Basaltic fissure eruptions emit an array of volatile and environmentally reactive gases and particulate matter (PM) into the lower troposphere (e.g., SO2, HCl, and HF in the gas phase; Se, As, Pb as complexes in the PM phase). Lava flows from fissure eruptions can be spatially extensive, but the composition and fluxes of their emissions are poorly characterized compared to those from main vent(s). Using UAS-mounted (drone) samplers and ground-based remote FTIR spectroscopy we investigate the down-flow compositional evolution of emissions from active lava flows during the Fagradalsfjall 2021-2023 eruptions. The calculated fluxes of volatile trace metals from lava flows are considerable relative to both main vent degassing and anthropogenic fluxes in Iceland. We demonstrate a fractionation in major gas emissions, with decreasing S/halogen ratio down-flow. This S-Cl fractionation is reflected in the trace element degassing profile, where the abundance of predominantly sulfur-complexing elements (e.g., Se, Te, As, Pb) decreases more rapidly in down-flow emissions relative to elements complexing as chlorides (e.g., Cu, Rb, Cs), oxides (e.g., La, Ce) and hydroxides (e.g., Fe, Mg, Al). Using thermochemical modeling, we explain this relationship through temperature and composition dependent element speciation as the lava flow ages and cools. As a result, some chloride-complexing elements (such as Cu) become relatively more abundant in emissions further down-flow, compared to emissions from the main vent or more proximal lava flows. This variability in down-flow element fluxes suggests that the output of metals to the environment may change depending on lava flow age and thermal evolution.

Sedimentary mercury (Hg) has become a widely used proxy for paleo-volcanic activity. However, scavenging and drawdown of Hg by organic-matter (OM) and sulfides are important non-volcanic factors determining variability in such records. Most studies, therefore, normalize total Hg (HgT) to a Hg “host-phase” proxy (e.g., HgT/TOC for OM, HgT/TS for sulfides), with the dominant host-phase determined based on the strongest observed (linear) correlations. This approach suffers from various non-linearities in Hg-host-phase behavior and does not account for succession-level, let alone sample-level, Hg speciation changes. Thermal desorption characteristics or ‘profiles’ (TDPs) for many Hg species during pyrolysis analysis are well-established with applications including distinguishing between OM-bound Hg and different Hg sulfides and oxides in (sub-)recent sediments. We explore the use of TDPs for geological sediment (rock) samples and illustrate the presence of multiple release phases (Hg species) – correlated to geochemical host-phase – in (almost) all the 65 analyzed Tithonian (146 – 145 Ma) silt and mudrock samples. By quantifying the Hg in each release phase for every sample, we find TOC concentration may determine ~60% of the variability in the first (lower temperature) Hg TDP release phase: a stark difference with the total Hg released from these samples, where ~20% of variation is explained by TOC variability. TDPs provide insight on sample-level Hg speciation and demonstrate that, while the common assumption of single-phase Hg speciation in sedimentary rocks is problematic, differences in Hg speciation can be detected, quantified, and accounted for using commonly applied techniques - opening potential for routine implementation.

While Hg in sediments is increasingly used as a proxy for deep-time volcanic activity, the behaviour of Hg in OM-rich sediments as they undergo thermal maturation is not well understood. In this study, we evaluate the effects of thermal maturation on sedimentary Hg contents and, thereby, the impact of thermal maturity on the use of the Hg/TOC proxy for large igneous province (LIP) volcanism. We investigate three cores (marine organic matter) with different levels of thermal maturity in lowermost Toarcian sediments (Posidonienschiefer) from the Lower Saxony Basin in Germany. We present Hg content, bulk organic geochemistry, and total sulfur in three cores with different levels of thermal maturity. The comparison of Hg data between the three cores indicates that Hg content in the mature/overmature sediments have increased > 2-fold compared to Hg in the immature deposits. Although difficult to confirm with the present data, we speculate that redistribution within the sedimentary sequence caused by the mobility and volatility of the element under relatively high temperatures may have contributed to Hg enrichment in distinct stratigraphic levels of the mature cores. Regardless of the exact mechanism, elevated Hg content together with organic-carbon loss by thermal maturation exaggerate the value of Hg/TOC in mature sediments, suggesting that thermal effects have to be considered when using TOC-normalised Hg as a proxy for far-field volcanic activity.

Volcanism is the dominant natural source of mercury (Hg) to the atmosphere, biosphere, ocean and sediments. In recent years, sedimentary Hg contents have emerged as a tool to reconstruct volcanic activity, and particularly activity of (subaerially emplaced) large igneous provinces (LIP) in geological deep time. More specifically, Hg has shown potential as a useful proxy to illuminate the previously elusive impact of such large-scale volcanism on marine and terrestrial paleo-environments. While Hg is now widely applied as volcanism tracer, non-volcanic factors controlling sedimentary Hg content are generally not well constrained. Part of this uncertainty stems from our inability to directly observe a natural unperturbed “steady-state” environment as a baseline, as the modern Hg cycle is heavily influenced by anthropogenic activity. Here we focus on the effects of ambient redox conditions in the water column and shallow sediments (early diagenesis), quantify their influence on the geological Hg record and thereby constrain their potential impact on the use of Hg as a proxy for deep-time volcanic activity. Constraining these factors is of critical importance for the application of Hg as a proxy. Many periods in the geological past for which records have been generated, such as the Mesozoic Oceanic Anoxic Events, are marked by a variety of high-amplitude environmental perturbations, including widespread deoxygenation and deposition of organic-rich sediments. We estimate the impact of redox changes and early diagenesis on the geological Hg record using a suite of (sub)recent–Pleistocene and Upper Cretaceous sediments representing oxic to euxinic marine conditions. Our sample set includes a transect through an oxygen minimum zone and cores that record transient shifts in oxygenation state, as well as post-depositional effects – all unrelated to volcanism, to the best of our knowledge. We find substantial alterations to the Hg record and the records of organic carbon and total sulfur, which are typically assumed to be the most common carrier phases of Hg in marine sediments. Moreover, these biases can lead to signal-alterations on a par with those interpreted to result from volcanic activity. Geochemical modifications are ubiquitous and their potential magnitude implies that the factors leading to biases in the geological record warrant careful consideration before interpretation. Factors of particular concern to proxy application are (1) the disproportionate loss of organic carbon and sulfur compounds relative to Hg during oxidation that strongly modulates normalized Hg records, (2) the evasion of Hg in anoxic and mildly euxinic sediments and (3) sharp focusing of Hg during post-depositional oxidation of organic matter.