Computer simulation of the transformation of natural living matter into kerogen

Thermodynamic simulation of the system living matter (algae, zooplankton, or green plants) + mineral matter (25% carbonates + 75% clay minerals) + standard seawater at temperatures and pressure corresponding to diagenesis indicates that kerogen can be synthesized, together with hydrocarbons and carbon dioxide, in the reaction mix. The removal of CO₂(g) and N₂(g) from the system is favorable for the reaction Δ₁C₂₉₂H₂₈₈O₁₂ (s; H/C = 0.99, O/C = 0.041) → Δ₂C₁₂₈H₆₈O₇ (s; H/C = 0.53, O/C = 0.055) + xСH₄(aq) + yCO₂(aq) + zH₂O, whose constant and stoichiometric coefficients were calculated based on the simulation results. It is demonstrated that a pressure increase is favorable, while a temperature increase is not, for the procedure of this reaction at P-T parameters of diagenesis: log K =–567 (20°C, 35 bar), 1170 (20°C, 200 bar),–1530 (20°C, 60 bar), and +1030 (20°C, 600 bar).     

Fluid-rock history of granulite facies humite-marbles from Ambasamudram, southern India.

An extensive humite‐bearing marble horizon within a supracrustal sequence at Ambasamudram, southern India, was studied using petrological and stable isotopic techniques to define its metamorphic history and fluid characteristics. At peak metamorphic temperatures of 775±73°C, based on calcite‐graphite carbon isotope thermometry, the mineral assemblages suggest layer‐by‐layer control of fluid compositions. Clinohumite + calcite‐bearing assemblages suggest X_CO2 < 0.4 (at 700°C and 5 kbar), calcite + forsterite + K‐feldspar‐bearing assemblages suggest X_CO2>0.9 (at 790°C); and local wollastonite + scapolite + grossular‐bearing zones formed at X_CO2 of c. 0.3. Retrograde reaction textures such as scapolite + quartz symplectites after feldspar and calcite and replacement of dolomite + diopside or tremolite+dolomite after calcite+forsterite or calcite+clinohumite are indicative of retrogression under high X_CO2 conditions. Calcite preserves late Proterozoic carbon and oxygen isotopic signatures and the marble lacks evidence for extensive retrograde fluid infiltration, while during prograde metamorphism the possible infiltration of aqueous fluids did not produce significant isotopic resetting. Isotopic zonation of calcite and graphite grains was likely produced by localized CO₂ fluid infiltration during retrogression. Contrary to the widespread occurrence of humite‐marbles related to retrograde aqueous fluid infiltration, the Ambasamudram humite‐marbles record a prograde‐to‐peak metamorphic humite formation and retrogression under conditions of low X_H2O.     

The effect of CO ratio on the condensation of planetary material

The condensation temperatures of refractory silicates and oxides in a gas of cosmic composition are strongly dependent on the $\text{C}\text{O}$ ratio. As the ratio increases from 0.4 to 0.9 (solar ~ cosmic ~ 0.6), condensation temperatures of compounds such as A1₂O₃, Ca₂Al₂SiO₇, MgAl₂O₄, Mg₂SiO₄ and MgSiO₃ decrease by 50–100°. As $\text{C}\text{O}$ increases from 0.9 to 1.0, these temperatures drop an additional 300–400°. Other chemical differences result when $\text{C}\text{O}\text{\$}\text{?}\text{0.9}$ include: a new suite of high temperature minerals appears (graphite, CaS, Fe₃C, SiC and TiN); the reaction CO + 3H₂ → CH₄ + H₂O proceeds to the right at higher temperatures; and iron, whose condensation temperature is unaffected, condenses at higher temperatures than any silicate or oxide.     

Gneiss-charnockite relation around Ponmudi,southern Kerala: evidences and implications of prograde charnockite formation in southern India

Isochemical conversion of garnet-biotite bearing paragneiss to charnockite in the Precambrian Khondalite belt of southern Kerala is described from Ponmudi area. Petrographic evidences indicate the formation of hypersthene by the breakdown of biotite in the presence of quartz following the reaction: Biotite + quartz → hypersthene + K-feldspar + vapour. The estimated pressure — temperature conditions of metamorphism are around 5–7 kbars and 750° ± 40°C. Presence of CO₂-rich, mixed CO₂-H₂O and H₂O-rich inclusions were noticed in gneiss as well as in charnockites. Charnockites contain abundant CO₂-rich inclusions.     

