Formation of ferrian chromite in podiform chromitites from the Golyamo Kamenyane serpentinite,Eastern Rhodopes,SE Bulgaria: a two-stage process

The Golyamo Kamenyane serpentinite is a portion of a metaophiolite, located in the Upper High-Grade Unit of the metamorphic basement of the Eastern Rhodope Metamorphic Complex, SE Bulgaria. It consists of metaharzburgite and metadunite hosting layers of metagabbro and some chromitite bodies. All these lithologies were affected by ultrahigh-pressure (UHP) metamorphism and subsequent retrograde evolution during exhumation. Chromite from chromitites can be classified into four textural groups: (1) partly altered chromite, (2) porous chromite, (3) homogeneous chromite and (4) zoned chromite. Partly altered chromite shows unaltered, Al-rich cores with unit cell size of 8.255 Å and Cr# Cr/(Cr + Al) atomic ratio] = 0.52–0.60, Mg# Mg/(Mg + Fe²⁺) atomic ratio] = 0.65–0.70 and Fe³⁺/(Fe³⁺ + Fe²⁺) = 0.20–0.30, surrounded by porous chromite, with a cell size of 8.325 Å, Fe³⁺/(Fe³⁺ + Fe²⁺) < 0.20 and values of Cr# and Mg# evolving from 0.60 to 0.91 and 0.65–0.44, respectively, from core to rim. The chemical composition of porous chromite varies within the following ranges: Cr# = 0.93–0.96, Mg# = 0.48–0.35 and Fe³⁺/(Fe³⁺ + Fe²⁺) = 0.22–0.53. Its unit cell size is very constant (8.350 Å). Most pores in porous and partly altered chromite are filled with chlorite, which also occurs between chromite grains. Homogeneous chromite has Fe³⁺/(Fe³⁺ + Fe²⁺) = 0.55–0.66, Cr# = 0.96–0.99, Mg# = 0.32–0.19 and a cell size of 8.385 Å. The cores of zoned chromite are similar to those of partially altered chromite, but the rims are identical to homogeneous chromite. Although chlorite predominates in the silicate matrix of homogeneous and zoned chromite, it coexists with some antigorite, talc and magnesiohornblende. Mineral data and thermodynamic modeling allow interpretation of the alteration patterns of chromite as the consequence of a two-stage process developed during retrograde metamorphic evolution coeval with fluid infiltration. During the first stage, chromite reacts in the presence of fluid with olivine to produce chlorite and Cr- and Fe²⁺-rich residual chromite (ferrous chromite) at ~700 to ~450 °C. This dissolution–precipitation reaction involves continuous chromite mass loss resulting in the development of a porous texture. This stage takes place progressively on cooling under water-saturated and reducing conditions. The second stage mainly consists of the formation of homogeneous chromite with ferrian chromite composition by the addition of magnetite to the porous ferrous chromite during a late oxidizing hydrothermal event.