Environmental Partitioning of Biomass Combustion Biomarkers in Arctic Rivers across the Spring Freshet Hydrograph

A number of studies have recently documented that pyrogenic carbon (PyC) is an integral and significant proportion of DOM in worldwide rivers, and that this material originates from all fractions of the PyC continuum, from highly resistant PyC to more soluble, labile components. Understanding the transfer of PyC to river systems is paramount for Arctic regions, given the projected increase in frequency and intensity of forest fires in boreal ecosystems. Considering this potential increase in the production of boreal PyC, constraining the PyC-cycle in Arctic environments is essential. However, one of the parameters that affect the fate of PyC in river systems, the environmental partitioning between soluble and particulate phases (Kd), has so far been unstudied. This is particularly important to quantify for low-temperature PyC, due to the greater experimental solubility of this portion of the PyC continuum. Here, we present for the first time a study that analyzes phase partitioning of low-temperature PyC biomarkers in two Arctic Rivers: a small Canadian river, the Great Whale River in northern Quebec, and the largest Arctic River, the Yenisei River in north-central Siberia. During the spring freshet increases in discharge in each river, mass-normalized sorption coefficients (Kd) increase by two orders of magnitude, whereas organic carbon-normalized sorption coefficients (KOC) vary by a much smaller range. The former trend implies that spring discharge events export potentially fresher materials in the sorbed fractions, as the PyC components may not yet have fully equilibrated with the aqueous phase. The latter observation suggests an association of combustion biomarkers with particulate organic matter (char particles or sorbed soil organic matter). The present work confirms that low temperature PyC biomarkers sorb to particles at a high enough level to enter sedimentary deposits and record wildfire signatures. However, the Kd-KOC values for these rivers are 3-4 orders of magnitude lower than those reported for organic markers of high-temperature combustion (e.g. hydrophobic pyrogenic PAHs), suggesting a high potential for exchange with the aqueous phase and thus accessibility to microbial degradation.