Carbon and oxygen isotopic composition of the Middle Miocene Badenian gypsum-associated limestones of West Ukraine

Abstract

The Middle Miocene Badenian basin of the Carpathian Foredeep is characterized by complex sedimentary and diagenetic carbonate-evaporite transitions. Six locations have been selected to evaluate the controls on the carbon and oxygen isotopic composition of the Badenian gypsum-associated limestones of the Tyras Formation in West Ukraine. At three locations marine limestones overlie the gypsum, at one location (Anadoly) the gypsum-associated limestones are polygenic, and at two locations (Pyshchatyntsi and Lozyna) gypsum deposits are lacking. The studied limestones have originated as primary, mostly peloidal carbonates as well as secondary carbonates formed by hypogene sulphate calcitization. They show a wide range of δ13C (from from -0.9‰ to -39.8‰) and δ18O values (from 0.9‰ to -12.2‰). The Badenian limestones formed in marine environments (either as deposits accumulated at the bottom of the sea or forming the infillings of solution cavities within gypsum) have less negative δ18O values compared to predominantly diagenetic formations. Wide ranges and usually very negative δ13C values and low δ18O values of those limestones indicate that they suffered important meteoric diagenesis as supported by common sparitic fabrics. In addition, a large range of δ13C values even in the group of samples characterized by less-negative δ18O values shows that bacterial sulphate reduction and methane oxidation were active processes in the pore fluids of the Tyras Formation. Very low carbon isotopic compositions (δ13C values from -22 to -40‰) of some sparitic limestones in the studied sections indicate the occurrence of oxidized methane within the diagenetic environment. Accordingly, the isotopic signatures of the studied limestones are a combination of both primary and secondary processes, the latter having a primordial importance. The common occurrence of similar negative δ13C and δ18O values in evaporite-related carbonates in other Miocene evaporite basins suggest that extensive dissolution- reprecipitation in diagenetic or vadose-phreatic environments was common in evaporite-related carbonates.