Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

An Experimental Study on Picromerite Equilkibrium in the Five—Component Brine System K—Na—Mg—Cl—SO4—H2O

This paper presents the results of experiments on the physicochemical conditions for the formation of picaromerite in the five-component brine system K-Na-Mg-Cl-SO4-H2O and the process of isothermal evaporation-crystallization of picromerite from brines.The metastable phase fields of picromerite at 15,10 and 5℃and its stable equilibrium phase field at -5℃ have been established.In addition,the phase equilibrium relationships have also been established for other salt minerals.The lower limit of formation temperature of picromerite has been deduced on the basis of experi-mental results.The isothermal evaporation crystallization path of the invariant assemblage(point D) of picromerite,epsomite,sylvite and halite at 25,15,10 and 5℃ has been revealed.Furthermore,some controversial problems are approached concerning the 25℃“solar” diagram and the 25℃ metastable phase diagram of this system.     

Degree of Brine Evaporation and Origin of the Mengyejing Potash Deposit: Evidence from Fluid Inclusions in Halite

The Mengyejing potash deposit is located in the southern port of the Simao Basin, Yunnan Province, and is hosted in mid-Cretaceous strata. The chemical compositions of fluid inclusions in halite crystals, collected from the level-610 adit in the deposit, were analysed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The results show that the brine is of the Na-K-Mg-Ca-Cl type and has K concentrations that are distinctly higher than those of Mg and Ca, unlike normal brines associated with Cretaceous halite. The high K concentrations indicate that the degree of evaporation of the ancient Mengyejing saline lake was very high, reaching the sylvite deposition stage but rarely reaching the carnallite deposition stage. The trajectory of the H and O isotopic compositions of the brines in the halite-hosted fluid inclusions corresponds to intense evaporation, indicating that the net evaporation exceeded the net inflow of brines. These brine compositions in halite-hosted fluid inclusions were likely formed by the dissolution of previously deposited K-bearing minerals by fresh continental and/or seawater, forming a type of modified seawater, with deep hydrothermal fluids potentially supplying additional potassium. The basin likely experienced multiple seawater incursion, dissolution and redeposition events in a high-temperature environment with high evaporation rates.     

Thermochemical Sulfate Reduction in the Tazhong District,Tarim Basin,Northeast China: Evidence from Formation Water and Natural Gas Geochemistry

<正>Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin(CUTB) show that gas invasion at the late stage is accompanied by an increase of the contents of H_2S and CO_2 in natural gas,by the forming of the high total dissolved solids formation water,by an increase of the content of HCO_3~-,relative to Cl~-,by an increase of the 2nd family ions(Ca~(2+),Mg~(2+),Sr~(2+) and Ba~(2+)) and by a decrease of the content of SO_4~(2-),relative to Cl~-.The above phenomena can be explained only by way of thermochemical sulfate reduction(TSR).TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula:ΣCH+CaSO_4+H-_2O→H_2S+CO_2+CaCO_3.(1) Dissolved SO_4~(2-) in the formation water is consumed in the above reaction,when H_2S and CO_2 are generated,resulting in a decrease of SO_4~(2-) in the formation water and an increase of both H_2S and CO_2 in the natural gas.If formation water exists, the generated CO_2 will go on reacting with the carbonate to form bicarbonate,which can be dissolved in the formation water,thus resulting in the enrichment of Ca~(2+) and HCO_3~-.The above reaction can be described by the following equation:CO_2+H_2O+CaCO_3→Ca~(2+)+2HCO_3~-.The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃,which is the minimum for TSR to occur.At the same time,dolomitization,which might be a direct result of TSR,has been found in both the Cambrian and the lower Ordovician.The above evidence indicates that TSR is in an active reaction,providing a novel way to reevaluate the exploration potentials of natural gas in this district.     