Thermal and redox equilibrium conditions of the upper-mantle xenoliths from the Quaternary volcanoes of NW Spitsbergen,Svalbard Archipelago

Upper-mantle xenoliths in Cenozoic basalts of northwestern Spitsbergen are rocks of peridotite (spinel lherzolites) and pyroxenite (amphibole-containing garnet and garnet-free clinopyroxenites, garnet clinopyroxenites, and garnet and garnet-free websterites) series. The upper-mantle section in the depth range 50–100 km is composed of spinel peridotites; at depths of 80–100 km pyroxenites (probably, dikes or sills) appear. The equilibrium conditions of parageneses are as follows: in the peridotites—730–1180 °C, 13–27 kbar, and oxygen fugacity of − 1.5 to + 0.3 log. un.; in the pyroxenites—1100–1310 °C, 22–33 kbar. The pyroxenite minerals have been found to contain exsolved structures, such as orthopyroxene lamellae in clinopyroxene and, vice versa, clinopyroxene lamella in orthopyroxene. The formation temperatures of unexsolved phases in orthopyroxene and clinopyroxene are nearly 100–150 °C higher than the temperatures of the lamellae–matrix equilibrium and the equilibrium of minerals in the rock. The normal distribution of cations in the spinel structure and the equilibrium distribution of Fe^2 + between the M1 and M2 sublattices in the orthopyroxenes point to the high rate of xenolith ascent from the rock crystallization zone to the surface. All studied Spitsbergen rock-forming minerals from mantle xenoliths contain volatiles in their structure: OH⁻, crystal hydrate water H₂O_cryst, and molecules with characteristic CH and CO groups. The first two components are predominant, and the total content of water (OH– + H₂O_cryst) increases in the series olivine → garnet → orthopyroxene → clinopyroxene. The presence of these volatiles in the nominally anhydrous minerals (NAM) crystallized at high temperatures and pressures in the peridotites and pyroxenites testifies to the high strength of the volatile–mineral bond. The possibility of preservation of volatiles is confirmed by the results of comprehensive thermal and mass-spectral analyses of olivines and clinopyroxene, whose structures retain these components up to 1300 °C. The composition of hypothetic C–O–H fluid in equilibrium (in the presence of free carbon) with the underlying mantle rocks varies from aqueous (> 80% H₂O) to aqueous–carbonic (~ 60% H₂O). The fluid becomes essentially aqueous when the oxygen activity in the system decreases. However, there is no strict dependence of the redox conditions on the depth of formation of xenoliths.     

Minor element- and carbonaceous material thermometry of high-grade metapelites from the Sauwald Zone, Southern Bohemian Massif (Upper Austria)

