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.

Master of Science / Department of Geology / Saugata Datta / Pamela Kempton / The Critical Zone is the realm where rocks meet life. This study examines the physicochemical interactions that occur when interbedded limestone-shale systems and kimberlitic rocks weather to form soils. Fast weathering processes with extensive soil loss have been a major environmental concern in the Flint Hills for decades. Knowledge of soil formation processes, rates of formation and subsequent loss, and understanding how these processes differ in different systems are critical for managing soil as a resource. Kimberlites are CO₂-rich igneous rocks that are high in Mg and Fe; they are compositionally distinct from the Paleozoic limestones and shales found throughout the rest of the region. This study will compare the geochemistry and mineralogy of the Stockdale Kimberlite in Riley county to that of interbedded limestone-shale system typical of the Flint Hills as sampled from Konza Prairie LTER. Bulk composition and mineralogy of the soils overlying these different bedrock types have been analyzed using X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), bulk elemental extractions, and particle size analyses. Results show that the kimberlitic soils have higher concentrations of Fe, Mg, Ca, K and some trace elements in greater proportions (e.g. Ti, Ni, Cu). The weathering products differ mineralogically as well, e.g. lizardite is abundant in kimberlitic soils and absent from the limestone terranes. Kimberlite derived soils also contain minerals as well such as kleberite (an alteration product of illminite), phlogopite, and magnetite. Kimberlite-sourced soils have different physical properties than the thin limestone-sourced soils surrounding them. Particle size analysis shows that the limestone-shale soils have different proportions of the clay size fraction in different core locations (~47% in highlands, ~51% at watershed base, ~41% in lowlands) whereas kimberlitic soils have a larger sand fraction than Konza (~19% vs. 10%). Clay minerals from the limestone-shale system reveals clay micas, kaolinite, and some expandable 2:1 layer silicates. Clay minerals from kimberlite-sourced soils are identified as primarily smectites with clay micas and kaolinites. Similarities between the kimberlite and limestone-shale soils are primarily seen in the shallower portions of the soil profile, suggesting that loess/wind-blown dust make a significant contribution to the soils in both areas. It could be concluded that kimberlite-sourced and limestone-shale-sourced soils produce weathering products that differ both chemically and mineralogically and could potentially have agricultural significance in terms of water retention as well as ionic and nutrient mobilities in these soils.

Notre connaissance des mécanismes d’acquisition de la chimie des eaux continentales est limitée par la fréquence des prélèvements qui peuvent être réalisés sur le terrain. Échantillonner une rivière tous les 15 jours, c’est négliger une variabilité de sa composition qu’on commence à suspecter et qui renseigne sur des processus ou des variations de sources de courte période intégrés sur l’ensemble du bassin versant. L’automatisation des prélèvements et la mesure en temps réel est un défi important non seulement du point de vue de la compréhension des mécanismes contrôlant la chimie des eaux, de leur dynamique temporelle, des relations entre concentrations et débits, mais aussi du point de vue appliqué pour la détection des pollutions ponctuelles. Ce développement intéresse les professionnels de l’eau qui ne sont pas à ce jour contraint par la loi, mais qui pourraient le devenir. Dans le cadre du projet équipex CRITEX, un prototype de maison chimique appelé ”RiverLab”, véritable laboratoire d’analyses en temps réel sur le terrain a été développé et installé en novembre 2014 sur la bassin versant expérimental de l’Orgeval, un site étudié depuis 50 ans par les équipes de l’IRSTEA. Ce prototype est destiné à être déployé sur deux autres sites du réseau national des bassins versants (dispositif SOERE). Nous nous focalisons sur les deux principaux forçages naturels que subi un bassin versant à savoir les apports de précipitations et l’énergie solaire revisité sous l’angle de la haute fréquence / Our knowledge of the mechanisms of acquisition of inland water chemistry is limited by the frequency of sampling that can be carried out in the field. Sampling a river every 15 days means neglecting a variability in its composition that is beginning to be suspected and which informs processes or variations of short-term sources integrated over the entire catchment area. The automation of sampling and real-time measurement is an important challenge not only from the point of view of understanding the mechanisms controlling water chemistry, their temporal dynamics, the relations between concentrations and flows, but also from the point of view of applied for the detection of point pollution. This development is of interest to water professionals who are not yet legally constrained, but who could become so.As part of the CRITEX team project, a prototype of a chemical house called "RiverLab", a real laboratory for real-time field analysis, was developed and installed in November 2014 on the experimental watershed of Orgeval, a site studied for 50 years by the IRSTEA teams. This prototype is intended to be deployed on two other sites of the national watershed network (SOERE device). We focus on the two main natural forces that have undergone a watershed, namely precipitation inputs and solar energy revisited in terms of high frequency

