Mg and Sr isotopic evidence for basin wide alteration of early diagenetic dolomite in the Williston Basin by ascending crustal fluids

Dolomite is a predominantly diagenetic mineral that forms by replacing marine calcite and aragonite during burial. Dolomitization requires subsurface fluid flow to deliver Mg and remove product Ca, and only forms abiotically in laboratory experiments at temperatures above ~100°C, equivalent to burial depths of 3 km or greater. Limited sources of Mg at these depths would appear to restrict most dolomite formation to shallow burial depths using seawater as a source of reactive Mg, despite the kinetic limitation imposed by lower temperatures. The Williston Basin is replete with evaporites and dolomites that appear to have formed using Mg from evaporatively concentrated seawater at near surface temperatures. However, two dolomite bodies examined in this study record basin wide gradients in ⁸⁷Sr/⁸⁶Sr ratios and δ²⁶Mg values that are inconsistent with dolomitization by seawater. We evaluate the processes that may have created these gradients. We propose a model whereby seepage reflux created early diagenetic protodolomite that was later altered during deep burial by ⁸⁷Sr and Mg-enriched fluids ascending from the deep structural center of the basin with the degree of alteration decreasing towards the edges. The ascending fluid flow event is tentatively linked to anomalous heating in the Late Devonian / Early Carboniferous. Vertical faults are hypothesized to have behaved as conduits for channeling ⁸⁷Sr and Mg-enriched crustal fluids upwards into the bottom of the Williston Basin, pressurizing the basal aquifer system and commencing up-dip directed fluid flow through confined aquifers. Clumped isotope and fluid inclusion thermometry indicate that the ascending fluids were hydrothermal with an estimated δ²⁶Mg value of –0.65 ±0.20‰, which is much lower than estimates of early Paleozoic seawater δ²⁶Mg values of +0.09 to +0.23‰. Two sources of crustal Mg are consistent with the low inferred δ²⁶Mg values of the ascending fluid: (1) chlorite, which preferentially releases isotopically light Mg, with literature values in the range of –0.78‰ to –1.8‰, and (2) magnesite, which forms during carbonation of serpentinite with literature values in the range –0.7‰ to –1.1‰. Ultramafic rocks belonging to the Thompson Nickel Belt pass beneath the center of the Williston Basin in North Dakota, indicating that dissolution of both chlorite and magnesite may have contributed reactive Mg to the Williston Basin during the ascending fluid flow event. As dolomite is a mineral that is easily altered during burial, our findings warrant caution in choosing dolomites for reconstructing the ²⁶Mg history of seawater.