Solubility of sulfur in some magmas at 1 atmosphere

In order to understand the distribution of sulfur in igneous rooks, we determined the solubility of sulfur in volcanic rock melts (tholeiite basalt, hawaiite and rhyodacite from Hawaii) at various gas compositions and at 1250° and 1300°C and 1 atm total pressure. The solubility of sulfur in the melt passes through a minimum with change in oxygen partial pressure, if other factors are held constant. For the basaltic liquid at 1200°C, most sulfur in the melt is as dissolved sulfide (S^?2) at oxygen partial pressures below 10^?8 atm and as dissolved sulfate at oxygen partial pressures above 10^?8 atm. Based on the present solubility data, 5 per cent is inferred for volcanic gas at 1 atm total pressure in equilibrium with subaerially extruded Hawaiian tholeiite basalt (Pele's hair with 180 ppm S) at 1200°C and 10^?8 atm P_O2.     

Armalcolite stability as a function of pressure and oxygen fugacity

The stability of synthetic armalcolite of composition (Fe_0.5Mg_0.5Ti₂O₅ was studied as a function of total pressure up to 15 kbar and 1200°C and also as a function of oxygen fugacity (?O₂) at 1200°C and 1 atm total pressure. The high pressure experiments were carried out in a piston-cylinder apparatus using silver-palladium containers. At 1200°C, armalcolite is stable as a single phase at 10 kbar. With increasing pressure, it breaks down ($\text{dT}\text{dP}\text{= 20°C/}\text{kbar}$), to rutile, a more magnesian armalcolite, and ilmenite solid solution. At 14 kbar, this three-phase assemblage gives way ($\text{dT}\text{dP}\text{= 30°C/}\text{kbar}$) to a two-phase assemblage of rutile plus ilmenite solid solution.A zirconian-armalcolite was synthesized and analyzed; 4 wt % ZrO₂ appears to saturate armalcolite at 1200°C and 1 atm. The breakdown of Zr-armalcolite occurs at pressures of 1–2 kbar less than those required for the breakdown of Zr-free armalcolite. The zirconium partitions approximately equally between rutile and ilmenite phases.The stability of armalcolite as a function of ?O₂ was determined thermogravimetrically at 1200°C and 1 atm by weighing sintered pellets in a controlled atmosphere furnace. Armalcolite, (Fe_0.5Mg_0.5)-Ti₂O₅, is stable over a range ?O₂ from about 10^?9.5to 10^?10.5 atm. Below this range to at least 10^?12.8 atm, ilmenite plus a reduced armalcolite are formed. These products were observed optically and by Mössbauer spectroscopy, and no metallic iron was detected; therefore, some of the titanium must have been reduced to Ti³⁺. This reduction may provide yet another mechanism to explain the common association of ilmenite rims around lunar armalcolites.     

Time-dependent changes of the electrical conductivity of basaltic melts with redox state

The electrical conductivity of basaltic melts has been measured in real-time after fO₂ step-changes in order to investigate redox kinetics. Experimental investigations were performed at 1 atm in a vertical furnace between 1200 and 1400 °C using air, pure CO₂ or CO/CO₂ gas mixtures to buffer oxygen fugacity in the range 10⁻⁸ to 0.2 bars. Ferric/ferrous ratios were determined by wet chemical titrations. A small but detectable effect of fO₂ on the electrical conductivity is observed. The more reduced the melt, the higher the conductivity. A modified Arrhenian equation accounts for both T and fO₂ effects on the electrical conductivity. We show that time-dependent changes in electrical conductivity following fO₂ step-changes monitor the rate of Fe²⁺/Fe³⁺ changes. The conductivity change with time corresponds to a diffusion-limited process in the case of reduction in CO-CO₂ gas mixtures and oxidation in air. However, a reaction at the gas-melt interface probably rate limits oxidation of the melt under pure CO₂. Reduction and oxidation rates are similar and both increase with temperature. Those rates range from 10⁻⁹ to 10⁻⁸ m²/s for the temperature interval 1200-1400 °C and show activation energy of about 200 kJ/mol. The redox mechanism that best explains our results involves a cooperative motion of cations and oxygen, allowing such fast oxidation-reduction rates.     

