Volcanogenic-related origin of sulfide-rich quartz veins: evidence from O and S isotopes at the Géant Dormant gold mine, Abitibi belt, Canada

The Géant Dormant gold mine is a sulfide-rich quartz vein gold deposit hosted by a volcano-sedimentary sequence and an associated felsic endogenous dome and dikes. The auriferous quartz-sulfide veins were preceded by two synvolcanic gold-bearing mineralizing events: early sulfidic seafloor-related and later disseminated pyrite in the felsic dome. This deposit differs from classical Archean auriferous quartz vein deposits by the low carbonate and high sulfide contents of the veins and by their formation prior to ductile penetrative deformation. The δ¹⁸O values of quartz associated with seafloor-related auriferous sulfides average 11.9 ± 0.6‰ (n = 3). The seafloor hydrothermal fluids had a δ¹⁸O value of 3.2‰ calculated at 250 °C. The oxygen isotope composition of quartz and chlorite from veins average 12.5 ± 0.3‰ (n = 20) and 5.9 ± 1.1‰ (n = 4) respectively. Assuming oxygen isotope equilibrium between quartz and chlorite, the veins formed at a temperature of ∼275 °C, which is consistent with the calculated temperature of 269 ± 10 °C from chlorite chemistry. The gold-bearing fluids had a δ¹⁸O value of 4.7‰ calculated at 275 °C. The δ³⁴S values of sulfides from the three gold events range from 0.6 to 2.8‰ (n = 32) and are close to magmatic values. Sulfur isotope geothermometry constrains the sulfide precipitation in the gold-bearing veins at a temperature of ∼350 °C. The similarity of the isotope data, the calculated δ¹⁸O of the mineralizing fluids and the likely seawater fluid source suggest that the three mineralizing events are genetically related to a volcanogenic hydrothermal system. The high value of the auriferous fluids (δ¹⁸O = 4.7‰) is attributed to a significant magmatic fluid contribution to the evolved seawater-dominated convective hydrothermal system. The two-stage filling of veins at increasing temperature from quartz-chlorite (275 °C) to sulfides (350 °C) may reflect the progressive maturation of volcanogenic hydrothermal systems. These results, together with field and geochemical data, suggest that formation of gold-rich volcanogenic systems require specific conditions that comprise a magmatic fluid contribution and gold from arc-related felsic rocks, coeval with the mineralizing events. This study shows that some auriferous quartz-vein orebodies in Archean terranes are formed in volcanogenic rather than mesothermal systems. Received: 12 December 1998 / Accepted: 5 July 1999     

Transport and Concentration of Gold in Metamorphic—hosted Reworked Gold Deposits,China

Calculations based on the available thermodynamic data of AuCl ₂ ⁻ and Au (HS) ₂ ⁻ indicate that AuCl ₂ ⁻ is responsible for the transport and enrichment of gold during the stage of pre-concentration in the source bed while Au (HS) ₂ ⁻ is the main gold species involved in the formation of gold deposits in response to hydrothermal reworking. Acid chloride solutions witha _Cl ⁻ > 10° and sulfur-rich solutions with a_Σs in excess of 10⁻² are held as important criteria for gold enrichment in the source bed and for the formation of gold deposits by subsequent hydrothermal event, respectively.     

Physicochemical Conditions of Differential Mineralization of Au and As in Gold Deposits,Southwest Guizhou Province,China

The conditions under which gold and arsenic are enriched separately during mineralization in gold deposits in southwestern Guizhou Province were described and the thermodynamic calculations gave: 200–150°C at 400 × 10⁻⁶ -300 × 10⁶ Pa (corresponding to a depth between 1.6 km and 1.2 km); lgf o₂,−40 to -35 Pa; lgf s₂, -20 to−16 Pa; pH 5.0 -4.2 and Eh -0.53 V. This project was jointly supported by the National Natural Science Foundation of China and the Open Lab. of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences.     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln = Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1100 K) and SmCaAl[Al₂O₇] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶×K⁻¹+3.6(7)×10⁻⁹ΔT×K⁻² and α₃=15.0(1)×10⁻⁶×K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶×K⁻¹+2.0(2)×10⁻⁹ΔT×K⁻² and α₃=8.5(2)×10⁻⁶×K⁻¹+2.0(3)×10⁻⁹ΔT×K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)×10⁻⁶×K⁻¹+1.7(2)×10⁻⁹ΔT×K⁻² and α₃=9.344(5)×10⁻⁶×K⁻¹. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)–(Ln ³⁺+Al³⁺) in the melilite-type structure. This article has been mistakenly published twice. The first and original version of it is available at .     