山东招平断裂带大磨曲家金矿床流体包裹体初步研究

The Damoqujia gold deposit,discovered recently and located in the north of Zhaoping fault zone,is a large altered rock type deposit.In this paper,we report the preliminary research results of the fluid inclusions and discuss its metallogenic implications. The homogenization temperatures of fluid inclusions fall into four ranges:310～350℃,230～270℃,160～200℃and 110～150℃; corresponding to the four stages of hydrothermal ore-forming processes:coarse grain pyrite-milk white quartz stage(Ⅰ),smoky gray Au-bearing quartz-fine grain pyrite stage(Ⅱ),Au-bearing polymetallic sulfide-quartz stage(Ⅲ),and quartz-carbonate stage(Ⅳ). Ore-forming fluid is with low salinity and low density,ranging from 1.4 Wt_(NaCl)% to 13.6 Wt_(NaCl)% and from 0.48g/cm~3 to 1.03g/cm~3 respectively.The inclusions are dominated by H_2O and CO_2 in gaseous compositions,and Na~ and K~ in positive ions,SO_4~(2-)and Cl~- in negative ions of liquid compositions.Au-S complex is the major form for transportation of gold.The pressure varied from 260MPa to 340MPa during the formation of CO_2-bearing inclusions at the early mineralization;the fluids are rich in SO_4~(2-)and Na~ .The pressure is 26-49×10~5 Pa during the formation of the aqueous salt inclusions in late mineralization,the inclusions are rich in CI~-(F~-), Na~ .δ~(18)O_(qurrtz)is 10.64～12.68%o,and the correspondingδ~(18)O_(H_2)O andδD is-5.44～6.47‰and-95.52～-106.48‰respectively.Based on the studies about compositions and hydrogen and oxygen isotopes of inclusions,it is evidenced that ore-forming fluid is magmatic hydrothermal fluid in early period,but affected by meteoric water in late.     

Fluid Inclusions in Surface‐temperature Halite: Sample Preparation and Application

Paleo-temperature and paleo-environment can be interpreted from measuring homogenization temperatures of fluid inclusions within halite. In order to conduct such measurements, vapor bubbles within low-temperature fluid inclusion often need to be created through cooling process by using cooling stage or freezer. Proper cooling is critical for interpreting measured temperature data. We tested two common cooling methods, using heating/freezing stage and freezer, for studying fluid inclusions in halite precipitated in laboratory at conrtolled temperature of 25℃. While using the heating/freezing stage, halite samples were kept at-18℃ for 40–50 min; whereas for freezer, samples were stored at-18℃ for 1, 10, 20 and 40 days, respectively. By comparing the homogenization temperatures of the two cooling processes, we explored the detailed experimental processes and developed an optimal cooling nucleation procedure for homogenization temperature analyses of fluid inclusions within surface-temperature halite. The results show that the maximum homogenization temperatures from both methods approximate the actual brine temperature of 25℃. However, extended refrigeration time has noticeable influence on the results. The refrigeration time of the experiment can be shortened to meet requirements.     

祁连造山带玉石沟地幔橄榄岩中挥发分的流体化学和稳定同位素组成及古大洋岩石圈演化意义

Fluid inclusions in olivine and orthopyroxene of mantle peridotites from the Yushigou ophiolite can be divided into three types based on decrepitation temperature,shape and distribution.Type-1 fluid inclusions are characterized by oval or negative crystal shapes and small size(<5μm across).They occur in the cores and mantles of the host crystals,and decrepitated at>840℃.Type- 2 fluid inclusions have irregular or tabular shapes with relatively large size(10～100μm in length).They occur in irregular or circular healed micro-fractures in the host crystals,and decrepitated at 612～710℃.Type-3 fluid inclusions have size and shape,similar to type-2 fluid inclusions but occur in micro-fractures restricted to the margins of the host crystals,and decrepitated at much lower temperature from 190℃to 340℃.The three different types of fluid inclusions are interpreted to represent primary,metasomatic (pseudo-secondary)and secondary inclusions,respectively.Stepwise heating reveals three concentration peaks of volatiles at 200～400℃,400～800℃and 800～1200℃released from olivine and orthopyroxene in harzburgite and dunite from the Yushigou ophiolite, which are considered to correspond to the decrepitation of secondary,metasomatic and primary fluid inclusions at similar temperature ranges.CO2 is a major constituent in the volatiles released at three different temperature intervals.Trace amounts of H_2 and N_2 are present in the volatiles released at<800℃and trace amounts of H_2O and SO_2 are mainly present in the volatiles at 400～800℃.TheδD(-95.2‰,-306.3‰)of H_2O and theδ~(13)C(-15.5～-12.5‰)andδ~(18)O values(1.4～1.9‰)of CO_2 released at<800℃are lower than normal mantle values and suggest the mixing origin of crustal fluids( sedimentary organic)with ocean water,implying that Yushigou AOLM had undergone an intensive metasomatism by a fluid composed of CO_2.H_2O and SO_2,and followed by degassing. In contrast,the volatiles released at 800～1200℃are characterized by trace amounts of H_2 and CO in dunite and SO_2 in harzburgite, much lighterδ~(13)C(-29.1‰～-19.5‰),heavierδ~(13)O(8.8‰)of CO_2 and positive relationship between these isotopic ratios and the concentration of CO_2.Such features can be best explained by mixing of significant terrestrial crustal(organic)and minor mantle volatiles.We proposed that the Yishigou peridotites are more likely to have derived from a continental lithosphere instead of an oceanic lithosphere comprising the Yishigou gabbros and pillowed basalts.A supra-subduction tectonic setting is thus inferred for the Yushigou ophiolite.     

