Garnet-clinopyroxene geothermometer

A garnet-clinopyroxene geothermometer based on the available experimental data on compositions of coexisting phases in the system MgO-FeO-MnO-Al₂O₃-Na₂O-SiO₂ is as follows: $$T({\text{}}K) = \frac{{8288 + 0.0276 P {\text{(bar)}} + Q1 - Q2}}{{1.987 \ln K_{\text{D}} + 2.4083}}$$ where P is pressure, and Q1, Q2, and K _D are given by the following equations $$Q1 = 2,710{\text{(}}X_{{\text{Fe}}} - X_{{\text{Mg}}} {\text{)}} + 3,150{\text{ }}X_{{\text{Ca}}} + 2,600{\text{ }}X_{{\text{Mn}}} $$ (mole fractions in garnet) $$\begin{gathered}Q2 = - 6,594[X_{{\text{Fe}}} {\text{(}}X_{{\text{Fe}}} - 2X_{{\text{Mg}}} {\text{)]}} \hfill \\{\text{ }} - 12762{\text{ [}}X_{{\text{Fe}}} - X_{{\text{Mg}}} (1 - X_{{\text{Fe}}} {\text{)]}} \hfill \\{\text{ }} - 11,281[X_{{\text{Ca}}} (1 - X_{{\text{Al}}} ) - 2X_{{\text{Mg}}} 2X_{{\text{Ca}}} ] \hfill \\{\text{ + 6137[}}X_{{\text{Ca}}} (2X_{{\text{Mg}}} + X_{{\text{Al}}} )] \hfill \\{\text{ + 35,791[}}X_{{\text{Al}}} (1 - 2X_{{\text{Mg}}} )] \hfill \\{\text{ + 25,409[(}}X_{{\text{Ca}}} )^2 ] - 55,137[X_{{\text{Ca}}} (X_{{\text{Mg}}} - X_{{\text{Fe}}} )] \hfill \\{\text{ }} - 11,338[X_{{\text{Al}}} (X_{{\text{Fe}}} - X_{{\text{Mg}}} )] \hfill \\\end{gathered} $$ [mole fractions in clinopyroxene Mg = MgSiO₃, Fe = FeSiO₃, Ca = CaSiO₃, Al = (Al₂O₃-Na₂O)] K _D = (Fe/Mg) in garnet/(Fe/Mg) in clinopyroxene. Mn and Cr in clinopyroxene, when present in small concentrations are added to Fe and Al respectively. Fe is total Fe²⁺+Fe³⁺.     

Enstatite-diopside solvus and geothermometry

The enstatite-diopside solvus presents certain interesting thermodynamic and crystal-structural problems. The solvus may be considered as parts of two solvi one with the ortho-structure and the other with clino-structure. By assuming the standard free energy change for the two reactions (MgMgSi₂O₆)opx ? (MgMgSi₂O₆)cpx and (CaMgSi₂O₆) opx ? (CaMgSi₂O₆) cpx as 500 and 1 000 to 3 000 cal/mol respectively, it is possible to calculate the regular solution parameter W for orthopyroxene and clinopyroxene. These W's essentially refer to mixing on M2 sites. The expression for the equilibrium constant by assuming ideal mixing for Fe-Mg, Fe-Ca and non-ideal mixing for Ca-Mg on binary M1 and ternary M2 sites is given by 1 $$K_a = \frac{{X_{{\text{Mg - cpx}}}^{{\text{M1}}} X_{{\text{Mg - cpx}}}^{{\text{M2}}} \exp \left[ {\frac{{W_{{\text{cpx}}} }}{{RT}}\left\{ {X_{{\text{Ca - cpx}}}^{{\text{M2}}} \left( {X_{{\text{Ca - cpx}}}^{{\text{M2}}} + X_{{\text{Fe - cpx}}}^{{\text{M2}}} } \right)} \right\}} \right]}}{{X_{{\text{Mg - cpx}}}^{{\text{M1}}} X_{{\text{Mg - opx}}}^{{\text{M2}}} \exp \left[ {\frac{{W_{{\text{cpx}}} }}{{RT}}\left\{ {X_{{\text{Ca - opx}}}^{{\text{M2}}} \left( {X_{{\text{Ca - opx}}}^{{\text{M2}}} + X_{{\text{Fe - opx}}}^{{\text{M2}}} } \right)} \right\}} \right]}}$$ where X's are site occupancies, R is 1.987 and T is temperature in ^oK. Temperature of pyroxene crystallization may be estimated by substituting for T in the above equation until the equation ?RT In K _a=500 is satisfied. The shortcomings of this method are the incomplete standard free energy data on the end member components and the absence of site occupancy data in pyroxenes at high temperatures. The assumed free energy data do, however, show the possible extent of inaccuracy in temperature estimates resulting from the neglect of Mg-Ca non ideality.     

Experimental determination of the temperature and pressure dependence of the Fe-Mg partition coefficient for coexisting garnet and clinopyroxene

An experimental study initiated to calibrate the distribution coefficient \(K_D = \frac{{({\text{FeO}}/{\text{MgO}})_{{\text{ga}}} }}{{{\text{(FeO}}/{\text{MgO)}}_{{\text{cpx}}} }}\) in eclogites as a geothermometer has been done on (a) a mineral mis, (b) a glass of the typical tholeiite composition and (c) a series of glasses of tholeiite compositions with \(6.2 < \frac{{100{\text{Mg}}}}{{{\text{Mg}} + {\text{Fe}}^{ + + } }} < 93.\) The mineral mix was found to be unsuitable as reactant due to incomplete equilibration but the minimum K _D of the mineral mix and the K _D from glass of tholeiite composition are identical within experimental uncertainty. These data constitute a reversal of the garnet/clinopyroxene partition relationship and provide justification of the use of glass as a reactant for the project. To eliminate any uncertainty in interpretation of mineral analyses due to possible variation in Fe⁺⁺⁺/Fe⁺⁺ between runs, experiments were carried out in iron capsules on the nine tholeiite glasses, thus maintaining iron as Fe⁺⁺. Microprobe analytical techniques yielded mineral analyses of comparable accuracy to analyses of natural phases for experiments within the temperature range from 600° C to 1500° C and a pressure range from 20 kb to 40 kb. It has been shown that for \(6.2 < \frac{{100{\text{Mg}}}}{{{\text{Mg}} + {\text{Fe}}^{ + + } }} < 85\) , the bulk chemical composition does not perceptibly affect the K _D value. At 30 kb the K _D value ranges from 18.0 at 600° C to 1.45 at 1400° C, defining the linear relationship in a ln K _D vs 1/T(°K) plot. The pressure dependence of the K _D -value has been shown to be greater than previously predicted. There is a straight line relationship in ln K _D vs Pressure (Kb) between 20 and 40 kb at constant temperature (1100°C). This enables us to determine K _D =fn (T, P) and \(T(^\circ {\text{K}}) = \frac{{3686 + 28.35 \times P({\text{Kb}})}}{{\ln K_D + 2.33}}\) . This expression uniquely determines the temperature of equilibration of natural eclogites of basaltic bulk composition when the K _D ^ga,cpx is known and a pressure estimate can be given.     

