Modern soil system constraints on reconstructing deep-time atmospheric CO2

Paleosol carbonate-based estimates of paleo-atmospheric CO2 play a prominent role in constraining radiative-forcing and climate sensitivity in the deep-time. Large uncertainty in paleo-CO2 estimates made using the paleosol-carbonate CO2-barometer, however, arises primarily from their sensitivity to soil-respired CO2 (S(z)). This parameter is poorly constrained due to a paucity of soil CO2 measurements during carbonate formation in modern soils and a lack of widely applicable proxies of paleo-soil CO2. Here the delta C-13 values of carbonate and soil organic matter (SOM) pairs from 130 Holocene soils are applied to a two-component CO2-mixing equation to define soil order-specific ranges of soil CO2 applicable for constraining S(z) in their corresponding paleosol analogs. Equilibrium carbonate-SOM pairs, characterized by Delta C-13(carb-SOM) values of 12.2-15.8 parts per thousand, define a mean effective fractionation of 14.1 parts per thousand and overall inferred total soil CO2 contents during calcite formation of <1000-10,000 ppmv. For those Aridisols and Alfisols, characterized by a net soil-moisture deficit, and their paleosol analogs (Calcisols and Argillisols), a best estimate of S(z) during calcite formation is 1500-2000 ppmv (range of 500-2500 ppmv). Overall higher values (2000-5000 ppmv) are indicated by the subset of these soils characterized by higher moisture content and productivity. Near atmospheric levels (400 +/- 200 ppmv) of estimated S(z) are indicated by immature soils, recording their low soil productivity. Vertisols define the largest range in total soil CO2 (<1000 to >25,000 ppmv) reflecting their seasonally driven dynamic hydrochemistry. A S(z) range of 1000-10,000 ppmv is suggested for paleo-Vertisols for which calcite precipitation can be constrained to have occurred in an open system with two-component CO2 mixing, with a best estimate of 2000 ppmv +/- 1000 ppmv appropriate for paleo-Vertisols for which evidence of protracted water saturation is lacking. Mollisol pairs define a best estimate of S(z) of 2500 ppmv (range of 600-4000 ppmv) for late Cretaceous and Cenozoic analogs. Non-equilibrium pairs with Delta C-13 values >16 parts per thousand make up 51% of the dataset, lending support to the hypothesis that pedogenic carbonate precipitation occurs during periods of low productivity in a soil atmosphere with a large component of atmospheric CO2. Predictable scaling between estimated soil CO2 and the difference in Delta C-13 between measured pedogenic carbonate and that predicted to have formed from soil-respired CO2 (inferred from measured SOM) can be used to further constrain appropriate ranges of S(z) for reconstruction of paleo-atmospheric pCO(2). Soil CO2 estimates are poorly correlated to mean annual precipitation likely reflecting that for carbonate-bearing soils, where moisture limits CO2 production, total soil CO2 is most strongly influenced by actual evapotranspiration. (C) 2012 Elsevier Ltd. All rights reserved.