Discontinuous Galerkin method for two-component liquid–gas porous media flows

We consider two-component (typically, water and hydrogen) compressible liquid–gas porous media flows including mass exchange between phases possibly leading to gas-phase (dis)appearance, as motivated by hydrogen production in underground repositories of radioactive waste. Following recent work by Bourgeat, Jurak, and Smaï, we formulate the governing equations in terms of liquid pressure and dissolved hydrogen density as main unknowns, leading mathematically to a nonlinear elliptic–parabolic system of partial differential equations, in which the equations degenerate when the gas phase disappears. We develop a discontinuous Galerkin method for space discretization, combined with a backward Euler scheme for time discretization and an incomplete Newton method for linearization. Numerical examples deal with gas-phase (dis)appearance, ill-prepared initial conditions, and heterogeneous problem with different rock types.     

Clinopyroxene–liquid thermometers and barometers specific to alkaline differentiated magmas

We present new thermometers and barometers based on clinopyroxene–liquid equilibria specific to alkaline differentiated magmas. The new models were calibrated through the regression analyses of experimental datasets obtained by merging phase equilibria experiments from the literature with new experiments performed by using trachytic and phonolitic starting compositions. The regression strategy was twofold: (1) we have tested previous thermometric and barometric equations and recalibrated these models using the new datasets; (2) we have calibrated a new thermometer and a new barometer including only regression parameters that closely describe the compositional variability of the datasets. The new models yield more precise estimates than previous thermometers and barometers when used to predict temperatures and pressures of alkaline differentiated magmas. We have tested the reliability of the new equations by using clinopyroxene–liquid pairs from trachytes and phonolites erupted during major explosive eruptions at the Phlegrean Fields and Mt. Vesuvius (central Italy). The test yielded crystallization conditions comparable to those determined by means of melt and fluid inclusion analyses and phase equilibria studies; this validates the use of the proposed models for precise estimates of crystallization temperatures and pressures in differentiated alkaline magmas. Because these magmas feed some of the most voluminous, explosive, and threatening volcanic eruptions in the world, a better understanding of the environmental conditions of their reservoirs is mandatory and this is now possible with the new models provided here.     

Decoupling the mechanical role of pore liquids in soils to liquid viscous effect and solid–liquid adhesion effect

Acta Geotechnica - This paper presents a novel conceptual approach for evaluating the mechanical effect of pore liquids on the overall geotechnical behavior. The approach is based on empiric...     

Density measurements of liquid Fe–Si alloys at high pressure using the sink–float method

The compositional dependence on the density of liquid Fe alloys under high pressure is important for estimating the amount of light elements in the Earth’s outer core. Here, we report on the density of liquid Fe–Si at 4 GPa and 1,923 K measured using the sink–float method and our investigation on the effect of the Si content on the density of the liquid. Our experiments show that the density of liquid Fe–Si decreases from 7.43 to 2.71 g/cm³ non-linearly with increasing Si content (0–100 at%). The molar volume of liquid Fe–Si calculated from the measured density gradually decreases in the compositional range 0–50 at% Si, and increases in the range 50–100 at% Si. It should be noted that the estimated molar volume of the alloys shows a negative volume of mixing between Fe and Si. This behaviour is similar to Fe–S liquid (Nishida et al. in Phys Chem Miner 35:417–423, 2008). However, the excess molar volume of mixing for the liquid Fe–Si is smaller than that of liquid Fe–S. The light element contents in the outer core estimated previously may be an underestimation if we take into account the possible negative value of the excess mixing volume of iron–light element alloys in the outer core.     

