Application of Ca stable isotopes to long-term changes in the Ca cycle of a Northern Hardwood forest

Abstract:

The Hubbard Brook Ecosystem Study (New Hampshire, USA) presents an unusual opportunity for the application of innovative isotope methods in forest biogeochemistry. Changes in biogeochemical cycling resulting from decades of acid deposition, subsequent reductions in acid deposition, and a series of experimental treatments (harvesting, Ca amendment) have been studied continuously for 60 years at this site. Importantly, researchers have archived soil, water, and vegetation samples for much of the site’s history. Our work seeks to complement earlier mass balance studies of Ca cycling by measuring Ca isotope ratios on archived samples. In the first component of our study, we examined the Ca isotopic response to an experimental clearcut in the early 1980’s. Earlier work showed that the clearcut promoted dramatic loss of Ca from the watershed, indicated by a 5-fold increase in streamwater Ca concentrations. The mechanism for this loss was unclear as no resolvable changes in soil Ca pools were observed. Our work shows that streamwater dissolved Ca becomes isotopically lighter as Ca concentrations increase. These data are best accounted for by an increase in Ca loss from the soil cation exchange complex. Soil exchangeable δ⁴⁴Ca itself evolves towards lighter values in the years following the experimental harvest. We interpret this as replenishment of the soil exchange complex by release of isotopically light Ca from root biomass. In the second component of our study, we examine decadal-scale changes in streamwater and soil Ca in an un-manipulated biogeochemical reference watershed. Historical data from Hubbard Brook show that streamwater Ca concentrations began decreasing sharply in the early 1970’s, attributed to decreased deposition of both acidity and Ca with the passage of the Clean Air Act. Preliminary data indicate no resolvable change in the average δ⁴⁴Ca of streamwater, with variability mostly attributable to discharge (flowpath control). Preliminary data similarly suggest that most of the variability in shallow soil exchangeable δ⁴⁴Ca is related to landscape position rather than temporal trends.