The Sauwald area is located at the southern rim of the Bohemian Massif and contains migmatites and high-grade metapelitic and granitic gneisses. These rocks were metamorphosed during the post-collisional high-T/low-P stage of the Variscan metamorphic event (~330 Ma). Metapelitic samples were taken from two localities near Kössldorf and Pyret in Upper Austria and the investigated samples contain the mineral assemblage garnet + cordierite + spinel + sillimanite + K-feldspar + quartz + biotite + muscovite + magnetite + graphite. An important aspect of this study is the evaluation of previously published P-T estimates for these high-grade metapelites (Knop et al. 1995; Tropper et al. 2006) involving Ti-in-biotite, Na-in-cordierite thermometry and the micro-Raman thermometer based upon the degree of crystallization of carbonaceous material. In the two samples studied three texturally and chemically different biotites are distinguished. Biotite inclusions in garnet have the highest Ti contents of 5–6 wt.% TiO₂. Matrix biotites contain 2–4 wt.% TiO₂ and biotites from late-stage muscovite-biotite symplectites contain <2 wt.% TiO₂. This corresponds to temperatures of 730–760°C (stage 1), 600–700°C (stage 2), and 550–610°C (stage 3). Since the Ti-in-biotite thermometer strongly depends on X _Mg of biotite, which is susceptible to changes during retrogression the calculated temperatures for stage 1 are interpreted as minimum temperatures of the peak metamorphic stage. The Na contents of the studied cordierites vary from 0.1 to 0.2 wt.% Na₂O. Application of the Na-in-cordierite thermometer yields temperatures in the range of 770–900°C; they are strongly dependent on the bulk Na₂O content of the samples. The micro-Raman geothermometer of graphite was applied to carbonaceous material, which occurs as inclusions in garnet and cordierite. It yielded a maximum temperature >650°C, i.e. above the calibration limit of this method. This study shows that the obtained temperature estimates agree well with the P-T estimates based on phase equilibrium thermobarometry (Knop et al. 1995; Tropper et al. 2006), thus illustrating the validity of these thermometers. Nevertheless in order to more precisely constrain the metamorphic evolution of these high-grade rocks, better constrained experimental calibrations of, for instance the Na-in-cordierite thermometer, are clearly needed.     

Mineral solution equilibria—II. An experimental study of mineral solubilities and the thermodynamic properties of aqueous CaCl2 in the system CaO-SiO2-H2O-HCl

Speciation of aqueous calcium chloride and the solubility of wollastonite represented by the reaction wollastonite + 2HCl° → CaCl₂° + quartz + H₂O were experimentally investigated at 1 and 2 kbar in the range 425–600°C using rapid-quench hydrothermal techniques and a modified Ag + AgCl buffer technique (Frantz and Popp, 1979). Variation in the measured concentration in HCl° as a function of total dissolved calcium was used to identify associated aqueous CaCl₂° as the predominant calcium species in the fluid at temperatures above 500°C at 2 kbar. The data were used to calculate the equilibrium constant for the above reaction as a function of temperature and pressure, from which the difference in Gibbs free energy of formation between CaCl₂° and HCl° at 1 and 2 kbar, 450°–600°C was calculated. Solubility constants for minerals in the system MgO-CaO-SiO₂-H₂O-HCl-CO₂ were calculated using the data from this study and from Frantz and Popp (1979). Calculated mineral solubilities were used to calculate the solution compositions and solid alteration products resulting from interactions of a Ca-Mg silicate mineral (diopside) with hydrothermal solutions containing a range of different total chloride concentrations. High total chloride (2.0 m) in the solution results in Si-Mg enrichment in the solids and Ca enrichment in the fluid, whereas low total chloride (0.008 m) results in Mg enrichment in the solids and Ca-Si enrichment in the fluid.     

Das P{\text{ - }}T{\text{ - }}X_{{\text{CO}}_{\text{2}} } Stabilitätsfeld von Lawsonit

At pressures which are expected in the earth's crust, the high temperature border of the lawsonite stability field is marked by reaction lawsonite = zoisite + kyanite/andalusite + pyrophyllite + H₂O. (1a) The equilibrium data of reaction (1a) have been experimentally determined, and the equilibrium curve is characterized by the following P, T-data: 4 kb; 360±20° C; 5 kb; 375 ±20° C; 7kb;410±20° C. In the P, T diagram the equilibrium curve of reaction lawsonite + quartz = zoisite + pyrophyllite + H₂O (6) is very close to the curve of reaction (1a); the distance is smaller than the error stated for curve (1a), i.e. below ±20° C. The stability fields of lawsonite and anorthite + H₂O are not adjacent fields in the P, T diagram. This means that no stable reaction of lawsonite to anorthite + H₂O can exist. Thus, the CaAl-silicate formed by the decomposition of lawsonite is always zoisite. Further, as shown by experimental determination of reaction calcite + pyrophyllite + H₂O = lawsonite + quartz + CO₂, (7) lawsonite can coexist with a gas phase only if the CO₂ content of the gas phase does not exceed 3±2 Mol-%. This means, for metamorphism of lawsonite glaucophane rocks, that the fluid phase that was present during metamorphism has been quite rich in H₂O. Ernst (1971, in press) who applied a different, indirect investigation method when studying the composition of the fluid-attending Franciscan and Sanbagawa metamorphism has come to the result that during metamorphism of lawsonite-glaucophane rocks the fluid phase did not contain more than 1–3 Mol-% of CO₂.     