(Ca,Mg)2Si2O6 clinopyroxenes: A solution model based on nonconvergent site-disorder

Experiments at high pressure and temperature indicate that excess Ca may be dissolved in diopside. If the (Ca, Mg)₂Si₂O₆ clinopyroxene solution extends to more Ca-rich compositions than CaMgSi₂O₆, macroscopic regular solution models cannot strictly be applied to this system. A nonconvergent site-disorder model, such as that proposed by Thompson (1969, 1970), may be more appropriate. We have modified Thompson's model to include asymmetric excess parameters and have used a linear least-squares technique to fit the available experimental data for Ca-Mg orthopyroxene-clinopyroxene equilibria and Fe-free pigeonite stability to this model. The model expressions for equilibrium conditions \(\mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction A) and \(\mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction B) are given by: 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Mg}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ W_{21} [2(X_{{\text{Ca}}}^{{\text{M2}}} )^3 - (X_{{\text{Ca}}}^{{\text{M2}}} ] \hfill \\ {\text{ + 2W}}_{{\text{22}}} [X_{{\text{Ca}}}^{{\text{M2}}} )^2 - (X_{{\text{Ca}}}^{{\text{M2}}} )^3 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{Wo}}}^{{\text{opx}}} )^2 \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Ca}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ 2W_{21} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^2 - (X_{{\text{Mg}}}^{{\text{M2}}} )^3 ] \hfill \\ {\text{ + W}}_{{\text{22}}} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^3 - (X_{{\text{Mg}}}^{{\text{M2}}} )^2 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{En}}}^{{\text{opx}}} )^2 \hfill \\ \hfill \\ \end{gathered} $$ where 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = 2.953 + 0.0602{\text{P}} - 0.00179{\text{T}} \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = 24.64 + 0.958{\text{P}} - (0.0286){\text{T}} \hfill \\ {\text{W}}_{{\text{21}}} = 47.12 + 0.273{\text{P}} \hfill \\ {\text{W}}_{{\text{22}}} = 66.11 + ( - 0.249){\text{P}} \hfill \\ {\text{W}}^{{\text{opx}}} = 40 \hfill \\ \Delta {\text{G}}_*^0 = 155{\text{ (all values are in kJ/gfw)}}{\text{.}} \hfill \\ \end{gathered} $$ . Site occupancies in clinopyroxene were determined from the internal equilibrium condition 1 $$\begin{gathered} \Delta G_{\text{E}}^{\text{O}} = - {\text{RT 1n}}\left[ {\frac{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}{{X_{{\text{Ca}}}^{{\text{M2}}} \cdot X_{{\text{Mg}}}^{{\text{M1}}} }}} \right] + \tfrac{1}{2}[(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} )(2{\text{X}}_{{\text{Ca}}}^{{\text{M2}}} - 1) \hfill \\ {\text{ + }}\Delta G_*^0 (X_{{\text{Ca}}}^{{\text{M1}}} - X_{{\text{Ca}}}^{{\text{M2}}} ) + \tfrac{3}{2}(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} ) \hfill \\ {\text{ (1}} - 2X_{{\text{Ca}}}^{{\text{M1}}} )(X_{{\text{Ca}}}^{{\text{M1}}} + \tfrac{1}{2})] \hfill \\ \end{gathered} $$ where δG _E ⁰ =153+0.023T+1.2P. The predicted concentrations of Ca on the clinopyroxene Ml site are low enough to be compatible with crystallographic studies. Temperatures calculated from the model for coexisting ortho- and clinopyroxene pairs fit the experimental data to within 10° in most cases; the worst discrepancy is 30°. Phase relations for clinopyroxene, orthopyroxene and pigeonite are successfully described by this model at temperatures up to 1,600° C and pressures from 0.001 to 40 kbar. Predicted enthalpies of solution agree well with the calorimetric measurements of Newton et al. (1979). The nonconvergent site disorder model affords good approximations to both the free energy and enthalpy of clinopyroxenes, and, therefore, the configurational entropy as well. This approach may provide an example for Febearing pyroxenes in which cation site exchange has an even more profound effect on the thermodynamic properties.     

Partitioning of iron and magnesium between crystals and partial melts in peridotite upper mantle

The iron-magnesium distribution coefficient, $$K'_D = (X_{\Sigma {\text{FeO}}} /X_{{\text{MgO}}} )^{{\text{olivine}}} (X_{{\text{MgO}}} /X_{\Sigma {\text{FeO}}} )^{{\text{liquid}}} ,$$ has frequently been used as a means of testing whether experimental and natural silicate liquids could have been in equilibrium with olivine of mantle composition. It is shown here that this K′ _D decreases with increasing oxygen fugacity (xxx) for a hydrous partial melt in equilibrium with a natural spinel peridotite assemblage under pressure and temperature conditions corresponding to those of the upper mantle (from 0.52 at the xxx of the iron-wüstite buffer to 0.04 at the xxx of the magnetite-hematite buffer). K′ _D also increases with increasing pressure, with decreasing temperature, and probably with increasing Mg/(Mg+∑ Fe) of the parental peridotite, suggesting that $$K_D = (X_{{\text{FeO}}} /X_{{\text{MgO}}} )^{{\text{olivine}}} (X_{{\text{MgO}}} /X_{{\text{FeO}}} )^{{\text{liquid}}}$$ also increases with increasing pressure and decreasing temperature. Thus, unless these four variables (P, T, xxx, silicate composition) are known for a natural magma, K′ _D and probably K _D are variables, and the Mg/(Mg+∑ Fe) of such a magma cannot be correlated to that of the parent. The K _D determined at 1 atm pressure by Roeder and Emslie has frequently been used to test whether the Mg/(Mg+∑ Fe) ratios of experimentally formed liquids at high pressure in equilibrium with olivine of known Fo content represent the equilibrium Mg/(Mg+Fe²⁺) of this liquid, assuming that ∑Fe=Fe²⁺ and that K′ _D does not vary with P, T, and composition of the system. Published data demonstrate that the oxygen fugacities of the experimental designs employed by different laboratories vary between those of the magnetite-hematite and magnetite-wüstite buffers (6 orders of magnitude), resulting in K′ _D between 0.04 and 0.31 at 1050° C and 15 kbar, for example. Thus, published arguments as to whether the quenched liquids represent equilibrium compositions based on iron-magnesium partitioning are inadequate. The effects of P, T, xxx, and the composition of the starting material must also be considered.     

