Carbon and Oxygen Isotopic Characteristics of REE—Fluorocarbonate Minerals and Their Genetic Implications,Bayan Obo Deposit,Inner Mongloia,China

REE－fluorocarbonates as major REE minerals in the Bayan Obo deposit,the largest REE deposit in the world,were analyzed for their stable isotopic compositions,The δ^13 C and δ^18 O values of huanghoite,cebaite and bastnaesite from late-stage veins vary in the ranges of 7.8--4.0‰ and 6.7-9.4‰,respectively,These data are relatively similar to those of bastnaesites from banded ores:δ^13C-5.6--5.2‰ andδ^18O3.6-5.5‰.The REE fluorocarbonates from both late-staege veins and banded ores are characterized by lower δ^13 C and δ^18O values,especially the δ^18O values of bastnaesites from banded ores.Compared with them,the disseminated bastnaesits the dolomite-type ores possess rather highδ^13 C and δ^18O values,i.e.,-2.1-0.4‰ and 8.6-12.9‰ respectively.The high values are typical of the sedimentary host dolomite rocks as well as of the dolomite-type-ores.The carbon and oxygen isotopic characteristics of REE fluorocarbonate minerals provide new evidence for the hypothesis on the origin of Bayan Obo deposit-epigenetic hydrothermal metasomatism.     

Chemical and Isotopic Characters of the Water and Suspended Particulate Materials in the Yellow River and Their Geological and Environmental Implications

The chemical and isotopic characteristics of the water and suspended particulate materials(SPM)in the Yellow River were investigated on the samples collected from 29 hydrological monitoring stations in the mainstem and several major tributaries during 2004 to 2007.TheδD andδ~(18)O values of the Yellow River water vary in large ranges from-32‰to-91‰and from-3.1‰to-12.5‰,respectively.The characters of H and O isotope variations indicate that the major sources of the Yellow River water are meteoric water and snow melting water,and water cycle in the Yellow River basin is affected strongly by evaporation process and human activity.The average SPM content(9.635g/L)of the Yellow River is the highest among the world large rivers.Compared with the Yangtze River,the Yellow River SPM has much lower clay content and significantly higher contents of clastic silicates and carbonates.In comparison to the upper crust rocks,the Yellow River SPM contains less SiO_2,CaO,K_2O and Na_2O,but more TFe_2O_3,Co,Ni,Cu,Zn,Pb and Cd.The abnormal high Cd contents found in some sample may be related to local industrial activity.The REE contents and distribution pattern of the Yellow River SPM are very close to the average value of the global shale.The averageδ~(30)Si_(SPM)in the Yellow River(-0.11‰)is slightly higher than the average value(-0.22‰)of the Yangtze River SPM.The major factors controlling theδ~(30)Si_(SPM)of the Yellow River are the soil supply,the isotopic composition of the soil and the climate conditions.The TDS in the Yellow River are the highest among those of world large rivers.Fair correlations are observed among Cl~-,Na~+,K~+,and Mg~(2+)contents of the Yellow River water,indicating the effect of evaporation.The Ca~(2+)and Sr~(2+)concentrations show good correlation to the SO_4~(2-)concentration rather than HCO_3~-concentration,reflecting its origin from evaporates.The NO_3~-contents are affected by farmland fertilization.The Cu,Zn and Cd contents in dissolved load of the Yellow River water are all higher than those of average world large rivers,reflecting the effect of human activity.The dissolved load in the Yellow River water generally shows a REE distribution pattern parallel to those for the Yangtze River and the Xijiang River.Theδ~(30)Si values of the dissolved silicon vary in a range from 0.4‰to 2.9‰,averaging1.34‰.The major processes controlling the D_(Si)andδ~(30)Si_(Diss)of the Yellow River water are the weathering process of silicate rocks,growth of phytolith in plants,evaporation,dissolution of phytolith in soil,growth of fresh water diatom,adsorption and desorption of aqueous monosilicic acid on iron oxide and human activities.The averageδ~(30)Si_(Diss)value of the Yellow River is significantly lower than that of the Nile River,Yangtze River and Siberia rivers,but higher than those of other rivers,reflecting their differences in chemical weathering and biological activity.Theδ~(34)S_(SO4)values of the Yellow River water range from-3.8‰to 14.1‰,averaging 7.97‰.There is some correlation between SO_4~(2-)content andδ~(34)S_(SO4).The factors controlling theδ~(34)S_(SO4)of the Yellow River water are the SO_4 in the meteoric water,the SO_4 from gypsum or anhydrite in evaporite rocks,oxidation and dissolution of sulfides in the mineral deposits,magmatic rocks and sedimentary rocks,the sulfate reduction and precipitation process and the sulfate from fertilizer.The~(87)Sr/~(86)Sr ratios of all samplesrange from 0.71041 to 0.71237,averaging 0.71128.The variations in the~(87)Sr/~(86)Sr ratio and Sr concentration of river water are primarily caused by mixing of waters of various origins with different~(87)Sr/~(86)Sr ratios and Sr contents resulting from water-rock interaction with different rock types.     