Evaporation Stage of Paleo-saline Lake in the Sichuan Basin, China: Insight from Fluid inclusions in Halite

Sichuan Basin is one of the most important marine–salt forming basins in China. The Simian and Triassic have a large number of evaporites. The Triassic strata have found a large amount of polyhalite and potassium-rich brine. However, no soluble potassium salt deposit were found. In this study, the halite in well Changping 3 which is located at the eastern part of the Sichuan basin was studied using the characteristics, hydrogen and oxygen isotopes of the fluid inclusion in halite to reconstruct the paleoenvironment. The salt rocks in well Changping 3 can be divided into two types: grey salt rock and orange salt rock. The result shows that the isotopic composition of the halite fluid inclusion is distinct from the global precipitation line reflecting that the salt formation process is under strong evaporation conditions and the climate is extremely dry. At the same time, compared with the hydrogen and oxygen isotopes of brine in the Sichuan Basin and the hydrous isotope composition of the inclusions in the salt inclusions of other areas in China, it is shown that the evaporation depth of the ancient seawater in the Sichuan Basin was high and reached the precipitation of potassium and magnesium stage.     

Production of Potash and N-Mg Compound Fertilizer via Mineral Shoenite from Kunteyi Salt Lake: Phase Diagrams of Quaternary System(NH_4)_2SO_4-Mg SO_4-K_2SO_4-H_2O in the Isothermal Evaporation and Crystallization Process

Based on the requirement of the new technology for producing potassium sulfate and N-Mg compound fertilizer,boussingaultite,by the reaction of the mineral shoenite from Kunteyi Salt Lake,Qinghai province,and the industrial byproduct ammonium sulfate,the solubilities of the quaternary system (NH_4)_2SO_4-Mg SO_4-K_2SO_4-H_2O at 25.0oC in the isothermal evaporation and crystallization process were measured using the isothermal evaporation method,and the corresponding phase diagrams were plotted.According to the diagram,this system contains six saturation points and six solid phase fields of crystallization,which correspond to (K_(1-m),(NH_4)_m)_2SO_4,(NH_4)_2SO_4·Mg SO_4·6H_2O,K_2SO_4·Mg SO_4·6H_2O,Mg SO_4·6H_2O,(K_(1-n),(NH_4)_n)_2SO_4·Mg SO_4·6H_2O and Mg SO_4·7H_2O,respectively.By analyzing and calculating the isothermal evaporation and dissolution phase diagram of this quaternary system at 25.0oC,K_2SO_4 and (NH_4)_2SO_4·Mg SO_4·6H_2O can be separated via K_2SO_4·Mg SO_4·6H_2O and (NH_4)_2SO_4 as raw materials.Theoretical calculations about the proposed process were carried out and verified by experiment,which indicated that the yield of potassium sulfate was improved and the magnesium resources were fully utilized.     