Thermodynamic mixing properties of Mg(Al,Cr)2O4 spinel crystalline solution at high temperatures and pressures

Three Al-Cr exchange isotherms at 1,250°, 1,050°, and 796° between Mg(Al, Cr)₂O₄ spinel and (Al, Cr)₂O₃ corundum crystalline solutions have been studied experimentally at 25 kbar pressure. Starting from gels of suitable bulk compositions, close approach to equilibrium has been demonstrated in each case by time studies. Using the equation of state for (Al, Cr)₂O₃ crystalline solution (Chatterjee et al. 1982a) and assuming that the Mg(Al, Cr)₂O₄ can be treated in terms of the asymmetric Margules relation, the exchange isotherms were solved for Δ G ^*, and . The best constrained data set from the 1,250° C isotherm clearly shows that the latter two quantities do not overlap within three standard deviations, justifying the choice of asymmetric Margules relation for describing the excess mixing properties of Mg(Al, Cr)₂O₄ spinels. Based on these experiments, the following polybaric-polythermal equation of state can be formulated: , P expressed in bars, T in K, G _m ^ex and W _G,i ^Sp in joules/mol. Temperature-dependence of G _m ^ex is best constrained in the range 796–1,250° C; extrapolation beyond that range would have to be done with caution. Such extrapolation to lower temperature shows tentatively that at 1 bar pressure the critical temperature, T _c, of the spinel solvus is 427° C, with dT_c/dP≈1.3 K/kbar. The critical composition, X _c, is 0.42 , and changes barely with pressure. Substantial error in calculated phase diagrams will result if the significant positive deviation from ideality is ignored for Al-Cr mixing in such spinels.     

The system Fe-Si-O: Oxygen buffer calibrations to 1,500K

The five solid-phase oxygen buffers of the system Fe-Si-O, iron-wuestite (IW), wuestite-magnetite (WM), magnetite-hematite (MH), quartz-iron-fayalite (QIF) and fayalite-magnetite-quartz (FMQ) have been recalibrated at 1 atm pressure and temperatures from 800°–1,300° C, using a thermogravimetric gas mixing furnace. The oxygen fugacity, \(f_{{\text{O}}_{\text{2}} }\) was measured with a CaO-doped ZrO₂ electrode. Measurements were made also for wuestite solid solutions in order to determine the redox behavior of wuestites with O/Fe ratios varying from 1.05 to 1.17. For FMQ, additional determinations were carried out at 1 kb over a temperature range of 600° to 800° C, using a modified Shaw membrane. Results agree reasonably well with published data and extrapolations. The reaction parameters K, ΔG _r ^o , ΔH _r ^o , and ΔS _r ^o were calculated from the following log \(f_{{\text{O}}_{\text{2}} }\) /T relations (T in K): $$\begin{gathered} {\text{IW }}\log f_{{\text{O}}_{\text{2}} } = - 26,834.7/T + 6.471\left( { \pm 0.058} \right) \hfill \\ {\text{ }}\left( {{\text{800}} - 1,260{\text{ C}}} \right), \hfill \\ {\text{WM }}\log f_{{\text{O}}_{\text{2}} } = - 36,951.3/T + 16.092\left( { \pm 0.045} \right) \hfill \\ {\text{ }}\left( {{\text{1,000}} - 1,300{\text{ C}}} \right), \hfill \\ {\text{MH }}\log f_{{\text{O}}_{\text{2}} } = - 23,847.6/T + 13.480\left( { \pm 0.055} \right) \hfill \\ {\text{ }}\left( {{\text{1,040}} - 1,270{\text{ C}}} \right), \hfill \\ {\text{QIF }}\log f_{{\text{O}}_{\text{2}} } = - 27,517.5/T + 6.396\left( { \pm 0.049} \right) \hfill \\ {\text{ }}\left( {{\text{960}} - 1,140{\text{ C}}} \right), \hfill \\ {\text{FMQ }}\log f_{{\text{O}}_{\text{2}} } = - 24,441.9/T + 8.290\left( { \pm 0.167} \right) \hfill \\ {\text{ }}\left( {{\text{600}} - 1,140{\text{ C}}} \right). \hfill \\ \end{gathered}$$ These experimentally determined reaction parameters were combined with published 298 K data to determine the parameters G_f, H_f, and S_f for the phases wuestite, magnetite, hematite, and fayalite from 298 K to the temperatures of the experiments. The T? \(f_{{\text{O}}_{\text{2}} }\) data for wuestite solid solutions were used to obtain activities, excess free energies and Margules mixing parameters. The new data provide a more reliable, consistent and complete reference set for the interpretation of redox reactions at elevated temperatures in experiments and field settings encompassing the crust, mantle and core as well as extraterrestrial environments.     