Fe Isotope Geochemistry of Hydrothermal Fe Exhalites

The sediments atop the sequence of ophiolite usually contain Fe(-Mn-Si)exhalites,chemical sediments that aremainlycomposedofamorphousFe-Mn oxy-hydroxides and chert/jasper.They were precipitated from hydrothermal fluids produced by deep leaching of basalt particularly during volcano activity or seafloor spreading.These hydrothermal Fe exhalites provide a good record for the depositional environment and the ocean environment as well.A well-preserved Phanerozoic Fe deposit,Motuosala Fe-Mn deposit,resulted from hydrothermal exhalation,was investigated for its trace element and Fe isotope geochemistry.The deposit is located in Xinjiang province,China and is hosted in a suit of Carboniferous volcano-sedimentary clastic rocks.The Fe deposit is mainly composed of massive hematite Fe oreand banded hematite-jasper ore.The hematite ore/band and jasper band were subjected to be analyzed.They are both composed mainly of Fe2O3 and Si O2,with very low contents of Al2O3 and Ti O2(1%),indicating they werechemical precipitates with little detrital contamination.They both show slightly LREE depleted or near flat PAAS-normalised REE patterns,with positive Eu anomalies and Y anomolies,indicating that they were sourced from a mixture of high-temperature fluids and seawater.Compared to the hematite Fe ore/band,the jasper band shows higher EuSN/EuSN*but lower Y/Ho values.δ56Fe values for the hematite Fe ores are clustered around-0.3‰,similar to those for high-temperature fluids.The jasper samples show heavier Fe isotope compositions varying from-0.1‰to0.5‰,indicating that they were resulted from partial Fe precipitation.For all samples,δ56Fe values are related to Y/Ho and EuSN/EuSN*values.The results indicate that the hematite Fe ore and jasper were deposited in different environments.The jasper was deposited in a more anoxic condition with higher hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was more intense;while the hematite Fe ore was deposited in a more oxic condition with lower hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was weaker.     

Isotope geochemistry of ore fluids for the Dongsheng sandstone-type uranium deposit, China

The Dongsheng sandstone-type uranium deposit is one of the large-sized sandstone-type uranium deposits discovered in the northern part of the Ordos Basin of China in recent years. Geochemical characteristics of the Dongsheng uranium deposit are significantly different from those of the typical interlayered oxidized sandstone-type uranium ore deposits in the region of Middle Asia. Fluid inclusion studies of the uranium deposit showed that the uranium ore-forming temperatures are within the range of 150–160℃. Their 3He/4He ratios are within the range of 0.02–1.00 R/Ra, about 5–40 times those of the crust. Their 40Ar/36Ar ratios vary from 584 to 1243, much higher than the values of atmospheric argon. The δ18OH2O and δD values of fluid inclusions from the uranium deposit are -3.0‰– -8.75‰ and -55.8‰– -71.3‰, respectively, reflecting the characteristics of mixed fluid of meteoric water and magmatic water. The δ18OH2O and δD values of kaolinite layer at the bottom of the uranium ore deposit are 6.1‰ and -77‰, respectively, showing the characteristics of magmatic water. The δ13CV-PDB and δ18OH2O values of calcite veins in uranium ores are -8.0‰ and 5.76‰, respectively, showing the characteristics of mantle source. Geochemical characteristics of fluid inclusions indicated that the ore-formation fluid for the Dongsheng uranium deposit was a mixed fluid of meteoric water and deep-source fluid from the crust. It was proposed that the Jurassic-Cretaceous U-rich metamorphic rocks and granites widespread in the northern uplift area of the Ordos Basin had been weathered and denudated and the ore-forming elements, mainly uranium, were transported by meteoric waters to the Dongsheng region, where uranium ores were formed. Tectonothermal events and magmatic activities in the Ordos Basin during the Mesozoic made fluids in the deep interior and oil/gas at shallow levels upwarp along the fault zone and activated fractures, filling into U-bearing clastic sandstones, thus providing necessary energy for the formation of uranium ores.     

