Hydrothermal, Biogenic, and Seawater Components in Metalliferous Black Shales of the Brooks Range, Alaska: Synsedimentary Metal Enrichment in a Carbonate Ramp Setting

Trace element and Os isotope data for Lisburne Group metalliferous black shales of Middle Mississippian (early Chesterian) age in the Brooks Range of northern Alaska suggest that metals were sourced chiefly from local seawater (including biogenic detritus) but also from externally derived hydrothermal fluids. These black shales are interbedded with phosphorites and limestones in sequences 3 to 35 m thick; deposition occurred mainly on a carbonate ramp during intermittent upwelling under varying redox conditions, from suboxic to anoxic to sulfidic. Deposition of the black shales at similar to 335 Ma was broadly contemporaneous with sulfide mineralization in the Red Dog and Drenchwater Zn-Pb-Ag deposits, which formed in a distal marginal basin. Relative to the composition of average black shale, the metalliferous black shales (n = 29) display large average enrichment factors (>10) for Zn (10.1), Cd (11.0), and Ag (20.1). Small enrichments (>2-<10) are shown by V, Cr, Ni, Cu, Mo, Pd, Pt, U, Se, Y, and all rare earth elements except Ce, Nd, and Sm. A detailed stratigraphic profile over 23 m in the Skimo Creek area (central Brooks Range) indicates that samples from at and near the top of the section, which accumulated during a period of major upwelling and is broadly correlative with the stratigraphic levels of the Red Dog and Drenchwater Zn-Pb-Ag deposits, have the highest Zn/TOC (total organic carbon), Cu/TOC, and Tl/TOC ratios for calculated marine fractions (no detrital component) of these three metals. Average authigenic (detrital-free) contents of Mo, V, U, Ni, Cu, Cd, Pb, Ge, Re, Se, As, Sb, Tl, Pd, and Au show enrichment factors of 4.3 x 10(3) to 1.2 x 10(6) relative to modern seawater. Such moderate enrichments, which are common in other metalliferous black shales, suggest wholly marine sources (seawater and biogenic material) for these metals, given similar trends for enrichment factors in organic-rich sediments of modern upwelling zones on the Namibian, Peruvian, and Chilean shelves. The largest enrichment factors for Zn and Ag are much higher (1.4 x 10(7) and 2.9 x 10(7), respectively), consistent with an appreciable hydrothermal component. Other metals such as Cu, Pb, and Tl that are concentrated in several black shale samples, and are locally abundant in the Red Dog and Drenchwater Zn-Pb-Ag deposits, may have a partly hydrothermal origin but this cannot be fully established with the available data. Enrichments in Cr (up to 7.8 x 10(6)) are attributed to marine and not hydrothermal processes. The presence in some samples of large enrichments in Eu (up to 6.1 x 10(7)) relative to modern seawater and of small positive Eu anomalies (Eu/Eu circle star up to 1.12) are considered unrelated to hydrothermal activity, instead being linked to early diagenetic processes within sulfidic pore fluids. Initial Os isotope ratios (Os-187/Os-188) calculated for a paleontologically based depositional age of 335 Ma reveal moderately unracliogenic values of 0.24 to 0.88 for four samples of metalliferous black shale. A proxy for the ratio of coeval early Chesterian seawater is provided by initial (Os-187/Os-188)335 Ma ratios of four unaltered black shales of the coeval Kuna Formation that average 1.08, nearly identical to the initial ratio of 1.06 for modern seawater. Evaluation of possible sources of unradiogenic Os in the metalliferous black shales suggests that the most likely source was mafic igneous rocks that were leached by externally derived hydrothermal fluids. This unradiogenic Os is interpreted to have been leached by deeply circulating hydrothermal fluids in the Kuna basin, followed by venting of the fluids into overlying seawater. We propose that metal-bearing hydrothermal fluids that formed Zn-Pb-Ag deposits such as Red Dog or Drenchwater vented into seawater in,a marginal basin, were carried by upwelling currents onto the margins of a shallow-water carbonate platform, and were then deposited in organic-rich muds, together with seawater- and biogenically derived components, by syngenetic sedimentary processes. Metal concentration in the black shales was promoted by high biologic productivity, sorption onto organic matter, diffusion across redox boundaries, a low sedimentation rate, and availability of H2S in bottom waters and pore fluids.