The reaction garnet+clinopyroxene+quartz =2 orthopyroxene+anorthite: A potential geobarometer for granulites

A mineralogic geobarometer based on the reaction garnet+clinopyroxene+quartz=2 orthopyroxene+anorthite is proposed. The geobarometric formulations for the Fe- and Mg- end member equilibria are $$\begin{gathered} P_{({\text{Fe}})} {\text{ }}({\text{bars}}){\text{ = 32}}{\text{.097 }}T{\text{ }} - {\text{ 26385 }} - {\text{ 22}}{\text{.79 (}}T - 848 - T1{\text{n(}}T/848{\text{))}} \hfill \\ {\text{ }} - (3.655 + 0.0138T){\text{ }}\left( {\frac{{{\text{(}}T - 848{\text{)}}^{\text{2}} }}{T}} \right) \hfill \\ {\text{ }} - {\text{(3}}{\text{.123) }}T1{\text{n }}\frac{{(a_{a{\text{n}}}^{{\text{Plag}}} )(a_{{\text{fs}}}^{{\text{P}}\ddot u{\text{x}}} )^2 }}{{(a_{{\text{alm}}}^{{\text{Gt}}} )(a_{{\text{hed}}}^{{\text{Opx}}} )}} \hfill \\ P_{({\text{Mg}})} {\text{ (bars) = 9}}{\text{.270 }}T + 4006 - 0.9305{\text{ }}(T - 848 - T1{\text{n (}}T/848{\text{)}}) \hfill \\ {\text{ }} - (1.1963{\text{ }} - {\text{ }}6.0128{\text{ x 10}}^{ - {\text{3}}} T)\left( {\frac{{(T - 848)^2 }}{T}} \right) \hfill \\ {\text{ }} - 3.489{\text{ }}T1{\text{n }}\frac{{(a_{an}^{{\text{Plag}}} ){\text{ }}(a_{{\text{ens}}}^{{\text{Opx}}} )}}{{{\text{(}}a_{{\text{pyr}}}^{{\text{Gt}}} {\text{) (}}a_{{\text{diop}}}^{{\text{Cpx}}} {\text{)}}}}. \hfill \\ \end{gathered}$$ The end member thermodynamic data have been taken from the data base of Helgeson et al. (1978) and Saxena and Erikson (1983). The activities of pyroxene components and anorthite in plagioclase have been modelled after Wood and Banno (1973) and Newton (1983) respectively. The activities of pyrope and almandine are calculated from the binary interaction parameters for garnet solid solutions proposed by Saxena and Erikson (1983). Pressures computed from these equations for fifty sets of published mineral data from several granulite areas are comparable with those obtained from dependable geobarometers. The pressure values determined from the Fe-end member equilibrium appear to be more reasonable than those from the Mg-end member reaction. It is likely that the difference in pressures computed from the Fe- and Mg-end members, ΔP ^*, have been caused by non-ideal mixing in the phases, especially in garnets.     

From the simplest chemical system to the natural one: garnet peridotite barometry

The available experimental data on garnet-bearing-assemblages for synthetic chemical systems (MAS, FMAS, CMAS) have been used to calibrate consistent models for the Al-solubility in orthopyroxene coexisting with garnet, on the basis of equilibrium reaction Py(opx) ? Py(gt). The alternative reaction En(opx)+MgTs(opx) ? Py(gt) is discarded as it yields larger a-posteriori uncertainties. To provide a reliable equation, directly applicable to natural garnet lherzolites, each successive synthetic-system calibration is tested against Mori and Green's (1978) natural-system reequilibration data. For the MAS system, an ideal solution model with constant ΔH°, ΔV° and ΔS° based on 12-oxygen structural formulae for aluminous pyroxenes yields the best fit (GPa, K), $${\text{25,134 + 9,941 }}P - 23.177{\text{ }}T{\text{ + }}RT{\text{ ln (}}X_{{\text{Al}}}^{TB'} {\text{) = 0}}$$ . The MAS synthetic-system calibration can be directly applied to the FMAS system by adding an empirical correction term (20,835 [X _Fe ^gt ]²) independent of either pressure and temperature. However, this correction term is not important because of the limited Fe content of mantle peridotites. When calcium is added to the MAS system, the equilibrium constant is calculated as: $$K_{{\text{CMAS}}} = {{[(1 - X_{{\text{Ca}}}^{M2} )^2 (X_{{\text{Al}}}^{TB'} )]} \mathord{\left/ {\vphantom {{[(1 - X_{{\text{Ca}}}^{M2} )^2 (X_{{\text{Al}}}^{TB'} )]} {[(1 - X_{{\text{Ca}}}^X )^3 (X_{{\text{Al}}}^Y )^2 ]}}} \right. \kern-\nulldelimiterspace} {[(1 - X_{{\text{Ca}}}^X )^3 (X_{{\text{Al}}}^Y )^2 ]}}$$ where M2 and TB′ are pyroxene sites and X and Y are garnet sites. Up to 5 GPa, X _Ca ^X ～ and the CMAS experimental data agree well with the MAS model, but for Yamada and Takahashi's (1983) higher pressure experiments (up to 10 GPa), this no longer holds. Indeed, the garnet solid solution does not behave ideally and an asymmetric regular solution model is needed for application to the deepest natural samples available (>7GPa). Calibration based on new high pressure data yields, $$\begin{gathered} \Delta G_{{\text{CMAS}}}^{XS} = (X_{{\text{Ca}}}^X )(1 - X_{{\text{Ca}}}^X )(0.147 - X_{{\text{Ca}}}^X ) \hfill \\ {\text{ }} \cdot {\text{(6,440,535 - 1,490,654 }}P{\text{)}} \hfill \\ \end{gathered}$$ . According to tests of the inferred solution model, the CFMAS system is a good analogue of natural systems in the pressure, temperature and composition ranges covered by the natural-system reequilibration data (up to 1,500° C and 4 GPa). Simultaneous application of this thermobarometer and of the two-pyroxene mutual solubility thermometer (Bertrand and Mercier 1985) to the phases of the garnet-peridotite xenoliths from Thaba Putsoa, Lesotho, yields a refined paleogeotherm for southern Africa strongly contrasting with previous results. The “granular” nodules yield a thermal gradient of about 8 K/km characteristic of a lithospheric-type environment, whereas the “sheared” ones show a lower gradient of about 1 K/km. This is a typical geotherm expected for a steady thermal state with an inflexion point at the depth of about 160 km corresponding to the lithosphere/asthenosphere boundary.     

