Sedimentology, C-S-Fe relationships and stable isotopic compositions in Devonian black mudrocks, Mackenzie Mountains, Northwest Territories, Canada

An integrated approach combining C-S-Fe relationships, stable isotopic compositions, and lithofacies characterization was utilized to constrain the palaeoenvironmental and early diagenetic conditions of Middle-Upper Devonian (Eifelian-Frasnian) mudrocks from the Mackenzie Mountains, Northwest Territories, Canada. These rocks include the Hare Indian Formation (informally subdivided into the lower Bluefish Member and the Hare Indian Upper Member), Carcajou Marker and Canol Formation. The Bluefish Member is dominated by black, laminated, organic-rich shales (TOC = 0.35-10.34 wt.%; av. 5.83 wt.%) with moderate degrees of pyritization (DOP) of 0.34-0.67 (av. 0.55). These mudrocks were deposited in dysoxic marine bottom-waters that became progressively more oxygenated with time. Variations in TOC, DOP and organic matter δ¹³C_PDB values (-29.7‰ to -19.9‰; av. -27.2‰) are attributed to repeated clastic dilution and increased input of terrestrial organic matter in association with shallowing-upward ramp-clinothem cycles. Pyrite δ³⁴S_CDT values (-32.7‰ to -18.8‰; av. -24.9‰) indicate an open system, bacteriogenic seawater-sulphate reduction. Conversely, the overlying Hare Indian Upper Member, characterized by clinothem facies, is composed of grey to green mudstone with minor argillaceous limestones and considerably less organic matter contents (TOC = 0.28-2.99 wt.%; δ¹³C = -29.5‰ to -22.5‰). Deposition occurred in oxic to slightly dysoxic waters (DOP = 0.20-0.54; δ³⁴S = -23.0‰ to -20.9‰), depending on the palaeotopographic location along the depositional slope. A rapid rise in sea level drowned the carbonate 'ramp' member of the Ramparts Formation and produced die thin, organic-rich Carcajou Marker. Bottom-water stagnation that resulted from subdued ramp palaeotopography produced anoxic sea bottom. Black, laminated, organic-rich shales from the Canol Formation (TOC = 1.37-6.68 wt.%) are very similar to those of the Bluefish Member, and are likewise basinal sediments. However, TOC, DOP and organic-matter δ¹³C_PDB values (-29.1‰ to -20.8‰; av. -26.2‰) do not show pronounced variations and indicate that low-energy, quiet-water conditions persisted over relatively long, uninterrupted periods of time. High DOP values (0.72-0.93) throughout the Canol Formation suggest that deposition occurred in anoxic bottom-waters, but as basin-fill conditions continued there was a shift to a dysoxic environment (DOP = 0.55-0.65), which grades into nearshore and offshore sequences of the overlying Imperial Formation. In contrast with the Hare Indian Formation, much heavier δ³⁴S_CDT values of pyrite in Canol mudrocks (-11.1‰ to +5.3‰; av. -3.1‰) point to bacterial sulphate reduction in a closed to semi-closed system with respect to seawater sulphate. The accumulation of large amounts of organic matter in the Bluefish Member, Carcajou Marker and Canol Formation is attributed to a combination of large inputs of terrestrially-derived organic matter during transgressive events and a high primary productivity, while preservation of this organic matter was facilitated by dysoxic-anoxic bottom-waters.