Profiling of dissolved organic compounds in the oil sands region using complimentary liquid–liquid extraction and ultrahigh resolution Fourier transform mass spectrometry

Understanding and characterizing organics in aquatic environments is a great challenge for environmental monitoring, especially for the oil sands industry due to the complexity and potential toxicity of dissolved organics in water. To date, significant efforts have been made in investigating the toxicity of naphthenic acids, although other compounds may also contribute to the toxicity of oil sands process-affected water (OSPW). Here, we present a case study showing a systematic approach for profiling the organic composition of OSPW and environmental water samples by concentrating and separating dissolved organics through complementary liquid–liquid extractions followed by positive- or negative-ion mode ultrahigh resolution mass detection. Our comparative investigation shows clear differences in the composition of dissolved organics (homologues particularly) not only between OSPW samples and environmental water samples, but also differences among oil sands operators. Sulfur-containing compounds (especially the SO _n classes) appear to have great potential to be used for evaluating the impact of OSPW, while our understanding of oxygen-only containing compounds should not be limited to O₂ (i.e., classic naphthenic acids), but rather can be broadened to include many other compound classes (for instance O _n , n = 1–9). Systematic profiling of water samples should be more widely implemented for monitoring the origin and transport of organics in aquatic ecosystems of the oil sands development region, northeastern Alberta, Canada.     

The effect of sulfur content on density of the liquid Fe–S at high pressure

The density of liquid Fe–S was measured at 4 GPa and 1,923 K using a sink/float method with a composite density marker. The density marker consisted of a Pt rod core and an Al₂O₃ tube surrounding. The uncertainty in the density of the composite marker is much smaller than that of the composite sphere, which had been used in previous density measurements. The density of liquid Fe–S decreases nonlinearly with increasing sulfur content at 4 GPa and 1,923 K. This tendency is consistent with the results measured at ambient pressure. The molar volume of FeS calculated from the measured density gradually increases with sulfur content. The excess molar volume from ideal mixing of Fe and S at 4 GPa was negative value. The new method proposed here is applicable to the density measurement of other Fe alloys at high pressure. The tendency of the molar volume and the excess molar volume with sulfur content at ambient pressure is consistent with these at high pressure at least up to 4 GPa. The excess molar volume at high pressure is essential for estimating the amount of light elements in the outer core.     

Comprehensive glycerol ether lipid fingerprints through a novel reversed phase liquid chromatography–mass spectrometry protocol

Glycerol ether lipid distributions have been developed as proxies for reconstructing past environmental change or, in their intact polar form, for fingerprinting the viable microbial community composition. However, due to their structural complexity, full characterization of glycerol ether lipids requires separate protocols for the analysis of the polar head groups and the alkyl chain moieties in core ether lipids. As a consequence, the valuable relationship between core ether lipid composition and specific polar head groups is often lost; this limits understanding of the diversity of ether lipids and their utility as biogeochemical proxies. Here, we report a novel reversed phase liquid chromatography–electrospray ionization-mass spectrometry (RP-ESI-MS) protocol that enables the simultaneous analysis of polar head groups (e.g. phosphocholine, phosphoglycerol, phosphoinositol, hexose and dihexose) and alkyl moieties (e.g. alkyl moieties modified with different numbers of cycloalkyl moieties, hydroxyl and alkyl groups and double bonds) in crude lipid extracts without further preparation. The protocol greatly enhances detection of archaeal intact polar lipids (IPLs) and core lipids (CLs) with double bond- and hydroxyl group-bearing alkyl moieties. With these improvements, widely used ratios that describe relative distributions of the core lipids, such as TEX₈₆ and ring index, can now be directly determined in specific intact polar lipids (IPL-specific TEX₈₆ and ring index). Since IPLs are the putative precursors of the environmentally persistent core lipids, their detailed examination using this protocol can potentially provide new insights into diagenetic and biological mechanisms inherent to these proxies. In a series of 12 samples from diverse settings, core and IPL-specific TEX₈₆ values followed the order: 2G-GDGTs > core GDGTs > 1G-GDGTs > 1G-GDGT-PI and the ring indices followed: 1G-GDGTs ≈ core GDGTs > 2G-GDGTs > 1G-GDGT-P1G > 2G-OH-GDGTs ≈ 1G-OH-GDGTs (1G, monoglycosyl; 2G, diglycosyl; P1G, phosphomonoglycosyl; GDGT, glycerol dialkyl glycerol tetraether).     