Ionic conductivity in sodium magnesium silicates

Na₂MgSiO₄ crystals prepared hydrothermally at 700° C and 3,000 atm are related to carnegieite with SG Pmn2₁, a=7.015(2), b=10.968(2), and c=5.260(1). Na conductivity in Na₂MgSiO₄ is 3.0×10^?5 (ohm-cm)^?1 at 300° C but can be raised to 1.1×10^?3 (ohm-cm)^?1 by creating Na vacancies in the composition Na_1.9Mg_0.9Al_0.1O₄. Na₄Mg₂Si₃O₁₀ is also a cristobalite-related carnegieite with the orthorhombic cell a=10.584(7), b=14.328(7), and c=5.233(5). The Na conductivity of Na₄Mg₂Si₃O₁₀ is 4.8×10^?3 (ohm-cm)^?1 at 300° C.     

EPR measurement of the effect of glass composition on the oxidation states of europium

The techniques of electron paramagnetic resonance (EPR) were used to measure the concentration ratio of Eu²⁺ to Eu³⁺ in quenched silicate liquids as a function of their compositions. The compositional end members were CaAl₂Si₂O₈ and either MSiO₃ or M₂Si0₄, M = Mg, (Ca_0.5, Mg_0.5), and Ca. All of the liquids were quenched from 1650 ± 25°C, 10^?6.9±0.6 atm of oxygen, and 10^?6.1±0.6 atm total pressure. For a particular choice of M, the ratio of Eu²⁺ to Eu³⁺ increased as much as a factor of 24 with increasing atomic ratio (Al + Si)/(O); for a constant value of (Al + Si)/(O), the ratio of Eu²⁺ to Eu³⁺ increased in the order Mg > (Ca_0.5,Mg_0.5) >Ca. In order to interpret the compositional dependence of the redox equilibrium of Eu in a systematic manner, the concept of a solvent coefficient was introduced.     

A thermochemical study of vaterite

Vaterite is shown to be unstable with respect to calcite at 25°C by measurements of the enthalpies of solution in 0·1 N HCl under 0·97 atm CO₂ and the solubilities in water under 0·97 atm CO₂ of the two polymorphs. For a pure, synthetic vaterite ΔH (tr) = ?1036 ±16 cal mol^?1 and ΔG(tr) = ?790 ± 25 cal mol^?1 for the transition to calcite. For other vaterites aged longer during preparation ΔH(tr) is smaller and shows a linear relationship with the X-ray line broadening which extrapolates to ΔH(tr) = ?545 ± 30 cal mo^?1 for zero broadening. The use of X-ray line broadening as a measure of crystal imperfection and stability is discussed for various synthetic and natural vaterites.     

A thermochemical study of monohydrocalcite

The thermodynamic properties of monohydrocalcite, CaCO₃ · H₂O, have been obtained using a well-characterized natural specimen. Equilibration of the solid with water at 25°C under 0.97 atm CO₂ led to an activity product [Ca²⁺][CO₃^2?] = 10^?7.60±0.03 and a free energy of formation ΔG_f^o = ?325,430 ± 270 calmol^?. The enthalpy of solution of monohydrocalcite in 0.1 N HCl at 25°C led to a standard enthalpy of formation ΔH_f^o = ?358,100 ± 280 cal mol^?1. Estimates of the variation of ΔG_f with temperature and pressure showed monohydrocalcite to be metastable with respect to calcite and aragonite.     

Equilibration temperatures in enstatite chondrites

Equilibration temperatures for enstatite chondrites are calculated using a method suggested by Larimer (1968). The temperatures range from 640° to 840°C. The method yields temperatures which, in principle, are correct on a relative scale but the absolute error may be a large as 150°. There is a good correlation between the calculated temperatures and petrologic type as well as other mineralogic characteristics and bulk composition. Partial pressures of sulfur and oxygen at the time of equilibration were: pS₂ ~ 10^?8?10^?12 atm and pO₂ ~ 10^?28?10^?37.     