Geochemistry of the Cenozoic Potassic Volcanic Rocks in the West Kunlun Mountains and Constraints on Their Sources

The geochemical characteristics of the Cenozoic volcanic rocks from the north Pulu, east Pulu and Dahongliutan regions in the west Kunlun Mountains are somewhat similar as a whole. However, the volcanic rocks from the Dahongliutan region in the south belt are geochemically distinguished from those in the Pulu region (including the north and east Pulu) of the north belt. The volcanic rocks of the Dahongliutan region are characterized by relatively low TiO2 abundance, but more enrichment in alkali, much more enrichment in light rare earth elements and large ion lithosphile elements than those from the Pulu region. Compared with the Pulu region, volcanic rocks from the Dahongliutan region have relatively low 87Sr/86Sr ratios, and high εNd, 207Pb/204Pb and 208Pb/204Pb. Their trace elements and isotopic data suggest that they were derived from lithospheric mantle, consisting of biotite- and hornblende-bearing garnet lherzolite, which had undertaken metasomatism and enrichment. On the primitive mantle-normali     

Geochemical Characteristics and Origin of Natural Gases in the Qaidam Basin, China

Sixty-five natural gas samples were collected from 19 oil-gasfields in the Qaidam basin, China. The chemical composition and carbon isotope values of the samples were measured, and the geochemical characteristics and origin of the natural gases were studied. The gases can be divided into biogenic gases, sapropelic oil-type gases, mixed type oil-type gases, coal-type gases and mixed gas. The δ13Ci values of the biogenic gases are very small and the C2+ contents of them are very low, ranging from -68.2‰ to -61.8‰ and 0.06% to 0.20% respectively. They have heavy δD and δ13Cco2> showing a CC>2 reduction pathway. They are distributed in the East depression region and derived from the Quaternary source rocks. The sapropelic oil-type gases have small δ13C2 values and high C2+ ranging from -36.6‰ to -28.6‰ and from 33.01% to 47.15% respectively. The mixed type oil-type gases have <5I3C2 values and C2+ contents varying from -28.6‰ to -24.8‰ and from 4.81% to 26.06% respectively. Both sapropelic oil-typ     

Geochemistry and Genesis of the Sodium-Charnockitic Gneisses, Eastern Hebei Province, China

High in sodium and low in potassium (Na_2O/ K_2O>1), the charnockitic gneiss series in theSantunying- Taipingzhai area, eastern Hebei province, consists of hypersthene- quartz- diorite,hypersthene-granodiorite and hypersthene-plagioclase-granite. Geological, petrological and large ion lithophileelement(LILE), high field strength element (HFSE) and REE geochemical studies suggest that themedium-coarse-grained hypersthene-granodiorite is the product of crystallization of anatectic magmas of thesame composition. Under granulite facies conditions, the equilibrium crystallization differentiation of themagmas yielded the early crystallization phase-high-SiO_2, LILE-depleted, low-∑REE, positive Eu anomalyand REE- saturated hypersthene- plagioclase- granite. The residual phase, coarse- grained to pegmatitichypersthene- granodiorite, is marked by low SiO_2, LILE-enrichment, high ∑REE and REE-undersaturation.These rocks and hypersthene-quartz-diorite enclaves constitute the sodium-charnockitic gneiss series in easternHebei province. Model calculation for trace elements in the granitoids was applied. On the basis of a systematicgeological study, the equation for calculation was chosen, the source magma was determined and the partitioncoefficients were obtained. The resulting curves are entirely consistent with those observed in the patterns of ac-tual rocks. The study indicates that whole-rock REE patterns can not be used directly in the comparison of thesources and genesis of granitoids.     

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.     