Deposition of Potash-Magnesium Salts in the Qarhan Playa, Qaidam Basin

The Qarhan potash-magnesium salt deposit, which consists from east to west of four playa districts, namely Huobuxun, Qarhan, Dabuxun and Bieletan, may be divided from bottom to top into three salt beds(S_1, S_2 and S_3), with potash salts mainly occurring in S_3. The paper lays emphasis on the evolutionary history of the deposition of Salt Bed S_3 and the modes of formation of potash salts in the Qarhan playa.The analysis of the data obtained from more than 170 boreholes and the geochemical studies on bromine, magnesium and calcium reveal the existence of four concentration stages and three dilution stages during the ormation of the Upper Salt Bed S_3. In the process of concentration, evaporation of brine and precipitation of salt minerals dominated, which obeyed the regularity indicated by the phase diagram of the quaternary system Mg-Na-K/Cl~-H_2O. In the dilution stages, however, mixing of brines, dissolution of salts(especially the playa) and mechanical clastic deposition played the leading role. The prerequisite for mixing in the Qarhan salt deposit lies in that chloride type brine of the northeastern part coexists with magnesium sulfate type brine of the southwestern part in the same salt lake. The appearance of bassanite has verified the process of mixing. The dissolution refers to the partial dissolution of the salt beds originally deposited. Particularly in the last dilution process, approximately 200 km~2 of the playa north of the Tuanjie Lake had been dissolved before a new-born lake took form.Solid potash salts were formed in three ways:(1) The surficial brine of the Dabuxun lake coexistent with the playa had an intercompensational relationship with the intercrystalline brine in the playa. As a result, K~+ ions were collected into the lake, and layered Carnallite precipitated from lake brine during the seasons of evaporation, which was accelerated by the action of wind.(2) Disseminated potash-magnesium salts were formed by further concentration of intercrystalline brine.(3) Dissolution and reformation of the playa resultedin the formation of a new-born salt lake, in the drying of which brine collected the potash-magnesium salts originally dispersed over the playa into local low-lying areas, forming finally stratoid potash-magnesium salts.     

http://www.sciencedirect.com/science/article/pii/S1674987115000961

The Jiaodong gold deposits are currently the most important gold resources(with Au reserves of4000 t) in China,and the leading gold-producing country globally(with Au production of ~428 t in2013).Jiaodong is also considered as perhaps the only world-class to giant gold accumulation on the planet where relatively young gold ores(ca.130-120 Ma) were deposited in rocks that are 2 Ga older.The Xincheng world-class high-grade gold deposit,with a proven reserve of 200 t gold,is one of the largest deposits in the giant gold province of the Jiaodong Peninsula.It is located in the northwestern part of the jiaobei Uplift,and hosted by ca.132-123 Ma Xincheng quartz monzonites and monzogranites.Ore zones are structurally controlled by the NE-trending and NW-dipping Jiaojia Fault and subsidiary faults,and are mainly restricted to the footwall of the fault.The dominant disseminated- and stockworkstyle ores are associated with strong sericitization,silicification,sulfidation and K-feldspathization,and minor carbonate wallrock alteration halos.The four mineralization stages are pyrite-quartz-sericite(stage 1),quartz-pyrite(stage 2),quartz-polysulfide(stage 3) and quartz-carbonate(stage 4).Gold occurs dominantly as electrum,with lesser amounts of sulfide-hosted native gold and rare native silver and argentite,normally associated with pyrite,chalcopyrite,galena and sphalerite:the latter with proven resources of about 105 t Ag,713 t Cu,and 5100 t S.There are three types of ore-related fluid inclusions:type 1 aqueous-carbonate(H_2O-CO_2),type 2aqueous(liquid H_2O+vapor H_2O),and type 3 CO_2(liquid CO_2 and vapor CO_2) inclusions.Homogenization temperatures range from 221 to 304℃ for type 1 inclusions,with salinities of 2.4-13.3 wt.%NaCl eq.,and bulk densities of 0.858-1.022 g/cm~3.The δ~(34)S_(CDT) values of hydrothermal sulfides are 4.3-10.6‰and δ~(18)O values of hydrothermal quartz have a median value of 13.0‰.δD values of fluid inclusions in hydrothermal quartz have a median value of-75‰.Calculated δ~(18)Owater has a median value of 5.2‰.The timing of gold mineralization at the Xincheng gold deposit is younger than 123±1 Ma,and likely between 120.9 and 119.9 Ma.A minerals system genetic model for the probable epizonal orogenic Xincheng deposit suggests an initial medium temperature,CO_2-rich,and low salinity H_2O-CO_2 deeply sourced metamorphic ore fluid associated with dehydration and decarbonization of subducting Paleo-Pacific lithosphere.The Jiaojia Fault constrained the migration of ore-forming fluids and metals at the brittle-ductile transition.Fluid immiscibility,caused by episodic pressure drops,led to significant high-grade gold deposition in the giant Xincheng gold deposit.     