Geophysical investigation of the subsurface through seismic refraction and reflection methods provides an efficient and non-invasive means towards addressing geologic problems across multiple scales. Both seismic techniques, in an active-source exploration setting, involve inducing acoustic waves into the subsurface and measuring their propagation velocities and amplitudes. These measurements have physically-based relationships with the properties of the underlying strata, thus allowing changes in the seismic measurements to be interpreted with respect to changes in the subsurface geology. Two applications of the seismic method are presented in this dissertation: (1) shallow seismic refraction acquisition and processing applied to the near-surface investigations of soil and regolith, which constitute the Critical Zone (CZ), beneath the upland hillslopes of the Valles Caldera, New Mexico; (2) interpretation of 2-D and 3-D marine seismic reflection data that image the upper 10-km of the crust beneath the Southern Guinea Plateau, offshore Guinea, West Africa. In both cases, the seismic data provide necessary constraints for the generation of accurate subsurface models that permit further geophysical modeling. The near-surface results, presented in Appendix A, provided a rich dataset of weathered thicknesses across hillslopes that supported an investigation of potential relationships between CZ geologic architecture and topographic attributes. Quantified relationships suggest that calibrated predictions based on the topography can provide first-order estimates of regolith thickness across upland landscapes. These results add to the ongoing CZ-science endeavor to understand proposed links between subsurface weathering processes and their surface expressions. In Appendix B, interpretations of high-resolution 3-D seismic data have illuminated deformational structures associated with Mesozoic rifting of the Southern Guinea Plateau. The interpretations were expanded onto regional 2-D seismic profiles, permitting a regional synthesis of the southern margin’s structural evolution. Additional tectonic subsidence and forward-gravity modeling highlight the influence of Jurassic rifting on the Southern Guinea Plateau prior to Early-Cretaceous rifting and separation, as well as crustal thickness estimates from the continental shelf out towards oceanic crust. Lastly, the Guinea-Demerara conjugate plateaus, and their associated deformations, were restored to 100 Ma, revealing an apparent upper-crustal asymmetry between the two margins. Appendix C presents two seismic-exploration methodologies based on 3-D seismic reflection data: (1) the calculation and interpretation of two co-rendered volumetric seismic attributes – most-positive curvature and semblance; (2) numerically modeling the tectonic subsidence of an entire 3-D seismic survey. Both techniques are used to address the inherent difficulty in interpreting the extent to which Jurassic rifting affected the Southern Guinea Plateau. Furthermore, the numerical model of subsidence provides a new exploration technique towards qualitatively and quantitatively assisting in the assessment of potential hydrocarbon-bearing basins.

Estimates of the depth and variation of lateritic weathering profiles are especially important in tropical areas such as Oahu, HI. Shear-wave velocity data were obtained by a new application of Multi-channel Analysis of Surface Waves (MASW) to map the base of the critical zone, to show variations in the LWP, and to derive weathering rates. The MASW technique proved highly capable of imaging the base of the critical zone, confirmed by lithological well data and direct field measurements. Profile thickness can be obtained without drilling, which has applications in engineering and geochemical studies. The measured rate of advance of the weathering front derived from the thickness measured by MASW ranged from 0.019 m/ka to 0.30 m/ka in mesic zones; about 1500 mm of annual rainfall, while a zone of 800 mm of annual rain fall revealed rates ranging from 0.011 m/ka to 0.013 m/ka. These rates are comparable to geochemically derived rates in previous studies. Standard p-wave seismic reflection data were insufficient for detecting boundaries as the weathering boundaries are gradational and do not produce reflections. Shear-wave models also showed internal velocity variations that may be caused by weathering heterogeneity due to textural differences in parental lava flows. Soil chemistry revealed the nature of weathering products as enriched in Al, Fe, Ni, and Cr, and commonly contain alteration minerals such as halloysite, kaolinite, maghemite, and ferrihydrite. Imaging depth limitations were overcome by innovative experiment designs, pushing the boundaries of the current technology. Increasing offsets and combining dispersion curves allowed for a more objective picking of the dispersion curve into the lower frequency domain. Even further improvements were made from a newly developed form of the active/passive technique. These advancements in technology allowed for detailed imaging of the subsurface with greater modeling confidence. This study showed that velocity models derived from MASW are accurately able to describe laterite weathering profiles in terms of depth and variability, expanding the use of the MASW technique beyond its traditional applications and making it a potential tool of interest for many fields of geoscience.