Sulfur isotopic systematics of granitoids from southwestern New Brunswick, Canada: implications for magmatic-hydrothermal processes, redox conditions, and gold mineralization

Bulk δ ³⁴S_rock values, sulfur contents, and magnetic susceptibility were determined for 12 gold-related granitoid intrusions in southwestern New Brunswick, the Canadian Appalachians. The sulfur isotope compositions of sulfide minerals in some of the granitoid samples were also analyzed. This new dataset was used to characterize two distinctive groups of granitoids: (1) a Late Devonian granitic series (GS) and (2) a Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS). The GS rocks have a large range in δ ³⁴S values of −7.1‰ to +13‰ with an average of 2.2 ± 5.0‰ (1σ), low bulk-S contents (33 to 7,710 ppm) and low magnetic susceptibility values (<10⁻⁴ SI), consistent with reduced ilmenite-series granites. The GMS rocks have a relatively narrower variation in δ ³⁴S values of −4.4‰ to +7.3‰ with an average 1.2 ± 2.9‰ but with larger ranges in bulk-S contents (45 to 11,100 ppm) and high magnetic susceptibility values (>10⁻³ SI), indicative of oxidized magnetite-series granites. The exceptions for the GMS rocks are the Lake George granodiorite and Tower Hill granite that display reduced characteristics, which may have resulted from interaction of the magmas forming these intrusions with graphite- or organic carbon-bearing sedimentary rocks. The bulk δ ³⁴S values and S contents of the GMS rocks are interpreted in terms of selective assimilation–fractional crystallization (SAFC) processes. Degassing processes may account for the δ ³⁴S values and S contents of some GS rocks. The characteristics of our sulfur isotope and abundance data suggest that mineralizing components S and Au in intrusion-related gold systems are dominantly derived from magmatic sources, although minor contaminants derived from country rocks are evident. In addition, the molar sulfate to sulfide ratio in a granitic rock sample can be calculated from the δ ³⁴S_rock value of the whole-rock sample and the δ ³⁴S_sulfide (or δ ³⁴S_sulfate) value of sulfide and/or sulfate mineral in the sample on the basis of S-isotope fractionation and mass balance under the condition of magmatic equilibrium. This may be used to predict the speciation of sulfur in granitic rocks, which can be a potential exploration tool for intrusion-related gold systems.     

Geochemical characteristics of pyrite in Duolanasayi gold deposit, Xinjiang

The Duolanasayi gold deposit, 60 km NW of Habahe County, Xinjiang Uygur Autonomous Region, is a mid-large-scale gold deposit controlled by brittle-ductile shearing, and superimposed by albitite veins and late-stage magma hydrothermal solutions. There are four types of pyrite, which are contained in the light metamorphosed rocks (limestone, siltstone), altered-mineralized rocks (chlorite-schist, altered albite-granite, mineralized phyllite), quartz veins and carbonatite veinlets. The pyrite is the most common ore mineral. The Au-barren pyrite is present mainly in a simple form and gold-bearing pyrite is present mainly in a composite form. From the top downwards, the pyrite varies in crystal form from {100} and {210} {100} to {210} {100} {111} to {100} {111}. Geochemical studies indicate that the molecular contents of pyrite range from Fe1.057S2 to Fe0.941S2. Gold positively correlates with Mn, Sr, Zn, Te, Pb, Ba and Ag. There are four groups of trace elements: Fe-Cu-Sr-Ag, Au-Te-Co, As-Pb-Zn and Mn-V-Ti-Ba-Ni-Cr in pyrite. The REE characteristics show that the total amount of REE (ΣREE) ranges from 32.35×10 -6 to 132.18×10 -6; LREE/HREE, 4.466-9.142; (La/Yb)N, 3.719-11.133; (Eu/Sm)N, 0.553-1.656; (Sm/Nd)N, 0.602-0.717; La/Yb, 6.26-18.75; δEu, 0.628-2.309; δCe, 0.308-0.816. Sulfur isotopic compositions (δ 34S=-2.46‰--7.02‰) suggest that the sulfur associated with gold mineralization was derived from the upper mantle or lower crust.     