Origin of Halite in the Lanping–Simao Basin, Southeastern Tibetan Plateau, China: Evidence from Sr and Cl Isotopes

The Lanping?Simao Basin is located on the southeastern Tibetan Plateau, China, and contains massive evaporites. The origin of evaporites in the basin has been hotly debated because of the strong transformation by tectonic movement. Forty halite samples from borehole MK-3 in the Mengyejing area of the basin were collected and analyzed using XRD, Cl-Sr isotopes and chemical compositions to trace the origin of the evaporites in the basin. The Br × 103/Cl ratios of the halite samples are between 0 and 0.55, most of which are synchronized with the law of seawater evaporation and at the stage of halite precipitation from seawater, indicating that the evaporites are mainly of marine origin. The 87Sr/86Sr ratios range from 0.707489 to 0.711279; after correction, the 87Sr/86Sr 145 Ma ratios range from 0.704721 to 0.707611, equivalent with the 87Sr/86Sr ratios of seawater at 145 Ma, indicating a marine origin. The decay of 87Rb in the evaporite during deposition, change of the depositional environment and the unsealed environment at a later period resulted in the present 87Sr/86Sr ratios of some samples being high. The δ37Cl value compositions range from ?0.38‰ to 0.83‰, which is consistent with the δ37Cl value composition of the world marine halite (?0.6‰ to 0.4‰), further confirming that seawater is the main origin. In addition, the high δ37Cl value of some samples at the boundary of the upper and lower evaporite layers might be related to the influence of δ37Cl-rich brine and the incomplete dissolution of the halite.     

Geology, Geochemistry, and Genesis of the Tongcun Reduced Porphyry Mo (Cu) Deposit, NW Zhejiang Province, China

The Tongcun Mo(Cu) deposit in Kaihua city of Zhejiang Province,eastern China,occurs in and adjacent to the Songjiazhuang granodiorite porphyry and is a medium-sized and important porphyry type ore deposit.Two irregular Mo(Cu) orebodies consist of various types of hydrothermal veinlets.Intensive hydrothermal alteration contains skarnization,chloritization,carbonatization,silicification and sericitization.Based on mineral assemblages and crosscutting relationships,the oreforming processes are divided into five stages,i.e.,the early stage of garnet + epidote ± chlorite associated with skarnization and K-feldspar + quartz ± molybdenite veins associated with potassicsilicic alteration,the quartz-sulfides stage of quartz + molybdenite ± chalcopyrite ± pyrite veins,the carbonatization stage of calcite veinlets or stockworks,the sericite + chalcopyrite ± pyrite stage,and the late calcite + quartz stage.Only the quartz-bearing samples in the early stage and in the quartzsulfides stage are suitable for fluid inclusions(FIs) study.Four types of FIs were observed,including1) CO_2-CH_4 single phase FIs,2) CO_2-bearing two- or three-phase FIs,3) Aqueous two-phase FIs,and4) Aqueous single phase FIs.FIs of the early stages are predominantly CO_2- and CH_4-rich FIs of the CO_2-CH4-H_2O-NaCl system,whereas minerals in the quartz-sulfides stage contain CO_2-rich FIs of the CO_2-H_2O-NaCl system and liquid-rich FIs of the H_2O-NaCl system.For the CO_2-CH_4 single phase FIs of the early mineralization stage,the homogenization temperatures of the CO_2 phase range from 15.4 ℃ to 25.3 ℃(to liquid),and the fluid density varies from 0.7 g/cm~3 to 0.8 g/cm~3;for two- or three-phase FIs of the CO_2-CH_4-H_2O-NaCl system,the homogenization temperatures,salinities and densities range from 312℃ to 412℃,7.7 wt%NaCl eqv.to 10.9 wt%NaCl eqv.,and 0.9 g/cm~3 to 1.0 g/cm~3,respectively.For CO_2-H_2O-NaCI two- or threephase FIs of the quartz-sulfides stage,the homogenization temperatures and salinities range from255℃ to 418℃,4.8 wt%NaCl eqv.to 12.4 wt%NaCl eqv.,respectively;for H_2O-NaCl two-phase FIs,the homogenization temperatures range from 230 ℃ to 368 ℃,salinities from 11.7 wt%NaCl eqv.to16.9 wt%NaCl eqv.,and densities from 0.7 g/cm~3 to 1.0 g/cm~3.Microthermometric measurements and Laser Raman spectroscopy analyses indicate that CO_2 and CH_4 contents and reducibility(indicated by the presence of CH_4) of the fluid inclusions trapped in quartz-sulfides stage minerals are lower than those in the early stage.Twelve molybdenite separates yield a Re-Os isochron age of 163 ± 2.4 Ma,which is consistent with the emplacement age of the Tongcun,Songjiazhuang,Dayutang and Huangbaikeng granodiorite porphyries.The S18OSMow values of fluids calculated from quartz of the quartz-sulfides stage range from 5.6‰ to 8.6‰,and the JDSMOw values of fluid inclusions in quartz of this stage range from-71.8‰ to-88.9‰,indicating a primary magmatic fluid source.534SV-cdt values of sulfides range from+1.6‰ to +3.8‰,which indicate that the sulfur in the ores was sourced from magmatic origins.Phase separation is inferred to have occurred from the early stage to the quartz-sulfides stage and resulted in ore mineral precipitation.The characteristics of alteration and mineralization,fluid inclusion,sulfur and hydrogen-oxygen isotope data,and molybdenite Re-Os ages all suggest that the Tongcun Mo(Cu) deposit is likely to be a reduced porphyry Mo(Cu) deposit associated with the granodiorite porphyry in the Tongcun area.     

