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Abstract The high primary porosity and permeability of eogenetic karst aquifers permit water recharged through secondary dissolution features to be temporarily stored in aquifer matrix porosity. The recharged water contains elevated dissolved organic carbon (DOC) concentrations that, when oxidized, enhance limestone dissolution and impact carbon cycling. We evaluate the relationship between DOC oxidation and limestone dissolution using observations at a stream sink‐rise system and reversing spring in the Floridan aquifer, north‐central Florida, USA, where subsurface residence times of recharged water are days and months, respectively. We estimate water chemical compositions during surface water‐groundwater interactions at these two systems with mixing models of surface water and groundwater compositions and compare them with measured DOC, dissolved inorganic carbon (DIC), Ca²⁺and dissolved organic nitrogen (DON) concentrations. Differences between measured and modelled concentrations represent net changes that can be attributed to calcite dissolution and redox reactions, including DOC oxidation. DOC losses and Ca²⁺gains exhibit significant (p < 0.01) inverse linear correlations at both the reversing spring (slope = −0.9, r² = 0.99) and the sink‐rise system (slope = −0.4, r² = 0.72). DOC oxidation in both systems was associated with decreases in the molar C:N ratio (DOC:DON). Significant (p < 0.01) positive linear correlations between increases in Ca²⁺and DIC concentrations after correcting for DIC derived from calcite dissolution occurred at both the reversing spring (slope = 1.3, r² = 0.99) and the sink‐rise system (slope = 1.61, r² = 0.75). Greater deviations from the expected slope of −1 or +1 at the sink‐rise system than at the reversing spring indicate DOC oxidation contributes less dissolution at the sink‐rise system than at the reversing spring, likely from shorter storage in the subsurface. A portion of the deviation from expected slope values can be explained by the dissolution of Mg‐rich carbonate or dolomite rather than pure calcite dissolution. Despite this, slope values reflect kinetic effects controlling incomplete consumption of carbonic acid during dissolution reactions. 

Abstract Earth's Critical Zone (CZ), the near‐surface layer where rock is weathered and landscapes co‐evolve with life, is profoundly influenced by the type of underlying bedrock. Previous studies employing the CZ framework have focused primarily on landscapes dominated by silicate rocks. However, carbonate rocks crop out on approximately 15% of Earth's ice‐free continental surface and provide important water resources and ecosystem services to ∼1.2 billion people. Unlike silicates, carbonate minerals weather congruently and have high solubilities and rapid dissolution kinetics, enabling the development of large, interconnected pore spaces and preferential flow paths that restructure the CZ. Here we review the state of knowledge of the carbonate CZ, exploring parameters that produce contrasts in the CZ in different carbonate settings and identifying important open questions about carbonate CZ processes. We introduce the concept of a carbonate‐silicate CZ spectrum and examine whether current conceptual models of the CZ, such as the conveyor model, can be applied to carbonate landscapes. We argue that, to advance beyond site‐specific understanding and develop a more general conceptual framework for the role of carbonates in the CZ, we need integrative studies spanning both the carbonate‐silicate spectrum and a range of carbonate settings. 

Abstract Sensitivity of ecosystem productivity to climate variability is a critical component of ecosystem resilience to climate change. Variation in ecosystem sensitivity is influenced by many variables. Here we investigate the effect of bedrock lithology and weathering products on the sensitivity of ecosystem productivity to variation in climate water deficit using Bayesian statistical models. Two thirds of terrestrial ecosystems exhibit negative sensitivity, where productivity decreases with increased climate water deficit, while the other third exhibit positive sensitivity. Variation in ecosystem sensitivity is significantly affected by regolith porosity and permeability and regolith and soil thickness, indicating that lithology, through its control on water holding capacity, exerts important controls on ecosystem sensitivity. After accounting for effects of these four variables, significant differences in sensitivity remain among ecosystems on different rock types, indicating the complexity of bedrock effects. Our analysis suggests that regolith affects ecosystem sensitivity to climate change worldwide and thus their resilience.