Fluid Inclusion Studies of Gold Deposits in the Gezhen Shear Zone,Hainan Province,China

The Tuwaishan, Baoban, Erjia, Bumo and other gold deposits in western Hainan occur in Precambrian metamorphic clastic rocks and are structurally controlled by the Gezhen shear zone. Fluid inclusion studies have been carried out of the gold deposits mentioned above. The homogenization temperatures of the whole fluid inclusion population range from 140°C to 370°C, indicating that gold was precipitated mainly at 240–250°C. The salinities are within the range of 2.0–9.2 wt% NaCl equiv. and the pressure of formation of the deposits was estimated at about 270×10⁵−500×10⁵Pa, corresponding to a depth of about 1.1–2.0 km under lithostatic confinement. Chemical studies show that the ore fluid is of the Na⁺(K⁺)-Ca²⁺-Cl⁻(F⁻) type. Theδ ¹⁸O andδD values of the fluid vary from −2.7‰- +4.4‰ and −50‰–−87‰ Evidence developed from fluid inclusions and geological setting indicates that the ore fluid was a mixture of magmatic and meteoric-hydrothermal waters. Changes in chemical composition andδ ¹⁸O andδD of fluid inclusions from one ore field to another seem to be related with regional tectonism, metamorphism and magmatism.     

Early Paleozoic adakite in the Liuyuan area from the Beishan orogenic belt,NW Gansu Province: Petrogenesis and implication for tectonic setting

The Liuyuan area,which is located on the southern margin of the Beishan orogenic belt,develops abundant Early Paleozic granitoids.SHRIMP zircon U-Pb dating yielded a weighted mean 206Pb/238U age of 421±8 Ma for the Liuyuan granodiorite(Zhao Zehui et al.,2007),implying its Late Silurian intrusion.Geochemical compositions showed that the Liuyuan granodiorite is characterized by high SiO2(65.01%-67.31%),A12O3(17.17%-18.05%) and Na2O(Na2O/K2O=1.67-1.87) but low Mg# contents calculated as 100×Mg2+/(Mg2++∑Fe2+) from 28.77 to 31.15,as well as being enriched in Sr(472×10-6-517×10-6) but depleted in Yb(1.2×10-6-1.42×10-6) and Y(12.8×10-6-14×10-6).The REEs are characterized by right-inclined patterns with LREE enrichment,HREE depletion and slightly negative Eu anomalies(Eu/Eu*=0.91-0.97).Major and trace elements indicate that the granodiorite is an adakite.The Nb/Ta values of the granodiorite vary from 10.80 to 18.01 and Nb/U from 6.32 to 10.09,both lying between the values of the crust and the mantle.The rock has low εNd(t) values(-2.5--0.8) and high ISr(0.706321-0.706495).Geochemical and Sr-Nd isotopic compositions indicate that the Liuyuan granodiorite is possibly derived from partial melting of thickening lower crust,related to mantle underplating.The Yb-Ta and Y+Nb-Rb discriminant diagrams imply the Liuyuan granodiorite intruded in a local extensional tectonic setting during late collision.Combined with previous studies on geochronology,geochemistry and tectonic setting of granitoids,we interprete that the constraint of this adakite in the Liuyuan area indicates that the tectonic setting may have transformed from collision to extension during the Early Devonian.     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln=Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1,100 K) and SmCaAl[Al₂O₇] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶ K⁻¹+3.6(7)×10⁻⁹ΔT K⁻² and α₃=15.0(1)×10⁻⁶ K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶ K⁻¹+2.0(2)×10⁻⁹ΔT K⁻² and α₃=8.5(2)×10⁻⁶ K⁻¹+2.0(3)×10⁻⁹ΔT K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)× 10⁻⁶ K⁻¹+1.7(2)×10⁻⁹ΔT K⁻² and α₃=9.344(5)×10⁻⁶ K⁻¹. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)-(Ln ³⁺+Al³⁺) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at     