Petrology and geothermobarometry of granulite facies metapelites from the Hisøy-Torungen area, south Norway: new data on the Sveconorvegian P–T–t path of the Bamble sector

ABSTRACT The high-grade rocks (metapelite, quartzite, metagabbro) of the Hisøy-Torungen area represent the south-westernmost exposures of granulites in the Proterozoic Bamble sector, south Norway. The area is isoclinally folded and a metamorphic P–T–t path through four successive stages (M1-M4) is recognized. Petrological evidence for a prograde metamorphic event (M1) is obtained from relict staurolite + chlorite + albite, staurolite + hercynite + ilmenite, cordierite + sillimanite, fine-grained felsic material + quartz and hercynite + biotite ± sillimanite within metapelitic garnet. The phase relations are consistent with a pressure of 3.6 ± 0.5 kbar and temperatures up to 750–850°C. M1 is connected to the thermal effect of the gabbroic intrusions prior to the main (M2) Sveconorwegian granulite facies metamorphism. The main M2 granulite facies mineral assemblages (quartz+ plagioclase + K-feldspar + garnet + biotite ± sillimanite) are best preserved in the several-metre-wide Al-rich metapelites, which represent conditions of 5.9–9.1 kbar and 790–884°C. These P–T conditions are consistent with a temperature increase of 80–100°C relative to the adjacent amphibolite facies terranes. No accompanying pressure variations are recorded. Up to 1-mm-wide fine-grained felsic veinlets appear in several units and represent remnants of a former melt formed by the reaction: Bt + Sil + Qtz→Grt + lq. This dehydration reaction, together with the absence of large-scale migmatites in the area, suggests a very reduced water activity in the rocks and XH₂O = 0.25 in the C–O–H fluid system was calculated for a metapelitic unit. A low but variable water activity can best explain the presence or absence of fine-grained felsic material representing a former melt in the different granulitic metapelites. The strongly peraluminous composition of the felsic veinlets is due to the reaction: Grt +former melt ± Sil→Crd + Bt ± Qtz + H₂O, which has given poorly crystalline cordierite aggregates intergrown with well-crystalline biotite. The cordierite- and biotite-producing reaction constrains a steep first-stage retrograde (relative to M2) uplift path. Decimetre- to metre-wide, strongly banded metapelites (quartz + plagioclase + biotite + garnet ± sillimanite) inter-layered with quartzites are retrograded to (M3) amphibolite facies assemblages. A P–T estimate of 1.7–5.6 kbar, 516–581°C is obtained from geothermobarometry based on rim-rim analyses of garnet–biotite–plagioclase–sillimanite–quartz assemblages, and can be related to the isoclinal folding of the rocks. M4 greenschist facies conditions are most extensively developed in millimetre-wide chlorite-rich, calcite-bearing veins cutting the foliation.     

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.     

Effect of sulfur concentration on diamond crystallization in the Fe–C–S system at 5.3–5.5 GPa and 1300–1370°C

The paper presents results of experiments aimed at diamond synthesis in the Fe–C–S system at 5.3–5.5 GPa and temperatures of 1300–1370°C and detailed data on the microtextures of the experimental samples and the composition of the accompanying phases (Fe₃C and Fe₇C₃ carbides, graphite, and FeS). It is demonstrated that diamond can be synthesized after temperatures at which carbides are formed are overcome and can crystallize within the temperature range of 1300°C (temperature of the peritectic reaction melt + diamond = Fe₇C₃) to 1370°C (of thermodynamically stable graphite) under the appearance experimental pressure. The possible involvement of natural metal- and sulfur-bearing compounds in the origin of natural diamond is discussed.     

