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Notes: The saturation surface of cassiterite, SnO2, was determined for liquids in the system K2O–Al2O3–SiO2 as a function of bulk composition and temperature. At fixed K2O/Al2O3 cassiterite solubility varies weakly with SiO2 concentration (76 to 84 mol%), temperature (1350° to 1550°C), and log (fO2) (−0.7 to −5.3). Cassiterite solubility is also approximately independent of composition in liquids with molar ratios of K2O/Al2O3 lessthan equal to 1 (peraluminous liquids). As K2O/Al2O3 increases from 1 (peralkaline liquids), however, cassiterite solubility increases steeply and approximately linearly with K2O in excess of Al2O3. It is proposed that potassium in excess of aluminum combines with Sn4+ to form quasi-molecular complexes with an effective stoichiometry of K4SnO4.

Notes: Abstract Crustal formation and evolution processes are of critical importance in the geochemical and thermal evolution of planets. As an aid to understanding these processes on Venus, we develop a general paradigm for: (1) the derivation of primary magmas, and (2) the range of possible conditions for remelting of crustal materials and the evolution of the products of remelting. We use as a basis for this paradigm the present knowledge of the bulk and surface composition, thermal structure, and surface geological and geochemical processes. For the range of conditions of derivation of primary magmas and crustal remelting, a wide range of magma types is possible, and no magma type can be arbitrarily excluded from consideration on Venus. We conclude that magmatic and volcanic activity on Venus, in its broadest sense, could be very similar to that on the Earth, although eruption styles are expected to vary due to environmental conditions (Head and Wilson, 1986). Major differences in magmatic and volcanic activity are likely to occur in two environments on Venus: (1) those analogous to terrestrial island arcs, where due to the absence of water, melts should be SiO2-undersaturated, and the more fluid melt products may produce widespread deposits of SiO2-poor ferrobasalts rather than more viscous SiO2-rich magmas and composite volcanoes, and (2) those in plains regions influenced by mantle plumes and hot spots, where highly picritic melts may periodically flood vast regions of the surface.

Notes: Abstract The saturation surface of pseudobrookite (Fe2TiO5) was determined for melts in the system SiO2-Al2O3-K2O-FeO-Fe2O3-TiO2 at 1400° C and 1 atm. The variation in concentrations of Fe2O3, TiO2 and Fe2TiO5 in liquids can be used to infer relative changes in activity coefficients of these components with changing K2O/(K2O+Al2O3) of the melts. Saturation concentrations of these components are low and relatively constant in the peraluminous melts and increase with increasing K2O/(K2O+Al2O3) in peralkaline liquids. The activity coefficients of Fe2O3 and TiO2 and Fe2TiO5, therefore, are higher in peraluminous liquids than in peralkaline liquids in this system. In addition, the iron redox ratio was measured as a function of K2O/(K2O+Al2O3) for liquids just below the saturation surface; $$f_{{\text{O}}_{\text{2}} }$$ was fixed so all variations in redox ratio are entirely due to changes in melt composition. The redox ratio from unsaturated liquids was applied to saturated liquids where redox analysis of the glass is impossible. The homogeneous equilibrium experiments indicate that the activity coefficient of Fe2O3 relative to that of FeO is significantly greater in peraluminous melts than peralkaline melts. Both the heterogeneous and homogeneous equilibria suggest that in peralkaline liquids K+in excess of that required to charge balance tetrahedral Al+3 is used to stabilize both Fe+3 and Ti+4. Calculations show that ferric iron and titanium compete equally effectively for charge-balancing potassium but neither can outcompete aluminum. The observed changes in solution properties of Fe2O3 and TiO2 in the synthetic melts are used to explain variations in Fe-Ti oxide stabilities in natural peraluminous and peralkaline rhyolites and granites. Since the activity coefficients of both ferric iron and titanium are significantly higher in peraluminous liquids than in peralkaline liquids, Fe-Ti oxides should occur earlier in the crystallization sequence in peraluminous rhyolites than in peralkaline rhyolites. In addition, iron will be reduced in peraluminous granites and rhyolites relative to peralkaline ones under comparable P, T, and $$f_{{\text{O}}_{\text{2}} }$$ . Finally, observed crystallization patterns for minerals containing highly charged cations other than ferric iron and titanium are evaluated in the context of this and other experimental studies.