内蒙古乌拉特中旗图古日格金矿辉钼矿Re-Os同位素年龄及其意义

图古日格是内蒙古宝音图地块内的一例具有中型规模的金矿床。含金石英脉呈NW向穿插于各类晚古生代岩体与下元古界宝音图群地层中,矿体走向、倾向延伸相对稳定。金属矿物主要为黄铁矿、黄铜矿、方铅矿等,脉石矿物为石英、方解石等。发育硅化、绢云母化、绿泥石化、绿帘石化等围岩蚀变。与金共生的辉钼矿Re-Os等时线年龄为(305.6±4.5)Ma、模式年龄为(313.5±4.8)Ma,限定图古日格金矿是晚石炭世构造-岩浆活动的产物。辉钼矿Re含量介于42.42×10-6~307.7×10-6,显示成矿物质可能为壳幔混合来源。     

Chemical composition of rock-forming minerals in gold-related granitoid intrusions,southwestern New Brunswick,Canada: implications for crystallization conditions,volatile exsolution,and fluorine-chlorine activity

Chemical composition of rock-forming minerals in Appalachian Siluro-Devonian granitoid intrusions, southwestern New Brunswick, was systematically determined by electron microprobe. The mineral chemical data together with petrographic examination was used to test magmatic equilibration and to constrain crystallization conditions, volatile exsolution, and fluorine-chlorine activity of fluids associated with these intrusions. Mineralogical distinction between Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS) and Late Devonian granitic series (GS) rocks is evident, although both are subsolvus I-type to evolved I-type granitoids. Oxidized to reduced GMS rocks consist of quartz, plagioclase (An>10), K-feldspar, biotite, apatite, titanite, zircon, monazite, ± hornblende, ± pyroxene, ± magnetite, ± ilmenite, and ± sulfide. GS rocks comprise quartz, K-feldspar, plagioclase (An<10), mica group minerals, zircon, monazite, apatite, sulfide, ± ilmente, ± magnetite, ± topaz, ± columbite, and ± xenotime. Inter-intrusion and intra-intrusion variations in mineral chemistry are interpreted to reflect petrogenetic processes (e.g., assimilation and fractional crystallization) during granitoid evolution. Although magmatic equilibration among rock-forming minerals are disturbed by subsolidus hydrothermal processes, GMS rocks appear to have higher magmatic temperatures, variable levels of emplacement, a range of (i.e., reduced intrusions 10^−16.7∼10^−13.4 and oxidized intrusions 10^−14.0∼10^−10.5 bars), and relatively low f _HF/f _HCl ratios (10^−3.0∼10^−1.0) in exsolved fluids, compared to GS rocks. Reduced GMS intrusions bear higher gold potential and thus may be prospective targets for intrusion-related gold systems. Electronic Supplementary Material Supplementary material is available for this article at     

Thermodynamic data of the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite)

 Calorimetric and P–V–T data for the high-pressure phase Mg₅Al₅Si₆O₂₁(OH)₇ (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B₂O₃) at T=700 ^∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets; they range from −221.1 to −259.4 kJ mol⁻¹ (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol⁻¹ (formation from the elements). The heat capacity of Mg₅Al₅Si₆O₂₁(OH)₇ has been measured from T=50 ^∘C to T=500 ^∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents the heat capacity over the entire temperature range to within the experimental uncertainty: C _P (Mg-sursassite) =(1571.104 −10560.89×T ^−0.5−26217890.0 ×T ⁻²+1798861000.0×T ⁻³) J K⁻¹ mol⁻¹ (T in K). The P V T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ^∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the bulk modulus was determined as 116.0±1.3 GPa, (K ^′=4), V _T,0 =446.49 ³ exp[∫(0.33±0.05) × 10⁻⁴ + (0.65±0.85)×10⁻⁸ T dT], (K _T/T) _P  = −0.011± 0.004 GPa K⁻¹. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg 1998); the best agreement was obtained with Δ_f H ⁰ ₂₉₈ (Mg-sursassite) = −13901.33 kJ mol⁻¹, and S ⁰ ₂₉₈ (Mg-sursassite) = 614.61 J K⁻¹ mol⁻¹. Received: 21 September 2000 / Accepted: 26 February 2001     