Phase relations in the carbon-saturated C–Mg–Fe–Si–O system and C and Si solubility in liquid Fe at high pressure and temperature: implications for planetary interiors

The phase and melting relations of the C-saturated C–Mg–Fe–Si–O system were investigated at high pressure and temperature to understand the role of carbon in the structure of the Earth, terrestrial planets, and carbon-enriched extraterrestrial planets. The phase relations were studied using two types of experiments at 4 GPa: analyses of recovered samples and in situ X-ray diffractions. Our experiments revealed that the composition of metallic iron melts changes from a C-rich composition with up to about 5 wt.% C under oxidizing conditions (ΔIW = ?1.7 to ?1.2, where ΔIW is the deviation of the oxygen fugacity (fO₂) from an iron-wüstite (IW) buffer) to a C-depleted composition with 21 wt.% Si under reducing conditions (ΔIW < ?3.3) at 4 GPa and 1,873 K. SiC grains also coexisted with the Fe–Si melt under the most reducing conditions. The solubility of C in liquid Fe increased with increasing fO₂, whereas the solubility of Si decreased with increasing fO₂. The carbon-bearing phases were graphite, Fe₃C, SiC, and Fe alloy melt (Fe–C or Fe–Si–C melts) under the redox conditions applied at 4 GPa, but carbonate was not observed under our experimental conditions. The phase relations observed in this study can be applicable to the Earth and other planets. In hypothetical reducing carbon planets (ΔIW < ?6.2), graphite/diamond and/or SiC exist in the mantle, whereas the core would be an Fe–Si alloy containing very small amount of C even in the carbon-enriched planets. The mutually exclusive nature of C and Si may be important also for considering the light elements of the Earth’s core.     

Resistivity saturation in liquid iron–light-element alloys at conditions of planetary cores from first principles computations

We present a comprehensive analysis of electrical resistivity for liquid Fe–Si, Fe–S, and Fe–O alloys from first principles computations, covering the pressure/temperature conditions and major light element candidates inside the cores of terrestrial planets. By fitting optical conductivity with the Drude formula, we explicitly calculate the effective electron mean free path, and show that it becomes comparable to the interatomic distance for high densities and Si/S concentrations (Ioffe–Regel criterion). In approaching the Ioffe–Regel criterion, the temperature coefficient of resistivity decreases with compression for all compositions, eventually vanishes (Fe–Si), or even changes sign (Fe–S). Differences in resistivity and the degree of saturation between the iron alloys studied are explained in terms of iron–light element coordination numbers and their density dependence. Due to competing temperature and pressure effects, resistivity profiles along proposed core adiabats exhibit a small negative pressure gradient.     

Properties of a diffuse interface model based on a porous medium theory for solid–liquid dissolution problems

In this paper, a local non-equilibrium diffuse interface model is introduced for describing solid–liquid dissolution problems. The model is developed based on the analysis of Golfier et al. (J Fluid Mech 457:213–254, 2002) upon the dissolution of a porous domain, with the additional requirement that density variations with the mass fraction are taken into account. The control equations are generated by the upscaling of the balance equations for a solid–liquid dissolution using a volume averaging theory. This results into a diffuse interface model (DIM) that does not require an explicit treatment of the dissolving interface, e.g., the use of arbitrary Lagrangian–Eulerian (ALE) methods, for instance. Test cases were performed to study the features and influences of the effective coefficients inside the DIM. In particular, an optimum expression for the solid–liquid exchange coefficient is obtained from a comparison with the referenced solution by ALE simulations. Finally, a Ra–Pe diagram illustrates the interaction of natural convection and forced convection in the dissolution problem.     