Notes: Abstract Partition coefficients (D) for Nb and Ta between rutile and haplogranite melts in the K2O-Al2O3-SiO2 system have been measured as functions of the K2O/Al2O3 ratio, the concentrations of Nb2O5 and Ta2O5, the temperature, in air and at 1 atmosphere pressure. The Ds increase in value as the K* [K2O/(K2O + Al2O3)] molar ratio continuously decreases from highly peralkaline [K* ∼ 0.9] to highly peraluminous [K* ∼ 0.35] melts. The D values increase more dramatically with a unit decrease in K* in peraluminous melts than in peralkaline melts. This compositional dependence of Ds can be explained by the high activity of NbAlO4 species in peraluminous melts and the high activity of KONb species (or low activity of NbAlO4 species) in peralkaline melts. A coupled substitution, Al+3 + Nb+5 (or Ta+5) = 2Ti+4, accounts for the Ds of Nb (Ta) being much greater in peraluminous melts than in peralkaline melts because this substitution allows Nb (Ta) to enter into the rutile structure more easily. The Ds of Ta between rutile and melt are greater than those of Nb at comparable concentrations because the molecular electronic polarizability of Ta is weaker than that of Nb. The Nb+5 with a large polarizing power forms a stronger covalent bond with oxygen than Ta+5 with a small polarizing power. The formation of the strong bond, Nb-O, distorts the rutile structure more severely than the weak bond, Ta-O; therefore, it is easier for Ta to partition into rutile than for Nb. These results imply that the utilization of the Nb/Ta ratio in liquid as a petrogenetic indicator in granitic melts must be done with caution if rutile (or other TiO2-rich phases) is a liquidus phase. The crystallization of rutile will increase the Nb/Ta ratio of the residual liquid because the Ds of Ta between rutile and melts are greater than those of Nb.

Notes: Abstract A petrogenetic grid is constructed for mineral assemblages occurring in metapelitic rocks, particularly those involved in the paragenesis of cordierite. The most useful assemblages for estimating pressures and temperatures are staurolite-cordierite, cordierite-biotite-Al2SiO5 and cordierite-hypersthene. Cordierite is stable with kyanite, sillimanite or andalusite. At high pressures cordierite is Mg-rich so that pelitic rocks typically do not contain the phase. Cordierite is stable at temperatures less than 500° C but does not commonly appear in metapelitic rocks until the garnet-chlorite, chlorite-staurolite or chlorite-Al2SiO5 tie-lines are broken. At high metamorphic grades, the assemblage garnet-hypersthene-cordierite indicates relatively low pressures, and the assemblage hypersthene-cordierite-sillimanite relatively high pressures. It is clear however, that the absence of cordierite is of little use in characterizing a metamorphic facies unless an alternate mineral assemblage can be shown to be more stable.

Notes: Abstract The saturation surfaces of rutile (TiO2), zircon (ZrSiO4), and hafnon (HfSiO4) were determined in anhydrous, peraluminous, high silica liquids of the system SiO2-Al2O3-Na2O-K2O as functions of silica concentration at 1,400° C in air. The saturation concentrations of TiO2, ZrO2, and HfO2 in rutile, zircon, and hafnon-saturated liquids, respectively, decrease smoothly and gradually as functions of increasing silica concentration. Thermodynamic analyses of the data demonstrate that the activity coefficients of TiO2, ZrO2, and HfO2 increase smoothly and gradually as silica concentration is increased from 67 wt-% to 80 wt-%, and that changes in SiO2 of 1 or 2 wt-% result in small changes in the saturation concentrations and activity coefficients of +4 cations. Because the solution behavior of +4 cations in highly siliceous liquids (〉75 wt-% SiO2) is predictably different than in less siliceous liquids (70 to 75 wt-% SiO2), classification of highly-siliceous igneous rocks on the basis of silica concentration alone should not be interpreted to mean that their solution chemistry differs significantly from that of less siliceous rocks. The results of this study are compared with other studies of +4 cation solution behavior. From this it is concluded that variations in liquid compositions observed in cogenetic suites of high silica rhyolites cannot cause the observed changes in +4 cation concentrations. Thus, even if a large change in solution behavior of +4 cations is inferred from the large variations in their concentrations, it cannot be due to changes in bulk composition of the parental liquid. In addition, the similarity in the solution behavior of Zr and Hf seen in this study suggests that their solution mechanisms are similar. It is thus unlikely that liquid-state processes can fractionate one with respect to another, and variations in Zr/Hf ratios in suites of extrusive rocks are likely due to crystal-liquid equilibria, e.g., zircon fractionation.

Notes: Abstract The redox ratio of iron is used as an indicator of solution properties of silicate liquids in the system (SiO−Al2O3−K2O−FeO−Fe2O3−P2O5). Glasses containing 80–85 mol% SiO2 with 1 mol% Fe2O3 and compositions covering a range of K2O/Al2O3 were synthesized at 1400°C in air (fixed fO2). Variations in the ratio FeO/FeO1.5 resulting from the addition of P2O5 are used to determine the solution behavior of phosphorus and its interactions with other cations in the silicate melt. In 80 mol% SiO2 peralkaline melts the redox ratio, expressed as FeO/FeO1.5, is unchanged relative to the reference curve with the addition of 3 mol% P2O5. Yet, the iron redox ratio in the 85 mol% SiO2 potassium aluminosilicate melts is decreased relative to phosphorus-free liquids even for small amounts of P2O5 (0.5 mol%). The redox ratio in peraluminous melts is decreased relative to phosphorus- free liquids at P2O5 concentrations of 3 mol%. In peraluminous liquids, complexing of both Fe+3−O−P+5 and Al+3−O−P+5 occur. The activity coefficient of Fe+3 is decreased because more ferric iron can be accommodated than in phosphorus-free liquids. In peralkaline melts, there is no evidence that P+5 is removing K+ from either Al+3 or Fe+3 species. In chargebalanced melts with 3 mol% Fe2O3 and very high P2O5 concentrations, phosphorus removes K+ from K−O−Fe+3 complexes resulting in a redox increase. P2O5 should be accommodated easily in peraluminous rhyolitic liquids and phosphate saturation may be suppressed relative to metaluminous rhyolites. In peralkaline melts, phosphate solubility may increase as a result of phosphorus complexing with alkalis. The complexing stoichiometry may be variable, however, and the relative influence of peralkalinity versus temperature on phosphate solubility in rhyolitic melts deserves greater attention.