Contents of Fixed-Ammonium （ NH4^＋ ） in Lamprophyres in the Zhenyuan Gold Orefield, Yunnan Province, China： Implications for Its Characteristics of the Source Region

This paper determined the fixed-ammonium (NH₄ ⁺) contents of lamprophyres in the Zhenyuan gold orefield, Yunnan Province, China. The results show that the NH₄ ⁺ contents of minettes in the orefield range from 120 × 10⁻⁶ to 469 × 10⁻⁶ and those of kersantites from 74.3 × 10⁻⁶ to 136 × 10⁻⁶. These values are higher than those of other mantle-derived rocks (less than 50 × 10⁻⁶), but lower than those of carbonaceous wall rocks in the orefield (from 1200 × 10⁻⁶ to 1343 × 10⁻⁶). Combining with the Sr isotopic composition, this paper suggested that lamprophyres in the orefield with high NH₄ ⁺ contents relative to other mantle-derived rocks would not have resulted from the primary magma contaminated by crustal materials in the process of rising or in the magma chamber, but from mantel metasomatism. This research project was financially supported jointly by the State Key Basic Research Program of the People’s Republic of China (No. G1999043203) and the Chinese Academy of Sciences Knowledge-Innovation Program (No. KZCX3-SW-125).     

Rare-earth elements as source indicators of Pan-African granites from Obudu Plateau,Southeastern Nigeria

The rare-earth element （REE） concentrations of representative granite samples from the southeast of the Obudu Plateau, Nigeria, were analyzed with an attempt to determine the signatures of their source, evolutionary history and tectonic setting. Results indicated that the granites have high absolute REE concentrations （190×10^-6-1191×10^-6; av.=549×10^-6） with the chondrite-normalized REE patterns characterized by steep negative slopes and prominent to slight or no negative Eu anomalies. All the samples are also characterized by high and variable concentrations of the LREE （151×10^-6-1169×10^-6; av.= 466×10^-6）, while the HREE show low abundance （4×10^-6-107×10^-6; av.=28×10^-6）. These are consistent with the variable levels of REE fractionation, and differentiation of the granites. This is further supported by the range of REE contents, the chondrite-normalized patterns and the ratios of LaN/YbN （2.30-343.37）, CeN/YbN （5.94-716.87）, LaN/SmN （3.14-11.68） and TbN/YbN （0.58-1.65）. The general parallelism of the REE patterns, suggest that all the granites were comagmatic in origin, while the high Eu/Eu＊ ratios （0.085-2.807; av.=0.9398） indicate high fo2 at the source. Similarly, irregular variations in LaN/YbN, CeN/YbN and Eu/Eu＊ ratios and REE abundances among the samples suggest behaviors that are related to mantle and crustal sources.     

Archaean Au−Ag mineralisation at Racetrack,near Kalgoorlie,Western Australia: a high crustal-level expression of the Archaean composite lode-gold system

The Racetrack Au−Ag deposit, in the Archaean Yilgarn Block, Western Australia, is hosted by a porphyritic basalt in a low greenschist facies setting and is associated with a brittle strike-slip fault system. Three distinct and successive stages of hydrothermal activity and late quartz-carbonate veining resulted in multiple veining and/or brecciation: Stages I and II are Au-bearing, whereas Stage III and late veins are barren. The ore shows features of both classic epithermal and mesothermal deposits. Alteration assemblages, typified by sericitization, carbonization, silicification and chloritization, are similar to those of mesothermal gold deposits, wheras the quartz vein-textures including comb, rosette, plumose and banded, ore mineralogyof arsenopyrite, pyrite, chalcopyrite, sphalerite, galena, freibergite, tetrahedrite, tennantite, fahlore, electrum and gold, and metal associations (Cu, As, Ag, Sn, Sb, W, Au and Pb) are more characteristics of epithermal deposits. Fluid inclusions related to Stage II are two phase and aqueous with 1–8 (average 4) wt. % NaCl equiv. and CO₂ content of <0.85 molal. Pressure-corrected homogenisation temperatures range from 190°C to 260°C. Mineral assemblages indicate that ore fluid pH ranged between 4.2 and 5.3, f_{O 2} between 10^−38.8 and 10^−39.6 bars, and m_Σs between 10^−3.2 and 10^−3.6. Calculated chemical and stable isotope compositions require a component of surface water in the ore fluid depositing the mineralisation, but evidence for deep crustal Pb indicates that deeply sourced fluids were also involved. The deposit is interpreted to have formed in a shallow environment via mixing of deeply sourced fluids, from at least as deep as the base of the greenstone belt, with surface waters. It therefore represents the upper crustal end-member of the crustal depth spectrum of Archaean lode-gold mineralisation.     