Crystallization sequences of Ca-Al-rich inclusions from Allende: An experimental study

The equilibrium crystallization sequence at 1 atmosphere in air of a melt corresponding in composition to the average composition of Type B Ca-Al-rich inclusions from the Allende meteorite is: spinel (1550°C) → melilite (1400°C; Åk22) → anorthite (1260°C) → Ti-Al-rich clinopyroxene (1230°C; “Ti-fassaite”). The melilite becomes increasingly åkermanitic with decreasing temperature. The pyroxene is similar in composition to fassaites from Type B inclusions. Preliminary results suggest that the crystallization sequence is similar at oxygen fugacities near the iron-wüstite buffer.The results of these experiments have been integrated with available phase equilibrium data in the system CaO-MgO-Al₂O₃-SiO₂TiO₂ and a phase diagram for predicting the crystallization sequences of liquids with compositions of coarse-grained Ca-Al-rich inclusions has been developed.Available bulk compositions of coarse-grained inclusions form a well-defined trend in terms of major elements, extending from Type A and Bl inclusions near the spinel-melilite join to more pyroxene-rich Type B2 inclusions. The trend deviates from the expected sequence of solid condensates from a nebular gas at P = 10^?3 atm if pure diopside is assumed to be the clinopyroxene that condenses. The Type A-B1 end of the trend is similar in composition to calculated equilibrium condensates at 1202–1227°C and the trend as a whole parallels the sequence of condensates expected from diopside condensation at ~ 1170°C. The trend is consistent to first order with the condensation of solid Ti-rich fassaite in place of pure diopside at higher temperatures than those at which pure diopside is predicted to condense. Partially molten condensates may be likely in this case or if the nebular pressure is higher than 10^?3 atm.     

Crystal growth of calcite from calcium bicarbonate solutions at constant PCO2 and 25°C: a test of a calcite dissolution model

A highly reproducible seeded growth technique was used to study calcite crystallization from calcium bicarbonate solutions at 25°C and fixed carbon dioxide partial pressures between 0.03 and 0.3 atm. The results are not consistent with empirical crystallization models that have successfully described calcite growth at low P_CO2 (< 10^?3 atm). Good agreement was found between observed crystallization rates and those calculated from the calcite dissolution rate law and mechanism proposed by Plummer et al. (1978).     

Liquidus karrooite stability and composition at reducing conditions

We have determined the stability of rutile and karrooite on the liquidus of pseudobinary silicate melts of anorthite–diopside eutectic composition with, in addition, of up to 32 wt% TiO₂ at one atm total pressure and at wide range of oxygen fugacities. At 1,300°C and at an fO₂ below 10^–11.2 atm rutile (TiO₂) is replaced as liquidus phase by the pseudobrookite-type MgTi₂O₅–Ti₃O₅ solid solution with some Al in the crystal structure. The composition of karrooite was found to be strongly dependent on oxygen fugacity. Crystalline phases were identified by transmission electron microscopy (TEM). The results obtained in this study are relevant for understanding the chemistry of lunar armalcolites. Using excess rutile solubility at reducing conditions, we estimated the Ti⁴⁺ /Ti³⁺ ratio in silicate melts at 1,300°C as function of fO₂.     

Partition of Sr,Ba, Ca,Y, Eu2+, Eu3+, and other REE between plagioclase feldspar and magmatic liquid: an experimental study

Plagioclase feldspar/magmatic liquid partition coefficients for Sr, Ba, Ca, Y, Eu²⁺, Eu³⁺ and other REE have been determined experimentally at 1 atm total pressure in the temperature range 1150–1400°C. Natural and synthetic melts representative of basaltic and andesitic bulk compositions were used, crystallizing plagioclase feldspar in the composition range An₃₅–An₈₅. Partition coefficients for Sr are greater than unity at all geologically reasonable temperatures, and for Ba are less than unity above approximately 1060°C. Both are strongly dependent upon temperature. Partition coefficients for the trivalent REE are relatively insensitive to temperature. At fixed temperature they decrease monotonically from La to Lu. The partition of Eu is a strong function of oxygen fugacity. Under extreme reducing conditions D_Eu approaches the value of D_Sr.     

