Diagenesis and pyritization of crinoid ossicles

Abstract

Diagenetic alteration of original high-Mg calcite crinoid skeletal material was achieved by reaction of the calcium carbonate with isotopically light meteoric water. The light δ18O values (−10.57 ± 0.74‰, PDB) are a reflection of the water source, whereas the δ13C values (−3.49 ± 2.63‰, PDB) are a consequence of the high reactive-organic-matter content in the sediments of the Brush Creek at Sewickley, Pennsylvania. High Fe (22 970 ± 30 440 ppm) and Mn (3760 ± 1450 ppm) contents suggest further that the diagenetic fluids were reducing waters that reacted with the crinoid ossicles in the shallow-burial marine and meteoric environments.Four different types of pyrite are found within crinoid ossicles. Framboidal pyrite, aggregate pyrite, and nanopyrite are generally found in the pores of the stereom. Micropyrite, which is present in the form of octahedral, dodecahedral, and pyritohedral crystals, and nanopyrite and aggregate pyrite replace the calcitic stereom. The degree of pyritization and the pore filling increase toward the outer periphery of the crinoid ossicles. Pyrite formation of the crinoid ossicles took place in two stages. In stage I, upon death, the crinoids disarticulated and were quickly buried. In this shallow sediment layer (1–10 cm) the pore water was both undersaturated with respect to calcite and oxidizing. This brought about oxidation of the organic tissue in the stroma of the crinoids and selective dissolution of the high-Mg calcite skeletons. With further burial in stage II, in the presence of reactive organic matter local iron was solubilized, marine sulphate was reduced to sulphide, and isotopically light carbon was produced by bacterial action. Reactive iron combined with sulphur to form framboidal and nanopyrite in the pores of the stereoms. With further burial the micropyrite formed in the crinoid ossicles. Termination of the pyritization process came about with depletion of the iron and (or) sulphur, and this process proceeded very rapidly under shallow-burial conditions while the crinoids resided in the microbial sulphate-reduction zone of the marine–phreatic environment.Fossils are preserved in different stages, with brachiopod valves preserved in their original low-Mg calcite mineralogy, whereas molluscs and crinoids show the complete trend from preserved aragonite and high-Mg calcite, respectively, to diagenetic low-Mg calcite. The preservation potential of fossils is closely linked to the thermodynamic stability of the skeletal carbonate in the presence of diagenetic fluids. Carbon/sulphur ratios support the assertion that Brush Creek sediments were deposited in normal marine waters and favour generally oxic redox conditions for Pennsylvanian seawater.