Notes: Abstract The effects of the addition of Al2O3 on the large stable two liquid field in the SiO2-TiO2-CaO-MgO-FeO system were experimentally determined. The increase of Al2O3 content in the starting composition results in the decrease of critical temperature, phase separation and liquidus temperature of the two liquid field until it is rendered completely metastable. The shrinkage of the two liquid field indicates that Al2O3 is acting in the role of a network former and homogenizes the structure of the two melts. In this alkali-free system Al+3 utilizes the divalent cations, Ca+2 and Mg+2, for local charge balance with a preference for Ca+2 over Mg+2. Thus, AlO4 tetrahedra combine with SiO4 tetrahedra to form an aluminosilicate framework which polymerizes the SiO2-poor melt and makes it structurally more similar to the SiO2-rich melt. However, Ca+2 and Mg+2 are not as efficient in a charge balancing capacity as the monovalent K+ and Na+ cations. The lack of alkalis in this system limits the stability of AlO4 tetrahedra in the highly polymerized SiO2-rich melt and results in the preference of Al2O3 for the SiO2-poor melt. The partitioning systematics of Ti are virtually identical to those of Al. It is concluded that Ti occurs in tetrahedral coordination as a network forming species in both the high — and low — SiO immiscible melts.

Notes: Abstract Partial electron microprobe analyses of garnet, biotite and cordierite in sillimanite-K feldspar gneisses of the Brimfield Formation in south-central Massachusetts indicate that the compositions of these minerals are not constant in a thin section. The FeO/MgO mol ratio of biotite is sensitive to the nature of other FeO-MgO minerals occurring in close proximity. The most iron-rich biotites are those that do not contact either cordierite or garnet. The most iron-poor biotites occur as inclusions in garnet. Biotites in direct contact with either cordierite or garnet have intermediate FeO/MgO ratios. The bulk of a given grain of garnet or cordierite is homogeneous in composition. Chemical zoning is absent. All grains of garnet and cordierite in a thin section are constant in composition. However, where garnet and cordierite abut biotite, the FeO/MgO ratio of the garnet rim is increased and that of cordierite is decreased. The FeO/MgO ratios of garnet, cordierite and biotite bare a regular relation to each other indicating a possible equilibrium state. However the distribution coefficient defined by the compositions of minerals in direct contact are greater than those defined by the compositions of the interiors of garnet and cordierite matched with the compositions of biotites removed from these phases. This pattern is believed to be the result of two thermal events. The first event produced the mineral assemblages and widespread equilibrium was obtained. A subsequent retrograde event left the mineralogy intact but caused cation exchange reactions at immediate contacts between garnet, cordierite and biotite. The physical conditions of the first event are estimated at P=5–6 kb, T=700–750° C. The retrograde event occurred at lower temperatures and very low activities of H2O since no muscovite is developed at microcline-sillimanite contacts.

Notes: Abstract Incremental amounts of Na2O and K2O added to immiscible melts in the MgO-CaO-TiO2-Al2O3 SiO2 system cause a decrease in critical temperature, phase separation and change in the pattern of Al2O3 partitioning. Al2O3, which is concentrated in the low SiO2 immiscible melts in the alkali-free system, is increasingly partitioned into the high-SiO2 immiscible melt as the alkali/aluminium ratio is increased. However, K2O is more effective than Na2O in stabilizing Al2O2 in the SiO2-rich melt. The coordination changes occurring in the aluminosilicate melts upon the addition of the alkali oxides are described by CaAl2O4+2SiOK=2KAlO2+SiOCaOSi where K (or Na) displaces Ca as the charge-balancing cation for the networkforming AlO4 tetrahedra. The increased stability of the AlO4 species in the highly polymerized SiO2-rich melt and the consequent shrinkage of the miscibility gap is ascribed to positive configurational entropy and negative enthalpy changes associated with the formation of K, Na-AlO4 species. Element partition systematics indicate that (Na, K)AlO2 species favor the more polymerized, CaAl2O4 and TiO2 species, the less polymerized silicate structure in the melt.