An experimental study of the partitioning of Fe and Mg between garnet and orthopyroxene

The partitioning of Fe and Mg between garnet and aluminous orthopyroxene has been experimentally investigated in the pressure-temperature range 5–30 kbar and 800–1,200° C in the FeO-MgO-Al₂O₃-SiO₂ (FMAS) and CaO-FeO-MgO-Al₂O₃-SiO₂ (CFMAS) systems. Within the errors of the experimental data, orthopyroxene can be regarded as macroscopically ideal. The effects of Calcium on Fe-Mg partitioning between garnet and orthopyroxene can be attributed to non-ideal Ca-Mg interactions in the garnet, described by the interaction term:W _CaMg ^ga -W _CaFe ^ga =1,400±500 cal/mol site. Reduction of the experimental data, combined with molar volume data for the end-member phases, permits the calibration of a geothermometer which is applicable to garnet peridotites and granulites: $$T(^\circ C) = \left\{ {\frac{{3,740 + 1,400X_{gr}^{ga} + 22.86P(kb)}}{{R\ln K_D + 1.96}}} \right\} - 273$$ with $$K_D = {{\left\{ {\frac{{Fe}}{{Mg}}} \right\}^{ga} } \mathord{\left/ {\vphantom {{\left\{ {\frac{{Fe}}{{Mg}}} \right\}^{ga} } {\left\{ {\frac{{Fe}}{{Mg}}} \right\}}}} \right. \kern-\nulldelimiterspace} {\left\{ {\frac{{Fe}}{{Mg}}} \right\}}}$$ and $$X_{gr}^{ga} = (Ca/Ca + Mg + Fe)^{ga} .$$ The accuracy and precision of this geothermometer are limited by largerelative errors in the experimental and natural-rock data and by the modest absolute variation inK _D with temperature. Nevertheless, the geothermometer is shown to yield reasonable temperature estimates for a variety of natural samples.     

Energetics of hydration of cordierite and water barometry in cordierite-granulites

The Gibbs free energy and volume changes attendant upon hydration of cordierites in the system magnesian cordierite-water have been extracted from the published high pressure experimental data at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P _total, assuming an ideal one site model for H₂O in cordierite. Incorporating the dependence of ΔG and ΔV on temperature, which was found to be linear within the experimental conditions of 500°–1,000°C and 1–10,000 bars, the relation between the water content of cordierite and P, T and \(f_{{\text{H}}_{\text{2}} {\text{O}}} \) has been formulated as $$\begin{gathered} X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} = \hfill \\ \frac{{f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }}{{\left[ {{\text{exp}}\frac{1}{{RT}}\left\{ {64,775 - 32.26T + G_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{1, }}T} - P\left( {9 \times 10^{ - 4} T - 0.5142} \right)} \right\}} \right] + f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }} \hfill \\ \end{gathered} $$ The equation can be used to compute H₂O in cordierites at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) <1. Our results at different P, T and partial pressure of water, assuming ideal mixing of H₂O and CO₂ in the vapour phase, are in very good agreement with the experimental data of Johannes and Schreyer (1977, 1981). Applying the formulation to determine \(X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} \) in the garnet-cordierite-sillimanite-plagioclase-quartz granulites of Finnish Lapland as a test case, good agreement with the gravimetrically determined water contents of cordierite was obtained. Pressure estimates, from a thermodynamic modelling of the Fe-cordierite — almandine — sillimanite — quartz equilibrium at \(P_{{\text{H}}_{\text{2}} {\text{O}}} = 0\) and \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P_total, for assemblages from South India, Scottish Caledonides, Daly Bay and Hara Lake areas are compatible with those derived from the garnetplagioclase-sillimanite-quartz geobarometer.     

Experimental calibration of Forsterite–Anorthite–Ca-Tschermak–Enstatite (FACE) geobarometer for mantle peridotites

The crystallization of plagioclase-bearing assemblages in mantle rocks is witness of mantle exhumation at shallow depth. Previous experimental works on peridotites have found systematic compositional variations in coexisting minerals at decreasing pressure within the plagioclase stability field. In this experimental study we present new constraints on the stability of plagioclase as a function of different Na₂O/CaO bulk ratios, and we present a new geobarometer for mantle rocks. Experiments have been performed in a single-stage piston cylinder at 5–10 kbar, 1050–1150?°C at nominally anhydrous conditions using seeded gels of peridotite compositions (Na₂O/CaO?=?0.08–0.13; X _Cr = Cr/(Cr?+?Al)?=?0.07–0.10) as starting materials. As expected, the increase of the bulk Na₂O/CaO ratio extends the plagioclase stability to higher pressure; in the studied high-Na fertile lherzolite (HNa-FLZ), the plagioclase-spinel transition occurs at 1100?°C between 9 and 10 kbar; in a fertile lherzolite (FLZ) with Na₂O/CaO?=?0.08, it occurs between 8 and 9 kbar at 1100?°C. This study provides, together with previous experimental results, a consistent database, covering a wide range of P–T conditions (3–9 kbar, 1000–1150?°C) and variable bulk compositions to be used to define and calibrate a geobarometer for plagioclase-bearing mantle rocks. The pressure sensitive equilibrium:

$$\mathop {{\text{M}}{{\text{g}}_{\text{2}}}{\text{Si}}{{\text{O}}_{\text{4}}}^{{\text{Ol}}}}\limits_{{\text{Forsterite}}} +\mathop {{\text{CaA}}{{\text{l}}_{\text{2}}}{\text{S}}{{\text{i}}_{\text{2}}}{{\text{O}}_{\text{8}}}^{{\text{Pl}}}}\limits_{{\text{Anorthite}}~} =\mathop {{\text{CaA}}{{\text{l}}_{\text{2}}}{\text{Si}}{{\text{O}}_{\text{6}}}^{{\text{Cpx}}}}\limits_{{\text{Ca-Tschermak}}} +{\text{ }}\mathop {{\text{M}}{{\text{g}}_{\text{2}}}{\text{S}}{{\text{i}}_{\text{2}}}{{\text{O}}_{\text{6}}}^{{\text{Opx}}}}\limits_{{\text{Enstatite}}} ,$$

has been empirically calibrated by least squares regression analysis of experimental data combined with Monte Carlo simulation. The result of the fit gives the following equation:

$$P=7.2( \pm 2.9)+0.0078( \pm 0.0021)T{\text{ }}+0.0022( \pm 0.0001)T{\text{ }}\ln K,$$

$${R^2}=0.93,$$

where P is expressed in kbar and T in kelvin. K is the equilibrium constant K?=?a _CaTs × a _en/a _an × a _fo, where a _CaTs, a _en, a _an and a _fo are the activities of Ca-Tschermak in clinopyroxene, enstatite in orthopyroxene, anorthite in plagioclase and forsterite in olivine. The proposed geobarometer for plagioclase peridotites, coupled to detailed microstructural and mineral chemistry investigations, represents a valuable tool to track the exhumation of the lithospheric mantle at extensional environments.

