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Earth and Planetary Science Letters, 47 (1980) 11-20 11 © Elsevier Scientific Publishing Company, Amsterdam - Printed in the Netherlands

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Earth and Planetary Science Letters, 47 (1980) 11-20 11 © Elsevier Scientific Publishing Company, Amsterdam - Printed in the Netherlands Earth and Planetary Science Letters, 47 (1980) 11-20 11 © Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands [6] THE EFFECT OF MANGANESE ON OLIVINE-QUARTZ-ORTHOPYROXENE STABILITY STEVEN R. BOHLEN 1 * ARTHUR L. BOETTCHER 2, WAYNE A. DOLLASE 3 and ERIC J. ESSENE 1 1 Department of Geology and Mineralogy, University of Michigan, Ann Arbor, M1 48104 (U.S.A.) 2 Institute of Geophysics and Planetary Physics and Department of Earth and Space Sciences, University of California at Los Angeles, Los Angeles, CA 90024 (U.S.A. ) 3 Department of Earth and Space Sciences, University of California at Los Angeles, Los Angeles, CA 90024 (U. S.A.J Received March 19, 1979 Revised version received October 23, 1979 The effect of manganese on the stability of ferrosilite relative to fayalite + quartz has been experimentally deter- mined to assess its importance to orthopyroxene barometry. Reaction reversals in a piston-cylinder apparatus were obtained to within 0.1-kbar intervals indicating instability of FsgsRhs below 10.3, 10.9, 11.4, 12.2, 12.9, 13.7 kbar and Fs9oRhl o below 9.8, 10.4, 10.9, 11.6, 12.4 and 13.2 kbar at 750, 800, 850, 900, 950 and 1000°C, respec- tively. Each mole % MnSiO3 extends the pyroxene stability by approximately 0.12 kbar relative to FeSiOa. Electron • • . opx-oliv microprobe analyses of run products indicate a small preference of Mn for pyroxene over olivine with K~ Mn-Fe = 1.2-1.5, similar to values observed for natural pairs. M6ssbauer spectra are consistent with a random distribution of Mn between the M1 and M2 sites in the orthopyroxene. These experimental data allow downward revision of pressure estimates based on the orthopyroxene barometer in areas where Mn is a significant component in ortho- pyroxene. 1. Introduction tion boundary, and the usefulness of many potential barometers and thermometers is greatly reduced unless Reactions involving minerals with solid solutions experimental data can be obtained• It has been shown have long been recognized for their potential in deter- in the previous paper [1 ] that the reaction olivine + mining or limiting pressure and temperature. Minor quartz ~ orthopyroxene is of potential use as a geo- components can shift the stabilities of reactants and barometer, but activity data are unavailable or insuffi- products of a solid-solid reaction over a wide range of ciently well refined to unambiguously calculate the pressures and temperatures. Theoretically, these types effects of solid solutions. Order-of-magnitude calcula- of reactions should be much more useful than uni- tions suggest that additional components can extend variant or nearly univariant that result from limited the stability of pyroxene to lower pressures• Smith solid solution. Unfortunately, there are rarely suffi- [2,3] experimentally investigated the effect of MgO cient activity data available to allow calculation of in olivine and in orthopyroxene in the system the effect of additional components on a given reac- Mg2SiO4-Fe2SiO4-SiO2. He showed that 30 mole % MgSiOa stabilizes the pyroxene over olivine + quartz * Present address: Institute of Geophysics and Planetary at 900°C and atmospheric pressure; in the Mg-free Physics, University of California, Los Angeles, Los Angeles, system (at 900°C), ferrosilite is stable only above CA 90024, U.S.A. 12.6 kbar [1 ]. Other components including Mn, Ca, Institute of Geophysics and Planetary Physics Publication Na, A1, Ti, and Fe a÷ will also probably enhance No. 1885. Mineralogy Laboratory, University of Michigan, pyroxene stability, because they are preferentially Contribution No. 348. concentrated in the pyroxene. MnSiOa is a major 12 impurity in some natural Fe-rich orthopyroxenes, CO2/H2 gas-mixing furnace and served as one set such as at Lofoten, Norway [4], where it is the most of starting materials. Fa9sTes + quartz and Fa9oTelo - significant additional component. Consequently, the quartz were reacted in a piston-cylinder device (20 writers have undertaken piston-cylinder experiments kbar, 900°C, 1-2 wt.