Thermodynamic analysis of Fe and Mg partitioning between plagioclase and silicate liquid

 Thermodynamic analysis of Fe- and Mg-bearing plagioclase and silicate liquid was carried out based on reported element partitioning data between plagioclase and silicate liquid in reduced conditions, solution properties of ternary feldspar, standard state properties of plagioclase endmembers and solution properties of multicomponent silicate liquid. Derived mixing properties of Fe- and Mg-bearing plagioclase are in harmony with estimated results from synthetic experiments in the systems CaAl₂Si₂O₈-CaFeSi₃O₈ and CaAl₂Si₂O₈-CaMgSi₃O₈. Based on the determined solution properties of the plagioclase, a computer program to calculate the element partition relationships between Fe- and Mg-bearing plagioclase and multicomponent silicate liquid was developed. The FeO, MgO and MgO/(MgO + FeO) in plagioclase predicted from known liquid compositions and pressure are in agreement with measurements within 0.2 wt%, 0.1 wt% and 0.1 (mol ratio), respectively. The Fe³⁺ content in plagioclase crystallized at high oxygen fugacity can be estimated with this program. The Fe³⁺/total Fe ratio in plagioclase crystallized near the quartz-fayalite-magnetite buffer ranges from 0 to 0.5, which is consistent with previous study on natural plagioclase in submarine basalt. Derived solution properties of the Fe- and Mg-bearing plagioclase are also used to calculate equilibrium composition relationship between olivine and plagioclase. Change of X _Fo in olivine coexisting with plagioclase affects MgO and FeO contents in plagioclase greatly. The present model predicts X _Fo of coexisting olivine from the chemical composition of plagioclase to ±0.1 accuracy at given pressure and temperature. Received: 27 March 1998 / Accepted: 30 September 1999     

Experimental constraints on Pt, Pd and Au partitioning and fractionation in silicate melt–sulfide–oxide–aqueous fluid systems at 800 °C, 150 MPa and variable sulfur fugacity

We have performed experiments to constrain the effect of sulfur fugacity (fS₂) and sulfide saturation on the fractionation and partitioning behavior of Pt, Pd and Au in a silicate melt–sulfide crystal/melt–oxide–supercritical aqueous fluid phase–Pt–Pd–Au system. Experiments were performed at 800 °C, 150 MPa, with oxygen fugacity (fO₂) fixed at approximately the nickel–nickel oxide buffer (NNO). Sulfur fugacity in the experiments was varied five orders of magnitude from approximately log fS₂ = 0 to log fS₂ = −5 by using two different sulfide phase assemblages. Assemblage one consisted initially of chalcopyrite plus pyrrhotite and assemblage two was loaded with chalcopyrite plus bornite. At run conditions pyrrhotite transformed compositionally to monosulfide solid solution (mss), chalcopyrite to intermediate solid solution (iss), and in assemblage two chalcopyrite and bornite formed a sulfide melt. Run-product silicate glass (i.e., quenched silicate melt) and crystalline materials were analyzed by using both electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. The measured concentrations of Pt, Pd and Au in quenched silicate melt in runs with log fS₂ values ranging from approximately 0.0 to −5.0 do not exhibit any apparent dependence on fS₂. The measured Pt, Pd and Au concentrations in mss do vary as a function of fS₂. The measured Pt, Pd and Au concentrations in iss do not appear dependent on fS₂. The data suggest that fS₂, working in concert with fO₂, via the determinant role that these variables play in controlling the magmatic sulfide phase assemblage and the solubility of Pt, Pd and Au as lattice bound components in magmatic sulfide phases, is a controlling factor on the budgets of Pt, Pd and Au during the evolution of magmatic systems.     

The gold–vanadium–tellurium association at the Tuvatu gold–silver prospect, Fiji: conditions of ore deposition

Summary The Tuvatu gold–telluride prospect is one of several epithermal gold systems along the >250 km northeast trending Viti Levu lineament, Fiji, which are genetically associated with alkalic magmatism. Vein structures contain a variety of sulfides, native elements, sulfosalts, and tellurides. Calaverite is intimately associated with various vanadium-bearing minerals: roscoelite, karelianite, vanadian muscovite, Ti-free nolanite, vanadian rutile, schreyerite, and an unnamed vanadium silicate. Thermodynamic calculations for the systems V–Al–K–Si–O–H (Cameron, 1998) and Au–Te–Cl–S–O–H at estimated conditions of formation of the telluride-native gold stage at Tuvatu (∼250 °C, ΣAu = 1 ppb, ΣTe = 1 ppb, ΣS = 0.001 m, ΣV = 0.0001 m, and a_K = 0.01), show that the stability fields of calaverite, roscoelite, and karelianite converge in pH-fO₂ space near the hematite–magnetite buffer and at neutral to slightly acid conditions. Thermodynamic and textural data suggest that these minerals were deposited together at Tuvatu and likely explain the common coexistence of roscoelite and calaverite in epithermal gold systems elsewhere. The presence of magnetite with up to 0.7 wt.% V₂O₃ in the Navilawa Monzonite is consistent with the derivation of V from the alkalic intrusive rocks, which are also considered to be the source of Au and Te in the Tuvatu deposit.     

