Rapid subsidence as a driver of phosphate deposition in the later Ordovician: Case study from the Alabama Appalachians

An increase in accumulation of phosphate-enriched sediment occurred in several areas of Earth's oceans during the later Ordovician, suggesting that some fundamental change (s) in seawater and/or pore water chemistry were taking place, either syndepositionally or during early diagenesis. One hypothesis is that widespread cooling of the water column led to this increase, but another is that the increase could have been forced primarily by changes in seawater chemistry that accompanied an influx of siliciclastic sediments associated with tectonically driven subsidence. Here, we report on findings from study of the upper ~30 m of the >200 m of Middle and Late Ordovician strata exposed near Tidwell Hollow, Blount County, Alabama, and what the results suggest about the competing hypotheses. This Ordovician sequence, deposited along the southeastern margin of Laurentia during the initial (Blountian) stage of the Taconic Orogeny, records the transition from a restricted peritidal carbonate shelf environment (the “Black River lithofacies”) into a more normal marine carbonate environment (the “Trenton lithofacies”). In particular, the younger carbonate strata are notable for their measurably higher amounts of secondary phosphate minerals. This stratigraphic interval is also well-constrained chronostratigraphically by the presence of the Deicke and Millbrig K-bentonite beds (altered volcanic tephra layers), thus it is ideal for a focused geochemical, petrographic, and stratigraphic investigation of the increased phosphate content of a specific Upper Ordovician sequence. Analyses of bulk rock samples and of extracted collophane grains (via x-ray fluorescence, XRF, and in-situ laser ablation inductively coupled plasma mass spectrometer, ICPMS) suggest that phosphogenesis in these strata was episodic rather than slow and steady, with a depositional pattern of abrupt increases followed by abrupt declines. Observed trace element changes in the 12 m to 18 m sample interval include the occurrence of elevated Th/U ratios (maximum of 5.7) accompanied by Y/Ho ratios that range from 27 (base) to 51 (top). We attribute these changes to increasing silicate influx into the basin and an accompanying increase in available Fe, which would preferentially scavenge MREEs and then release them to the pore waters leading to MREE enrichment, which we also observe in this interval. In a rapidly subsiding basin, MREE enrichment could have resulted from initial restriction of bottom water cir