GEOCHEMICAL AND MINEROLOGIC STUDY OF A STONY METEORITE FROM THE VICINITY OF THE VILLAGE OF SEVRYUKOVO

In studying the conditions of formation of stony meteorites, we assume that 1) they are fragments of asteroids fallen to the surface of the earth. During their flight through the atmosphere, the meteorites develop a melted surface layer but their texture and mineralogic composition remain unchanged. 2) According to V. M. Goldschmidt, stone meteorites crystallize in a lesser gravity field than that of the earth, which is the reason for their chondritic texture and high porosity (about 4%). 3) Meteorites were formed in a medium with a deficiency of free oxygen. As a result, part of their iron and nickel was segregated as native metal; in addition, lawrencite and oldhamite, sulfides typical of meteorites, were formed.

We identify three stages of meteorite formation: magmatic, pneumatolytic, and hydrothermal. The interval 1450-850°C. corresponds to the magmatic stage at which a silicate phase and native iron with nickel were formed. As a result of thermal dissociation of water and because of the deficiency of oxygen required for a complete oxidation of metals and carbon, in the gaseous phase, free oxygen and H₂O were absent and the phase consisted probably of H₂, CH₄, CO₂, and CO.

The temperature interval 750-500°C. corresponds to the pneumatolytic phase. Here, H₂S, CH₄, CO₂, and CO were the principal agents of the gaseous phase. CH₄ was formed in a high temperature reaction between hydrogen and elementary carbon. As the temperature dropped to 750°C., electrolytic dissociation of H₂O rendered possible the formation of sulfides, especially of troilite.

Mineralization at the hydrothermal stage with a temperature interval of 400 to 300°C. has been observed only in carbon meteorites with a considerable graphitic carbon content. Here, a small portion of the ferrous iron is oxidized to the ferric, in the presence of CO₂ and at a temperature of 450° to 500°C.; the iron sulfide so formed is represented by pyrrhotite. Simultaneously, colored silicates are chloritized, with a separation of CaCO₃.—Auth. English summ.     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

Calcite–graphite isotope thermometry in amphibolite facies marble, Bancroft, Ontario

This study presents calcite–graphite carbon isotope fractionations for 32 samples from marble in the northern Elzevir terrane of the Central Metasedimentary Belt, Grenville Province, southern Ontario, Canada. These results are compared with temperatures calculated by calcite–dolomite thermometry (15 samples), garnet–biotite thermometry (four samples) and garnet–hornblende thermometry (three samples). Δ_cal‐gr values vary regularly across the area from >6.5‰ in the south to 4.0‰ in the north, which corresponds to temperatures of 525 °C in the south to 650 °C in the north. Previous empirical calibration of the calcite–graphite thermometer agrees very well with calcite–dolomite, garnet–biotite and garnet–hornblende thermometry, whereas, theoretical calibrations compare less well with the independent thermometry. Isograds in marble based on the reactions rutile + calcite + quartz =titanite and tremolite + calcite + quartz = diopside, span temperatures of 525–600 °C and are consistent with calculated temperature–X(CO₂) relations. Results of this study compare favourably with large‐scale regional isotherms, however, local variation is greater than that revealed by large‐scale sampling strategies. It remains unclear whether the temperature–Δ_cal‐gr relationship observed in natural materials below 650 °C represents equilibrium fractionations or not, but the regularity and consistency apparent in this study demonstrate its utility for thermometry in amphibolite facies marble.     

Compositions and Pressure–Temperature Conditions of Metamorphic Fluids Overprinting the Talate VMS Pb–Zn Deposit, Southern Altay, China