Te and Se mineralogy of the high-sulfidation Kochbulak and Kairagach epithermal gold telluride deposits (Kurama Ridge, Middle Tien Shan, Uzbekistan)

Summary The Late Paleozoic Kochbulak and Kairagach deposits are located on the northern slope of the Kurama Ridge, Middle Tien Shan, in the same volcanic structure and the same ore-forming system. Au–Ag–Cu–Bi–Te–Se mineralization is confined to veins and dissemination zones accompanied by quartz-sericite wall-rock alteration. The tellurides, calaverite, altaite, hessite, and tetradymite are widespread at both deposits; at Kairagach selenides and sulfoselenides of Bi and Pb are common, while at Kochbulak Bi and Pb telluroselenides and sulfotelluroselenides are typical. The paragenetic sequence of telluride assemblages are similar for both deposits and change from calaverite + altaite + native Au to sylvanite + Bi tellurides + native Te, Bi tellurides + native Au, and, finally, to Au + Ag tellurides with time. These mineralogical changes are accompanied by an increase in the Ag content of native gold that correlates with a decrease in temperature, fTe₂ and fO₂ and an increase in pH.     

Gaseous transport and deposition of gold in magmatic fluid: evidence from the active Kudryavy volcano, Kurile Islands

The distribution of gold in high-temperature fumarole gases of the Kudryavy volcano (Kurile Islands) was measured for gas, gas condensate, natural fumarolic sublimates, and precipitates in silica tubes from vents with outlet temperatures ranging from 380 to 870°C. Gold abundance in condensates ranges from 0.3 to 2.4 ppb, which is significantly lower than the abundances of transition metals. Gold contents in zoned precipitates from silica tubes increase gradually with a decrease in temperature to a maximum of 8 ppm in the oxychloride zone at a temperature of approximately 300°C. Total Au content in moderate-temperature sulfide and oxychloride zones is mainly a result of Au inclusions in the abundant Fe–Cu and Zn sulfide minerals as determined by instrumental neutron activation analysis. Most Au occurs as a Cu–Au–Ag triple alloy. Single grains of native gold and binary Au–Ag alloys were also identified among sublimates, but aggregates and crystals of Cu–Au–Ag alloy were found in all fumarolic fields, both in silica tube precipitates and in natural fumarolic crusts. Although the Au triple alloy is homogeneous on the scale of microns and has a composition close to (Cu,Ni,Zn)₃(Au,Ag)₂, transmission electron microscopy (TEM) shows that these alloy solid solutions consist of monocrystal domains of Au–Ag, Au–Cu, and possibly Cu₂O. Gold occurs in oxide assemblages due to the decomposition of its halogenide complexes under high-temperature conditions (650–870°C). In lower temperature zones (<650°C), Au behavior is related to sulfur compounds whose evolution is strongly controlled by redox state. Other minerals that formed from gas transport and precipitation at Kudryavy volcano include garnet, aegirine, diopside, magnetite, anhydrite, molybdenite, multivalent molybdenum oxides (molybdite, tugarinovite, and ilsemannite), powellite, scheelite, wolframite, Na–K chlorides, pyrrhotite, wurtzite, greenockite, pyrite, galena, cubanite, rare native metals (including Fe, Cr, Mo, Sn, Ag, and Al), Cu–Zn–Fe–In sulfides, In-bearing Pb–Bi sulfosalts, cannizzarite, rheniite, cadmoindite, and kudriavite. Although most of these minerals are fine-grained, they are strongly idiomorphic with textures such as gas channels and lamellar, banded, skeletal, and dendrite-like crystals, characteristic of precipitation from a gas phase. The identified textures and mineral assemblages at Kudryavy volcano can be used to interpret geochemical origins of both ancient and modern ore deposits, particularly gold-rich porphyry and related epithermal systems.     

