Partitioning of Fe2O3 in peridotite partial melting experiments over a range of oxygen fugacities elucidates ferric iron systematics in mid-ocean ridge basalts and ferric iron content of the upper mantle

Abstract

Basalts and peridotites from mid-ocean ridges record fO2 near the quartz-fayalite-magnetite buffer (QFM), but peridotite partial melting experiments have mostly been performed in graphite capsules (~ QFM-3), precluding evaluation of ferric iron’s behavior during basalt generation. We performed experiments at 1.5 GPa, 1350–1400 °C, and fO2 from about QFM-3 to QFM+3 to investigate the anhydrous partitioning behavior of Fe2O3 between silicate melts and coexisting peridotite mineral phases. We find spinel/melt partitioning of Fe2O3 ($${D}_{\mathrm{Fe}2\mathrm{O}3}^{\mathrm{spl}/\mathrm{melt}}$$ D Fe 2 O 3 spl / melt ) increases as spinel Fe2O3 concentrations increase, independent of increases in fO2, and decreases with temperature, which is consistent with new and previous experiments at 0.1 MPa. We find $${D}_{\mathrm{Fe}2\mathrm{O}3}^{\mathrm{opx}/\mathrm{melt}}$$ D Fe 2 O 3 opx / melt = 0.63 ± 0.10 and $${D}_{\mathrm{Fe}2\mathrm{O}3}^{\mathrm{cpx}/\mathrm{melt}}$$ D Fe 2 O 3 cpx / melt = 0.78 ± 0.30. MORB Fe2O3 and Na2O concentrations are consistent with a modeled MORB source with Fe2O3 = 0.48 ± 0.03 wt% (Fe3+/ΣFe = 0.053 ± 0.003) at potential temperatures (TP) from 1320 to 1440 °C. The temperature-dependence of the $${D}_{\mathrm{Fe}2\mathrm{O}3}^{\mathrm{spl}/\mathrm{melt}}$$ D Fe 2 O 3 spl / melt function alone allows ~ 40% of the variation in MORB compositions. If we allow $${D}_{\mathrm{Fe}2\mathrm{O}3}^{\mathrm{opx}/\mathrm{melt}}$$ D Fe 2 O 3 opx / melt and $${D}_{\mathrm{Fe}2\mathrm{O}3}^{\mathrm{opx}/\mathrm{melt}}$$ D Fe 2 O 3 opx / melt to also vary with temperature by tying them to spinel Fe2O3 through intermineral partitioning, then all the MORB data are within error of the model. Our model Fe2O3 concentration for the MORB source would require that the convecting mantle be more oxidized at a given depth than recorded by continental mantle xenoliths. Our result is supported by thermodynamic models of mantle with Fe3+/ΣFe = 0.03 that predict fO2 of ~ QFM-1 near the garnet-spinel transition, which is inconsistent with fO2 of MORB. Our results support previous suggestions that redox melting may occur between 200 and 250 km depth.

Garnet crystallization does not drive oxidation at arcs

“…Pyroxenitic garnets contain subequal Fe and Mg components and only become almandine-rich during crystallization at low temperatures. Our measurements and the literature data show that the compatibility of Fe 2+ is greater than that of Fe 3+ in garnet [and is likely greater in cpx ( 25 , 26 )], but the partition coefficients for both species in each phase are of similar magnitudes at the conditions relevant for cumulate fractionation in primitive arc magmas. Consequently, the crystallization of garnet pyroxenites, modeled using our measured partition coefficients, will only increase the Fe 3+ /∑Fe ratio of the magma by 0.04, corresponding to a 0.8 logarithmic unit increase in the f O 2 of the residual melt after 65% fractional crystallization (Fig.…”

“…Both ferrous and ferric iron are compatible in garnet at these conditions, but the difference between their partition coefficients is minimal (D Fe2+grt/melt=2.1; D Fe3+grt/melt=1.4; this study). We applied D Fe3+cpx/melt between 0.3 and 0.8 ( 25 , 26 ), represented by the width of the red-orange envelope around the modeled value (solid line) of D Fe3+cpx/melt=0.6 in Fig. 3.…”

“…Coefficients for the partitioning of ferric iron between garnet and melt and our K D grt Fe/Mg values were recalculated at each crystallization step. We assumed clinopyroxene-melt partition coefficients to be insensitive to changing pressure and temperature, and K D cpx Fe/Mg was set at 0.25 ( 25 , 26 ). Additional assumptions, parameters, and other details can be found in ( 23 ).…”

“…Fe/Mg was set at 0.25 (25,26). Additional assumptions, parameters, and other details can be found in (23).…”

Ferric iron in chrome-bearing spinels: implications for microprobe correction procedures

“…Gaetani (2016) showed that (Fe 3+ /ΣFe) spin decreases with increasing temperature and pressure although there is some uncertainty about the role of f O 2 (Sorbadere et al, 2018). Of significance however, is the observation by Davis and Cottrell (2021) Lenaz et al (2007Lenaz et al ( , 2014, Rollinson et al (2017) and Perinelli et al (2012Perinelli et al ( , 2014.…”