Abstract

Global emissions of atmospheric CO₂ and tropospheric O₃ are rising and expected to impact large areas of the Earth's forests. While CO₂ stimulates net primary production, O₃ reduces photosynthesis, altering plant C allocation and reducing ecosystem C storage. The effects of multiple air pollutants can alter belowground C allocation, leading to changes in the partial pressure of CO₂ (pCO₂) in the soil , chemistry of dissolved inorganic carbonate (DIC) and the rate of mineral weathering. As this system represents a linkage between the long- and short-term C cycles and sequestration of atmospheric CO₂, changes in atmospheric chemistry that affect net primary production may alter the fate of C in these ecosystems. To date, little is known about the combined effects of elevated CO₂ and O₃ on the inorganic C cycle in forest systems. Free air CO₂ and O₃ enrichment (FACE) technology was used at the Aspen FACE project in Rhinelander, Wisconsin to understand how elevated atmospheric CO₂ and O₃ interact to alter pCO₂ and DIC concentrations in the soil. Ambient and elevated CO₂ levels were 360±16 and 542±81 μl l^-1, respectively; ambient and elevated O₃ levels were 33±14 and 49±24 nl l^-1, respectively. Measured concentrations of soil CO₂ and calculated concentrations of DIC increased over the growing season by 14 and 22%, respectively, under elevated atmospheric CO₂ and were unaffected by elevated tropospheric O₃. The increased concentration of DIC altered inorganic carbonate chemistry by increasing system total alkalinity by 210%, likely due to enhanced chemical weathering. The study also demonstrated the close coupling between the seasonal δ¹³C of soil pCO₂ and DIC, as a mixing model showed that new atmospheric CO₂ accounted for approximately 90% of the C leaving the system as DIC. This study illustrates the potential of using stable isotopic techniques and FACE technology to examine long- and short-term ecosystem C sequestration.