Clinopyroxene/liquid trace element partitioning in natural trachyte–trachyphonolite systems: insights from Campi Flegrei (southern Italy)

Trace element partition coefficients between clinopyroxenes and associated glassy matrix (^Cpx/L D) have been determined for 13 REE, HFSE^4+,5+, U, Th, Sr, Pb, Sc and V from combined LA-ICP-MS/EMP analyses in selected trachytes and trachyphonolites from Campi Flegrei. Composition of clinopyroxene and glass is pretty homogeneous in the trachyphonolites, pointing to an overall attainment of the equilibrium conditions. In trachytes, conversely, phases show some compositional heterogeneity (due to the presence of clinopyroxene xenocrysts) that requested a more careful petrographic and geochemical inspection of the samples to assess the equilibrium clinopyroxene composition. In the trachyte clinopyroxenes, REE are compatible from Nd to Lu (^Cpx/L D up to 2.9), like Y, Ti, Sc and V. The ^Cpx/L D for Eu is lower than those of the adjacent REE, highlighting Eu²⁺ contribution. High D values are also shown by U, Th, Pb, Zr, Hf, Nb and Ta relatively to basaltic and andesitic systems, whereas the D _Sr is roughly similar to that found for less evolved magmas. Trachyphonolites are characterized by an overall decrease of the ^Cpx/L D for highly-charged cations (with the exception of V), and by a slight increase of D _Sr. REE are still compatible from Nd to Lu (^Cpx/L D up to 2.1), like Ti, Y, Sc and V. This variation is also predicted for REE and Y by models based on the elastic strain theory, being consistent with the slightly lower polymerization degree estimated for the trachyphonolites. However, the observed ^Cpx/L D _(REE,Y) are matched by the modelled ones only considering very low T (≤825°C), which are believed unlikely. This mismatch cannot be attributed to effects induced by the water-rich composition of the trachyte–trachyphonolite suite, since they would lower the observed ^Cpx/L D _(REE,Y). Moreover, the anomalous inflections of measured ^Cpx/L D for HREE suggests some crystal-chemical control, such as the entrance of these elements in a site distinct from M2. It is concluded that the large ^Cpx/L D determined for trachytes and trachyphonolites are likely induced by hitherto unconstrained changes of the Z³⁺ activities related to the composition of melt and/or solid. All these considerations strongly highlight the importance of a direct characterization of trace element partitioning in natural samples from magmatic systems poorly characterized by experimental studies. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Solid–liquid Phase Equilibria in the Aqueous Ternary System Containing Lithium, Potassium, and Sulfate ions at 288.15 K

正1 Introduction Salt lakes are widely distributed in the western of China,especially in the area of Qinghai-Xizang(Tibet)Plateau.A series of salt lakes in the Qaidam Basin,located in Qinghai Province,China,is famous for their abundance of lithium,potassium and boron resources(Zheng et al,1988;Deng et al,2012).It is well known that the     

Phosphorus distribution between potassic alkali feldspar and metaluminous haplogranitic liquid at 200 MPa (H<Subscript>2</Subscript>O): the effect of undercooling on crystal–liquid systematics

