Diagenetic barite-pyrite-wurtzite formation and redox signatures in Triassic mudstone, Brooks Range, northern Alaska

Abstract

Mineralogical and geochemical studies of interbedded black and gray mudstones in the Triassic part of the Triassic-Jurassic Otuk Formation (northern Alaska) document locally abundant barite and pyrite plus diverse redox signatures. These strata, deposited in an outer shelf setting at paleolatitudes of ~45 to 60°N, show widespread sedimentological evidence for bioturbation. Barite occurs preferentially in black mudstones (TOC = 0.93–6.46 wt%), forming displacive euhedral crystals with pyrite inclusions and rims, and late albite inclusions or intergrowths. Pyrite also occurs as small (3–20 μm) framboids, discontinuous laminae, euhedral and anhedral crystals, and replacements of barite and fossils (mainly radiolarians). Paragenetically early wurtzite is present as clusters of very small (1–3 μm) aggregates of radiating crystals 0.5 to 1.0 μm long with cores of organic matter that overgrow framboidal pyrite; later wurtzite forms 10- to 30-μm bladed crystals. Equant grains (3–30 μm) and small (20 μm) angular clusters of zinc sulfide that include <1-μm-long, comb-like structures are sphalerite or wurtzite, or both. Minor siderite forms euhedral crystals intergrown with albite that enclose wurtzite and barite. Illite shows intergrowths with sphalerite; rare K-feldspar is intergrown with barite. Formation of these minerals and assemblages is attributed to early diagenetic processes. Whole-rock geochemical data for 15 samples show large ranges in redox proxies including Post Archean Average Shale (PAAS)-normalized enrichment factors (EFs) for V, U, Mo, and Re, and Al-normalized ratios for V, U, and Mo. Results for most black mudstones, with or without abundant barite and/or pyrite, suggest deposition within an oxygen minimum zone. Cerium anomalies, PAAS-normalized and calculated on a detrital-free basis, range widely from 0.49 to 0.96 and may reflect diagenetic overprinting by Ce-depleted fluids. Considering data for both black and gray mudstones, the overall geochemical pattern together with evidence from pyrite framboid sizes suggest that redox conditions fluctuated greatly from euxinic to oxic, like the redox profiles reported for modern shelf sediments offshore Peru and Namibia. The euxinic redox signatures in some Otuk black mudstones may correlate with widespread Early to Middle Triassic ocean anoxic events proposed for other regions. Calculations of median EFs for trace elements in Otuk black mudstones reveal both enrichments and depletions. Normalizations to the median composition of the three least-mineralized black mudstones show that barite- and/or pyrite-rich samples display large (>50%) positive changes for Li (+80.4%), V (+75.6%), Sr (+75.9%), Ba (+790%), Cu (+92.1%), Ni (+169%), Ag (+156%), Au (+3091%), As (+109%), Sb (+476%), and Se (+205%); Zn shows a moderate positive change of +42.1%. Moderate negative changes are evident only for Ge (−47.2%) and W (−30.6%). The local enrichments may reflect one or more factors including redox variations in bottom waters and pore fluids, element mobility during diagenesis, and selective fractionation into minerals such as barite, pyrite, and wurtzite. Anomalously low U/Al and UEF values, compared to those for other modern and ancient organic-rich sediments and sedimentary rocks, are attributed to increased solubility and loss of U during bioturbation-related oxygenation in the subsurface. Physicochemical constraints on barite, pyrite, and wurtzite formation are informed by use of a pH-fO2 plot constructed at 10 °C. Based on paragenetic evidence for multistage deposition of these three minerals, together with the presence of illite intergrown with ZnS and K-feldspar with barite, proposed diagenetic trends involve an increase in pH and fO2 related to the ingress of sulfate-rich pore fluids during bioturbation, followed by a return to lower then higher pH and fO2 conditions linked to carbon, sulfur, barium, and iron cycling during diagenesis. Labile Ba of marine pelagic origin was mobilized from organic-rich sediment upward to the sulfate-methane transition zone where barite precipitated during the interaction of reduced Ba- and CH4-rich fluids with sulfate-bearing pore fluids. The formation of paragenetically early wurtzite (ZnS) crystals, as well as locally high EF values for Cu, Ni, Ag, and Au, is attributed to metal enrichment of pore fluids, with sources being derived in part from water-column deposition from hydrothermal plumes related to coeval Triassic seafloor vent systems including a volcanogenic massive sulfide deposit in British Columbia and the Wrangellia Large Igneous Province in Alaska.