Phase Equilibria in the Ternary Systems KBr–K2B4O7–H2O and KCl–K2B4O7–H2O at 373 K

According to the compositions of the underground gasfield brines in the west of Sichuan Basin,the phase equilibria in the ternary systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K were studied using the isothermal dissolution equilibrium method.The solubilities of salts and the densities of saturated solutions in these ternary systems were determined.Using the experimental data,phase diagrams and density-composition diagrams were constructed.The two phase diagrams were simple co-saturation type,each having an invariant point,two univariant curves and two crystallization regions.The equilibrium solid phases in the ternary system KBr-K2B4O7-H2O are potassium bromide （KBr） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）,and those in the ternary system KCl-K2B4O7-H2O are potassium chloride （KCl） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）.Comparisons of the phase diagrams of the two systems at different temperatures show that there is no change in the crystallization phases,but there are changes in the size of the crystallization regions.As temperature increases,the solubility of K2B4O7·4H2O increases rapidly,so the crystallization field of K2B4O7·4H2O becomes smaller.     

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.     

An Insight on Future Development Approaches of Salt Lake Magnesium Resources: from the Current Situation of China’s Magnesium Industry

正Magnesium-bearing minerals discovered on the earth so far occur mainly as solid or liquid.The former include magnesite(Mg CO3),dolomite(Mg CO3·Ca CO3),carnallite(Mg Cl2·KCl·6H2O),bischofite(Mg Cl2·6H2O)and     

A simulation experimental study on oxidative kinetics of sphalerite under hypergene condition

The sphalerite oxidative kinetics under hypergene condition was simulated and studied by means of a mixed flow reactor over a pH range of 1.0 7.8,and at dissolution temperatures from 20 to 55℃,ferric ion concentrations from 1.0×10-5 to 1.0×10-2 mol/L,O 2 flux of 0.5 L/min,and oxidants of ferric ion and O 2.It is indicated that with ferric ion as oxidant,the oxidation rate of sphalerite increases with increasing ferric ion concentration,temperature and decreasing pH value,and under the studied conditions,the dissolution rates of Zn and Cd are approximately identical,with the values of activation energy being 41.75 and 42.51 kJ·mol-1,respectively,suggesting that the oxidation rate of sphalerite is controlled by chemical reactions on mineral surface.However,with O 2 as oxidant,the oxidation mechanism of sphalerite varies with pH value.Oxidation rate decreases with increasing pH value when pH is lower than 5.95,whereas the increase of pH value results in an increase in oxidation rate when pH value is higher than 7.The oxidation rate of sphalerite can be expressed as:R Zn =10 1.1663 [Fe3+] 0 0.154 ·[H+] 0.2659 ·e-41.75/RT or R Cd =10 1.7292 [Fe3+] 0 0.170 ·[H+] 0.2637 ·e-42.51/RT     

Study on the Physical and Chemical Conditions of Ore Formation of Hetai Ductile Shear Zone—Hosted Gold Deposit and Discovery of Melt Inclusions

The Hetai ductile shear zone-hosted gold deposit occurs in the deep-seated fault mylonite zone of the Sinian-Silurian metamorphic rock series. In this study there have been discovered melt inclusions, fluid-melt inclusions and organic inclusions in ore-bearing quartz veins of the ore deposit and mylonite for the first time. The homogenization temperatures of the various types of inclusions are 160℃, 180 - 350℃, 530℃ and 870℃ for organic inclusions, liquid inclusions, two-phase immiscible liquid inclusions and melt inclusions, respectively. Ore fluid is categorized as the neutral to basic K+ -Ca2+ -Mg2+ -Na+ - SO2- 4-HCO3-Cl- system. The contents of trace gases follow a descending order of H2O＞CO2＞CH4＞(or ＜ ) H2＞CO＞C2H2＞C2I-I6＞O2＞N2.The concentrations of K , Ca2 + ,SO2-4,HCO3-,Cl- H2O and C2H2 in fluid inclusions are related to the contents of gold and the Au/Ag ratios in ores from different levels of the gold deposit. This is significant for deep ore prospecting in the region. Daughter minerals in melt inclusions were analyzed using SEM. Quartz, orthoclase, wollastonite and other silicate minerals were identified. They were formed in different mineral assemblages.This analysis further proves the existence of melt inclusions in ore veins. Sedimentary metamorphic rocks could form silicate melts during metamorphic anatexis and dynamic metamorphism, which possess melt-solution characteristics. Ore formation is related to the multi-stage forming process of silicate melt and fluid.     