Microthermometric measurement of fluid inclusions and its constraints on genesis of PGE-polymetallic deposits in Lower Cambrian black rock series, southern China

Systematic microthermometric measurements of fluid inclusions in the PGE-polymetallic deposits hosted in the Lower Cambrian black rock series in southern China were performed, and the results suggest: (1) there exist two types of fluid inclusions. TypeⅠis of NaCl-H2O system with low-medium salinity, and its homogenization temperatures (Th) and salinities are 106.9- 286.4℃ and ( 0.8- 21.8) wt%NaCl eq. respectively; TypeⅡ is of CaCl2-NaCl-H2O system with medium-high salinities, and its homogenization temperatures and salinities range from 120.1℃ to 269.6℃ and ( 11.4- 31.4) wt%NaCl eq., respectively. The typeⅡ fluid inclusions have been discovered for the first time in this kind of deposits; (2) two generations of ore-forming fluids were recognized. Characteristics of fluid inclusions in the PGE-polymetallic ores and carbonate-quartz stockworks in the underlying phosphorites are almost of no difference, they may represent ore-forming fluids at the main metallogenic stage. The peak value of homogenization temperature of those fluid inclusions is about 170℃, while their salinities possess a remarkable bimodal distribution pattern with two peak values of (27-31) wt%NaCl eq. and (4-6) wt%NaCl eq. On the contrary, fluid inclusions in the carbonate-quartz veins in the hanging wall may represent ore-forming fluids at the post-metallogenetic stage. The homogenization temperatures and the peak values of salinities are mostly 130-170℃ and (12-14) wt%NaCl eq., respectively; (3) nobel gas isotopic composition analyses in combination with the microthermometric measurements of fluid inclusions suggest that the ore-forming fluids at the main metallogenetic stage were probably derived from mixing of basinal hot brines with the CaCl2-NaCl-H2O system and seawater with the NaCl-H2O system; (4) in the Early Cambrian, the basinal hot brines were trapped in the Caledonian basins, which were distributed along the southern margin of the Yangtze Craton, and where giant thick sediments were accumulated, and expelled and migrated laterally along the strata because of the pressure caused by overlying sediments. The basinal hot brines absorbed Ni, Mo, V, PGE from the surrounding rocks and were transformed into ore-bearing hydrothermal fluids with the CaCl2-NaCl-H2O system and medium-high salinities, then ascended along faults and mixed with seawater of the NaCl-H2O system, and finally PGE-polymetallic deposits or occurrences were formed in the black rock series.     

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.     

Experimental study of subsolidus phase relations and mixing properties of pyroxene and plagioclase in the system Na2O-CaO-Al2O3-SiO2

In the system Na₂O-CaO-Al₂O₃-SiO₂ (NCAS), the equilibrium compositions of pyroxene coexisting with grossular and corundum were experimentally determined at 40 different P-T conditions (1,100–1,400° C and 20.5–38 kbar). Mixing properties of the Ca-Tschermak — Jadeite pyroxene inferred from the data are (J, K): $$\begin{gathered} G_{Px}^{xs} = X_{{\text{CaTs}}} X_{{\text{Jd}}} [14,810 - 7.15T - 5,070(X_{{\text{CaTs}}} - X_{{\text{Jd}}} ) \hfill \\ {\text{ }} - 3,350(X_{{\text{CaTs}}} - X_{{\text{Jd}}} )^2 ] \hfill \\ \end{gathered} $$ The excess entropy is consistent with a complete disorder of cations in the M2 and the T site. Compositions of coexisting pyroxene and plagioclase were obtained in 11 experiments at 1,190–1,300° C/25 kbar. The data were used to infer an entropy difference between low and high anorthite at 1,200° C, corresponding to the enthalpy difference of 9.6 kJ/mol associated with the C \(\bar 1\) =I \(\bar 1\) transition in anorthite as given by Carpenter and McConnell (1984). The resulting entropy difference of 5.0 J/ mol · K places the transition at 1,647° C. Plagioclase is modeled as ideal solutions, C \(\bar 1\) and I \(\bar 1\) , with a non-first order transition between them approximated by an empirical expression (J, bar, K): $$\Delta G_T = \Delta G_{1,473} \left[ {1 - 3X_{Ab} \tfrac{{T^4 - 1,473^4 }}{{\left( {1,920 - 0.004P} \right)^4 - 1,473^4 }}} \right],$$ where $$\Delta G_{1,473} = 9,600 - 5.0T - 0.02P$$ The derived mixing properties of the pyroxene and plagioclase solutions, combined with the thermodynamic properties of other phases, were used to calculate phase relations in the NCAS system. Equilibria involving pyroxene+plagioclase +grossular+corundum and pyroxene+plagioclase +grossular+kyani te are suitable for thermobarometry. Albite is the most stable plagioclase.     