Experiments on silicate melt immiscibility in the system Fe2SiO4–KAlSi3O8–SiO2–CaO–MgO–TiO2–P2O5 and implications for natural magmas

The effect of CaO and MgO, with or without TiO₂ and P₂O₅, on the two-melt field in the simplified system Fe₂SiO₄–KAlSi₃O₈–SiO₂ has been experimentally determined at 1,050°–1,240°C, 400 MPa. Despite the suppressing effect of MgO, CaO, and pressure on silicate melt immiscibility, our experiments show that this process is still viable at mid-crustal pressures when small amounts (0.6–2.0 wt%) of P₂O₅ and TiO₂ are present. Our data stress that the major element partition coefficients between the two melts are highly correlated with the degree of polymerisation (nbo/t) of the SiO₂-rich melt, whatever temperature, pressure, or exact composition. Experimental immiscible melt compositions in natural systems at 0.1 MPa from the literature (lunar and tholeiitic basalts) plot on similar but distinct curves compared to the simplified system. These relations between melt polymerisation and partition coefficients, which hold for a large range of compositions and fO₂, are extended to various volcanic and plutonic rocks. This analysis strengthens the proposal that silicate melt immiscibility can be important in volcanic rocks of various compositions (from tholeiitic basalts to lamprophyres). However, the majority of proposed immiscible compositions in plutonic rocks are at least not coexisting melts, but may have suffered accumulation of early crystallized minerals.     

Gold in the Brunswick No. 12 volcanogenic massive sulfide deposit,Bathurst Mining Camp,Canada: Evidence from bulk ore analysis and laser ablation ICP─MS data on sulfide phases

The 329-Mt Brunswick No. 12 volcanogenic massive sulfide deposit (total resource of 163 Mt at 10.4% Zn, 4.2% Pb, 0.34% Cu, and 115 g/t Ag) is hosted within a Middle Ordovician bimodal volcanic and sedimentary sequence. Massive sulfides are for the most part syngenetic, and the bulk of the sulfide ore occurs as a Zn–Pb-rich banded sulfide facies that forms an intimate relationship with a laterally extensive Algoma-type iron formation and defines the Brunswick Horizon. Zone refining of stratiform sulfides is considered to have resulted in the development of a large replacement-style Cu-rich basal sulfide facies, which is generally confined between the banded sulfide facies and an underlying stringer sulfide zone. Complex polyphase deformation and associated lower- to upper-greenschist facies regional metamorphism is responsible for the present geometry of the deposit. Textural modification has resulted in a general increase in grain size through the development of pyrite and arsenopyrite porphyroblasts, which tend to overprint primary mineral assemblages. Despite the heterogeneous ductile deformation, primary features have locally been preserved, such as fine-grained colloform pyrite and base and precious metal zonation within the Main Zone. Base metal and trace element abundances in massive sulfides from the Brunswick No. 12 deposit indicate two distinct geochemical associations. The basal sulfide facies, characterized by a proximal high-temperature hydrothermal signature (Cu–Co–Bi–Se), contains generally low Au contents averaging 0.39 ppm (n = 34). Conversely, Au is enriched in the banded sulfide facies, averaging 1.1 ppm Au (n = 21), and is associated with an exhalative suite of elements (Zn–Pb–As–Sb–Ag–Sn). Finely laminated sulfide lenses hosted by iron formation at the north end of the Main Zone are further enriched in Au, averaging 1.7 ppm (n = 41) and ranging up to 8.2 ppm. Laser ablation inductively coupled plasma-mass spectrometry (ICP-MS) analyses of pyrite (n = 97) from the north end of the Main Zone average 2.6 ppm Au and range from the detection limit (0.015 ppm) to 21 ppm. Overall, these analyses reveal a distinct Au–Sb–As–Ag–Hg–Mn association within pyrite grains. Gold is strongly enriched in large pseudo-primary masses of pyrite that exhibit relict banding and fine-grained cores; smaller euhedral pyrite porphyroblasts, and euhedral rims of metamorphic origin surrounding the pyrite masses, contain much less Au, Sb, Ag, As, and Sn. Arsenopyrite, occurring chiefly as late porphyroblasts, contains less Au, averaging 1.0 ppm and ranging from the detection limit (0.027 ppm) to 6.9 ppm. Depth profiles for single-spot laser ablation ICP-MS analyses of pyrite and arsenopyrite display uniform values of Au and an absence of discrete microscopic inclusions of Au-bearing minerals, which is consistent with chemically bonded Au in the sulfide structure. The pervasive correlation of Au with Sn in the Zn–Pb-rich banded sulfide facies suggests similar hydrothermal behavior during the waxing stages of deposition on the seafloor. Under high temperature (>350oC) and moderate- to low-pH conditions, Au and Sn in hydrothermal fluids would be transported as chlorocomplexes. An abrupt decrease in temperature and aH₂S, accompanied by an increase in fO₂ and pH during mixing with seawater, would lead to the simultaneous destabilization of both Au and Sn chlorocomplexes. The enrichment of Au in fine-grained laminated sulfides on the periphery of the deposit, accompanied by sporadic occurrences of barite and Fe-poor sphalerite, supports lower hydrothermal fluid temperatures analogous to white smoker activity on the flanks of a large volcanogenic massive sulfide system. In lower temperature (<350oC) and mildly acidic hydrothermal fluids, Au would be transported by thiocomplexes, which exhibit multifunctional (retrograde–prograde) solubility and a capacity to mobilize Au to the outer parts of the sulfide mound. The sluggish nature of this low-temperature venting together with larger variations in ambient fO₂ could lead to a sharp enrichment of Au towards the stratigraphic hanging wall of massive sulfide deposits. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Experimental determination of activities in FeTiO3-MnTiO3 ilmenite solid solution by redox reversals