The Talate Pb-Zn deposit,located in the east of the NW-SE extending Devonian Kelan volcanic-sedimentary basin of the southern Altaides,occurs in the metamorphic rock series of the upper second lithological section of the lower Devonian lower Kangbutiebao Formation(D_1k_1~2).The Pb-Zn orebodies are stratiform and overprinted by late sulfide—quartz veins.Two distinct mineralization periods were identified:a submarine volcanic sedimentary exhalation period and a metamorphic hydrothermal mineralization period.The metamorphic overprinting period can be further divided into two stages:an early stage characterized by bedding-parallel lentoid quartz veins developed in the chlorite schist and leptite of the ore-bearing horizon,and a late stage represented by pyritechalcopyrite-quartz veins crosscutting chlorite schist and leptite or the massive Pb-Zn ores.Fluid inclusions in the early metamorphic quartz veins are mainly CO_2-H_2O-NaCI and carbonic(CO_2±CH_4±N_2) inclusions with minor aqueous inclusions.The CO_2-H_2O-NaCl inclusions have homogenization temperatures of 294-368℃,T_(m,CO2) of-62.6 to-60.5℃,T_(h,CO2) of 7.7 to 29.6℃(homogenized into liquid),and salinities of 5.5-7.4 wt%NaCl eqv.The carbonic inclusions have T_(m,CO2)of-60.1 to-58.5℃,and T_(h,Co2) of-4.2 to 20.6℃.Fluid inclusions in late sulfide quartz veins are also dominated by CO_2-H_2O-NaCl and CO_2±CH_4 inclusions.The CO_2-H_2O-NaCl inclusions have T_(b,tot) of142 to 360℃,T_(m,CO2)of-66.0 to-56.6℃,T_(h,CO2) of-6.0 to 29.4℃(homogenized into liquid) and salinities of 2.4-16.5 wt%NaCl eqv.The carbonic inclusions have T_(m,Co2)of-61.5 to-57.3℃,and T_(h,CO2) of-27.0to 28.7℃.The aqueous inclusions(L-V) have T_(m,ice) of-9.8 to-1.3℃ and T_(h,tot) of 205 to 412℃.The P-T trapping conditions of CO_2-rich fluid inclusions(100-370 MPa,250-368℃) are comparable with the late- to post-regional metamorphism conditions.The CO_2-rich fluids,possibly derived from regional metamorphism,were involved in the reworking and metal enrichment of the primary ores.Based on these results,the Talate Pb-Zn deposit is classified as a VMS deposit modified by metamorphic fluids.The massive Pb-Zn ores with banded and breccia structures were developed in the early period of submarine volcanic sedimentary exhalation associated with an extensional subduction-related back-arc basin,and the quartz veins bearing polymetallic sulfides were formed in the late period of metamorphic hydrothermal superimposition related to the Permian-Triassic continental collision.     

Graphite and diamond formation via the interaction of iron carbide and Fe,Ni-sulfide under mantle <Emphasis Type="Italic">P–T</Emphasis> parameters

Experimental research in the Fe₃C–(Fe,Ni)S system was carried out. The objective of the investigation was to model the reactions of carbide–sulfide interaction related to graphite (diamond) formation in reduced lithosphere mantle domains. T ≤ 1200°C is the formation temperature of the Ni-cohenite + graphite assemblage coexisting with two immiscible melts such as sulfide (Fe₆₀–Ni₃–S₃₇)_L and metal–sulfide (Fe₇₁–Ni₇–S₂₁–C₁)_L containing dissolved carbon. Т ≥ 1300°C is the generation temperature of a unified melt such as (Fe₈₀–Ni₆–S₁₀–C₄)_L characterized by graphite crystallization and diamond growth. The extraction of carbide carbon during the interaction with the sulfide melt can be considered as one of the potential mechanisms of graphite and diamond formation in the reduced mantle.     

The stability of annite+quartz: reversed experimental data for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite +2 H2O

