Decomposition of soil organic matter (SOM) can be stimulated by fresh organic matter input, a phenomenon known as the ‘priming effect’. Despite its global importance, the relationship of the priming effect to mineral weathering and nutrient release remains unclear. Here we show close linkages between mineral weathering in the critical zone and primed decomposition of SOM. Intensified mineral weathering and rock-derived nutrient release are generally coupled with primed SOM decomposition resulting from “triggered” microbial activity. Fluxes of organic matter products decomposed via priming are linearly correlated with weathering congruency. Weathering congruency influences the formation of organo-mineral associations, thereby modulating the accessibility of organic matter to microbial decomposers and, thus, the priming effect. Our study links weathering with primed SOM decomposition, which plays a key role in controlling soil C dynamics in space and time. These connections represent fundamental links between long-term lithogenic element cycling (= weathering) and rapid turnover of carbon and nutrients (= priming) in soil.

Critical zone science seeks to develop mechanistic theories that describe critical zone structure, function, and long‐term evolution. One postulate is that hydrogeochemical controls on critical zone evolution can be inferred from solute discharges measured down‐gradient of reactive flow paths. These flow paths have variable lengths, interfacial compositions, and residence times, and their mixing is reflected in concentration‐discharge (C‐Q) relations. Motivation for this special section originates from a U.S. Critical Zone Observatories workshop that was held at the University of New Hampshire, 20–22 July 2015. The workshop focused on resolving mechanistic CZ controls over surface water chemical dynamics across the full range of lithogenic (e.g., nonhydrolyzing and hydrolyzing cations and oxyanions) and bioactive solutes (e.g., organic and inorganic forms of C, N, P, and S), including dissolved and colloidal species that may cooccur for a given element. Papers submitted to this special section on “concentration‐discharge relations in the critical zone” include those from authors who attended the workshop, as well as others who responded to the open solicitation. Submissions were invited that utilized information pertaining to internal, integrated catchment function (relations between hydrology, biogeochemistry, and landscape structure) to help illuminate controls on observed C‐Q relations.

This study investigates the influence of water, carbon, and energy fluxes on solute production and transport through the Jemez Critical Zone (CZ) and impacts on C‐Q relationships over variable spatial and temporal scales. Chemical depletion‐enrichment profiles of soils, combined with regolith thickness and groundwater data indicate the importance to stream hydrochemistry of incongruent dissolution of silicate minerals during deep bedrock weathering, which is primarily limited by water fluxes, in this highly fractured, young volcanic terrain. Under high flow conditions (e.g., spring snowmelt), wetting of soil and regolith surfaces and presence of organic acids promote mineral dissolution and provide a constant supply of base cations, Si, and DIC to soil water and groundwater. Mixing of waters from different hydrochemical reservoirs in the near stream environment during “wet” periods leads to the chemostatic behavior of DIC, base cations, and Si in stream flow. Metals transported by organic matter complexation (i.e., Ge, Al) and/or colloids (i.e., Al) during periods of soil saturation and lateral connectivity to the stream display a positive relationship with Q. Variable Si‐Q relationships, under all but the highest flow conditions, can be explained by nonconservative transport and precipitation of clay minerals, which influences long versus short‐term Si weathering fluxes. By combining measurements of the CZ obtained across different spatial and temporal scales, we were able to constrain weathering processes in different hydrological reservoirs that may be flushed to the stream during hydrologic events, thereby informing C‐Q relationships.

Despite a multitude of small catchment studies, we lack a deep understanding of how variations in critical zone architecture lead to variations in hydrologic states and fluxes. This study characterizes hydrologic dynamics of 15 catchments of the U.S. Critical Zone Observatory (CZO) network where we hypothesized that our understanding of subsurface structure would illuminate patterns of hydrologic partitioning. The CZOs collect data sets that characterize the physical, chemical, and biological architecture of the subsurface, while also monitoring hydrologic fluxes such as streamflow, precipitation, and evapotranspiration. For the first time, we collate time series of hydrologic variables across the CZO network and begin the process of examining hydrologic signatures across sites. We find that catchments with low baseflow indices and high runoff sensitivity to storage receive most of their precipitation as rain and contain clay‐rich regolith profiles, prominent argillic horizons, and/or anthropogenic modifications. In contrast, sites with high baseflow indices and low runoff sensitivity to storage receive the majority of precipitation as snow and have more permeable regolith profiles. The seasonal variability of water balance components is a key control on the dynamic range of hydraulically connected water in the critical zone. These findings lead us to posit that water balance partitioning and streamflow hydraulics are linked through the coevolution of critical zone architecture but that much work remains to parse these controls out quantitatively.