions and by desorption under alkaline conditions.     

Experimental Studies of the Solubility of Cassiterite and the Extraction of Tin from Granitic Melts

Experiments indicate that the solubility of cassiterite can be enhanced by increasing either acidity or alkalinity in hydrothermal solutions as a consequence of the duality of tin.The minimum solubility of cassiterite is found in neutral solutions.F-and CL-coordination compounds of Sn can alternate with hydroxyl coordination compounds with changing pH in the solutions.In this case,F^- and Cl^- and OH^- can be substituted with each other.The dissolution reaction of cassiterite is of reducing nature.High temperature and acidic reducing environment are favorable for the dissolution of cassiterite and the trans-port of Sn^2 compounds in fluids or solutions.High-temperature fluoride and chloride fluids can all dissolve,extract and enrich Sn to form F^- and /or Cl-coordination compounds,However,Fplays a more important role than Cl.F-coordination compounds are more stable and efficient than Cl-coordination compounds during the transport an enrichment of Sn in melts or solutions.The solubili-ty of cassiterite and the amount of Sn extracted from granitic melt depend not only on T,P,pH and Eh in the fluids or solutions,but also on the amounts of dissociated F^- and Cl^- in the fluids.     

某地钽铌钨铍矿化花岗岩

The tantalum-, niobium-, tungsten-, beryllium-mineralized granite described in this paper is identified as albitizied fine-grained muscovite granite and occurs as a small discordant taeolity with a bulging central part, dipping and finning out outwards.A crust of quartz-pegmatoid, several tens of centimeters thick, dsvelopes in its apices. Major rock-forming minerals are plagioclase, mierocline, albite, muscovite and quartz. Partsehinite, fluorite and topaz are characteristically abundant among accessory minerals. Rare element and base metal minerals include wolframite,scbeellte, microlite, raanganese-rich columbite, berly, phenacite, xenotirae, monazite,cassitcrite, raolybdenite, bisrauthinite, etc. Niobium and beryllium mineralizations are uniformly present throughout the rock body, but tantalum is feund richer in upper parts than in lower parts. It is tentatively suggested that this is a differentiationmctasomatic deposit of fracture-filling type originated during late magmatic stage.     

中国若干钨矿床相平衡关系

This paper reviews the features of several tungsten ore deposits in southern China, including the Shezhuyuan, Yaogangxian, Xihuashan, Danping, Yiatang and Dajishan mines. The authors think that the formation depth of greisen-type deposits is intermediate between the depths of pegmatite- and porphyry- type deposits. Using phase diagrams of the model system K2O-AhO3-SiO2-H2O-HF, the formation mechanism of greisens has been argued. The variation of mineral assemblages from K-feldspar, muscovite to topaz reflects a gradual increase in acidity. This variation can be used as a criterion to appreciate the depth of mineralization. Equilibria of tungsten minerals in greisen and skarn deposits can be depicted on chemical potential diagrams of the model system CaO-FeO-WO3-CO2-F2O-1. The assemblage wolframite fluorite is shown to have been transformed to scheelite magnetite with decreasing μHP. Depending on CO2 activity in the fluids, there are two distinct phase diagrams.One shows that wolframite is incompatible with calcite, and the other demonstrates that scheelite is incompatible with rhodochrosite. On the phase diagrams of the model system FeO-MnO-WO3-F2S-1, huebnerite is transformed to ferberite with increasing μP1O-1orμF2S-1,During the replacement of wolframite by scheelite, the wolframite residue must have been enriched in Mn.     

Geochemistry of the Rare Earth Elements in Natural Terrestrial Waters：A Review of What Is Currently Knows

The range of observed chemical compositions of natural terrestrial waters varies greatly especially when compared to the essentially constant global composition of the oceans.The concentrations of the REEs in natural terrestrial waters also exhibit more variation than what was reported in seawater,In terrestrial waters ,pH values span the range from acid up to alkaline,In addition,terrestrial waters can range from very dilute waters through to highly concentrated brines.The REE concentrations and their behavior in natural terrestrial waters reflect these compositional ranges,Chemical weathering of rocks represents the source of the REEs to natural terrestrial waters and ,consequently,the REE signature of rocks can impart their REE signature to associated waters,In addition,Because of the typical low solubilities of the REEs both surface and solution complexation can be important in fractionating REEs in aqueous solution.Both of these processes are important in all natural terrestrial waters,however,their relative importance varies as a function of the overall solution composition,In alkaline waters,for example,Solution complexation of the REEs with carbonate ions appears to control their aqueous distributions whereas in acid waters,the REE signature of the labile fraction of the REEs is readily leached from the rocks.In circumneutral pH waters,both processes appear to be important and their relative significance has not yet been determined.     

