Mercury sequestration pathways under varying depositional conditions during Early Jurassic (Pliensbachian and Toarcian) Karoo-Ferrar volcanism

Major extinction events appear coincident with the emplacement of large igneous provinces (LIPs) throughout Earth's past, but the cause-and-effect relationship is often poorly understood due to challenges in the stratigraphical correlation between LIP occurrence and sedimentary archives. Large igneous provinces are thought to have released large amounts of greenhouse gasses and toxic compounds (including mercury) into the global ocean-atmosphere system, leading to major climatic and environmental perturbations and ecosystem deterioration. In recent years, the analyses of bulk sedimentary mercury (Hg) concentrations have increasingly been used to assess the temporal occurrence and geographic reach of LIPs, as observed through elevated Hg concentrations in sedimentary archives which otherwise show no direct evidence of volcanism at those times. Mercury can be sequestered into sediments in different ways, but dominant Hg sequestration pathways can vary through space and time depending on the depositional environment and changes therein, which may disguise changes in global Hg fluxes into Earth's surficial environments, significantly complicating the interpretation of sedimentary Hg-records. Here, we statistically analyse sedimentary geochemical records from three distinctly different depositional environments that occurred during the Toarcian Oceanic Anoxic Event (T-OAE, at ∼183 Ma, and coincident with Karoo-Ferrar LIP volcanism), and assess the temporal and spatial variability in dominant Hg sequestration pathways during LIP volcanism. The geochemical data show significantly different affinities of mercury with assessed sedimentary geochemical parameters in each of the studied successions. Principal component analyses (PCA) of sedimentary geochemical data (including Hg), from the restricted, anoxic-euxinic Cleveland Basin (Yorkshire, UK) show that Hg covaries mostly with organic-sulphide-associated elements and to a lesser extent with the redox-sensitive elements, as opposed to the semi-restricted, sub-oxic Cardigan Bay Basin (Wales, UK) and the well-connected, oxygenated Subbetic Basin (South Iberian Palaeomargin, SE Spain), where Hg covaries dominantly with the redox-sensitive elements and secondarily with detrital elements. These findings show that mineral phases and materials other than organic matter need to be considered as dominant Hg carriers in non-anoxic depositional settings. Furthermore, observed differences between the studied sites regarding the dominant Hg-sequestration processes, suggest temporal and spatial variance in Hg drawdown fluxes, and possibly local marine residence times.