Micro-XANES determination of ferric iron and its application in thermobarometry

Micro-X-ray absorption near-edge structure (XANES) analysis was employed to determine the content of ferric iron in minerals formed in ultrahigh-pressure (UHP) eclogites. It is observed that omphacite and phengite contain significant amounts of Fe³⁺/Fe_tot (0.2–0.6), whereas only very low contents are present in garnet (Fe³⁺/Fe_tot=0.0–0.03), the latter being consistent with results from stoichiometric charge-balance calculations. Furthermore, considerable variations in the Fe³⁺/Fe_tot ratios of omphacite and phengite are observed depending on the textural sites and local bulk chemistry (eclogite and calc-silicate matrix) within one thin section. The oxidation state of isofacial minerals is thus likely to depend on the local fluid composition, which, in the studied case, is controlled by calcareous and meta-basic mineral compositions. These first in-situ measurements of ferric iron in an eclogite sample from the Dabie Shan, E China, are used to recalculate geothermobarometric data. Calculations demonstrate that the temperature during UHP metamorphism was as high as 780 °C, about 80–100 °C higher than previously estimated. Temperatures based on charge balance calculations often give erroneous results. Pressure estimates are in good agreement with former results and confirm metamorphism in the stability field of diamond (43.7 kbar at 750 °C). These P–T data result in a geothermal gradient of ca. 6 °C/km during UHP metamorphism in the Dabie Shan. However, accounting for ferric iron contents in geothermobarometry creates new difficulties inasmuch as calibrations of geothermometers may not be correctable for Fe³⁺ and the actual effect on Mg–Fe²⁺ partitioning is unknown. The present study further shows that micro-XANES is a promising technique for the in situ determination of ferric iron contents without destroying the textural context of the sample: a clear advantage compared to bulk methods.