Reactions between olivine and CO_2-rich seawater at 300℃:Implications for H_2 generation and CO_2 sequestration on the early Earth

To understand the influence of fluid CO_2 on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth,we monitored the reaction between San Carlos olivine and a CO_2-rich NaCl fluid at 300 C and 500 bars.During the experiments,the total carbonic acid concentration(∑XO_2) in the fluid decreased from approximately 65 to 9 mmol/kg.Carbonate minerals,magnesite,and subordinate amount of dolomite were formed via the water-rock interaction.The H_2 concentration in the fluid reached approximately 39 mmol/kg within 2736 h,which is relatively lower than the concentration generated by the reaction between olivine and a CO2-free NaCl solution at the same temperature.As seen in previous hydrothermal experiments using komatiite,ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H_2 generation during the olivine alteration.Considering carbonate mineralogy over the temperature range of natural hydrothermal fields,H_2 generation is likely suppressed at temperatures below approximately 300℃ due to the formation of the Mg-bearing carbonates.Nevertheless,H_2 concentration in fluid at 300℃ could be still high due to the temperature dependency of magnetite stability in ultramafic systems.Moreover,the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth.Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO_2 species into the deep mantle.This process may have reduced the huge initial amount of CO_2 on the surface of the early Earth.Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO_2 carriers from the surface to the deep mantle,even in hot subduction zones.     

Fluid Inclusion and Carbon-Oxygen Isotope Studies of the Hujiayu Cu Deposit, Zhongtiao Mountains, China: Implications for Syn-metamorphic Copper Remobilization