Energetics of hydration of cordierite and water barometry in cordierite-granulites

The Gibbs free energy and volume changes attendant upon hydration of cordierites in the system magnesian cordierite-water have been extracted from the published high pressure experimental data at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P _total, assuming an ideal one site model for H₂O in cordierite. Incorporating the dependence of ΔG and ΔV on temperature, which was found to be linear within the experimental conditions of 500°–1,000°C and 1–10,000 bars, the relation between the water content of cordierite and P, T and \(f_{{\text{H}}_{\text{2}} {\text{O}}} \) has been formulated as $$\begin{gathered} X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} = \hfill \\ \frac{{f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }}{{\left[ {{\text{exp}}\frac{1}{{RT}}\left\{ {64,775 - 32.26T + G_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{1, }}T} - P\left( {9 \times 10^{ - 4} T - 0.5142} \right)} \right\}} \right] + f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }} \hfill \\ \end{gathered} $$ The equation can be used to compute H₂O in cordierites at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) <1. Our results at different P, T and partial pressure of water, assuming ideal mixing of H₂O and CO₂ in the vapour phase, are in very good agreement with the experimental data of Johannes and Schreyer (1977, 1981). Applying the formulation to determine \(X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} \) in the garnet-cordierite-sillimanite-plagioclase-quartz granulites of Finnish Lapland as a test case, good agreement with the gravimetrically determined water contents of cordierite was obtained. Pressure estimates, from a thermodynamic modelling of the Fe-cordierite — almandine — sillimanite — quartz equilibrium at \(P_{{\text{H}}_{\text{2}} {\text{O}}} = 0\) and \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P_total, for assemblages from South India, Scottish Caledonides, Daly Bay and Hara Lake areas are compatible with those derived from the garnetplagioclase-sillimanite-quartz geobarometer.     

The ferric-ferrous ratio of natural silicate liquids equilibrated in air

Results of chemical analyses of glasses produced in 46 melting experiments in air at 1,350° C and 1,450° C on rocks ranging in composition from nephelinite to rhyolite have been combined with other published data to obtain an empirical equation relating in \((X_{{\text{Fe}}_{\text{2}} {\text{O}}_{\text{3}} }^{{\text{liq}}} /X_{{\text{FeO}}}^{{\text{liq}}} )\) to T, \(\ln f_{{\text{O}}_{\text{2}} } \) and bulk composition. The whole set of experimental data range over 1,200–1,450° C and oxygen fugacities of 10^?9.00 to 10^?0.69 bars, respectively. The standard errors of temperature and \(\log _{10} f_{{\text{O}}_{\text{2}} } \) predictions from this equation are 52° C and 0.5 units, respectively, for 186 experiments.     

(Ca,Mg)2Si2O6 clinopyroxenes: A solution model based on nonconvergent site-disorder