Chemical weathering reactions are important for the physical, chemical, and biological development of the critical zone. We present findings from aqueous phase chemical analyses of surface and soil pore waters during a 15 month study in a small semi-arid mountain catchment of the Santa Catalina Mountain Critical Zone Observatory. Stream water geochemical solutes are sourced to two distinct locations - fractured bedrock baseflow stores and soil quickflow stores. Solid phase observations of albite, anorthite, and K-feldspar transformation to Ca-montmorillonite and kaolinite are supported by stream water saturation states calculated via a PHREEQC geochemical model. While differences in mineral assemblages, soil depths, and horizonation suggest greater weathering in schist versus granite lithologies and in hillslope divergent versus convergent zones, soil pore water solute ratio analysis does not readily distinguish these differences. However, preliminary investigation of aqueous rare earth elements suggests detectable lithologic and landscape positional differences warranting focus for future research efforts.

The critical zone is the interface between abiotic and biotic constituents that spans from the vegetation canopy through the groundwater and represents an open system shaped by the climate, topography, and vegetation communities of a given environment. Four studies were completed to examine soil development, specifically mineral weathering and soil carbon storage, across semiarid sites spanning the Santa Catalina Mountain Critical Zone Observatory (SCM-CZO). The Santa Catalina Mountain Critical Zone Observatory is located along an environmental gradient in southern Arizona where co-varying climate and vegetation community properties have generated distinct changes in soil development across a relatively short distance (<20 miles). Soil, saprock, and parent rock were sampled on north-facing slopes from five climate-vegetation zones spanning desert scrub to mixed conifer forest. Within each climate-vegetation zone, samples were collected from two divergent summit and two convergent footslope landscape positions to account for topographic controls on mineral transformation. In the first study, the soil morphologic, physical, and chemical properties collected for all samples were combined with profile development indices to quantify soil variation with landscape position across the SCM-CZO. The results of this research demonstrated that climate and landscape position exert significant control on soil development in semiarid ecosystems, and that the profile development index is an effective tool for detecting these regional to hillslope scale variations in soil properties. The second study consisted of a cross-scale analysis of feldspar mineral transformation across the selected research sites to connect measures of pedon-scale soil development, depletions of feldspar and sodium in bulk soil, and elemental losses across feldspar grains at the microscale. Results indicated that greater soil development in the mixed conifer pedons corresponded to increased total feldspar and sodium losses. Desert scrub soils presented less evidence for feldspar transformation including lower profile development indices, gains in total feldspar percentages attributed to dust deposition, and less Na chemical depletion at the microscale. Greater soil development in convergent positions relative to adjacent divergent sites was consistent across all sites, with the highest degree of total feldspar depletion occurring in the conifer convergent locations. The third study focused on the physical distribution and mean residence time of soil organic carbon (SOC) in the SCM-CZO soils described for the first two studies. Surface (0-10 cm) and subsurface (30-40 cm) samples were collected from the aforementioned granitic regolith profiles. The soils were characterized using total C and N, δ¹³C, Δ¹⁴C, and radiocarbon derived mean residence time (MRT) estimates of bulk soil and physically separated C fractions to quantify SOC change with climate, vegetation, and landscape position. The results document a shift in SOC stabilization mechanisms across bioclimatically distinct ecosystems from mineral-associated SOC in the desert scrub soils to a mixture of mineral and occluded SOC in the conifer soils. Soils in the convergent landscapes concentrated the most SOC and typically exhibited the longest residence times across all locations. The fourth study examined the geochemical and mineralogical properties of the SCM-CZO soils across regional and hillslope scales of study to quantify soil development in semiarid environments. X-ray fluorescence and x-ray diffraction were used to characterize the elemental and mineralogical properties of the soils and parent material. Desert scrub dust samples were analyzed using x-ray fluorescence. The results indicate that mineral and base cation depletion were greatest in the convergent landscape positions at both sites and increased from the hot, moisture-limited desert scrub sites to the wetter, more productive conifer ecosystems. Enrichments in mica and select elements (i.e., Fe, Mg) suggested that dust deposition was a significant contributor to soil development across all sites. Geochemical estimates of dust fraction inputs confirmed this finding with dust composing up to 35% of the regolith material in the mixed conifer convergent soils. Clay mineral assemblage was dominated by halloysite and smectite minerals in the desert scrub site, reflecting complex climatic and mineral microtextural interactions in the dry, silica-rich desert environment. Clay minerals at the mixed conifer site exhibited the greatest degree of mineral transformation in the SCM, consisting of vermiculite, illite, kaolinite, and minor amounts of smectite and gibbsite. These findings confirm the interactive role of climate, vegetation, and landscape position in shaping the critical zone, where greater moisture availability and biological production are likely driving increased soil organic carbon storage and mineral weathering across various scales of study.