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

<正>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℃and 25℃.The crystallization sequence of the primary salts from the brine at 25℃is halite(NaCl)→aphthitalite (3K_2SO_4·Na_2SO_4)→zabuyelite(Li_2CO_3)→trona(Na_2CO_3·NaHCO_3·2H_2O)→thermonatrite (Na_2CO_3·H_2O)→sylvite(KCl),while the sequence is halite(NaCl)→sylvite(KCl)→trona (Na_2CO_3·NaHCO_3·2H_2O)→zabuyelite(Li_2CO_3)→thermonatrite(Na_2CO_3·H_2O)→aphthitalite (3K_2SO_4·Na_2SO_4) at 15℃.They are in accordance with the metastable phase diagram of the Na~+,K~+-Cl~-, CO_3~(2-),SO_4~(2-)-H_2O quinary system at 25℃,except for Na_2CO_3·7H_2O which is replaced by trona and thermonatrite.In the 25℃experiment,zabuyelite(Li_2CO_3) was precipitated in the early stage because Li_2CO_3 is supersaturated in the brine at 25℃,in contrast with that at 15℃,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.     

Ore Genesis of the Kalatongke Cu–Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu–Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt (CAOB). The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200–400°C, 400–900°C and 900–1200°C. The released volatiles from silicate mineral separates at 400–900°C and 900–1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O (av. ~92 mol%) with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values (from ?20.86‰ to ?12.85‰) of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantle-derived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200–400°C are dominated by H2O with minor CO2, N2+CO and SO2, with δ13CCO2 values (?25.66‰ to ?22.98‰) within the crustal ranges, and are considered to be related to secondary tectonic– hydrothermal activities.     

The Activity of H2O,Fugacity of O2 and Variation of Their Chemical Potential During Metamorphic Peak of the Granulite Complex Near Taipingzhai—Louzishan Region,East Hebei Province

The thermodynamic calculation of dehydration reacton suggests very low activity of H2O during metamorphic peak of the Archaean granulite complex in the region studied.The αH2O values for Al-rich gneiss and hypersthene biotite gneiss-granulite in the Taipingzhai region are usually between 0.10 and 0.20,and those in the Louzishan region are 0.15-0.25.The fugacity of O2 in terms of lgf O2 in whole region ranges form-8to-14.The average coefficients of (δμH2O/δHMg^Bt)and(δμO2/δXMg^Bt)in the Taipingzhai region are-0.293 and-1.60 respectively,and those in the Louzishan region are-0.364and-1.420.The activity of H2O is very low in the whole region,but its values and other data mentioned above are considerably constant from place to place within a given region,even in rocks of dirrerent lithological characters.However,they show a certain gradient between different regions.Such characteristics are compatible with the genetic mechanism known as“carbonic metamorphism” put forward by Newton et al.,i.e.,the α H2O during the peak stage is controlled by permeation of pervasive CO2 influx of the mantle source,and shows features of external buffering.     