 Solid solutions of (Fe,Mn)TiO₃ were synthesized, mostly at 0.10 X_Mn intervals, at 1 bar, 900°C and log f _{O 2} = –17.50. Analysis by EMP indicate an ideal stoichiometry for the Fe-Mn ilmenites with (Fe+Mn) = Ti = 1.000 when normalized to 3 oxygens. Their unit cell volume increases linearly with X_Mn. The composition of Fe-Mn ilmenite coexisting with metallic Fe and rutile was reversed at 1 bar, 700–900°C and fixed f _{O 2} in a gas-mixing furnace. Oxygen fugacity was controlled by mixing CO₂ and H₂ gas and was continuously monitored with an yttrium-stabilized zirconia electrolyte. Solution properties of Fe-Mn ilmenite were derived from the experimental data by mathematical programming (Engi and Feenstra, in preparation) including notably the results of Fe-Mn exchange experiments between ilmenite and garnet (Feenstra and Engi, submitted) and anchoring the standard state properties to the updated thermodynamic dataset of Berman and Aranovich (1996). The thermodynamic analysis resulted in positive deviations from ideality for (Fe,Mn)TiO₃ ilmenite, which is well described by an asymmetric Margules model with W^H _FeFeMn = –9.703 and W^H _FeMnMn = –23.234 kJ/mol, W^S _FeFeMn = –19.65 and W^S _FeMnMn = –22.06 J/(K·mol). The excess free energy for Fe-Mn ilmenite derived from the redox reversals is larger than in the symmetric ilmenite model (W^G _FeMn = +2.2 kJ/mol) determined by O'Neill et al. from emf measurements on the assemblage iron-rutile-(Fe,Mn)ilmenite. Received: 10 January 1996 / Accepted: 11 July 1996     

Experimental determination of the activity of chromite in multicomponent spinels

We determined activity-composition relationships in Pt-Cr and Pt-Fe-Cr alloys at 1300°C experimentally and used the results to constrain the thermodynamic properties of chromite-picrochromite spinels. The Pt-Cr binary is characterized by strong negative deviations from ideality throughout the investigated composition range and the activity-composition relationship can be fit by a four-suffix asymmetric regular solution with three binary interaction parameters. The ternary alloy was modeled as a four-suffix asymmetric regular solution; the three ternary interaction parameters in this model were constrained by combining interaction parameters for the three bounding binaries taken from this and previous work with results for a set of experiments in which the activity of Cr in Pt-Fe-Cr-alloys was fixed by coexisting Cr₂O₃ at known f_O2.The free energy of formation of FeCr₂O₄ at 1300°C was determined using the activities of Fe and Cr in Pt-alloys in equilibrium with oxide mixes of FeCr₂O₄ and Cr₂O₃. The free energy of formation of chromite from Fe+Cr₂O₃+O₂ is −202.7 ± 0.4 kJ/mol (1σ), indistinguishable from literature values. The corresponding free energy of formation of FeCr₂O₄ from the elements is −923.5 ± 2.1 kJ/mol (1σ), and the enthalpy of formation at 298 K is −1438 kJ/mol. The activity-composition relationship for the chromite component in (Fe,Mg)Cr₂O₄ solid solutions was determined from a set of experiments in which Pt-alloys were equilibrated with spinel + Cr₂O₃. (Fe,Mg)Cr₂O₄ spinels are nearly ideal at 1300°C; modeling our data with a one-site symmetric regular solution yields an interaction parameter of +2.14 ± 0.62 kJ/mol (1σ), similar to values based on data from the literature.     