% H20) to synthesize ferro- to calibrate the effects of 5 and 10 mole % rhodonite silite9s rhodonites and ferrosilitego rhodonitelo, solid solution on the stability of Fe-rich ortho- respectively. These served as the other set of starting pyroxene. materials. Starting materials were analyzed by optical, X-ray, electron microprobe and M6ssbauer techniques to insure that they were stoichiometric and homo- 2. Experimental methods geneous. The experimental apparatus, furnace assem- blies, capsules, run procedures and criteria for reac- With a few exceptions the experimental methods tion direction for the piston-cylinder experiments are used in this study are identical to those described also identical to those discussed in the previous paper. in detail in the previous paper. Starting materials were For most runs (see Table 1 and 2 for run data) equi- prepared from electrolytically reduced iron powder, molar mixtures of Fs9sRhs-FagsTes + quartz and synthetic Mn304 and Brazilian quartz. Equimolar FsgoRhlo-Fa90Tel0 + quartz were used for deter- mixtures of fayalite95 tephroites + quartz and mination of the 5 and 10 mole % boundaries respec- fayalite90 tephroitelo + quartz were synthesized in a tively. To reverse the Ko, an initially high-K0 starting TABLE 1 Run data (5 mole % Mn2SiO4, MnSiO3) Run No. T (°C) P (kbar) Duration Products (hours) 62 750 10.5 26.3 opx + oliv + qtz 64 750 10.3 24 opx + oliv + qtz 67 750 10.2 23.5 oliv + qtz + opx 55 800 11.0 23.5 opx + (oliv + qtz) 58 800 10.8 24 oliv + qtz + (opx) 61 800 10.9 24 oliv + qtz + opx 63 850 11.5 24 opx + (oliv + qtz) 70 850 11.4 24 oliv + qtz + (opx) 54 900 12.0 24 oliv + qtz + (opx) 57 900 12.2 24 oliv + qtz + opx 1133 * 900 12.2 10 oliv + qtz + opx 60 900 12.3 24 opx + (oliv + qtz) 65 950 13.1 19 opx + (oliv + qtz) 68 950 12.9 19.5 opx + oliv + qtz 69 950 12.8 22.5 oliv + qtz + opx 37 1000 12.5 27 oliv + qtz 40 1000 12.9 22 oliv + qtz 48 1000 13.2 24 oliv + qtz + (opx) 50 1000 13.5 23 oliv + qtz + (opx) 51 1000 13.4 21.5 oliv + qtz + (opx) 52 1000 13.6 24 oliv + qtz + opx 56 1000 13.7 22.5 oliv + qtz + opx 59 1000 13.8 25 opx + (oliv + qtz) Italics show the dominant phase(s). Parentheses indicate very minor to trace amounts. * Starting material was equal-weight mixture of Fe 1.80Mn0.20Si206 and FalO0 (+ SiO2). 13 TABLE 2 Run data (10 mole % Mn2SiO4, MnSiO3) Run No. T (°C) P (kbar) Duration Products (hours) 77 750 9.5 23.5 oliv + qtz + (opx) 80 750 9.9 24 opx + oliv + qtz 84 750 9.8 24 oliv + qtz + opx 1152 750 23.0 193 opx + qtz 72 800 10.3 24 oliv + qtz + (opx) 79 800 10.5 23.5 opx + oliv + qtz 83 800 10.4 23.5 oliv + qtz + (opx) 95 850 11.0 24 opx + (oliv + qtz) 96 850 10.8 21.5 oliv + qtz + (opx) 73 900 11.7 21 opx + (oliv + qtz) 78 900 11.5 29 oliv + qtz + (opx) 87 900 11.6 22 opx + oliv + qtz 76 950 12.4 22.5 opx + (oliv + qtz) 82 950 12.2 22 oliv + qtz + (opx) 86 950 12.3 24 oliv + qtz + opx 75 1000 13.3 23 opx + (oliv + qtz) 81 1000 13.0 19 oliv + qtz + (opx) 85 1000 13.2 23 opx + oliv + qtz Italics show dominant phase(s). Parentheses indicate very minor to trace amounts. material (Fs90Rh I 0-Fal 0o + quartz) of average com- by Ruby [15] were calculated for each fitted spec- position Fs95 Rh s was used. Microprobe analyses of trum. run products were obtained using equipment and techniques described in the previous paper. The analyses are listed in Tables 3 and 4. Each analysis 3. Experimental results and discussion represents an average of 4-5 points taken on different grains in each run product. Maximum deviations The effect of 5 and 10 mole % rhodonite solid among the points within a single analysis were less solution on the stability of ferrosilite has been cali- than 1.5-2% of the amount present for each element brated at 50°C intervals from 750 to 1000°C, and the analyzed. results are shown in Figs. 1 and 2. For comparison, M6ssbauer spectra of a few powdered run products the end-member reaction boundary is also shown. It were obtained at room temperature using a constant can be seen that 5 and 10 mole % rhodonite extend acceleration, mechanically driven M6ssbauer spectrom- the stability of the pyroxene by nearly 0.6 and 1.2 eter. Samples of 50-100 mg were used with a 10 kbar, respectively, relative to fayalitic olivine + quartz. mCi STCo in Pd source. Duplicate spectra were All three reaction boundaries change slope from recorded in 512 channels of a multichannel analyzer approximately dP/dT = 10 bar/°C to dP/dT = 15 bar/ using a velocity increment of 0.03 mm per second per °C, where they intersect the a-/3 quartz transition. channel. Counting times were sufficient to obtain Our indirect location of the a-/3 quartz transition several million counts per channel and peak dips on agrees well with the determination of Cohen and the order of l0 s counts. The spectra were fit with Klement [5]. We have obtained microprobe analyses lorentzian doublets constrained to equal widths for of run products of coexisting orthopyroxene and the low- and high-velocity components. Chi-squared olivine to determine the partitioning of manganese. and additional goodness-of-fit parameters suggested The analyses are compiled in Tables 3 and 4, and the 14 15 / 15 ~.
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