Assessment of Hg speciation changes from thermal desorption characteristics in sedimentary rocks

The total Hg (Hg_T) concentration data for geological samples, of interest as it may link to enhanced volcanic activity or other environmental changes, is a complex amalgamation of numerous surface and sediment processes. Drawdown by organic matter (OM) and sulfides (often approximated by total sediment sulfur concentrations, TS) have long been recognized as key drivers of variability in sedimentary Hg_T data. Most studies, therefore, employ a degree of normalization to a Hg “host” (Hg_T/TOC, Hg_T/TS) to extract anomalous Hg cycle behavior. The dominant host is often determined solely based on the strongest observed (linear) correlation but this widely applied method has been shown to suffer from various non-linearities in environmental processes and conditions that underlie the host-Hg relations and, crucially, does not allow succession-level, let alone sample-level, Hg speciation changes to be taken into account.

We here explore the use of thermal desorption characteristics for geological sediment (rock) samples. Thermal desorption profiles (TDPs) for many Hg species are well-established and have been used to, for example, distinguish between OM-bound Hg and different Hg sulfides, as well as Hg-oxides in (sub-)recent sediments. The typical method of analysis for TDPs is to use long (>15 minutes) multi-step temperature ramps. We adapt this technique to use only the rapid (< 3 minute) desorption that is obtained as standard for each sample analyzed in continuous-flow direct Hg analyzers. Using the rapid TDPs, we can clearly distinguish at least two Hg release phases, and find that (almost) all of the analyzed sedimentary silt and mud rock samples of Tithonian age (ca. 146 – 145 Ma) contain multiple Hg release phases. Analysis of each TDP allows quantification of the abundance of each phase, which can then be compared to potential hosts (TOC, TS) and other geochemical data on a sample and succession level.

Initial analyses of the TDP-informed Hg release for our samples indicate TOC concentration may determine 60 – 70% of the variability in the first (lower temperature) Hg release phase in our succession. This is a stark difference with the total Hg released from the same samples, for which only 20% of variation can be explained by TOC variability. The difference results from the variable presence of a later-stage (higher temperature) Hg phase that is anti-correlated with TOC.

The TDPs provide insight into sample-level Hg speciation and clearly demonstrate that the common assumption that Hg is exclusively associated with a single phase in sedimentary rocks throughout a succession is a large oversimplification. Further, we show that differences in Hg speciation can be detected and quantified in individual samples with minor adaptations of existing techniques. The TDPs offer a novel perspective on Hg analyses in geological samples and have the potential to test, validate, and supplement existing statistical models to detect anomalous Hg cycle behavior.