Iron in monticellite as an oxygen barometer for kimberlite magmas

Monticellite is a common magmatic mineral in the groundmass of kimberlites. A new oxygen barometer for kimberlite magmas is calibrated based on the Fe content of monticellite, CaMgSiO₄, in equilibrium with kimberlite liquids in experiments at 100 kPa from 1,230 to 1,350°C and at logfO₂ from NNO-4.1 to NNO+5.3 (where NNO is the nickel–nickel oxide buffer). The XFe_Mtc/XFe_liq was found to decrease with increasing fO₂, consistent with only Fe²⁺ entering the monticellite structure. Although the XFe-in-monticellite varies with temperature and composition, these dependencies are small compared to that with fO₂. The experimental data were fitted by weighted least square regression to the following relationship: \Updelta \textNNO = \frac{ log[ 0.858( ±0.021)\fracX_\textFe^\textLiq X_\textFe^\textMtc ] - 0.139( ±0.022) }0.193( ±0.004) \Updelta {\text{NNO}} = \frac{{\left\{ {\log \left[ {0.858( \pm 0.021)\frac{{X_{\text{Fe}}^{\text{Liq}} }}{{X_{\text{Fe}}^{\text{Mtc}} }}} \right] - 0.139( \pm 0.022)} \right\}}}{0.193( \pm 0.004)} where ΔNNO is the fO₂ relative to that of the Nickel-bunsenite (NNO) buffer and XFe_liq/XFe_Mtc is the ratio of mole fraction of Fe in liquid and Fe-in-monticellite (uncertainties at 2σ). The application of this oxygen barometer to natural kimberlites from both the literature and our own investigations, assuming the bulk rock FeO is that of their liquid FeO, revealed a range in fO₂ from NNO-3.5 to NNO+1.7. A range of Mg/(Mg + Fe²⁺) (Mg#) for kimberlite melts of 0.46–0.88 was derived from the application of the experimentally determined monticellite-liquid Kd Fe²⁺–Mg to natural monticellites. The range in Mg# is broader and less ultramafic than previous estimates of kimberlites, suggesting an evolution under a wide range of petrologic conditions.     

Differentiation and crystallization conditions of basalts from the Kerguelen large igneous province: an experimental study

Phase relations of basalts from the Kerguelen large igneous province have been investigated experimentally to understand the effect of temperature, fO₂, and fugacity of volatiles (e.g., H₂O and CO₂) on the differentiation path of LIP basalts. The starting rock samples were a tholeiitic basalt from the Northern Kerguelen Plateau (ODP Leg 183 Site 1140) and mildly alkalic basalt evolved from the Kerguelen Archipelago (Mt. Crozier on the Courbet Peninsula), representing different differentiation stages of basalts related to the Kerguelen mantle plume. The influence of temperature, water and oxygen fugacity on phase stability and composition was investigated at 500 MPa and all experiments were fluid-saturated. Crystallization experiments were performed at temperatures between 900 and 1,160°C under oxidizing (log fO₂ ~ ΔQFM + 4) and reducing conditions (log fO₂ ~ QFM) in an internally heated gas-pressure vessel equipped with a rapid quench device and a Pt-Membrane for monitoring the fH₂. In all experiments, a significant influence of the fO₂ on the composition and stability of the Mg/Fe-bearing mineral phases could be observed. Under reducing conditions, the residual melts follow a tholeiitic differentiation trend. In contrast, melts have high Mg# [Mg²⁺/(Mg²⁺ + Fe²⁺)] and follow a calk-alkalic differentiation trend at oxidizing conditions. The comparison of the natural phenocryst assemblages with the experimental products allows us to constrain the differentiation and pre-eruptive conditions of these magmas. The pre-eruptive temperature of the alkalic basalt was about 950–1,050°C. The water content of the melt was below 2.5 wt% H₂O and strongly oxidizing conditions (log fO₂ ~ ΔQFM + 2) were prevailing in the magma chamber prior to eruption. The temperature of the tholeiitic melt was above 1,060°C, with a water content below 2 wt% H₂O and a log fO₂ ~ ΔQFM + 1. Early fractionation of clinopyroxene is a crucial step resulting in the generation of silica-poor and alkali-rich residual melts (e.g., alkali basalt). The enrichment of alkalis in residual melts is enhanced at high fO₂ and low aH₂O.     

The effects of sulfidation and oxidation during metamorphism on compositionally varied rocks adjacent to the Bleikvassli Zn–Pb–(Cu) deposit, Nordland, Norway