To evaluate the applicability of P₂O₅ concentration in potassic alkali feldspar as a monitor of P₂O₅ in melt for undercooled systems, crystal–melt partitioning for P was evaluated via feldspar growth experiments in P-bearing ((3 wt% P₂O₅), water-saturated haplogranitic liquids at 200 MPa, with liquidus undercoolings (ΔT) of 25, 50, 100, 200, and 300°C. Increasing undercooling in the range ΔT=25–200°C shows an evolution of crystal morphologies, from euhedral and well-filled individuals at ΔT=25–50°C to radial clusters with increasingly skeletal habit at greater undercooling. Experiments at ΔT=100–200°C also document the development of P- (up to (9 wt% P₂O₅) and Si-enriched, more alkaline boundary layers adjacent to crystals. Experiments at ΔT=300°C show an additional change in crystallization fabric in which spherulites of skeletal crystals form in open (vapor) space created by the dissolution of bulk silicate, and compositional boundary layers are not observed. We interpret the changes in reaction products at ΔT=300°C to indicate conditions below a glass transition; hence, partition coefficients were not determined for this undercooling. Values of K _d(P)^Kfs/melt from experiments at ΔT=25–200°C, calculated from pairs of crystal and immediately adjacent liquid compositions (including boundary layers at higher undercooling), are mostly in the range of 0.25–0.55 and show no effective change with increased undercooling. Essentially no change in K _d(P)^Kfs/melt with undercooling apparently stems from an interplay between boundary layer composition and a change in the substitution mechanism for P in feldspar from AlPSi₋₂, common in peraluminous to metaluminous liquids near equilibrium, to increasing proportions of ([ ],P)(M⁺,Si)₋₁ with increased undercooling. Bulk glass and liquid beyond boundary layers in experiments with significant percentages of crystallization are homogeneous, and show pronounced fractionation primarily due to the removal of an orthoclase component. Because crystallization was still in progress in experiments with ΔT≤200°C, compositional homogeneity in the bulk liquid requires extremely rapid diffusion of most haplogranite components (Na, K, and Al), apparently resulting from chemical potential gradients stemming from the removal of components from the liquid by crystal growth. Similar homogeneity and bulk fractionation in experiments with ΔT=300°C requires rapid diffusive equilibration for the alkalis even at temperatures below an apparent glass transition. Unlike the haplogranite components, P is only concentrated in liquid boundary layers (ΔT≤200°C) or low-density aqueous vapor (ΔT=300°C) adjacent to crystals. Hence, the P₂O₅ contents of melt inclusions likely are not representative of bulk melt concentrations in significantly undercooled systems (ΔT≤50–100°C).     

Clinopyroxene + liquid equilibria to 100 kbar and 2450 K

One of the most active issues in igneous petrology is the investigation of mantle melting, and subsequent differentiation. To evaluate alternative hypotheses for melting and differentiation it is essential to accurately predict clinopyroxene compositions in natural systems. Expressions have thus been derived that describe clinopyroxene-melt equilibria, and allow equilibrium clinopyroxene compositions to be calculated. These equations were constructed from least-squares regression analysis of experimental clinopyroxene-liquid pairs. The calibration database included clinopyroxenes synthesized from both natural and synthetic basalt compositions; experimental conditions ranged from 0 to 100 kbar and 1350 to 2450 K. Regression equations were based on thermodynamic functions. Empirical expressions were also derived, since such models yield more precise estimates of clinopyroxene compositions, and may be easily incorporated into existing liquid line-of-descent models. Such equations may be useful for calculation of high pressure liquid fractionation, or for constraining P-T conditions for basalts produced by partial melting of a pyroxene-bearing source. Models of mantle melting often rely on expressions involving simple element ratios. Partition coefficients (K _d ^cpx/liq ) for the minor elements, Na and Ti, were thus also calibrated as a function of P, T and composition. K _Ti ^cpx/liq , while sensitive to composition was relatively insensitive to P and T. In contrast, K _Na ^cpx/liq increases substantially with increasing P, and exceeded 1 in some experiments. Since oceanic basalts show variations in Na/Ti ratios, the potential exists for partial melting depths to be inferred from K _Na ^cpx/liq . Received: 28 May 1997 / Accepted: 20 November 1998     

Origin of epithermal Ag–Au–Cu–Pb–Zn mineralization in Guanajuato, Mexico

The Guanajuato epithermal district is one of the largest silver producers in Mexico. Mineralization occurs along three main vein systems trending dominantly northwest–southeast: the central Veta Madre, the La Luz system to the northwest, and the Sierra system to the east. Mineralization consists dominantly of silver sulfides and sulfosalts, base metal sulfides (mostly chalcopyrite, galena, sphalerite, and pyrite), and electrum. There is a broad zonation of metal distribution, with up to 10 % Cu+Pb+Zn in the deeper mines along the northern and central portions of the Veta Madre. Ore occurs in banded veins and breccias and as stockworks, with gangue composed dominantly of quartz and calcite. Host rocks are Mesozoic sedimentary and intrusive igneous rocks and Tertiary volcanic rocks. Most fluid inclusion homogenization temperatures are between 200 and 300 °C, with salinities below 4 wt.% NaCl equivalent. Fluid temperature and salinity decreased with time, from 290 to 240 °C and from 2.5 to 1.1 wt.% NaCl equivalent. Relatively constant fluid inclusion liquid-to-vapor ratios and a trend of decreasing salinity with decreasing temperature and with increasing time suggest dilution of the hydrothermal solutions. However, evidence of boiling (such as quartz and calcite textures and the presence of adularia) is noted along the Veta Madre, particularly at higher elevations. Fluid inclusion and mineralogical evidence for boiling of metal-bearing solutions is found in gold-rich portions of the eastern Sierra system; this part of the system is interpreted as the least eroded part of the district. Oxygen, carbon, and sulfur isotope analysis of host rocks, ore, and gangue minerals and fluid inclusion contents indicate a hydrothermal fluid, with an initial magmatic component that mixed over time with infiltrating meteoric water and underwent exchange with host rocks. Mineral deposition was a result of decreasing activities of sulfur and oxygen, decreasing temperature, increasing pH, and, in places, boiling.     