Experiments at high pressure and temperature indicate that excess Ca may be dissolved in diopside. If the (Ca, Mg)₂Si₂O₆ clinopyroxene solution extends to more Ca-rich compositions than CaMgSi₂O₆, macroscopic regular solution models cannot strictly be applied to this system. A nonconvergent site-disorder model, such as that proposed by Thompson (1969, 1970), may be more appropriate. We have modified Thompson's model to include asymmetric excess parameters and have used a linear least-squares technique to fit the available experimental data for Ca-Mg orthopyroxene-clinopyroxene equilibria and Fe-free pigeonite stability to this model. The model expressions for equilibrium conditions \(\mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction A) and \(\mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction B) are given by: 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Mg}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ W_{21} [2(X_{{\text{Ca}}}^{{\text{M2}}} )^3 - (X_{{\text{Ca}}}^{{\text{M2}}} ] \hfill \\ {\text{ + 2W}}_{{\text{22}}} [X_{{\text{Ca}}}^{{\text{M2}}} )^2 - (X_{{\text{Ca}}}^{{\text{M2}}} )^3 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{Wo}}}^{{\text{opx}}} )^2 \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Ca}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ 2W_{21} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^2 - (X_{{\text{Mg}}}^{{\text{M2}}} )^3 ] \hfill \\ {\text{ + W}}_{{\text{22}}} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^3 - (X_{{\text{Mg}}}^{{\text{M2}}} )^2 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{En}}}^{{\text{opx}}} )^2 \hfill \\ \hfill \\ \end{gathered} $$ where 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = 2.953 + 0.0602{\text{P}} - 0.00179{\text{T}} \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = 24.64 + 0.958{\text{P}} - (0.0286){\text{T}} \hfill \\ {\text{W}}_{{\text{21}}} = 47.12 + 0.273{\text{P}} \hfill \\ {\text{W}}_{{\text{22}}} = 66.11 + ( - 0.249){\text{P}} \hfill \\ {\text{W}}^{{\text{opx}}} = 40 \hfill \\ \Delta {\text{G}}_*^0 = 155{\text{ (all values are in kJ/gfw)}}{\text{.}} \hfill \\ \end{gathered} $$ . Site occupancies in clinopyroxene were determined from the internal equilibrium condition 1 $$\begin{gathered} \Delta G_{\text{E}}^{\text{O}} = - {\text{RT 1n}}\left[ {\frac{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}{{X_{{\text{Ca}}}^{{\text{M2}}} \cdot X_{{\text{Mg}}}^{{\text{M1}}} }}} \right] + \tfrac{1}{2}[(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} )(2{\text{X}}_{{\text{Ca}}}^{{\text{M2}}} - 1) \hfill \\ {\text{ + }}\Delta G_*^0 (X_{{\text{Ca}}}^{{\text{M1}}} - X_{{\text{Ca}}}^{{\text{M2}}} ) + \tfrac{3}{2}(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} ) \hfill \\ {\text{ (1}} - 2X_{{\text{Ca}}}^{{\text{M1}}} )(X_{{\text{Ca}}}^{{\text{M1}}} + \tfrac{1}{2})] \hfill \\ \end{gathered} $$ where δG _E ⁰ =153+0.023T+1.2P. The predicted concentrations of Ca on the clinopyroxene Ml site are low enough to be compatible with crystallographic studies. Temperatures calculated from the model for coexisting ortho- and clinopyroxene pairs fit the experimental data to within 10° in most cases; the worst discrepancy is 30°. Phase relations for clinopyroxene, orthopyroxene and pigeonite are successfully described by this model at temperatures up to 1,600° C and pressures from 0.001 to 40 kbar. Predicted enthalpies of solution agree well with the calorimetric measurements of Newton et al. (1979). The nonconvergent site disorder model affords good approximations to both the free energy and enthalpy of clinopyroxenes, and, therefore, the configurational entropy as well. This approach may provide an example for Febearing pyroxenes in which cation site exchange has an even more profound effect on the thermodynamic properties.     

The reversed alumina contents of orthopyroxene in equilibrium with spinel and forsterite in the system MgO-Al2O3-SiO2