Petrographic, electron microprobe, and bulk-rock geochemical analyses indicate that the distribution and composition of ferromagnesian silicates (biotite, garnet, and staurolite) in and adjacent to the metamorphosed Bleikvassli Zn–Pb–(Cu) volcanogenic massive sulfide deposit, Norway, are dependent upon the competing effects of f O₂–f S₂ and host-rock composition. The enrichment in magnesium content of these silicates within the orebody and at distances of as much as 5–10 m away is due to the increased f O₂ and f S₂ conditions imposed on the silicates in zones subject to minor hydrothermal alteration during regional metamorphism. Alternatively, within pelitic country rocks at distances >5–10 m from ore, the host-rock chemistry controls the composition of metamorphic silicate minerals. Also, country rocks within a few meters of ore are distinguished by the common presence of zinc-bearing staurolite (up to 9 wt% ZnO) coexisting with biotite ± garnet. Rocks in the Bleikvassli deposit were hydrothermally enriched in zinc and fluorine prior to metamorphism. The fluorine resides mainly in biotite, which is an additional contributing factor to the magnesium enrichment of that mineral due to Fe²⁺–F avoidance. Our inference that the sulfidation–oxidation halo around the Bleikvassli ore deposit is only meters in width contrasts with the view of Maiga (1983), who proposed the effects of sulfidation could be identified at distances >159 m from ore. It is evident that the delineation of a sulfidation–oxidation halo bordering a metamorphosed massive sulfide deposit must be done carefully in order to discriminate between the effects due to variations in primary rock composition versus those resulting from a sulfur and oxygen fugacity gradient between the massive sulfides and the sulfur-poor country rocks. Received: 1 March 1998 / Accepted: 3 May 2000     

Influence of oxygen fugacity on the solubility of carbon and hydrogen in FeO-Na<Subscript>2</Subscript>O-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> melts in equilibrium with liquid iron at 1.5 GPa and 1400°C

Equilibria in the model melt (NaAlSi₃O₈(80) + FeO(20))-C-H₂ system were experimentally studied at ΔlogfO₂(IW) from −2.2 to −5.6, a pressure of 1.5 GPa, and a temperature of 1400°C. The experiments were conducted in a piston-cylinder apparatus using Pt capsules. The low fO₂ values were imposed during the experiments by adding 2, 5, and 7 wt % of finely dispersed SiC to NaAlSi₃O₈(80) + FeO(20) powder. The experimental products were investigated by electron microprobe analysis and Raman spectroscopy. The investigations showed that melting at 1.5 GPa and 1400°C in the stability field of a metallic iron phase produces silicate liquids containing both oxidized and reduced H and C species. Carbon and hydrogen are dissolved in the melt as C-H (CH₄) complexes. In addition, OH⁻ groups, molecular hydrogen H₂, and molecular water H₂O were observed in the melts. The proportions of dissolved C and H species strongly depend on oxygen fugacity. With decreasing fO₂, the content of O-H species decreases and that of H-C species increases. The obtained data and previous results (Kadik et al., 2004, 2006) allow us to suppose a fundamental change in the character of magmatic transfer of C-O-H components during the evolution of the redox state of the Earth’s mantle in geologic time toward higher fO₂ in its interiors.     

Olivine/Fe-metal equilibrium under high pressure: an ATEM investigation

San Carlos olivine samples enclosed in soft iron capsules were annealed in an uniaxial split-sphere apparatus, at pressures ranging from 4.6 to 9.0 GPa and temperature ranging from 1310o to 1595 oC. We estimated the annealing fO₂, theoretically controlled by the olivine/Fe-metal equilibrium, to be 1 to 2 log units above the fO₂ of the iron/wustite buffer. Samples were investigated by analytical transmission electron microscopy (ATEM) in order to verify that olivine and Fe capsule did equilibrate during the annealings. TEM imaging of the olivine bulk shows a and c dislocations confined in the (010) plane, and small (0.5 μm) spatially coupled precipitates of (1) Al-rich spinel and (2) enstatite (volumic proportion of precipitates ≃60 ppm). These coupled precipitates are surrounded by split c dislocation loops. Olivine composition profiles, determined by ATEM near the Fe-capsule/olivine contact, reveal a weak loss of Ni from the olivine matrix toward the capsule, as expected in such reducing conditions. These profiles also reveal a marked incorporation of Fe from the capsule into the olivine matrix. These observations, and their interpretation in terms of olivine point defect chemistry, lead to the following conclusions: (1) the starting olivine contained a high concentration of vacancies on octahedral sites (≥1000 ppm per site); such a high vacancy concentration is expected in San Carlos olivine which equilibrated in nature at relatively high fO₂; (2) the olivine/Fe-metal equilibrium did control fO₂ during the annealings, that resulted in a rapid re-equilibration of olivine at the beginning of the runs to the lower fO₂ imposed by the Fe capsule; this led to a strong decrease of the octahedral vacancy concentration in olivine. (3) Such a fO₂ decrease promoted in olivine the coupled precipitation of both types of Al-rich spinel and enstatite precipitates. These observations show that the use of Fe-capsule in high pressure experiments is an efficient method for controlling fO₂ when studying olivine, and more generally Fe-bearing silicates. Received: 5 November 1997 / Accepted: 5 May 1998     

Fe–Mg diffusion in olivine II: point defect chemistry,change of diffusion mechanisms and a model for calculation of diffusion coefficients in natural olivine

