Ferroan calcite replacement indicates former magnesian calcite skeletons

The replacement by ferroan calcite with preservation of the original structures can be used as a new criterion for identifying skeletons originally composed of high-magnesian calcite. This applies to bryozoa, rugose corals, echinoderms, many foraminifera, most ostracods, red algae, and serpulids. On the other hand, skeletons originally composed of low-magnesian calcite were never replaced by ferroan calcite, as shown by belemnites, brachiopods, and most of the pelecypods. Using this criterion, an original low-magnesian calcite composition is inferred for Tentaculites and some ostracods and foraminifera, whereas a previous high-magnesian calcite composition is inferred for trilobites, oligostegina and certain ooids. Chemical instability of high-magnesian calcite is suggested to be the driving force of the replacement by ferroan calcite. In most of the thirty-seven samples investigated, of Oligocene to Devonian age, the ferrous iron concentration of the interstitial fluid increased during diagenesis, as shown by well established sequences of cement A and B and fissure fill. This offers a relative time scale for diagenetic processes. Ferroan calcites contain up to 6 mol % FeCO₃ and up to 5 mol % MgCO₃. In this range of concentration, the distribution coefficients for Fe and Mg between calcite and solution at about 25°C are about 1 to 0-03, respectively, according to experiments. Possible sources of iron are iron oxides and hydroxides as well as clay minerals including glauconite. Though a submarine origin below the sediment surface is conceivable for ferroan calcite, there are serious limiting conditions such as low Eh and, at the same time, lack in sulphate-reducing bacteria. On the other hand, ferroan ‘dedolomite’, compositional zonality in individual ferroan calcite overgrowths, low δ¹⁸C and δ¹⁸O values, and low Mg concentrations point more to a meteoric-phreatic origin of many ferroan calcite occurrences.