Groundwater Carbon Within a Boreal Catchment: Spatiotemporal Variability of a Hidden Aquatic Carbon Pool

Groundwater is an essential resource providing water for societies and sustaining surface waters. Although groundwater at intermediate depth could be highly influential at regulating lake and river surface water chemistry, studies quantifying organic and inorganic carbon (C) species in intermediate depth groundwater are still rare. Here, we quantified dissolved and gaseous C species in the groundwater of a boreal catchment at 3- to 20-m depth. We found that the partial pressure of carbon dioxide (pCO(2)), the stable carbon isotopic composition of dissolved inorganic carbon (delta C-13-DIC), and pH showed a dependency with depth. Along the depth profile, a negative relationship was observed between pCO(2) and delta C-13-DIC and between pCO(2) and pH. We attribute the negative pCO(2)-pH relationship along the depth gradient to increased silicate weathering and decreased soil respiration. Silicate weathering consumes carbon dioxide (CO2) and release base cations, leading to increased pH and decreased pCO(2). We observed a positive relationship between delta C-13-DIC and depth, potentially due to diffusion-related fractionation in addition to isotopic discrimination during soil respiration. Soil CO2 may diffuse downward, resulting in a fractionation of the delta C-13-DIC. Additionally, the dissolved organic carbon at greater depth may be recalcitrant consisting of old degraded material with a greater fraction of the heavier C isotope. Our study provides increased knowledge about the C biogeochemistry of groundwater at intermediate depth, which is important since these waters likely contribute to the widespread CO2 oversaturation in boreal surface waters.