Reversals for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite+2 H₂O have been experimentally determined in cold-seal pressure vessels at pressures of 2, 3, 4 and 5?kbar, limiting annite +quartz stability towards higher temperatures. The equilibrium passes through the temperature intervals 500–540°?C (2?kbar), 550–570°?C (3?kbar), 570–590°?C (4?kbar) and 590–610°?C (5?kbar). Starting materials for most experiments were mixtures of synthetic annite +fayalite+sanidine+quartz and in some runs annite+quartz alone. Microprobe analyses of the reacted mixtures showed that the annites deviate slightly from their ideal Si/Al ratio (Si per formula unit ranges between 2.85 and 2.92, Al^VI between 0.06 and 0.15). As determined by Mössbauer spectroscopy, the Fe³⁺ content of annite in the assemblage annite+fayalite +sanidine+quartz is around 5–7%. The experimental data were used to extract the thermodynamic standard state enthalpy and entropy of annite as follows: H ⁰ _f,?Ann =?5125.896±8.319 [kJ/mol] and S ⁰ _Ann=432.62±8.89 [J/mol/K] (consistent with the Holland and Powell 1990 data set), and H ⁰ _f,Ann =?5130.971±7.939 [kJ/mol] and S ⁰ _Ann=424.02±8.39 [J/mol/K] (consistent with the TWEEQ data base, Berman 1991). The preceeding values are close to the standard state properties derived from hydrogen sensor data of the redox reaction annite=sanidine+magnetite+H ₂ (Dachs 1994). The experimental half-reversal of Eugster and Wones (1962) on the annite +quartz breakdown reaction could not be reproduced experimentally (formation of annite from sanidine+fayalite+quartz at 540°?C/1.035?kbar/magnetite-iron buffer) and probable reasons for this discrepancy remain unclear. The extracted thermodynamic standard state properties of annite were used to calculate annite and annite+quartz stabilities for pressures between 2 and 5?kbar.     

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.     

K-rich fluid metasomatism at high-pressure metamorphic conditions: Lawsonite decomposition in rodingitized ultramafite of the Maksyutovo Complex, Southern Urals (Russia)

Fine grained rodingite‐like rocks containing epidote, clinozoisite, garnet, chlorite, phengite and titanite occur within antigorite serpentinite boudins from the high‐pressure metamorphic Maksyutovo Complex in the Southern Urals. Pseudomorphs after lawsonite, resorption of garnet by chlorite and phengite and stoichiometry suggest the reaction lawsonite + garnet + K‐bearing fluid → clinozoisite + chlorite + phengite, and define a relic assemblage of lawsonite + garnet + chlorite + titanite ± epidote as well as a later post‐lawsonite assemblage of clinozoisite + phengite + chlorite + titanite. The reaction lawsonite + titanite → clinozoisite + rutile + pyrophyllite + H₂O delimits the maximum stability of former lawsonite + titanite to pressures >13 kbar. P–T conditions of 18–21 kbar/520–540 °C result, if the average chlorite, Mg‐rich garnet rim and average epidote compositions are used as equilibrium compositions of the former lawsonite assemblage. These estimates indicate a similar depth of formation but lower temperatures to those recorded in nearby eclogites. The metamorphic conditions of the lawsonite assemblage are considerably higher than previously suggested and, together with published structural data, support a model in which a normal fault within the Maksyutovo complex acted as the major transport plane of eclogite exhumation. The maximum Si content of phengite and minimum Fe content in clinozoisite constrain the metamorphic conditions of the later pseudomorph assemblage to be >4.5 kbar and <440 °C. Rb–Sr isotopic dating of the pseudomorph assemblage results in a formation age of 339 ± 6 and 338 ± 5 Ma, respectively. These results support the recent exhumation models for this complex.     

Formation of the Fe,Mg-Silicates,Fe<Superscript>0</Superscript>, and Graphite (Diamond) Assemblage as a Result of Cohenite Oxidation under Lithospheric Mantle Conditions

Experimental studies in the Fe₃C–SiO₂–MgO system (P = 6.3 GPa, T = 1100–1500°C, t = 20–40 h) have been carried out. It has been established that carbide-oxide interaction resulted in the formation of Fe-orthopyroxene, graphite, wustite, and cohenite (1100 and 1200°C), as well as a Fe–C–O melt (1300–1500°C). The main processes occurring in the system at 1100 and 1200°C are the oxidation of cohenite, the extraction of carbon from carbide, and the crystallization of metastable graphite, as well as the formation of ferrosilicates. At T ≥ 1300°C, graphite crystallization and diamond growth occur as a result of the redox interaction of a predominantly metallic melt (Fe–C–O) with oxides and silicates. The carbide–oxide interaction studied can be considered as the basis for modeling a number of carbon-producing processes in the lithospheric mantle at fO₂ values near the iron–wustite buffer.