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 (δ 13 C-DIC), and pH showed a dependency with depth. Along the depth profile, a negative relationship was observed between pCO 2 and δ 13 C-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 (CO 2 ) and release base cations, leading to increased pH and decreased pCO 2 . We observed a positive relationship between δ 13 C-DIC and depth, potentially due to diffusion-related fractionation in addition to isotopic discrimination during soil respiration. Soil CO 2 may diffuse downward, resulting in a fractionation of the δ 13 C-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 CO 2 oversaturation in boreal surface waters.
Plain Language SummaryGroundwater is the second largest reservoir of freshwater on Earth, sustaining rivers and lakes and providing water for humans. Groundwater can have high concentrations of carbon and be a source of carbon dioxide, both to surface waters and to the atmosphere. We performed our study to get a better understanding of how much carbon and carbon dioxide there is in groundwater at intermediate depths, between 3 and 20 m, as this water will eventually reach downstream rivers and lakes. Our results show that the groundwater in the studied catchment contained much higher levels of carbon dioxide than the atmosphere. We also observed large variation in the concentrations of carbon dioxide at different depths and at different locations across the catchment. Several factors are responsible for the observed carbon dioxide variations, with soil respiration and weathering of silicate minerals being the most important ones. Our study provides a better understanding of the distribution and dynamics of carbon at intermediate depth groundwater, which is important since it is an essential regulator of surface water chemistry in lakes and rivers, and indirectly being a source of carbon dioxide to the atmosphere.