High pressure study of ScAlO3 perovskite

The crystal structure of orthorhombic (Pbnm) ScAlO₃ perovskite has been refined to 5 GPa using single-crystal X-ray diffraction. The compression of the structure if anisotropic with β _a =1.39(3)×10⁻³ GPa⁻¹, β _b =1.14(3)×10⁻³ GPa⁻¹ and β _c =1.84(3)×10⁻³ GPa⁻¹. The isothermal bulk modulus of ScAlO₃, K _T , determined from fitting a Birch-Murnaghan equation of state (K ^′ _T =4) to the volume compression data is 218(1) GPa. The interoctahedral angles to not vary significantly with pressure, and the compression of the structure is entirely attributable to compression of the AlO₆ octahedra. The compressibilities of the constituent AlO₆ and ScO₁₂ are well matched: β_Al−O=1.6×10⁻³ GPa⁻¹ and β_Sc−O=1.5×10⁻³ GPa⁻¹. Therefore the distortion of the structure shows no significant change with increasing pressure. Received: 18 August 1997 / Revised, accepted: 11 November 1997     

Low T heat capacity measurements and new entropy data for titanite (sphene): implications for thermobarometry of high-pressure rocks

The accepted standard state entropy of titanite (sphene) has been questioned in several recent studies, which suggested a revision from the literature value 129.3 ± 0.8 J/mol K to values in the range of 110–120 J/mol K. The heat capacity of titanite was therefore re-measured with a PPMS in the range 5 to 300 K and the standard entropy of titanite was calculated as 127.2 ± 0.2 J/mol K, much closer to the original data than the suggested revisions. Volume parameters for a modified Murgnahan equation of state: V _P,T  = V ₂₉₈° × [1 + a°(T − 298) − 20a°(T − 298)] × [1 – 4P/(K ₂₉₈ × (1 – 1.5 × 10⁻⁴ [T − 298]) + 4P)]^1/4 were fit to recent unit cell determinations at elevated pressures and temperatures, yielding the constants V ₂₉₈° = 5.568 J/bar, a° = 3.1 × 10⁻⁵ K⁻¹, and K = 1,100 kbar. The standard Gibbs free energy of formation of titanite, −2456.2 kJ/mol (∆H°_f = −2598.4 kJ/mol) was calculated from the new entropy and volume data combined with data from experimental reversals on the reaction, titanite + kyanite = anorthite + rutile. This value is 4–11 kJ/mol less negative than that obtained from experimental determinations of the enthalpy of formation, and it is slightly more negative than values given in internally consistent databases. The displacement of most calculated phase equilibria involving titanite is not large except for reactions with small ∆S. Re-calculated baric estimates for several metamorphic suites yield pressure differences on the order of 2 kbar in eclogites and 10 kbar for ultra-high pressure titanite-bearing assemblages.     

Water-rock interactions and chemical compositional variations during ductile deformation of the NW-striking shear zone in the Jiapigou gold belt,China

