Evolution of Radiocarbon in a Sandy Aquifer Across Large Temporal and Spatial Scales: Case Study from Southern Poland

We present the results of a comprehensive study aimed at tracing the evolution of carbon isotopic composition of the TDIC (total dissolved inorganic carbon) reservoir from the unsaturated zone down to the discharge area, in a sandy aquifer near Kraków, southern Poland. A multilevel well penetrating the unsaturated zone in the study area was equipped with horizontally mounted lysimeters with ceramic suction cups to collect samples of pore water and metal probes to collect soil air. Strong seasonal fluctuations were observed of soil pCO2 extending down to the water table, coupled with distinct, well-defined depth profiles of δ13CTDIC reaching approximately −10′ at 8 m depth and almost constant radiocarbon content in the TDIC pool, comparable to 14CO2 levels in the local atmosphere. Simple models (closed/open system) do not account for the observed depth variations of carbon isotopic composition of the TDIC pool. This suggests that the TDIC reservoir of pore waters is evolving under conditions gradually changing from an open towards a closed system. In order to explain 13C and 14C content of dissolved carbonates in groundwater in the recharge area of the studied aquifer, additional sources of carbon in the system are considered, such as organic matter decomposition accompanied by reduction of dissolved nitrates and sulfates. The piston-flow l4C ages of groundwater in the confined part of the studied system were calculated using 2 approaches: 1) the correction model proposed by Fontes and Garnier (1979) was used to calculate groundwater ages, utilizing the chemical and carbon isotopic data available for the sampled wells; and 2) inverse geochemical modeling was performed for selected pairs of wells using NETHPATH code. The calculated 14C ages of groundwater range from approximately 0.6 to 37.5 ka BP. Although both methods appeared to be in a broad agreement, NETHPATH calculations revealed that isotopic exchange processes between TDIC pool and solid carbonates present in relatively small amounts in the aquifer matrix play an important role in controlling the 13C and 14C signatures of the dissolved carbonate species in groundwater and should be taken into account when 14C ages are calculated.