Analysis of existing data and models on point defects in pure (Fe,Mg)-olivine (Phys Chem Miner 10:27–37,1983; Phys Chem Miner 29:680–694, 2002) shows that it is necessary to consider thermodynamic non-ideality of mixing to adequately describe the concentration of point defects over the range of measurement. In spite of different sources of uncertainties, the concentrations of vacancies in octahedral sites in (Fe,Mg)-olivine are on the order of 10⁻⁴ per atomic formula unit at 1,000–1,200 °C according to both the studies. We provide the first explicit plots of vacancy concentrations in olivine as a function of temperature and oxygen fugacity according to the two models. It is found that in contrast to absolute concentrations at ∼1,100 °C and dependence on fO₂, there is considerable uncertainty in our knowledge of temperature dependence of vacancy concentrations. This needs to be considered in discussing the transport properties such as diffusion coefficients. Moreover, these defect models in pure (Fe,Mg)-olivine need to be extended by considering aliovalent impurities such as Al, Cr to describe the behavior of natural olivine. We have developed such a formulation, and used it to analyze the considerable database of diffusion coefficients in olivine from Dohmen et al. (Phys Chem Miner this volume, 2007) (Part - I) and older data in the literature. The analysis documents unequivocally for the first time a change of diffusion mechanism in a silicate mineral—from the transition metal extrinsic (TaMED) to the purely extrinsic (PED) domain, at fO₂ below 10⁻¹⁰  Pa, and consequently, temperatures below 900 °C. The change of diffusion mechanism manifests itself in a change in fO₂ dependence of diffusivity and a slight change in activation energy of diffusion—the activation energy increases at lower temperatures. These are consistent with the predictions of Chakraborty (J Geophys Res 102(B6):12317–12331, 1997). Defect formation enthalpies in the TaMED regime (distinct from intrinsic defect formation) lie between −66 and + 15 kJ/mol and migration energies of octahedral cations in olivine are most likely ∼ 260 kJ/mol, consistent with previous inferences (Phys Chem 207:147–162, 1998). Plots are shown for diffusion at various constant fO₂ as well as along fO₂ buffers, to highlight the difference in behavior between the two. Considering all the diffusion data and constraints from the point defect models, (Fe–Mg) diffusion in olivine along [001] is best described by the Master equations: (1) At oxygen fugacities greater than 10⁻¹⁰ Pa:

Ore metal redistribution by hydrocarbon–brine and hydrocarbon–halide melt phases, North Range footwall of the Sudbury Igneous Complex, Ontario, Canada

We report methane-dominant hydrocarbon (fluid) inclusions (CH₄±C₂H₆–C₂H₂, C₃H₈) coexisting with primary brine inclusions and secondary halide melt (solid NaCl) inclusions in Au–Pt-rich quartz-sulfide-epidote alteration veins associated with the footwall-style Cu–PGE (platinum-group element)–Au deposits at the Fraser Mine (North Range of the Sudbury Igneous Complex). Evidence for coentrapment of immiscible hydrocarbon–brine, and hydrocarbon–halide melt mixtures is demonstrated. A primary CH₄–brine assemblage was trapped during quartz growth at relatively low T (min. T _trapping∼145–315°C) and P (max. P _trapping∼500 bar), prior to the crystallization of sulfide minerals in the veins. Secondary inclusions contain solid halite and a mixture of CH₄, C₂H₆–C₂H₂ and C₃H₈ and were trapped at a minimum T of ∼710°C. The halite inclusions may represent halide melt that exsolved from crystallizing sulfide ores that texturally postdate (by replacement) early alteration quartz hosting the primary, lower T brine–CH₄ assemblage. Laser ablation ICP-MS analyses show that the brine, hydrocarbon and halide melt inclusions contain significant concentrations of Cu (0.1–1 wt% range), Au, Bi, Ag and Pt (all 0.1–10 ppm range). Cu:Pt and Cu:Au ratios in the inclusions are significantly (up to 4 log units) lower than in the host alteration veins and adjacent massive sulfide ore veins, suggesting either (1) early Cu loss from the volatiles by chalcopyrite precipitation or (2) enhanced Au and Pt solubilities relative to Cu at the temperatures of entrapment. Concentration ratios between coexisting brine and CH₄ inclusions are lower for Cu, Au, Bi and Ag than for other elements (Na, Ca, Fe, Mn, Zn, Pb) indicating that during interaction with the brine, the hydrocarbon phase was enriched in ore metals. The high concentrations of ore metals in hydrocarbon, brine and halide melt phases confirm that both aqueous and non-aqueous volatiles were carriers of precious metals in the Sudbury environment over a wide range of temperatures. Volatile evolution and magmatic sulfide differentiation were clearly part of a single, continuous process in the Sudbury footwall. The exsolution of H₂O-poor volatiles from fractionated sulfide liquid may have been a principal mechanism controlling the final distribution of PGE and Au in the footwall ore systems. The study reports the first measurements of precious metal concentrations in fluid inclusions from a magmatic Ni–Cu–PGE environment (the Sudbury district). Electronic Supplementary Material Supplementary material is available for this article at     