The Hujiayu Cu deposit,representative of the "HuBi-type" Cu deposits in the Zhongtiao Mountains district in the southern edge of the North China Craton,is primarily hosted in graphitebearing schists and carbonate rocks.The ore minerals comprise mainly chalcopyrite,with minor sphalerite,siegenite[(Co,Ni)_3S_4],and clausthalite[Pb(S,Se)].The gangue minerals are mainly quartz and dolomite,with minor albite.Four fluid inclusion types were recognized in the chalcopyrite-pyrite-dolomite-quartz veins,including CO_2-rich inclusions(type Ⅰ),low-salinity,liquid-dominated,biphase aqueous inclusions(type Ⅱ),solid-bearing aqueous inclusions(type Ⅲ),and solid-bearing aqueous-carbonic inclusions(type Ⅳ).Type I inclusion can be further divided into two sub-types,i.e.,monophase CO_2 inclusions(type Ⅰa) and biphase CO_2-rich inclusions(with a visible aqueous phase),and type Ⅲ inclusion is divided into a subtype with a halite daughter mineral(type Ⅲa) and a subtype with multiple solids(type Ⅲb).Various fluid inclusion assemblages(FIAs) were identified through petrographic observations,and were classified into four groups.The group-1 FIA,consisting of monophase CO_2 inclusions(type Ⅰa),homogenized into the liquid phase in a large range of temperatures from-1 to 28℃,suggesting post-entrapment modification.The group-2 FIA consists of type Ⅰb,Ⅲb and Ⅳ inclusions,and is interpreted to reflect fluid immiscibility.The group-3 FIA comprises type Ⅱ and Ⅲa inclusions,and the group-4FIA consists of type Ⅱ inclusions with consistent phase ratios.The group-1 and group-2 FIAs are interpreted to be entrapped during mineralization,whereas group-3 and group-4 FIAs probably represent the post-mineralization fluids.The solid CO_2 melting temperatures range from-60.6 to56.6℃ and from-66.0 to-63.4℃ for type Ⅰa and type Ⅳ inclusions,respectively.The homogenization temperatures for type Ⅱ inclusions range from 132 to 170℃ for group-3 FIAs and115 to 219℃ for group-4 FIAs.The halite melting temperatures range from 530 to 562℃ for typeⅢ b and Ⅳ inclusions,whereas those for type Ⅲa inclusions range from 198 to 398℃.Laser Raman and SEM-EDS results show that the gas species in fluid inclusions are mainly CO_2 with minor CH_4,and the solids are dominated by calcite and halite.The calcite in the hosting marble and dolomite in the hydrothermal veins have δ~(13)C_(V-pdb) values of-0.2 to 1.2‰ and-1.2 to-6.3‰,and δ~(18)O_(v-smow) values of 14.0 to 20.8 ‰ and 13.2 to 14.3‰,respectively.The fluid inclusion and carbon-oxygen isotope data suggest that the ore-forming fluids were probably derived from metamorphic fluids,which had reacted with organic matter in sedimentary rocks or graphite and undergone phase separation at 1.4-1.8 kbar and 230-240℃,after peak metamorphism.It is proposed that the Hujiayu Cu deposit consists of two mineralization stages.The early stage mineralization,characterized by disseminated and veinlet copper sulfides,probably took place in an environment similar to sediment-hosted stratiform copper mineralization.Ore minerals formed in this precursor mineralization stage were remobilized and enriched in the late metamorphic hydrothermal stage,leading to the formation of thick quartz-dolomite-sulfides veins.     

Factors Controlling Precipitation of Barite and Witherite and Genesis of the Ankang–Xunyang Barium Deposits, Shaanxi, China

The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids.     

A Simulated Test of Algal Influence of Formation and Deposition of Phosphates

This paper deals with a simulated test of biogenic mineralization made with a blue-green alga species,Spirulina platensix. The data in the experiment were recorded by a computerized surveying system. The influ-ence of algae on the accumulation of phosphorus by changing their microenvironment to promote the forma-tion and deposition of phosphate was studied. The results show that the pH value of cultural liquor rose up to 10 and the redox potential (Eh) may dropby 100-200 mV during the algal logarithmic growth stage, and the cultrual liquor was changed into a mediumwith a weakly reducing condition. At the end of the logarithmic growth stage white deposits of Na_2Ca(CO_3)_2·5H_2O and Ca_2Mg (PO_4)_2·2H_2O were formed on the floor of cultural containers. The test presented a wduableevidence for the theory of biogenic mineralization.     