An Experimental Styudy on Gold Solubility in Amino Acid Solution and Its Geological Significance

The experiments on gold solubility in amino acid solution mdicate that gold is very intensively soluble in amino acid(or other organic acids),which is extensively present in geological bodies,and is most soluble in histidine.The temperature and concentration,acidity and type of amino acid in the solution are important factors affecting gold-amino acid complexing. The solubility of gold in amino acid is different under different conditions of temperature, amino acid concentration and pH value of the solution,At 80℃ and pH=6-8,gold is most soluble in amino acid.Gold dispersed in water and rocks could be concentrated and transported by amino acid and then precipitated in favorable loci.Amino acids might have played an important role in metallogenesis as well as in the formation of source beds of gold.Nitrogen,oxygen and sulfur in amino acid might have reacted with gold to form soluble complex ions.     

Experimental Study on Formation Conditions of Ammoniojarosite and Its Environmental Significance

Formation conditions of ammoniojarosite in system Fe2（SO4）3-（NH4）2SO4-H2O are investigated in this paper. The results show that ammoniojarosite can be formed rapidly under normal temperature and pressure by controlling suitable pH value and Fe2（SO4）3 and （NH4）2SO4 concentrations. The pH value, temperature and concentration of Fe2（SO4）3 medium are key factors influencing the formation of ammoniojarosite. Under normal temperature, precipitation of ammoniojarosite can be seen within 24 hours at pH values between 2.6-3.1, and a great quantity of ammoniojarosite is formed within 48 hours. At about 90℃, the pH value range forming ammoniojarosite extends to 1.2-3.1, and within this range the rise of pH value is advantageous to the formation of ammoniojarosite and high Fe2（SO4）3 concentration is also advantageous. Relative pure ammoniojarosite is synthesized under high Fe2（SO4）3 concentration （≥0.05 M） and ammoniojarosite containing melanterite and colloid amorphous hydroxide vitriol iron is formed at low Fe2（SO4）3 concentration. The deposition process of ammoniojarosite can be used to harness wastewater from mines and other industries and remove S, Fe and other toxic and harmful elements, such as As, Cr, Hg, Pb in water. Rapid formation of ammoniojarosite and other jarosite analogs under normal temperature and pressure has a good potential prospect for harnessing acid wastewater by means of precipitation of jarosite and its analogs.     

Experimental study of the selective adsorption of heavy metals onto clay minerals

The interaction between minerals and heavy metals has been a hot object of study in environmental science,mineralogy and soil science,Through the selective adsorption experiment of Ca-montomorillonite,illite and kaolinite to Cu2 ,Pb^2 ,Zn^2 ,Cd^2 ,and Cr^3 ions at certain conditions,it could be concluded that Cr^3 is most effectively sorbed by all the three minerals.Also,it can be found that Pb^2 shows a strong affinity for illite and kaolinite while cu^2 for montmorillonite .Based on the adsorption experiment at varying pH of solution,it can be found that the amount of heavy etals sorbed by minerals increases with increasing pH of the solution.     

断裂带里的粘土岩化问题

Fault clay is the combined results of 10 ig-term dynamic-, thermal-metamorphism and tectonic geochemical process. Approximately similar fault clay can be produced from different rocks as long as the abovemeutioned actions develope to a certain extent.Fault clay is characterized by a great variety of clay minerals as a result of the depletion in silica and the relative enrichment in Ah Different types of clayization can be recognized depending on the environmen and the extent to which alkalis are leached. The process that results in the formation Of fault clay, i.e., the disintegration of rocks, dissolution, transportation, deposition mstasormatism, re-crystallization and the alteration of clay minerals already formed goes Under the heading of tectonic geochemistry. It is induced by the pressure and temperature that prevail under dynamic-, the rmal-metamorphism and is controlled entirely by tectonic movement. Therefore, it differs from weathering and leaching in terms of either the mechanism or the characteristies of material exchange or the texture and structure of the resulted clays. Clayization is an indieator that the fault activity has reached to a stage of matoration. On the other hand, clayization is also a process of mineralization which gives rise under favorite conditions elay deposit of economic slginficance.     