Equilibrium alumina contents of orthopyroxene coexisting with spinel and forsterite in the system MgO-Al₂O₃-SiO₂ have been reversed at 15 different P-T conditions, in the range 1,030–1,600° C and 10–28 kbar. The present data and three reversals of Danckwerth and Newton (1978) have been modeled assuming an ideal pyroxene solid solution with components Mg₂Si₂O₆ (En) and MgAl₂SiO₆ (MgTs), to yield the following equilibrium condition (J, bar, K): $$\begin{gathered} RT{\text{ln(}}X_{{\text{MgTs}}} {\text{/}}X_{{\text{En}}} {\text{) + 29,190}} - {\text{13}}{\text{.42 }}T + 0.18{\text{ }}T + 0.18{\text{ }}T^{1.5} \hfill \\ + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP = 0,} \hfill \\ \end{gathered} $$ where $$\begin{gathered} + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP} \hfill \\ = [0.013 + 3.34 \times 10^{ - 5} (T - 298) - 6.6 \times 10^{ - 7} P]P. \hfill \\ \end{gathered} $$ The data of Perkins et al. (1981) for the equilibrium of orthopyroxene with pyrope have been similarly fitted with the result: $$\begin{gathered} - RT{\text{ln(}}X_{{\text{MgTs}}} \cdot X_{{\text{En}}} {\text{) + 5,510}} - 88.91{\text{ }}T + 19{\text{ }}T^{1.2} \hfill \\ + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP = 0,} \hfill \\ \end{gathered} $$ where $$\begin{gathered} + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP} \hfill \\ = [ - 0.832 - 8.78{\text{ }} \times {\text{ 10}}^{ - {\text{5}}} (T - 298) + 16.6{\text{ }} \times {\text{ 10}}^{ - 7} P]{\text{ }}P. \hfill \\ \end{gathered} $$ The new parameters are in excellent agreement with measured thermochemical data and give the following properties of the Mg-Tschermak endmember: $$H_{f,970}^0 = - 4.77{\text{ kJ/mol, }}S_{298}^0 = 129.44{\text{ J/mol}} \cdot {\text{K,}}$$ and $$V_{298,1}^0 = 58.88{\text{ cm}}^{\text{3}} .$$ The assemblage orthopyroxene+spinel+olivine can be used as a geothermometer for spinel lherzolites, subject to a choice of thermodynamic mixing models for multicomponent orthopyroxene and spinel. An ideal two-site mixing model for pyroxene and Sack's (1982) expressions for spinel activities provide, with the present experimental calibration, a geothermometer which yields temperatures of 800° C to 1,350° C for various alpine peridotites and 850° C to 1,130° C for various volcanic inclusions of upper mantle origin.     

Experimentelle Untersuchung der Reaktion Dolomit + Kalifeldspat + H2O ⇌ Phlogopit + Calcit + CO2

The equilibrium curve for the reaction 3 dolomite + 1 K-feldspar + 1 H₂O=1 phlogopite + 3 calcite + 3 CO₂ was determined experimentally at a total gas pressure of 2000 bars using two different methods.

1. In the first case water alone was added to the reactants. The CO₂ component of the gas phase was producted solely by the reaction under favourable P-T conditions. This manner of carrying out the reaction is called the “water method”. With this method sufficient time must be allowed for the gas phase to attain a constant composition (see Fig. 1). Reverse reactions were carried out using reaction products of the forward reaction.
2. In the second case silver oxalate + water were added to the reactants. Breakdown of the silver oxalate leads to formation of a CO₂-H₂O gasphase of definite composition. At constant temperature and gas pressure the \(X_{{\text{CO}}_{\text{2}} } \) determines whether the reaction products will be phlogopite + calcite or dolomite + K-feldspar. In this case it is not necessary to wait for equilibrium to be attained. This method is abbreviated the “oxalate method”. Reactants for reverse reactions are not identical with the products of the forward reaction.

At high temperatures the results of the two different methods agree well (see Tables 1 and 2). Equilibrium was attained in one case at 490° C and \(X_{{\text{CO}}_{\text{2}} } \) of approximately 0.77, and in the other case at 520° C and \(X_{{\text{CO}}_{\text{2}} } \) of 0.90. At lower temperatures there are considerable differences in the results. With the water method an \(X_{{\text{CO}}_{\text{2}} } \) of about 0.25 was reached at 450° C. With the oxalate method dolomite K-feldspar and water still react with each other at even higher \(X_{{\text{CO}}_{\text{2}} } \) values. Phlogopite, calcite and CO₂ are formed together with metastable talc. There are no criteria to indicate which of the methods is the correct one at lower temperatures and in Fig. 2, therefore, both equilibrium curves are plotted.     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

P,T, f_{{\text{CO}}_{\text{2}} } and f_{{\text{H}}_{\text{2}} {\text{O}}} during metamorphism of calcareous sediments in the Waterville-Vassalboro area,south-central Maine