Water／Rock Interactions and Changes in Chemical Composition During Zeolite Mineralization

Systematic analysis and comparative study of the chemical compositons of rocks and ores from the main types of zeolite deposits in the surroundings of the Songliao Basic have shown that the process of formation of zeolite from volcanic and pyroclastic rocks is generally characterized by the relative purification of SiO2,i.e.,SiO2/Al2O3 ratios tend to increase,alkali eart elements (CaO MgO)and H2O are relatively enriched,and the alkali metals(K2O Na2O)are depleted in their total amount.The alkali metals K and Na follow different rules of migration and enrichment during the formation of mordenite and clinoptilolite.In the process of formation of mordenite more Na^ will be imported and K^ will be lost remarkably.On the contrary,in the process of formation clinoptilolite more K^ will be incorporated and Na^ will become obviously depleted.     

Melt–Fluid and Fluid–Fluid Immiscibility in a Na2SO4–SiO2–H2O System and Implications for the Formation of Rare Earth Deposits

Liquid–liquid immiscibility has crucial influences on geological processes, such as magma degassing and formation of ore deposits. Sulfate, as an important component, associates with many kinds of deposits. Two types of immiscibility, including (i) fluid–melt immiscibility between an aqueous solution and a sulfate melt, and (ii) fluid–fluid immiscibility between two aqueous fluids with different sulfate concentrations, have been identified for sulfate–water systems. In this study, we investigated the immiscibility behaviors of a sulfate- and quartz-saturated Na2SO4–SiO2–H2O system at elevated temperature, to explore the phase relationships involving both types of immiscibility. The fluid–melt immiscibility appeared first when the Na2SO4–SiO2–H2O sample was heated to ~270°C, and then fluid–fluid immiscibility emerged while the sample was further heated to ~450°C. At this stage, the coexistence of one water-saturated sulfate melt and two aqueous fluids with distinct sulfate concentrations was observed. The three immiscible phases remain stable over a wide pressure–temperature range, and the appearance temperature of the fluid–fluid immiscibility increases with the increased pressure. Considering that sulfate components occur extensively in carbonatite-related deposits, the fluid–fluid immiscibility can result in significant sulfate fractionation and provides implications for understanding the formation of carbonatite-related rare earth deposits.     

Degradation of petroleum contaminants in oil

The treatment of diesel-contaminated soil with hydrogen peroxide oxidation is investigated in this paper. The factors influencing reactions such as initial oil content, H2O2 dosage, pH-value, catalyst and so on are studied. The results indicate that it is feasible to remediate diesel-contaminated soil by adding oxidant directly at room temperature because of higher absolute removal content although the degradation efficiency is low for the contaminated soil of 1%, 2% and 5% initial oil content. The more the H2O2 dosage, the better the degradation efficiency; it is economical and efficient to add 4 mL H2O2 to 10 g diesel-contaminated soil （2% or so） directly in-situ chemical oxidation （ICO）. For the contaminated soil of 5% initial oil content, when pH-value is 5-8 and H202 dosage is 20 mL, the removal efficiency reaches more than 96%; when pH-value is 1-3 and volume ratios of H2O2 to Fe^2＋ are 1 ： 1, 2：2, the degradation efficiencies are all very high （i.e., 86%-88% or so）. It can be concluded that the degradation efficiencies are comparative when adding 1 mL or 2 mL H2O2 of Fenton Reagent or adding 4 mL of H2O2 only to 10 g diesel-contaminated soil.     

Volatile Constituents in Magmatic Inclusions

Laser Raman microprobe has been applied to the analysis of volatile components in shrinkage gas bubbles of individual magmatic inclusions in quartz crystal fragments and phenocrystals from the Mesozoic volcanic complexes of Tonglu and Shouchang,Zhejiang Province.Quantitative analyses are given for CO2,CH4,H2O,CO,H2 N2,H2S, and SO2.In conjunction with the microthermometry and microbarometry data and the chemical composition of magmatic inclusions,the results permit one to calculate the physico-chemical parameters Ptotal,?O2,?CO2,?CH4,?H2O,?CO,and ?H2 at the time individual magmatic inclusions were trapped.Based on the data obtained,some physico-chemical conditions for the Mesozoic volcanic magma evolution in the Tonglu and Shouchang areas are discussed.This work shows that this type of studies has become an indispensable new and rising domain in modern magmatic petrology,especially modern volcanic petrology.It can help us to reconstruct the physico-chemistry of the crystallization-evolution of a natural magma.     