Fluid Inclusion and Stable Isotope Study at the Southeastern Martabe Deposit: Purnama,Barani and Horas Ore Bodies,North Sumatra,Indonesia

The Martabe Au–Ag deposit, North Sumatra Province, Indonesia, is a high sulfidation epithermal deposit, which is hosted by Neogene sandstone, siltstone, volcanic breccia, and andesite to basaltic andesite of Angkola Formation. The deposit consists of six ore bodies that occurred as silicified massive ore (enargite–luzonite–pyrite–tetrahedrite–tellurides), quartz veins (tetrahedrite–galena–sphalerite–chalcopyrite), banded sulfide veins (pyrite–tetrahedrite–sphalerite–galena) and cavity filling. All ore bodies are controlled by N–S and NW–SE trending faults. The Barani and Horas ore bodies are located in the southeast of the Purnama ore body. Fluid inclusion microthermometry, and alunite‐pyrite and barite‐pyrite pairs sulfur isotopic geothermometry show slightly different formation temperatures among the ore bodies. Formation temperature and salinity of fluid inclusions of the Purnama ore body range from 200 to 260 C and from 6 to 8 wt.% NaCl equivalent, respectively. Formation temperature and salinity of fluid inclusions of the Barani ore body range from 200 to 220 °C and from 0 to 2.5 wt.% NaCl equivalent and those of the Horas ore body range from 240 to 275 °C and from 2 to 3 wt.% NaCl equivalent, respectively. The Barani and Horas ore bodies are less silicified and sulfides are less abundant than the Purnama ore body. A relationship between enthalpy and chloride content indicates mixing of hot saline fluids with cooler dilute fluids during the mineralization of each of the ore bodies. The δ¹⁸O values of quartz samples from the southeast ore bodies exhibit a wide range from +4.2 to +12.9‰ with an average value of +7.0‰. The δ¹⁸O values of H₂O estimated from δ¹⁸O values of quartz, barite and calcite confirm the oxygen isotopic shift to near meteoric water trend, which support the incorporation of meteoric water. Salinity of the fluid inclusions decrease from >5 wt.% NaCl equivalent in the Purnama ore body to <3 wt.% NaCl equivalent in the Barani ore body, indicating different fluid systems during mineralization. The δ³⁴S values of sulfide and sulfate in Purnama range from ? 4.2 to +5.5‰ and from +1.2 to +26.7‰, those in the Barani range from ? 4.3 to +26.4‰ and from +3.9 to +18.5‰ and those in the Horas ore body range from ? 11.8 to +3.5‰ and from +1.4 to +25.7‰, respectively. The δ³⁴S of total bulk sulfur in southeastern ore bodies (Σδ³⁴S) was estimated to be approximately +6‰. The estimated sulfur fugacity during formation of the Purnama and Horas ore bodies is relatively high. It was between 10^?4.8 and 10^?10.8 atm at 220 to 260 °C. Tellurium fugacity was between 10^?7.8 and 10^?9.5 atm at 260 °C and between 10^?9 and 10^?10.6 atm at 220 °C in the Purnama ore body. The Barani ore body was formed at lower fS₂, lower than about 10^?14 atm at 200 to 220 °C based on the presence of arsenopyrite and pyrrhotite in the early stage, and between 10^?14 and 10^?12 atm based on the existence of enargite and tennantite in the last stage. © 2016 The Society of Resource Geology     

In situ observation of crystal growth in a basalt melt and the development of crystal size distribution in igneous rocks

The speciation of CO₂ in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO₂ into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO₂ re-appeared. Infrared extinction coefficients of both carbonate and molecular CO₂ decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO₂ + O^2? = CO₃ ^2? in the melt shifts toward CO₂ with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 10³ T ^?1 for dacite melt (ΔH = ?42 kJ mol^?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 10³ T ^?1 for phonolite melt (ΔH = ?65 kJ mol^?1), where K is the molar ratio of carbonate over molecular CO₂ and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO₂ speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO₂, and therefore, the diffusion coefficient of CO₂ is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO₂ solubility and speciation on melt composition, in accordance with available solubility data.     