     

Optical absorption and mössbauer spectra of purple and green yoderite,a kyanite-related mineral

Mössbauer and polarized optical absorption spectra of the kyanite-related mineral yoderite were recorded. Mössbauer spectra of the purple (PY) and green yoderite (GY) from Mautia Hill, Tanzania, show that the bulk of the iron is Fe³⁺ in both varieties, with Fe²⁺/(Fe²⁺+Fe³⁺) ratios near 0.05. Combining this result with new microprobe data for PY and with literature data for GY gives the crystallochemical formulae: $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.95}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{0}}{\text{.01}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.34}}}^{{\text{3 + }}} {\text{Mn}}_{{\text{0}}{\text{.07}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.57}}} )_{5.97}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.98}}} {\text{P}}_{{\text{0}}{\text{.03}}} ){\text{O}}_{{\text{18}}{\text{.02}}} ({\text{OH)}}_{{\text{1}}{\text{.98}}} ] \hfill \\ \end{gathered}$$ and PY and $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.98}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{< 0}}{\text{.001}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.45}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.56}}} )_{6.02}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.91}}} {\text{O}}_{{\text{17}}{\text{.73}}} {\text{(OH)}}_{{\text{2}}{\text{.27}}} ] \hfill \\ \end{gathered}$$ for GY. The Mössbauer spectra at room temperature contain one main doublet with isomer shifts and quadrupole splittings of 0.36 (PY), 0.38 (GY) and 1.00 (PY), 0.92 (GY) mm s^?1, respectively. These values correspond to Fe³⁺ in six or five-fold coordination. The doublet components have anomalously large half widths indicating either accomodation of Fe³⁺ in more than one position (e.g., octahedraA1 and five coordinatedA2) or the yet unresolved superstructure. Besides strong absorption in the ultraviolet (UV) starting from about 25,000 cm^?1, the polarized optical absorption spectra are dominated by strong bands around 16,500 and 21,000 cm^?1 (PY) and a medium strong band at around 13,800 cm^?1 (GY). Position and polarization of these bands, in combination with the UV absorption, explain the colour and pleochroism of the two varieties. The bands in question are assigned to homonuclear metal-to-metal charge transfer transitions: Mn²⁺(A1) Mn³⁺(A1′) ? Mn³⁺(A1) Mn²⁺(A1′) and Mn²⁺(A1) Mn³⁺(A2 ? Mn³⁺(A1) Mn²⁺(A2) in PY and Fe²⁺(A1) Fe³⁺(A1′) ? Fe³⁺(A1) Fe²⁺(A1′) in GY. The evidence for homonuclear Mn²⁺ Mn³⁺ charge transfer (CTF) is not quite clear and needs further study. Heteronuclear FeTi CTF does not contribute to the spectra. In PY, additional weak bands were resolved at energies around 17,700, 18,700, 21,000, and 21,900 cm^?1 and assigned to Mn³⁺ in two positions. Weak bands around 10,000 cm^?1 in both varieties are assigned to Fe²⁺ spin-alloweddd-transitions. Very weak and sharp bands, around 15,400, 16,400, 21,300, 22,100, 23,800, and 25,000 cm^?1 are identified in GY and assigned to Fe³⁺ spin-forbiddendd-transitions.     

Genesis of the calc-alkaline igneous rock suite

A high pressure experimental study of the partial melting fields of synthetic high-alumina olivine tholeiite, high-alumina quartz tholeiite, basaltic andesite, andesite, dacite and rhyodacite under dry and wet conditions has been conducted in order to investigate possible origins of the calc-alkaline series from the upper mantle. Detailed analyses of crystallizing phases using the electron microprobe has enabled calculation of the liquid line of descent in these compositions at various pressures.At 27–36 kb garnet and clinopyroxene are the liquidus or near-liquidus phases in dry tholeiite, basaltic andesite and andesite, while quartz is the liquidus phases in dry dacite and rhyodacite. Under wet conditions at 27 kb garnet, not quartz, is the liquidus phase in the dacite. Qualitatively these results show that the low melting fraction of a quartz eclogite at 27–36 kb under dry conditions is of andesitic composition whereas under wet conditions it is rhyodacitic or granodioritic. At these pressures under dry conditions the andesite liquidus lies in a marked low temperature trough between the more basic and more acid compositions. Quantitatively, the calculated compositions of liquid fractionates for varying degrees of melting of the quartz eclogite bulk composition broadly follow the calc-alkaline trend.At 9–10 kb under wet conditions sub-silicic amphibole and pyroxenes are the near-liquidus phases in tholeiite and basaltic andesite compositions. Calcic plagioclase and garnet occur nearer the solidus. The calculated liquid fractionates follow the calc-alkaline trend and demonstrate that the calc-alkaline series may be derived by the partial melting of amphibolite at lower crustal depths under wet conditions , Or by the fractional crystallization of a hydrous basalt magma at similar depths.These experimental results support two complementary hypotheses for the derivation of the calc-alkaline igneous rock suite from the mantle by a two stage igneous process. In the first stage of both hypotheses large piles of basalt are extruded on the earth's surface. Subsequently this pile of basalt may, under dry conditions, transform to quartz eclogite, sink into the mantle and finally undergo partial melting at 100–150 kms depth. This partial melting gives rise to the calc-alkaline magma series leaving a residuum of clinopyroxene and garnet. Alternatively, if wet conditions prevail in the basalt pile and the geotherms remain high, partial melting of the basalt may take place near the base of the pile, at about 10 kb pressure . The liquids so formed constitute the calc-alkaline suite and the residuum consists of amphibole, pyroxenes and possibly minor garnet and calcic plagioclase. Both models may be directly linked to the hypothesis of sea-floor spreading.     

