Mantle hydrogen

Water in the Earth s mantle hydrogen analysis of mantle olivine, pyroxenes and garnet using the SIMS. Proc. Lunar Planet. Sci. Conf. 24th, Lunar and Planetary Institute, Houston, pp. 839-840. 

The ice bath is replaced, and 250 ml, of ethylene dichloride is added to the mixture. When the internal temperature has been lowered to 5°, a solution of 67 g. (1.0 mole) of freshly distilled pyrrole in 250 ml. of ethylene dichloride is added through a clean dropping funnel to the stirred, cooled mixture over a period of 1 hour. After the addition is complete, the ice bath is replaced with a heating mantle, and the mixture is stirred at the reflux temperature for 15 minutes, during which time there is copious evolution of hydrogen chloride. 

Fig. 3.1.2 The apparatus used in 1956 for the methanol extraction of Cypridina luciferin. The dried Cypridina (500 g) is extracted at a temperature lower than 40°C with refluxing methanol under reduced pressure for two days. The atmosphere inside the apparatus is completely replaced with hydrogen gas that was purified by its passing through a quartz tube containing red-heated copper fragments. The temperature of the mantle heater is adjusted, the system evacuated, and then all stopcocks are closed. The extraction with refluxing methanol continues for many hours without any further adjustment. From the author s 1957 notebook.

The reaction is carried out in a 500-ml. three-necked flask equipped with a reflux condenser, mechanical stirrer, heating mantle, and nitrogen inlet. The equipment is similar to that pictured in Fig. 11, except that an addition funnel is not required. In the reaction flask 20 g. (0.36 mol, 100% excess) of potassium hydroxide is dissolved in 300 ml. of absolute ethanol. The spare neck is closed with a ground-glass stopper, and the solution is stirred until it reaches room temperature. Addition of the carborane to the warm basic solution may result in an initial vigorous reaction. To this solution is added 30.0 g. (0.175 mol) of solid dimethylcarborane. The solution is stirred for one hour at room temperature and is then heated at the reflux temperature for 14 hours or until hydrogen evolution has stopped. 

In a recent note [61] about mixed oxides containing rare earths, it was speculated that the time might come when hydrogen were handled in large quantities with the result that illumination would be cheaper by burning Ha in air on mantles... 

For geologic purposes, the dependence of the equilibrium constant K on temperature is the most important property (4). In principle, isotope fractionation factors for isotope exchange reactions are also slightly pressure-dependent because isotopic substitution makes a minute change in the molar volume of solids and liquids. Experimental studies up to 20kbar by Clayton et al. (1975) have shown that the pressure dependence for oxygen is, however, less than the limit of analytical detection. Thus, as far as it is known today, the pressure dependence seems with the exception of hydrogen to be of no importance for crustal and upper mantle environments (but see Polyakov and Kharlashina 1994). 

Fig. 3.4 Hydrogen isotope variations in mantle-derived materials (modified after Bell and Ihinger, 2000)...

Water in the mantle is fonnd in different states as a fluid especially near sub-duction zones, as a hydrous phase and as a hydroxyl point defect in nominally anhydrous minerals. 8D-values between -90 and -110%c have been obtained by Bell and Ihinger (2000) analyzing nominally anhydrous mantle minerals (garnet, pyroxene) containing trace quantities of OH. Nominally anhydrous minerals from mantle xenoliths are the most D-depleted of all mantle materials with 5D-values 50%c lower than MORE (O Leary et al. 2005). This difference may either imply that these minerals represent an isotopically distinct mantle reservoir or that the samples analyzed have exchanged hydrogen dnring or after their ascent from the mantle (meteoric/water interaction ). 

Fig. 3 Apparatus for high pressure hydrogenation. A, autoclave B, hydrogen inlet valve C, pressure release valve D, pressure gauge E, heating mantle F rocking device.

Mackwell S.J. (1992) Oxidation kinetics of fayalite (Fe2Si04). Phys. Chem. Miner. 19, 220-228. Mackwell S.J. and Kohlstedt D.J. (1990) Diffusion of hydrogen in olivine implications for water in the mantle. /. Geophys. Res. 95, 5079-5088. 

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