- Pedogenic carbonates in loess formation rates, formation conditions and source apportionment assessed by isotopes and molecular proxies (2011)
- Interest in secondary (pedogenic) carbonates as an archive for paleoclimatic reconstructions in arid and semiarid regions has increased during recent decades. Their carbon (C) isotope composition represents the conditions prevailing during their formation because they are formed by precipitation of Ca2+ from soil solution with dissolved CO2 from soil air originating from root and rhizomicrobial respiration. Thus, pedogenic carbonates are an important tool for estimation of age of pedogenesis and for reconstruction of the local paleovegetation. Potential reequilibration of pedogenic carbonates with younger soil CO2 can entail loss of chronological and paleoenvironmental information. Although methodological resolution of these studies depends on the time scale of pedogenic carbonate formation and recrystallization, its rates and periods remain unknown. The first objective therefore was the first-time assessment of the time frame of pedogenic CaCO3 formation and recrystallization under controlled conditions. The other aim was to reveal the potential of rhizoliths, a special form of pedogenic carbonates (calcified roots), from a loess-paleosol sequence for paleoenvironmental studies. In loess as a common soil parent material, initial CaCO3 recrystallization rates were successfully determined with the 14C isotopic exchange approach by exposing loess to artificially labeled 14CO2 and subsequent quantification of 14C incorporated in secondary (recrystallized) CaCO3. Within the range of natural soil CO2 concentrations, recrystallization rates increased strongly with CO2 concentration. In further studies, loess was exposed to 14CO2 respired by roots and rhizomicrobial organisms of plants labeled in 14CO2 atmosphere, to estimate the effects of several factors (root vicinity, temperature, accumulation depth) on the recrystallization rate. Rates from planted loess were two orders of magnitude higher than those from unplanted loess, mostly in the range of 10-5 day-1. Significantly higher CaCO3 recrystallization rates in rhizosphere than in loess distant from roots were attributed to three factors: high CO2 concentration from root and rhizomicrobial respiration, low pH caused by release of CO2 and root exudates, and high Ca2+ and HCO3- concentration caused by water uptake by roots. Considerable influence of the latter was demonstrated by low CaCO3 recrystallization rates at low temperatures and vice versa, reflecting the increasing transpirational pull with increasing temperatures. Assuming repeated recrystallization of both primary and secondary CaCO3, extrapolation of initial CaCO3 recrystallization rates showed that at least 102 – 103 years are necessary for complete recrystallization of CaCO3 in ‘root-free’ loess by formation of secondary CaCO3, depending on length of the growing season. Increasing temperature promoted CaCO3 recrystallization rates, but the contrast was compensated for recrystallization periods because of the negative effect of increasing temperature on length of the growing season. In contrast, pedogenic carbonates can form much faster close to roots (101 – 102 years) because of mass flow to the roots leading to rhizolith formation. As a consequence of this wide temporal spectrum of pedogenic carbonate formation, variable methodological resolution has to be considered in paleoenvironmental studies based on stable isotope composition of pedogenic carbonates, depending on climatic factors and formation of carbonate concretions. Rhizoliths, formed by encrustation of roots with secondary CaCO3, yield high potential for paleoenvironmental studies. At the late Pleistocene loess-paleosol sequence of Nussloch, SW Germany, rhizolith CaCO3 was completely secondary and not contaminated by postsegregational alteration. Radiocarbon dating of one rhizolith sample reinforced the assumption of potential postsedimentary formation of rhizoliths. In the investigated profile, stable C isotope composition indicated C3 source vegetation for organic matter (OM) of both loess and rhizoliths, but lipid molecular proxies revealed grass biomass as origin of loess OM, and shrub or tree roots as source of rhizoliths. Moreover, OM in loess adjacent to rhizoliths was considerably contaminated by rhizomicrobial and root remains at least up to a distance of 5 cm. Alteration of loess OM and its isotope composition by postsedimentary penetration of deep-rooting plants might entail uncertainties for paleoenvironmental studies based on loess OM. In summary, the important role of vegetation on pedogenic CaCO3 formation and recrystallization was shown under controlled and field conditions. Plant roots and associated microorganisms have direct influence on these processes, while further factors of pedogenesis like climate exert an indirect effect, but on the long term probably are of greater importance than effects on the rhizosphere scale.