The combined effect of F and H2O on interdiffusion between peralkaline dacitic and rhyolitic melts

The effective binary diffusion coefficient (EBDC) of silicon has been measured during the interdiffusion of peralkaline, fluorine-bearing (1.3 wt% F), hydrous (3.3 and 6 wt% H₂O), dacitic and rhyolitic melts at 1.0 GPa and temperatures between 1100°C and 1400°C. From Boltzmann-Matano analysis of diffusion profiles the diffusivity of silicon at 68 wt% SiO₂ can be described by the following Arrhenius equations (with standard errors): $$\begin{gathered} {\text{with 1}}{\text{.3 wt\% F and 3}}{\text{.3\% H}}_{\text{2}} {\text{O:}} \hfill \\ {\text{D}}_{{\text{Si}}} = \begin{array}{*{20}c} { + {\text{3}}{\text{.59}}} \\ {{\text{3}}{\text{.66}} \times {\text{10}}^{ - {\text{9}}} } \\ { - {\text{1}}{\text{.86}}} \\ \end{array} {\text{exp}}\left( {{{ - {\text{86}}{\text{.1}} \pm {\text{8}}{\text{.9}}} \mathord{\left/ {\vphantom {{ - {\text{86}}{\text{.1}} \pm {\text{8}}{\text{.9}}} {{\text{RT}}}}} \right. \kern-\nulldelimiterspace} {{\text{RT}}}}} \right) \hfill \\ {\text{with 1}}{\text{.3 wt\% F and 6}}{\text{.0\% H}}_{\text{2}} {\text{O:}} \hfill \\ {\text{D}}_{{\text{Si}}} = \begin{array}{*{20}c} { + {\text{3}}{\text{.59}}} \\ {{\text{3}}{\text{.51}} \times {\text{10}}^{ - {\text{8}}} } \\ { - {\text{1}}{\text{.77}}} \\ \end{array} {\text{exp}}\left( {{{ - {\text{109}}{\text{.5}} \pm {\text{8}}{\text{.9}}} \mathord{\left/ {\vphantom {{ - {\text{109}}{\text{.5}} \pm {\text{8}}{\text{.9}}} {{\text{RT}}}}} \right. \kern-\nulldelimiterspace} {{\text{RT}}}}} \right) \hfill \\ \end{gathered} $$ where D is in m²s^?1 and activation energies are in kJ/mol. Diffusivities measured at 64 and 72 wt% SiO₂ are only slightly different from those at 68 wt% SiO₂ and frequently all measurements are within error of each other. Silicon, aluminum, iron, magnesium, and calcium EBDCs were also calculated from diffusion profiles by error function inversion techniques assuming constant diffusivity. With one exception, silicon EBDCs calculated by error function techniques are within error of Boltzmann-Matano EBDCs. Average diffusivities of Fe, Mg, and Ca were within a factor of 2.5 of silicon diffusivities whereas Al diffusivities were approximately half those of silicon. Alkalies diffused much more rapidly than silicon and non-alkalies, however their diffusivities were not quantitatively determined. Low activation energies for silicon EBDCs result in rapid diffusion at magmatic temperatures. Assuming that water and fluorine exert similar effects on melt viscosity at high temperatures, the viscosity can be calculated and used in the Eyring equation used to determine diffusivities, typically to within a factor of three of those measured in this study. This correlation between viscosity and diffusivity can be inverted to calculate viscosities of fluorine- and water-bearing granitic melts at magmatic temperatures; these viscosities are orders of magnitude below those of hydrous granitic melts and result in more rapid and effective separation of granitic magmas from partially molten source rocks. Comparison of Arrhenius parameters for diffusion measured in this study with Arrhenius parameters determined for diffusion in similar compositions at the same pressure demonstrates simple relationships between Arrhenius parameters, activation energy-E_a, kJ/mol, pre-exponential factor-D_o, m²s^?1, and the volatile, X=F or OH^?, to oxygen, O, ratio of the melt {(X/X+O)}: $$\begin{gathered} {\text{E}}a = - {\text{1533\{ }}{{\text{X}} \mathord{\left/ {\vphantom {{\text{X}} {\left( {{\text{X}} + {\text{O}}} \right)}}} \right. \kern-\nulldelimiterspace} {\left( {{\text{X}} + {\text{O}}} \right)}}{\text{\} }} + {\text{213}}{\text{.3}} \hfill \\ {\text{D}}_{\text{O}} = {\text{2}}{\text{.13}} \times {\text{10}}^{ - {\text{6}}} {\text{exp}}\left[ { - {\text{6}}{\text{.5\{ }}{{\text{X}} \mathord{\left/ {\vphantom {{\text{X}} {\left( {{\text{X}} + {\text{O}}} \right)}}} \right. \kern-\nulldelimiterspace} {\left( {{\text{X}} + {\text{O}}} \right)}}{\text{\} }}} \right] \hfill \\ \end{gathered} $$ These relationships can be used to estimate diffusion in various melts of dacitic to rhyolitic composition containing both fluorine and water. Calculations for the contamination of rhyolitic melts by dacitic enclaves at 800°C and 700°C provide evidence for the virtual inevitability of diffusive contamination in hydrous and fluorine-bearing magmas if they undergo magma mixing of any form.     

Experimental investigation and application of the equilibrium rutile + orthopyroxene = quartz + ilmenite

Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: $${\text{SiO}}_{\text{2}} + ({\text{Mg,Fe}}){\text{TiO}}_{\text{3}} {\text{ + (Mg,Fe)SiO}}_{\text{3}} $$ have been calibrated in the range 800–1100° C and 12–26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs_40–70, using Ag₈₀Pd₂₀ capsules with \(f_{{\text{O}}_{\text{2}} } \) buffered at or near iron-wüstite. Ilmenite compositions coexisting with orthopyroxene are \(X_{{\text{MgTiO}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.06 to 0.15 and \(X_{{\text{Fe}}_{\text{2}} {\text{O}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.00 to 0.01, corresponding toK _D values of 13.3, 10.2, 9.0 and 8.0 (±0.5) at 800, 900, 1000 and 1100° C, respectively, whereK _D =(XMg/XFe)^Opx/(XMg/XFe)^Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models for ilmenite available from the literature to calculatea/X relations in orthopyroxene of intermediate composition. Data from this study indicate that FeSiO₃?MgSiO₃ orthopyroxene exhibits small, positive deviations from ideality over the range 800–1100°C.     

