Experimental study of chloritoid stability at high pressure and various fO2 conditions

The reaction chloritoid (ctd)=almandine (alm)+diaspore+H₂O (CAD) has been reversed using Fe³⁺-free synthetic chloritoid and almandine, under fO₂ conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO₂ conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO₂ conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH₂O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H₂O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H₂O bracketed on the Fe/FeO buffer and under unbuffered fO₂ conditions. For fO₂ buffered by the assemblage Fe/FeO, aH₂O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO₂ buffered by the assemblage Ni/NiO, aH₂O=1. The aH₂O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H₂O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H ^o f,ctd and S ^octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and K_D=(Fe³⁺/Al)ctd/(Fe³⁺/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe³⁺ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl₂SiO₅(OH)₂ formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe³⁺ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H₂O (CQGK), calculated for intermediate Fe–Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65<(XFe)gt<0.8, CQKG calculated from FASH and MASH overlap for K_D=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the K_D values reported from chloritoid+garnet+quartz+kyanite natural assemblages.     

Fugacity control and dissociation constants of HBr and HI

Two new hydrothermal acid-base buffers have been developed and calibrated. The Ag+AgBr and the Ag+AgI buffers in conjunction with an external hydrogen buffer control the fugacities of HBr and HI respectively at the pressure and temperature of the experiment. Both buffers are much less acid than the Ag+AgCl buffer of Frantz and Eugster (1973). For corresponding conditions, the molalities of HBr and HI are one and three orders of magnitudes smaller respectively than the molality of HC1.Both buffers have been calibrated using quench bromide, iodide and pH measurements. At higher temperatures HBr and HI are apparently not dissociated and the measured molalities agree closely with those calculated from thermochemical data. At lower temperatures the degree of dissociation increases greatly, and dissociation constants for HBr and HI at P and T have been calculated from the data.The Ag+AgBr and Ag+AgI buffers have been tested by measuring constants for the quartz-talc reaction in H-O-Br and H-O-I solutions respectively. These constants in conjunction with available thermochemical data can be used to calculate the free energies of formation for MgBr₂ and MgI₂.The Ag+AgBr and Ag+AgI buffers extend the pH range towards neutral solutions over which acid-base reactions in supercritical fluids can now be measured. This allows the use of less concentrated solutions and of minerals which are not stable in acid solutions.     

Carbon isotope geochemistry of the Precambrian Lomagundi carbonate province,Rhodesia

Carbon isotope measurements carried out on 67 dolomite samples from the Middle Precambrian Lomagundi Group (Rhodesia) have yielded a δ¹³C mean of +8.2 ± 2.6%. vs PDB. With the outcrop of these dolomites extending over a distance of almost 300 km, the Lomagundi dolomite faces is likely to represent the largest isotopically anomalous sedimentary carbonate province ever recorded. It is concluded that the anomalous carbonates formed in a closed basin whose δ¹³C level had been substantially increased as a result of a preferential removal (within sedimentary organics) of the light carbon isotope.     

Petrology and geochemistry of plagiogranite in the Canyon Mountain ophiolite,Oregon

Plagiogranites in the Canyon Mountain ophiolite, Oregon, include a wide range of rock types ranging from diorite to trondhjemite. The plagiogranites are mostly concentrated as an intrusive sill swarm at the top of a section of gabbroic cumulates. The plagiogranites are typically low in K₂O and high in Na₂O, and are enriched 10–20 times chondrites in REE, and overlap with abundances in basic rocks from Canyon Mountain. All samples of plagiogranite are relatively depleted in LREE, with more silicic samples characterized by a slightly lesser degree of LREE depletion. Total REE content is not consistently correlated with contents of major and other trace elements. Fractional crystallization of basaltic magma may give rise to plagiogranites; however this model applied to Canyon Mountain plagiogranites is discounted because of the significant volume of plagiogranites relative to basic rocks, and the complete overlap of REE abundances of the basic rocks and the plagiogranites. The latter is also a major reason for rejecting the hypothesis of silicate liquid immiscibility in the generation of the plagiogranites. Field observations coupled with major-element and trace element chemistry lend support to a model by which the plagiogranites were produced by partial melting of basic rocks under hydrous conditions. REE data for the plagiogranites were used in calculations to delimit source REE contents. Relevant parameters in the calculations were estimated from experimentally determined phase relations of basalt under hydrous conditions. The resulting calculated source patterns are similar to those of basic rocks in ophiolites and oceanic settings, and suggest boundary conditions for the model. Partial melting as suggested for the Canyon Mountain plagiogranites probably occurred at relatively shallow depths (i.e., total pressures less than 5 kb).     

Coupling among the terrestrial sulfur,carbon and oxygen cycles: numerical modeling based on revised Phanerozoic carbon isotope record

Numerical modeling of the terrestrial oxygen budget based on the revised δ¹³C_carb record by Veizeret al. (1980) has shown that total photosynthetic oxygen has varied between ±7% and ±10% of its average reservoir size (～3.2 × 10²² g) during the last 800 myr as a result of oscillations of the sedimentary reservoir of organic carbon. Calculated curves of oxygen evolution display a distinct minimum in the Early Paleozoic framed by two maxima in the Latest Proterozoic and the Mesozoic. The sympathetic relationship observed between the curves of total oxygen evolution and respective functions for the partial reservoir of sulfate-bound oxygen suggests that the O₂ required for an additional conversion of sulfide to sulfate was most probably provided by excess burial of organic carbon, the results of the modeling thus adding credence to current interpretations proposed for the negative correlation between the secular ${}^{13}\text{C}{}^{12}\text{C}$ and ${}^{34}\text{S}{}^{32}\text{S}$ trends.     

Optimization of the freeze pipe arrangement and the necessary refrigeration plant capacity by a femcomputer program

The number and the arrangement of freeze pipes and the energy needed to freeze a certain amount of soil are important factors for the economic success of a freeze project. A thermal design in which these factors are considered is based on the solution of a nonlinear unsteady heat conduction equation including phase transition. The equation is solved by means of a finite-element-method (FEM), considering boundary conditions related to artificial ground freezing.

In this paper the basic mathematical techniques to deal with the transient heat conduction problem, with temperature-dependent soil properties, and the release of latent heat are described. The significance of the convective heat transfer coefficient and the temperature distribution in the coolant running through the freeze pipes are shown and their dependencies to other factors as refrigeration plant capacity or type of flow in the pipes are considered. Finally an example is presented.     

Lateral coherence of longitudinal wind components in strong winds

A combination of lateral coherence measurements of wind speed at five locations suggests that the decay constant is a monotonically increasing function of the ratio of separation to height, under neutral conditions.