The Coexisting Clinopyroxene-Garnet Acidometer and Acidity Facies of Skarn Deposits

On the basis of geological studies of skarn deposits in China and by using thermodynamic models of thesolid solution, the coexisting clinopyroxene-garnet pair in skarn deposits has been analysed and a coexistingclinopyroxene-garnet acidometer developed. They can be used to estimate the medium condition under whichthe skarn was formed. The research on the acidity for the formation of various metallic skarn deposits in Chinasuggests that skarns endowed with dissimilar types of mineralization and occurring in diverse environments dif-fer in the acidity conditions for their formation and in the trend of acidity variation of ore-bearing fluid. This,coupled with the study of oxygen fugacity of coexisting minerals, makes it possible to establish the oxygenfugacity-acidity facies of skarn deposits, which reflect the close genetic relationship between the metallizationand the formation of skarn.     

Metamorphism of the Bikou Group in the Shanxi-Gausu-Sichuan Border Region

The Blkou Group on the Shaanxi-Gansu-Sichuan border is composed of Mid-Late Proterozoic metamorphosed bimodal volcanic rocks and flysch sediments. Its metamorphism may be divided into the blueschist and greenschist facies. Three metamorphlc zones, i.e. zones A, B, and C, may be distinguished on the basis of the field distribution of metamorphlc rocks and the variation of b0 values of muscovite. Blueschists are characterized by coexistence of sodic amphiboles and epidote and occur as stripes or relict patches in extensive greenschists of zone A. Studies of metamorphic minerals such as amphiboles, chlorite, epidote and muscovite and their textural relationships indicate that blueschists and greenschists were not formed under the same metamorphic physico-chemical conditions. The blueschist facies was formed at temperatures of 300-400℃ and pressures of 0.5-0.6 GPa. The greenschist facies in zones A and B has similar temperatures but its pressure is only 0.4 GPa or so. The transition from the blueschist to     

Genetic Mechanism of Dolomitization in Fengcheng Formation in the Wu‐Xia area of Junggar Basin,China

The dolomitic rocks of the Fengcheng Formation are considered to be formed under special geologic conditions, and are significant hydrocarbon reservoir rocks in the Wu-Xia area in the Junggar Basin. Analyses of petrologic characteristics and stable isotope composition indicate that the dolomitizing host rock is volcanic and the dolomitizing fluids probably consists of brine from shore-shallow lakes with great evaporation and salinity in the Fengcheng Formation, which have formed under arid climatic conditions, as well as residual Mg-rich seawater from the underlying Jiamuhe Formation and Carboniferous. Dust tuff in the area has significant plagioclase content. Anorthite and labradorite hydrolysis by CO2 can be coupled with calcite precipitation. Late Mg-rich brine percolated and replaced calcite formed in the early time, which lead to precipitate dolostones with different occurrences, such as graniphyric, random bedded or lumpy. The diagenetic dolostones with different occurrences resulting from particular formation conditions occurred in different tectonic settings. The dolomitizing fluid has been driven by the thermal convection flow generated by volcanic eruptions. At the same time, the overthrusts of the Wu-Xia growth fault?have speeded up the flow of deep Mg-rich water upwards, and induced the water to quickly?penetrate and horizontally migrate in the strata. Fracture is the major and the most important reservoir space in dolomitic reservoir of the Fengcheng Formation. Fracture and fault plays a decisive role in controlling the formation of dolostone and the distribution of favorable reservoirs. The deliverability of oil and gas is determined by the development and match relations of dissolved pores and fractures to a certain degree.     

某含钽铌花岗岩成岩成矿温度的研究

Formation temperatures are obtained for a tantalum-niobium-bearing granite(512-530℃）,the feldspar-quartz zone(495℃）,the quartz zone(483℃）in the pegmatoid and wolframite-quartz vein(262-273℃,no pressure corection has been made through studies of fluid inclusions in quartz,wolframite,Mn-rich columbite microlite and other minerals,The results demonstrate that petrogenesis and metallogenesis of this district are a protracted,multistage process.     

Complexation of Si in hydrothermal systems

The Au-SiO2 and Sn-SiO2 complexes have been experimentally calibrated at varying temperature,silica comcentration and pH: Au^ H2SiO4^-=AuH3SiO4 lgK=-1.65436 9611.21/T; Sn^4 4H3SiO4^-=Sn(H3SiO4)4 lgK200℃=42.73 Compared with Au-Cl,Au-HS and Sn-OH complexes,AuH3SiO4 and Sn(H3SiO4)4complexes can be recognized as the dominant transport forms in Si-bearing solurtions under pH and Eh conditions of general interest.The decrease of SiO2 concentration and oxygen fugacity would reverse the direction of dissolution-complexing reactions,resulting in the precipitation of gold and silica,as well as cassiterite and silica.This study illustrates the significance of SiO2-complexation in hydrothermal solutions for gold,tin and other metallizations.