Hydrostratigraphy and geochemistry at a coastal sandfill in Singapore

A characterization study was carried out in a 10-m-thick sandfill, formed by hydraulic filling with marine sand, in Singapore. Placement methods and compaction were found to influence hydrostratigraphy. The deepest part of the sandfill consists of a loose sand layer and is overlain by a medium sand layer extending to mean sea level (MSL). At certain locations, a thin silty-sand layer was found. The different layers within the saturated zone were found to have different values for hydraulic conductivity (K) and groundwater flow velocity. Estimates for K increase according to the following sequence of methods: repacked sand column, step-pumping test, grain-size analysis and slug test. Slug tests and grain-size analysis yielded comparable estimates of K. The freshwater lens in the older part of the sandfill is about 2 m thicker than in a recently completed area. Comparisons of Ca²⁺/Cl^?, Mg²⁺/Cl^?, K ⁺/Cl^? and \({\text{Cl}}^{{\text{ - }}} {\text{/}}{\left( {{\text{Cl}}^{{\text{ - }}} {\text{ + HCO}}^{{\text{ - }}}_{{\text{3}}} } \right)}\) ratios indicate that the chemical composition of the groundwater at shallower depths has probably been altered by mineral dissolution. Weathering of carbonate minerals was found to be a major contributor to the major ions at these depths. The molar ratios approach the value for seawater at greater depths. The groundwater is close to equilibrium with calcite.     

Kanonaite, (Mn 0.76 3+ Al0.23Fe 0.02 3+ )[6]Al[5][O¦SiO4], a new mineral isotypic with andalusite

Kanonaite forms rare porphyroblasts up to 12mm long in a gahnite— Mg-chlorite — coronadite — quartz schist occurring near Kanona, Zambia. The composition is (microprobe analysis): SiO₂ 32.2, Al₂O₃ 33.9, Mn as Mn₂O₃ 32.2, Fe₂O₃ 0.66, ZnO 0.13, MgO 0.04, BaO 0.04, TiO₂ 0.01, CaO 0.01, PbO 0.01, CuO 0.01, total 99.21, corresponding to $$\left( {{\text{Mn}}_{{\text{0}}{\text{.76}}}^{{\text{3 + }}} {\text{Al}}_{{\text{0}}{\text{.23}}} {\text{Fe}}_{{\text{0}}{\text{.015}}}^{{\text{3 + }}} } \right)_{1.005}^{\left[ 6 \right]} {\text{AL}}_{1.00}^{\left[ 5 \right]} \left[ {{\text{O}}_{{\text{1}}{\text{.00}}} |{\text{Si}}_{{\text{0}}{\text{.99}}} {\text{O}}_{{\text{4}}{\text{.00}}} } \right]$$ The mineral is greenish black, strongly pleochroic with X(∥a) yellow green, Y(∥b) bluish green, Z(∥c) deep golden yellow, biaxial positive, with 2V = 53°(3°), α = 1.702, β = 1.730, γ = 1.823. Vickers microhardness (100 gram load) ranges between 906 and 1017kp/mm². The structure is orthorhombic, isotypic with andalusite, space group Pnnm, a = 0.7953(2), b = 0.8038(2), c = 0.5619(2) nm, V = 0.3592(1) nm³, a/b = 0.9895(3), c/b = 0.6990(3), S.G.(_x) = 3.395 g/cm³, Z = 4. The strongest X-ray powder lines are (d in nm, I, hkl):0.5669, 100, 110; 0.4590, 75, 011 and 101; 0.3577, 90, 120 and 210; 0.2827, 94, 220; 0.2517, 90, 310 and 112; 0.2212, 83, 320, 122 and 212. Comparison of the intensities of 373 observed X-ray reflections with those calculated for several models of Mn³⁺-distribution indicates octahedral coordination of all or most of the manganese present. Interpretation of magnetic measurements (μ_eff = 3.15B.M. per Mn atom at 25 ° C) indirectly supports octahedral coordination of Mn³⁺. The name of the mineral is for Kanona, a town near the type locality. The name is proposed for the end member Mn^{3+ [6]}Al^[5][O¦SiO₄] and for members of the solid-solution series towards andalusite with octahedral Mn³⁺>Al. The presently described mineral may be referred to as aluminian kanonaite.     

Thermodynamic properties of almandine-grossular garnet solid solutions

The mixing properties of Fe₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ garnet solid solutions have been studied in the temperature range 850–1100° C. The experimental method involves measuring the composition of garnet in equilibrium with an assemblage in which the activity of the Ca₃Al₂Si₃O₁₂ component is fixed. Experiments on the assemblage garnet solid solution, anorthite, Al₂SiO₅ polymorph and quartz at known pressure and temperature fix the activity of the Ca₃Al₂Si₃O₁₂ component through the equilibrium: 1 $$\begin{gathered} {\text{3CaAl}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{8}} \rightleftarrows {\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} \hfill \\ {\text{Anorthite garnet}} \hfill \\ {\text{ + 2Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + SiO}}_{\text{2}} \hfill \\ {\text{ sillimanite/kyanite quartz}}{\text{.}} \hfill \\ \end{gathered}$$ This equilibrium, with either sillimanite or kyanite as the aluminosilicate mineral, was used to control \({\text{a}}_{{\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} }^{{\text{gt}}} \) . The compositions of the garnet solutions produced were determined by measurement of their unit cell edges. At 1 bar Fe₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ garnets exhibit negative deviations from ideality at the Fe-rich end of the series and positive deviations at the calcium end. With increasing pressure the activity coefficients for the Ca₃Al₂Si₃O₁₂ component increase because the partial molar volume of this component is greater than the molar volume of pure grossular. Previous studies indicate that the activity coefficients for the Ca₃Al₂Si₃O₁₂ component also increase with increasing (Mg/Mg+Fe) ratio of the garnet. The region of negative deviation from ideality implies a tendency towards formation of a stable Fe-Ca garnet component. Evidence in support of this conclusion has been found in a natural Fe-rich garnet which was found to contain two different garnet phases of distinctly different compositions.