In a regional metamorphic terrain where six isograds have been mapped based on mineral reactions that are observed in metacarbonate rocks, the P-T conditions and fugacities of CO₂ and H₂O during metamorphism were quantified by calculations involving actual mineral compositions and experimental data. Pressure during metamorphism was near 3,500 bars. Metamorphic temperatures ranged from 380° C (biotite-chlorite isograd) to 520° C (diopside isograd). \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{CO}}_{\text{2}} }\) / \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) in general is higher in metacarbonate rocks below the zoisite isograd than in those above the zoisite isograd. Calculated \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) are consistent with carbonate rocks above the zoisite isograd having equilibrated during metamorphism with a bulk supercritical fluid in which \(P_{{\text{CO}}_{\text{2}} }\) + \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) = P _total. Calculations indicate that below the zoisite isograd, however, \(P_{{\text{CO}}_{\text{2}} }\) + \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) was less than P_total, and that this condition is not due to the presence of significant amounts of species other than CO₂ and H₂O in the system C-O-H-S. Calculated \(P_{{\text{CO}}_{\text{2}} }\) /( \(P_{{\text{CO}}_{\text{2}} }\) + \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) ) is low (0.06–0.32) above the zoisite isograd. The differences in conditions above and below the zoisite isograd may indicate that the formation of zoisite records the introduction of a bulk supercritical H₂O-rich fluid into the metacarbonates. The results of the study indicate that \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) are constant on a thin section scale, but that gradients in \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) existed during metamorphism on both outcrop and regional scales.     

Interaction of B(OH)_3^0 and HCO_3^ - in Seawater: Formation of B(OH)_2 CO_3^ -

Boron is known to interact with a wide variety of protonated ligands(HL) creating complexes of the form B(OH)₂L^-.Investigation of the interaction of boric acid and bicarbonate in aqueoussolution can be interpreted in terms of the equilibrium $B(OH)_3^0 + HCO_3^ - \rightleftharpoons B(OH)_2 CO_3^ - + H_2 O$ The formation constant for this reaction at 25 °C and 0.7 molkg^-1 ionic strength is $K_{BC} = \left[ {B(OH)_2 CO_3^ - } \right]\left[ {B(OH)_3^0 } \right]^{ - 1} \left[ {HCO_3^ - } \right]^{ - 1} = 2.6 \pm 1.7$ where brackets represent the total concentration of each indicatedspecies. This formation constant indicates that theB(OH)₂ $CO_3^ - $ concentration inseawater at 25 °C is on the order of 2 μmol kg^-1. Dueto the presence of B(OH)₂ $CO_3^ - $ , theboric acid dissociation constant ( $K\prime _B $ ) in natural seawaterdiffers from $K\prime _B $ determined in the absence of bicarbonate byapproximately 0.5%. Similarly, the dissociation constants of carbonicacid and bicarbonate in natural seawater differ from dissociation constantsdetermined in the absence of boric acid by about 0.1%. Thesedifferences, although small, are systematic and exert observable influenceson equilibrium predictions relating CO₂ fugacity, pH, totalcarbon and alkalinity in seawater.     

A multi-isotope approach for understanding sources of water,carbon and sulfur in natural springs of the Central Appalachian region

Natural springs have been reliable sources of domestic water and have allowed for the development of recreational facilities and resorts in the Central Appalachians. The structural history of this area is complex and it is unknown whether these natural springs receive significant recharge from modern precipitation or whether they discharge old water recharged over geological times scales. The main objective of this study was to use stable isotopes of water ( $\delta^{18} {\text{O}}_{{{\text{H}}_{2} {\text{O}}}}$ and $\delta^{2} {\text{H}}_{{{\text{H}}_{2} {\text{O}}}}$ ), dissolved inorganic carbon ( $\delta^{13} {\text{C}}_{\text{DIC}}$ ) and dissolved sulfate ( $\delta^{34} {\text{S}}_{{{\text{SO}}_{4} }}$ and $\delta^{18} {\text{O}}_{{{\text{SO}}_{4} }}$ ) to delineate sources of water, carbon and sulfur in several natural springs of the region. Our preliminary isotope data indicate that all springs are being recharged by modern precipitation. The oxygen isotope composition indicates that waters in thermal springs did not encounter the high temperatures required for O isotope exchange between the water and silicate/carbonate minerals, and/or the residence time of water in the aquifers was short due to high flow rates. The carbon isotopic composition of dissolved inorganic carbon and sulfur/oxygen isotopic composition of dissolved sulfate provide evidence of low-temperature water–rock interactions and various biogeochemical transformations these waters have undergone along their flow path.