--> In-Situ, Micron-Scale δ13C & δ18O Analyses (by SIMS) of Chemo-Isotopically Zoned Carbonate Cements of Diagenetic Origin — A Case Study on the Implications for the Thermal and Burial History of the Eau Claire Fm., Illinois Basin (USA)
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In-Situ, Micron-Scale δ13C & δ18O Analyses (by SIMS) of Chemo-Isotopically Zoned Carbonate Cements of Diagenetic Origin — A Case Study on the Implications for the Thermal and Burial History of the Eau Claire Fm., Illinois Basin (USA)

Abstract

The δ13C & δ18O of zoned carbonate cements of diagenetic origin can be measured in-situ on the sub-10-μm scale using Secondary Ion Mass Spectrometry (SIMS). A critical aspect of analytical methods advancement is the continued development of standards for correcting systematic, compositionally-dependent - but generally highly non-linear - sample matrix effects that bias measured isotope ratios. Precision is a trade-off with Previous HitbeamNext Hit size and, depending on the isotope system, varies between ±0.3‰ (2SD; 10μm Previous HitbeamNext Hit, δ18O) and ±1.0‰ (2SD; 3μm Previous HitbeamNext Hit for δ18O, 5–10μm Previous HitbeamTop for δ13C). Analyses on this scale enhance the spatial resolution in applied problems relating to carbonate diagenesis and carbonate cementation of sandstone-shale systems. For example, by preserving petrographic relations between two different authigenic cement phases exhibiting equilibrium growth textures (e.g. dolomite-quartz overgrowths), in-situ δ18O measurements provide a temperature constraint for a particular stage of cementation that is independent of assumptions about the δ18O of porewaters from which cements precipitated. Transects across early-to-late cement generations provide a clearly-resolved, zone-by-zone account of changes in δ13C & δ18O which elucidate the evolution of diagenetic conditions, including 1) temperature during progressive burial and heating, 2) isotopically-distinct fluid/brine migration events, 3) the progression of organic matter (OM) maturation and 4) the reaction of smectite⇒illite clay, which affects porewater δ18O. A regional case study of dolomite-ankerite cements in the sandy-shaly Late Cambrian Eau Claire Fm of the Illinois Basin reveals systematic depth-related C- and O-isotope zoning (early-to-late δ18O: -5⇒-16‰ VPDB, δ13C ~0⇒-10‰ VPDB). δ18O-based T-modeling - using both internal and external constraints on porewater δ18O - indicates heating to ~90°C during basin subsidence, and additional conductive heating to ~130°C during the basin-scale, late Paleozoic hot brine migrations through the underlying Mt. Simon sandstone aquifer that resulted in regional Mississippi Valley-type ore body formation. The δ13C of the latest cement generations indicates only a moderate contribution of OM-derived, isotopically-light C, reflecting the overall organic-leanness of Eau Claire sediments (TOC <0.5%). These results compliment SIMS studies of δ18O in quartz-overgrowths of the Eau Claire and Mt Simon Fms (Hyodo et al., 2014, Chem Geol; Pollington et al., 2011, Geology).