Influence of oxygen fugacity and temperature on the redox state of iron in natural silicic aluminosilicate melts

The influence of oxygen fugacity (fO₂) and temperature on the valence and structural state of iron was experimentally studied in glasses quenched from natural aluminosilicate melts of granite and pantellerite compositions exposed to various T-fO₂ conditions (1100–1420°C and 10^?12–10^?0.68 bar) at a total pressure of 1 atm. The quenched glasses were investigated by Mössbauer spectroscopy. It was shown that the effect of oxygen fugacity on the redox state of iron at 1320–1420°C can be described by the equation log(Fe³⁺/Fe²⁺) = k log(fO₂) + q, where k and q are constants depending on melt composition and temperature. The Fe³⁺/Fe²⁺ ratio decreases with decreasing fO₂ (T = const) and increasing temperature (fO₂ = const). The structural state of Fe³⁺ depends on the degree of iron oxidation. With increasing Fe³⁺/Fe²⁺ ≥ 1, the dominant coordination of Fe³⁺ changes from octahedral to tetrahedral. Ferrous iron ions occur in octahedral (and/or five-coordinated) sites independent of Fe³⁺/Fe²⁺.     

Numerical simulation of the origin of red sandstone and Cu accumulation in pore solutions

Interaction of igneous rocks with river (rain) water in the systems granite-water, basalt-water, and dunite-water open with respect to carbon dioxide (PCO₂ = 10^?4, 10^?3, and 10^?2 bar) and oxygen (PO₂ from 10^?81 to 10^?1 bar) is numerically simulated at 25 and 50°C and a mass ratio of water and rock R/W ≤ 10. Equilibrium simulations indicate that, first, the differences in the mineralogical composition of the transformation products of the igneous rocks are insignificant, and second, Cu extraction from minerals of the rocks is optimal at Eh from +200 to ?100 mV. Simulations of the systems with regard for the dissolution rates of minerals indicate that the chemical weathering time of the rocks is few hundred thousands years.     

Volatilization of sodium from silicate melt spheres and its application to the formation of chondrules

The rates of volatilization of Na from liquid spheres of chondrule compositions have been determined as functions of time, temperature, partial pressure of oxygen, and sizes of the spheres. The Na₂O content in the sphere is uniform in each run. but it decreases with time of the run, indicating that the rate of diffusion of Na in the liquid is greater than that of volatilization, and that the latter is the rate-controlling process. The rate of sodium volatilization becomes greater with increasing temperature and with decreasing P_O2 and size of the spheres. The relation of the Na₂O content in the liquid sphere with time and its size indicate that the amount of Na₂O volatilized from the liquid spheres within unit time is proportional to the surface area of the spheres and the concentration of Na₂O in the liquid. From these relations, the rate of volatilization of sodium can be obtained at constant temperature and P_o2. The rate of volatilization of sodium satisfies the Arrhenius relation within the temperature range from about 1450–1600 C at 10^?9,2 atm p_O2; the activation energy for the sodium volatilization is approximately 100 kcal-mole^?1. The rate is also approximately proportional to within the range of p_O2 from 10^?10.2 to 10^?5.0 atm at about 1500° C. Based on the present results and the Na₂O contents in chondrules. it is suggested that they experienced an instant heating with maximum temperature of 1400–2200° C followed by an immediate cooling.     

Laboratory actinide partitioning: Whitlockite/liquid and influence of actinide concentration levels