First Occurrence of M andarinoite in China

This report describes the first occurrence of the rare mineral mandarinoite (Fe3+2 Se3Og · 6H2O) in China. It occurs in the Lower Permian Maokou Formation carbonaceous shale in Yutangba Village east of Enshi City in southwestern Hubei Province. The shale is selenium-rich and contains native selenium, V-Mo-Cr-bearing iron oxide, clay and quartz. Weathering of the selenium in the bedrock under moderate to high redox conditions in the presence of ferric iron has formed mandarinoite.     

The Dissolution Experiment of Polyhalite at Different Temperature and Pressure

正Polyhalite(K2SO4·Mg SO4·2Ca SO4·2H2O)is one of the insoluble potassium mineral which is widely distributed in sulfate-type potassium-bearing deposit,and the theoretical concentration of K2SO4 is 28%.It can be directly used as a     

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.     

无机气相色谱仪在气液包裹体成分研究中的应用

CXL-101 inorganic gas chromatography is eharacterised by its high sensitivity,high speed, small quantity of sample required, less adsorption and reliability of result. It is especially suitable for the determination of H2O and CO2 in fluid inclusions. H2O and CO2 contents in fluid inclusions of 41 samples were measured by this instrument from a number of types of tungsten and quarts deposits, Regular variation has heen found in the content of H2O, i.e., it decreases with decreasing distance toward the parent rock, or with increasing temperature, and vice versa. This regularity may be ascribed to the origin of fluid, distance between parent rock and ore deposit, temperature of form.ation, changes in the way of fluid movement as well Hs the nature of country rocks.     

Preparation of Mn3O4 from low-grade rhodochrosite ore by chemical bath deposition method

Mn3O4was prepared with the chemical bath deposition(CBD) method. A Mn SO4 solution was obtained by the leaching and purifying of low-grade rhodochrosite ore(LGRO), which was used as raw material. The prepa ration procedures were studied and promoted. The result showed that the Mn3O4 with the highest purity and highes specific surface area could be obtained under the following processes. An Mn SO4 solution of 1.0 mol/L was added into a beaker under a flow rate of 30 m L/h. The p H of the reaction solution was adjusted to 10 using NH3 H2 O a80 °C. Then the solids were washed and dried at 200 °C fo2.5 h. The total Mn content(TMC) of Mn3O4 was 72.0 %The ionic distributions was formulated as [Mn2?[Mn2??0.3024Mn30.2937Mn4?h0.37860.0254]2O4. The average crys tallite size of Mn3O4 with a tetragonal hausmannite struc ture was found to be about 35 nm by X-ray diffraction(XRD) analysis. The BET specific surface area of the Mn3O4 measured was 32 m2/g.     

On the Relationship between Mantle Metasomatism and Partial Melting-Evidence from Mantlederived Lherzolite Xenoliths from Nueshan,China

Studies of the mantle-derived iherzolites from Nushan show that in addition to CO2,there were present H2O and small amounts of CO, CH4, SO2,Cl and F in the initial mantlc fluids derived fron the asthenospheric mantlc plumc .The imitial fluids accumulated in some regions of the mantle, resulting in lowering of the mantle solidus (and liquidus) and partial melting of the upper mantle. Melts formed from low-degree of fluid-involved partial melting of the upper mantle would be highly enriched in incompatible elements.Fluies and melts are allthe metasomatic agents for mantle metasomatism, and the interaction between them and the depleted mantle could result in the substan-tial local enrichment of LREE and incompatible elements in the latter.In case that the concentration of H2O in the fluids (and melts) is lower ,only cryptic metasomatism would occur, in case that the concentration of H2O is higher,the degree of partial melting would be higher and hydrous metasomatic phases(e.g. amphiboles )would nucleate. Under such circumstances, there would occur model metasomatism.     