Origin of the Yinshan epithermal-porphyry Cu–Au–Pb–Zn–Ag deposit,southeastern China: insights from geochemistry,Sr–Nd and zircon U–Pb–Hf–O isotopes

The Yinshan deposit is a large epithermal-porphyry polymetallic deposit, and the timing and petrogenesis of ore-hosting porphyries have been hotly debated. We present new results from geochemical, whole-rock Sr–Nd and zircon U–Pb–Hf–O isotopic investigations. Zircon U–Pb data demonstrate that the quartz porphyry, dacitic porphyry, and quartz dioritic porphyry formed at ?172.2 ± 0.4 Ma, ?171.7 ± 0.5 Ma, and ?170.9 ± 0.3 Ma, respectively. Inherited zircon cores show significant age spreads from ?730 to ?1390 Ma. Geochemically, they are high-K calc-alkaline or shoshonitic rocks with arc-like trace element patterns. They have similar whole-rock Nd and zircon Hf isotopic compositions, yet an increasing trend in ?_Nd(t) and ?_Hf(t) values typifies the suite. Older (inherited) zircons of the three porphyries display Hf compositions comparable to those of the Jiangnan Orogen basement rocks. In situ zircon oxygen isotopic analyses reveal that they have similar oxygen isotopic compositions, which are close to those of mantle zircons. Moreover, a decreasing trend of δ¹⁸O values is present. We propose that the ore-related porphyries of the Yinshan deposit were emplaced contemporaneously and derived from partial melting of Neoproterozoic arc-derived mafic (or ultra-mafic) rocks. Modelling suggests that the quartz porphyries, dacitic porphyries, and quartz dioritic porphyries experienced ?25%, ?10%, and ?10% crustal contaminations by Shuangqiaoshan rocks. Our study provides important constraints on mantle–crust interaction in the genesis of polymetallic mineralization associated with Mesozoic magmatism in southeastern China.     

水泥–粉煤灰–煤渣–吹填粉细砂混合料强度试验

针对大型堆填场基层结构工程,本着就地取材节约成本的原则,利用吹填砂作为骨料,添加粉煤灰、煤渣和水泥,采用正交试验方法,编制正交设计表,配制不同比例的混合料进行无侧限抗压强度试验。采用方差对不同龄期的混合料抗压强度进行分析,并对混合料加固机理进行研究,给出了混合料最佳质量配比,即水泥20%,粉煤灰15%,煤渣10%,此时混合料的强度最大;其水泥掺量对混合料强度起着关键作用,随着龄期的增长粉煤灰与煤渣对混合料强度影响程度逐渐增强,不过煤渣对混合料初期强度影响不及粉煤灰。     