An improved thermodynamic model of metal-olivine-pyroxene stability domains

 Interactions between several silicate and metallic phases are studied by applying a self consistent thermodynamic approach and using recent thermodynamic data. We compute proportions and compositions of oxidized silicates and of reduced metallic phase in equilibrium at various temperatures and oxygen fugacities. The empirically observed activity-composition relationships for ternary metallic alloys are used and their applications to a general thermodynamic expression for a non-regular ternary system is explicitly discussed. We show that the stability limits of olivines and pyroxenes with respect to precipitation of metallic phases under reducing conditions are directly related to the presence of nickel impurities. We precisely evaluate the modifications of the stability limits as a function of nickel content. For typical mantle olivines [Fe/(Fe+Mg) = 0.1] the stability limits are given for values of x _Ni= Ni/(Ni+Fe+Mg) ranging from 10 ppm to 1% by: ln f _O2=−39.83+ 7.86 ln x _Ni, ln f _O2=−14.68+6.21 ln x _Ni, at 900 K and 1600 K, respectively. Received: 17 November 1999 / Accepted: 14 May 2000     

Phase relations in Fe–Ni–C system at high pressures and temperatures

We performed comparative study of phase relations in Fe_1−x Ni _x (0.10 ≤ x ≤ 0.22 atomic fraction) and Fe_0.90Ni_0.10−x C _x (0.1 ≤ x ≤ 0.5 atomic fraction) systems at pressures to 45 GPa and temperatures to 2,600 K using laser-heated diamond anvil cell and large-volume press (LVP) techniques. We show that laser heating of Fe,Ni alloys in DAC even to relatively low temperatures can lead to the contamination of the sample with the carbon coming from diamond anvils, which results in the decomposition of the alloy into iron- and nickel-rich phases. Based on the results of LVP experiments with Fe–Ni–C system (at pressures up to 20 GPa and temperatures to 2,300 K) we demonstrate decrease of carbon solubility in Fe,Ni alloy with pressure.     

Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions

To get deeper insight into the phase relations in the end-member system Fe₂SiO₄ and in the system (Fe, Mg)₂SiO₄ experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO₂ corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe₂SiO₄ + O₂ = 6 FeSiO₃ + 5 Fe_2.40Si_0.60O₄. Refinement of site occupancies in combination with stoichiometric Fe³⁺ calculations show that 32% of the total Fe is incorporated as Fe³⁺ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe³⁺ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe³⁺ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K _D independent on composition and a bulk composition of x _Fe = 0.44 this fractionation would stabilize spl with x _Fe = 0.72. Thus, spl could be a potential Fe³⁺ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.

Ternary Ca–Fe–Mg carbonates: subsolidus phase relations at 3.5 GPa and a thermodynamic solid solution model including order/disorder

Subduction carries atmospheric and crustal carbon hosted in the altered oceanic crystalline basement and in pelagic sediments back into the mantle. Reactions involving complex carbonate solid solutions(s) lead to the transfer of carbon into the mantle, where it may be stored as graphite/diamond, in fluids or melts, or in carbonates. To constrain the thermodynamics and thus reactions of the ternary Ca–Mg–Fe carbonate solid solution, piston cylinder experiments have been performed in the system CaCO₃–MgCO₃–FeCO₃ at a pressure of 3.5 GPa and temperatures of 900–1,100°C. At 900°C, the system has two miscibility gaps: the solvus dolomite–calcite, which closes at X _MgCO3 ~0.7, and the solvus dolomite–magnesite, which ranges from the Mg to the Fe side of the ternary. With increasing temperature, the two miscibility gaps become narrower until complete solid solutions between CaCO₃–Ca_0.5Mg_0.5CO₃ is reached at 1,100°C and between CaCO₃–FeCO₃ at 1,000°C. The solvi are characterized by strong compositional asymmetry and by an order–disorder mechanism. To deal with these features, a solid solution model based on the van Laar macroscopic formalism has been calculated for ternary carbonates. This thermodynamic solid solution model is able to reproduce the experimentally constrained phase relations in the system CaCO₃–MgCO₃–FeCO₃ in a broad P–T range. To test our model, calculated phase equilibria were compared with experiments performed in carbonated mafic protolithes, demonstrating the reliability of our solid solution model at pressures up to 6 GPa in complex systems.