Development of calcium stable isotopes as a new tool to understand calcium cycling in terrestrial ecosystems

Calcium stable isotope ratios are a relatively new tool that biogeochemists can use to investigate the biogeochemical cycle of calcium in terrestrial ecosystems, having seen widespread application only in the past 15 years. To advance the application of calcium isotopes in biogeoscience research, I conducted three investigations focused on interpreting calcium isotope ratios in streamwater and in the cation exchange pool of forest soils. In the first study, we observe a shift toward lower 44Ca/40Ca ratios in streamwater draining a New Hampshire watershed after an experimental clearcutting event. Isotope ratio measurements of ecosystem calcium pools indicate that enhanced leaching of the soil exchangeable pool produced the observed shift in 44Ca/40Ca ratios. A trend towards decreased 44Ca/40Ca ratios in soils in the years following the harvesting indicates that calcium leached from the soil exchangeable reservoir was likely replaced by calcium released by the decay of belowground biomass, maintaining pre-harvest levels of exchangeable calcium even in the face of a significant ecosystem disturbance. In a second study, we observed significant differences in the 44Ca/40Ca of the soil exchange pool between two neighboring tropical watersheds, although 44Ca/40Ca of calcium inputs (bedrock and atmospheric deposition) at the two sites were indistinguishable. Further, both sites had higher 44Ca/40Ca ratios compared with external inputs, a relatively rare observation globally. We propose that hurricane disturbance best explains the high 44Ca/40Ca at each site, and that the difference in 44Ca/40Ca between the two sites can be accounted for by the magnitude of disturbance at each site. Finally, a synthesis of our new data with previously published results shows that globally, soil exchangeable 44Ca/40Ca ratios can be higher, lower or equal to external inputs. Modeling work indicates that in addition to isotopic fractionation, the balance in fluxes between vegetation and soil is critical in determining how soil exchangeable 44Ca/40Ca ratios vary relative to external inputs. When plant uptake and return to the soil are equal, soil and external inputs 44Ca/40Ca are equal, while high soil 44Ca/40Ca ratios develop when uptake exceeds return. Soil develops low 44Ca/40Ca when biomass obtains calcium from sources other than the exchangeable reservoir