Formation of gold–silver sulfides and native gold in Fe–Ag–Au–S system

We carried out experiments on crystallization of Fe-containing melts FeS₂Ag_0.1–0.1xAu_0.1x (x = 0.05, 0.2, 0.4, and 0.8) with Ag/Au weight ratios from 10 to 0.1. Mixtures prepared from elements in corresponding proportions were heated in evacuated quartz ampoules to 1050 ºC and kept at this temperature for 12 h; then they were cooled to 150 ºC, annealed for 30 days, and cooled to room temperature. The solid-phase products were studied by optical and electron microscopy and X-ray spectroscopy. The crystallization products were mainly from iron sulfides: monoclinic pyrrhotite (Fe_0.47S_0.53 or Fe₇S₈) and pyrite (Fe_0.99S_2.01). Gold–silver sulfides (low-temperature modifications) are present in all synthesized samples. Depending on Ag/Au, the following sulfides are produced: acanthite (Ag/Au = 10), solid solutions Ag_2–xAu_xS (Ag/Au = 10, 2), uytenbogaardtite (Ag/Au = 2, 0.75), and petrovskaite (Ag/Au = 0.75, 0.12). They contain iron impurities (up to 3.3 wt.%). Xenomorphic micro- (<1–5 μm) and macrograins (5–50 μm) of Au–Ag sulfides are localized in pyrite or between the grains of pyrite and pyrrhotite. High-fineness gold was detected in the samples with initial ratio Ag/Au ≤ 2. It is present as fine and large rounded microinclusions or as intergrowths with Au–Ag sulfides in pyrite or, more seldom, at the boundary of pyrite and pyrrhotite grains. This gold contains up to 5.7 wt.% Fe. Based on the sample textures and phase relations, a sequence of their crystallization was determined. At ~1050 ºC, there are probably iron sulfide melt L₁ (Fe,S ? Ag,Au), gold–silver sulfide melt L₂ (Au,Ag,S ? Fe), and liquid sulfur L_S. On cooling, melt L₁ produces pyrrhotite; further cooling leads to the crystallization of high-fineness gold (macrograins from L₁ and micrograins from L₂) and Au–Ag sulfides (micrograins from L₁ and macrograins from L₂). Pyrite crystallizes after gold–silver sulfides by the peritectic reaction FeS + L_S = FeS₂ at ~743 ºC. Elemental sulfur is the last to crystallize. Gold–silver sulfides are stable and dominate over native gold and silver, especially in pyrite-containing ores with high Ag/Au ratios.     

The Fe–C–O–H–N system at 6.3–7.8 GPa and 1200–1400 °C: implications for deep carbon and nitrogen cycles

Interactions in a Fe–C–O–H–N system that controls the mobility of siderophile nitrogen and carbon in the Fe⁰-saturated upper mantle are investigated in experiments at 6.3–7.8 GPa and 1200–1400 °C. The results show that the γ-Fe and metal melt phases equilibrated with the fluid in a system unsaturated with carbon and nitrogen are stable at 1300 °C. The interactions of Fe₃C with an N-rich fluid in a graphite-saturated system produce the ε-Fe₃N phase (space group P6₃/mmc or P6₃22) at subsolidus conditions of 1200–1300 °C, while N-rich melts form at 1400 °C. At IW- and MMO-buffered hydrogen fugacity (fH₂), fluids vary from NH₃- to H₂O-rich compositions (NH₃/N₂?>?1 in all cases) with relatively high contents of alkanes. The fluid derived from N-poor samples contains less H₂O and more carbon which mainly reside in oxygenated hydrocarbons, i.e., alcohols and esters at MMO-buffered fH₂ and carboxylic acids at unbuffered fH₂ conditions. In unbuffered conditions, N₂ is the principal nitrogen host (NH₃/N₂?≤?0.1) in the fluid equilibrated with the metal phase. Relatively C- and N-rich fluids in equilibrium with the metal phase (γ-Fe, melt, or Fe₃N) are stable at the upper mantle pressures and temperatures. According to our estimates, the metal/fluid partition coefficient of nitrogen is higher than that of carbon. Thus, nitrogen has a greater affinity for iron than carbon. The general inference is that reduced fluids can successfully transport volatiles from the metal-saturated mantle to metal-free shallow mantle domains. However, nitrogen has a higher affinity for iron and selectively accumulates in the metal phase, while highly mobile carbon resides in the fluid phase. This may be a controlling mechanism of the deep carbon and nitrogen cycles.