Geochemical Characteristics of the Fluid Inclusions Trapped in Primary Gypsum of the Lop Nor Basin

正Objective The Lop Nor Basin is a very important Quaternary potash-formation basin in China.It is a typical sulphatepotash brine mine with an average grade of 1.4%(KG)in underground concentrated brines.It is extraordinary that the reservoir of potassium-rich brines is glauberite stratum rather than halite rock.The anomalous potassium enrichment,advanced in relative early stage of lake     

Mineralogy and Geochemistry of Major,Trace and Rare Earth Elements in Sediments of the Hypersaline Urmia Salt Lake,Iran

Urmia Salt Lake(USL) is a hypersaline lake located at the NW corner of the Iran platform. The lake area is estimated to have been over 5000 km~2 at one point, but has now decreased to 1000 km~2 in the last two decades. It contains 4.6×10~9 tons of halite and other detrital and evaporative minerals such as calcite, aragonite, dolomite, quartz, feldspars, augite and sylvite. This study examined the mineralogy and geochemistry of bed sediments along the mid-east toward NE bank sediments collected from 1.5 meters depth and nearby augite placer. Due to the diverse lithology of the surrounding geology, bed sediments vary from felsic in the mid-east to mafic in the northeast. Weathering of tephrite and adakite rocks of the Islamic Island at the immediate boundary has produced a large volume of augite placer over a 40 km length, parallel to the shoreline. Based on the study result, weathering increases from south to north and the geochemistry of the sediments shows enrichment of Mg O, Ca O, Sr and Ba associated with Sr deployment in all samples. Rare earth elements(REE) patterns normalized to the upper continental crust(UCC) indicated LREEs enrichment compared to HREEs with an elevated anomaly of Eu, possibly due to surface absorbance of Mn and Fe minerals, associated with Sr elevation originating from adakites in the lake basin vicinity.     

A Fluid Inclusion Study of Vein-type Copper Mineralization in the East Wulasigou Pb–Zn–Cu Deposit, Altay, Northwestern China

The Wulasigou Cu-Pb-Zn deposit,located 15 km northwest of Altay city in Xinjiang,is one of many Cu-Pb-Zn polymetallic deposits in the Devonian Kelan volcanic-sedimentary basin in southern Altaids.Two mineralizing periods can be distinguished:the marine volcanic sedimentary PbZn mineralization period,and the metamorphic hydrothermal Cu mineralization period,which is further divided into an early bedded foliated quartz vein stage(Q1) and a late sulfide-quartz vein stage(Q2) crosscutting the foliation.Four types of fluid inclusions were recognized in the Q1 and Q2 quartz from the east orebodies of the Wulasigou deposit:H_2O-CO_2 inclusions,carbonic fluid inclusions,aqueous fluid inclusions,and daughter mineral-bearing fluid inclusions.Microthermometric studies show that solid CO_2 melting temperatures(T_(m,CO2)) of H_2O-CO_2 inclusions in Ql are from-62.3℃ to-58.5C,clathrate melting temperatures(T_(m,clath)l) are from 0.5 C to 7.5 C,partial homogenization temperatures(T_(h,CO2)) vary from 3.3℃ to 25.9℃(to liquid),and the total homogenization temperatures(T_(h,tot)) vary from 285℃ to 378℃,with the salinities being 4.9%-15.1%NaCl eqv.and the CO_2-phase densities being 0.50-0.86 g/cm~3.H_2O-CO_2 inclusions in Q2 have T_(m,CO_2) from-61.9℃ to-56.9℃,T_(m,clath)from 1.3℃ to 9.5℃,T_(h,CO2) from 3.4℃ to 28.7℃(to liquid),and T_(h,tot) from 242℃ to 388℃,with the salinities being 1.0%-15.5%NaCl eqv.and the CO_2-phase densities being 0.48-0.89 g/cm~3.The minimum trapping pressures of fluid inclusions in Q1 and Q2 are estimated to be 260-360 MPa and180-370 MPa,respectively.The δ~(34)S values of pyrite from the volcanic sedimentary period vary from2.3‰ to 2.8‰(CDT),and those from the sulfide-quartz veins fall in a narrow range of-1.9‰ to 2.6‰(CDT).The δD values of fluid inclusions in Q2 range from-121.0‰ to-100.8‰(SMOW),and theδ~(18)O_(H2O) values calculated from δ~(18)O of quartz range from-0.2‰ to 8.3‰(SMOW).The δD-δ~(18)O_(H2O)data are close to the magmatic and metamorphic fields.The fluid inclusion and stable isotope data documented in this study indicate that the vein-type copper mineralization in the Wulasigou Pb-Zn-Cu deposit took place in an orogenic-metamorphic enviroment.