Two kinds of mylonite series rocks, felsic and mafic, have been recognized in the NW-striking shear zone of the Jiapigou gold belt. During ductile deformation, a large amount of fluid interacted intensively with the mylonite series rocks: plagioclases were sericitized and theAn values declined rapidly, finally all of them were transformed to albites; dark minerals were gradually replaced by chlorites (mostly ripidolite). Meanwhile, large-scale and extensive carbonation also took place, and the carbonatization minerals varied from calcite to dolomite and ankerite with the development of deformation. The δ¹³C values of the carbonates are −3.0‰ – −5.6‰ suggesting a deep source of carbon. The ductile deformation is nearly an iso-volume one (f _v≈1). With the enhancement of shear deformation, SiO₂ in the two mylonite series rocks was depleted, while volatile components suchs as CO₂ and H₂O, and some ore-forming elements such as Au and S were obviously enriched. But it is noted that the enrichment of Au in both the mylonite series rocks did not reach the paygrade of gold. The released SiO₂ from water-rock interactions occurred in the form of colloids and absorbed gold in the fluid. When brittle structures were formed locally in the ductile shear zone, the ore-forming fluids migrated to the structures along microfractures, and preciptated auriferous quartz because of reduction of pressure and temperature. Fluid inclusion study shows that the temperature and pressure of the ore-forming fluids are 245–292°C and 95.4–131.7 MPa respectively; the salinity is 12.88–16.33wt% NaCl; the fluid-phase is rich in Ca²⁺, K⁺, Na⁺, Mg²⁺, F⁻ and Cl⁻, while the gaseous phases are rich in CO₂ and CH₄. The δD and δ¹⁸O, values of the ore-forming fluid are −84.48‰ – −91.73‰ and −0.247‰ – +2.715‰ respectively, suggesting that the fluid is composed predominantly of meteoric water. This project is financially supported by the National Natural Science Foundation of China (No. 9488010).     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores: Part III: Eh-pH diagrams of the Me-As-H<Subscript>2</Subscript>O systems (Me = Co,Ni, Fe,Cu, Zn,Pb) at 25°C

The behavior of arsenic at the Earth’s surface and nearby at low temperatures and pressures depends mainly on the redox potential and the acidity-alkalinity of the crystallization media. These parameters determine the migration of arsenic compounds and their precipitation as various solid phases. Understanding the mechanism of arsenic’s behavior under surface conditions, which is important for solving environmental problems, is an urgent task of contemporary mineralogy and geochemistry. The activities of the components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with arsenic (a _ΣAs = 3 × 10⁻⁸, a _ΣFe = 10⁻⁵, a _ΣCu = 10⁻⁷, a _ΣZn = 5 × 10⁻⁷, a _ΣCo = 10⁻⁸, a _ΣNi = 6 × 10⁻⁸, a _ΣPb = 10⁻⁸) and in waters formed in the oxidation zone (a _ΣSe = 10⁻³, a _ΣFe = 10⁻², a _ΣCu = 10⁻², a _ΣZn = 5 × 10⁻², a _ΣCo = 10⁻³, a _ΣNi = 10⁻², a _ΣPb = 10⁻⁴) have been estimated. Eh-pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams of the Me-As-H₂O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) were plotted for the average contents of these elements in the underground water and for their higher contents in the oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb arsenates at the surface is discussed.     

Thermal equations of state of dioctahedral micas on the join muscovite–paragonite

 Powder diffraction measurements at simultaneous high pressure and temperature on samples of 2M1 polytype of muscovite (Ms) and paragonite (Pg) were performed at the beamline ID30 of ESRF (Grenoble), using the Paris-Edinburgh cell. The bulk moduli of Ms, calculated from the least-squares fitting of V–P data on each isotherm using a second-order Birch–Murnaghan EoS, were: 57.0(6), 55.1(7), 51.1(7) and 48.9(5) GPa on the isotherms at 298, 573, 723 and 873 K, respectively. The value of (∂K _T /∂T) was −0.0146(2) GPa K⁻¹. The thermal expansion coefficient α varied from 35.7(3) × 10⁻⁶ K⁻¹ at P ambient to 20.1(3) × 10⁻⁶ K⁻¹ at P = 4 GPa [(∂α/∂P) _T = −3.9(1) × 10⁻⁶ GPa⁻¹ K⁻¹]. The corresponding values for Pg on the isotherms at 298, 723 and 823 K were: bulk moduli 59.9(5), 55.7(6) and 53.8(7) GPa, (∂K _T /∂T) −0.0109(1) GPa K⁻¹. The thermal expansion coefficient α varied from 44.1(2) × 10⁻⁶ K⁻¹ at P ambient to 32.5(2) × 10⁻⁶ K⁻¹ at P = 4 GPa [(∂α/∂P) _T = −2.9(1) × 10⁻⁶ GPa⁻¹ K⁻¹]. Thermoelastic coefficients showed that Pg is stiffer than Ms; Ms softens more rapidly than Pg upon heating; thermal expansion is greater and its variation with pressure is smaller in Pg than in Ms. Received: 28 January 2002 / Accepted: 5 April 2002