Radioactive Genesis of Hydrogen Gas under Geological Conditions: an Experimental Study

The coexistence of hydrogen-containing materials and radioactive substances in source rocks is universal. Few documents have researched whether the latter can radiate the former to generate hydrogen gas (H2) as well as the factors controlling this process. This work conducted a series of radiation experiments to address this issue. Samples were placed in sealed Pyrex glass containers and subject to cobalt (60Co) γ irradiation and components and contents of resultant gases were analyzed using gas-chromatography. The results show that all the samples released variable amounts of H2 after irradiation and that the yield (H2) of decane is lower than that of 3-tetradecylthiophene but higher than that of distilled water, which implies that a weaker H-X bond energy (X indicates O, C or other element) in homogeneous materials corresponds with increased yield (H2). The yields (H2) of samples decreased with the decreasing solutions concentrations in sequence from mixed salts solution, KCl solution, Yellow Sea water, oil field water, gypsum solution to distilled water. The experimental results also show that the yield (H2) of distilled water with montmorillonite is higher than that of distilled water with kaolinite, because due to the larger specific surface area, ion exchange capacity and more effective energy transfer effect of montmorillonite. Meanwhile, the irradiation of oxygen- and carbon-containing materials also releases O2 and CH4. The production of H2 via the irradiation of hydrogen-containing materials makes the involvement of exogenous H2 into hydrocarbon generation possible, which can enhance the hydrocarbon volume and optimize crude oil.     

Sedimentary Environments of Cambrian–Ordovician Source Rocks and Ultra-deep Petroleum Accumulation in the Tarim Basin

The Tarim Basin is the only petroliferous basin enriched with marine oil and gas in China. It is presently also the deepest basin for petroleum exploration and development in the world. There are two main sets of marine Source Rocks (SRs) in the Tarim Basin, namely the high over-mature Cambrian–Lower Ordovician (∈–O1) and the moderately mature Middle–Upper Ordovician (O2–3). The characteristic biomarkers of SRs and oils indicate that the main origin of the marine petroleum is a mixed source of ∈–O1 and O2–3 SRs. With increasing burial, the hydrocarbon contribution of the ∈–O1 SRs gradually increases. Accompanied by the superposition of multi-stage hydrocarbon-generation of the SRs and various secondary alteration processes, the emergence and abnormal enrichment of terpenoids, thiophene and trimethylaryl isoprenoid in deep reservoirs indicate a complex genesis of various deep oils and gases. Through the analysis of the biofacies and sedimentary environments of the ∈–O1 and O2–3 SRs, it is shown that the lower Paleozoic high-quality SRs in the Tarim Basin were mainly deposited in a passive continental margin and the gentle slope of the platform, deep-water shelf and slope facies, which has exhibited a good response to the local tectonic-sedimentary environment. The slope of the paleo-uplift is the mutual area for the development of carbonate reservoirs and the deposition of marine SRs, which would be favorable for the accumulation of petroleum. Due to the characteristics of low ground temperature, the latest rapid and deep burial does not cause massive oil-cracking in the paleo-uplift and slope area. Therefore, it is speculated that the marine reservoirs in the slope of the Tabei Uplift are likely to be a favorable area for deep petroleum exploration, while the oil-cracking gas would be a potential reserve around the west margin of the Manjiaer Depression. Hydrocarbons were generated from various unit SRs, mainly migrating along the lateral unconformities or reservoirs and the vertical faults. They eventually brought up three major types of exploration fields: middle and lower Cambrian salt-related assemblages, dolomite inner reservoirs and Middle and Lower Ordovician oil-bearing karst, which would become the most favorable target of marine ultra-deep exploration in the Tarim Basin.