Fission and alpha track radiography techniques have been used to measure partition coefficients (D) at trace (ppm) concentration levels for the actinide elements Th, U, and Pu between synthetic whitlockite and coexisting “haplobasaltic” silicate liquid at 1 bar pressure and 1250°C at oxygen fugacities from 10^?8.5 and 10^?0.7 bars. Pu is much more readily incorporated into crystalline phases than is U or Th under reducing conditions (fO₂ = 10^?8.5), because Pu is primarily trivalent, whereas U and Th are tetravalent. Definitive valence state assignments cannot be made, but our best estimates of corrected partition coefficients for Pu⁺³, Pu⁺⁴, Th⁺⁴, U⁺⁴, and U⁺⁶ are, for whitlockite 3.6/<?0.6/1.2/0.5/?0.002. The effect of changing pressure and liquidus temperature is relatively small, which probably reflects a weak temperature dependence for D (whitlockite) but possibly could be due to cancellation of opposing temperature and pressure effects. Comparison of experiments at trace U levels with those containing percent concentrations of UO₂ indicate that Si is involved in the substitution of U in whitlockite with U + 2Si ? Ca + 2P being the most likely mechanism. D_u is lower. 0.3 vs 0.5. at percent levels compared to 20 ppm. This is best explained by the effect of U on melt structure or by a decrease in the fraction of tetravalent U at high U concentrations.     

Grain growth in porous olivine aggregates

Grain growth experiments have been performed at 1 atm on fine grain size (<10 μm) synthetic olivine (Fo₉₁) aggregates at various temperatures (1200° to 1400° C), oxygen fugacities (10^-4 to 10^-11 atm) and total anneal times (10, 30, 60, 100 and 200 h). The rate of grain growth increased with increasing temperature and with increasing oxygen fugacity. The presence of a second phase (residual porosity), introduced during sample fabrication, has a significant effect on grain growth, with evolution in grain size paralleled by changes in the size and frequency of the pores. When the grain growth data were fit to a growth law G ⁿ ?G _O ⁿ =κ₀ tf ₀ ^m ₂e^?Q/RT, the growth exponents fall in the range of n=4 to 5, suggesting that grain growth may be controlled by the coalescence of the second phase. The evolution in pore size and frequency may occur either by the transport of the ionic species constituting olivine between the pores or by the movement of the pores themselves along the grain boundaries and edges. Thus, the rate of growth of the pores and grains is probably limited by diffusion of the slowest ionic species constituting olivine (magnesium, iron, silicon, or oxygen) moving along the fastest path for that species (through the lattice, along the grain boundaries, around the surface of the moving pores, or through the vapor phase in the pores). Activation energies for grain growth of Q=290 ± 20 kJ/mol and 345 ± 25 kJ/mol were calculated from our results for n=4 and 5, respectively. These activation energies preclude vapor-phase transport and iron diffusion along grain boundaries but do not otherwise permit a discrimination between the rate limiting species or path. The oxygen fugacity exponent of m ≈0.12 suggests that lattice diffusion does not control the grain growth. However, the lack of data for magnesium, iron, silicon and oxygen surface and grain boundary diffusion in olivine makes definitive determination of the mechanism controlling grain growth difficult.     

Chemical fractionations in meteorites—VII. Cosmothermometry and cosmobarometry

The fractional condensation of Bi, Cd, In, Pb and Tl from a cooling gas of cosmic composition is calculated. Predicted absolute and relative abundances of the elements are in good to excellent agreement with the analytical data. This strongly suggests that the presently observed abundances were established at the time of accretion. There is no need to invoke non-equilibrium during condensation or element redistribution after accretion to explain the observations. The elements may therefore be used as cosmothermometers to predict accretion temperatures.Calculated accretion temperatures fall in the range of 420 to 540°K. But a large percentage of each chrondrite group (H, L, LL and E) fall within much narrower intervals, ≤20°K. This implies that the bulk of each group accreted over a narrow temperature range which is consistent with their uniform oxidation states and $\text{O}{}^{18}\text{O}{}^{16}$ ratios. In fact, temperatures inferred from the oxidation state and oxygen isotopes are in excellent agreement with the trace element data.The condensation curves of all these elements are pressure-dependent but are confined to fall in the temperature interval 400 to 600°K owing to the absence of Fe₃O₄ and the presence of FeS in ordinary chrondrites. Absolute upper and lower limits on the total pressure can thus be deduced: 10^?3 to 10^?6 atm. In addition, the condensation curves for Bi and In cross over at T = 462°K and P_t = 2 × 10^?5 atm. The observed relative abundances of Bi and In suggest the L-group formed at slightly lower and the H-group at slightly higher P and T.