The Critical Zone (CZ) is the surficial layer of the planet that sustains life on Earth and extends from the base of the weathered bedrock to the top of the vegetation canopy. Its structure influences water fluxes, biogeochemistry and vegetation. In this dissertation, I explore the relationships between climate, water fluxes, vegetation dynamics, biogeochemistry, and effective energy and mass transfer fluxes (EEMT) in a semi-arid critical zone. This research was carried out in the upper Jemez River Basin in northern New Mexico across gradients of climate and elevation. The main research objectives were to (i) quantify relations among inputs of mass and energy (EEMT), hydrological and biogeochemical processes within the CZ, (ii) determine water fluxes and vegetation dynamics in high elevation mountain catchments with different terrain aspect and solar radiation, and (iii) study temporal variability of climate and its influence on the CZ water availability, forest productivity and energy and mass fluxes. The key findings of this study include (i) significant correlations between EEMT, water transit times (WTT) and mineral weathering products around Redondo Peak. Significant correlations were observed between dissolved weathering products (Na⁺ and DIC) and maximum EEMT. Similarly, ³H concentrations measured at the springs were significantly correlated with maximum EEMT; (ii) terrain aspect strongly controls energy, water distribution, and vegetation productivity in high elevation ecosystems in catchments draining different aspects of Redondo Peak. The predominantly north facing catchment, when compared to the other two eastern catchments, receives less solar radiation, exhibits less forest cover and smaller biomass, has more surface runoff and smaller vegetation water consumption. Furthermore, the north facing catchment showed smaller NDVI values and shorter growing season length as a consequence of energy limitation, and (iii) from 1984 to 2012 a decreasing trend in water availability, increased vegetation water use, a reduction in both forest productivity and EEMT was observed at the upper Jemez River Basin. These changes point towards a hotter, drier and less productive ecosystem which may alter critical zone processes in high elevation semi-arid systems.

Urbanized areas with increased amounts of impervious surfaces alter hydrologic systems by increasing stormwater runoff, decreasing infiltration, and reducing vegetation cover and evapotranspiration. Modeling hydrologic systems here is especially difficult due to the increased impervious land cover, which makes predicting processes such as urban streamflow and flooding challenging. By understanding the drivers of hydraulic processes, such as soil characteristics, bedrock depth, and land use, the quality and accuracy of models can be improved. The goal of this study was to use soil moisture loggers and electrical resistivity tomography (ERT) along the Pennypack Creek (Philadelphia, PA) to evaluate soil infiltration and bedrock depth in urban areas to ultimately access their impact on critical zone modeling. ERT was also used to validate or dispute recent seismic interpretations. Four study sites adjacent to Pennypack Creek were selected based on variations in underlying geology: Triassic basin sedimentary rock (Lukens), Paleozoic mafic gneiss (Meadow), Piedmont mica schist (Pine Road), and coastal plain weathered down to mica schist (Rhawn Street). Soil moisture sensors were installed at each site to a depth of up to 50 cm. ERT surveys were conducted at Pine Road and Rhawn Street sites. High infiltration variation at Pine Road and Meadow indicated macropores, which create preferential flow paths whereas low infiltration variation at Rhawn Street and Lukens indicated compaction associated with their land use (public parks). Comparing field capacity data to USDA soil type maps indicated the soil type was not a good predictor and in situ sampling was needed to estimate soil properties. ERT demonstrated bedrock was not shallow at the streambed as predicted by the seismic inversion and showed the need to corroborate depth to bedrock from seismic surveys beneath streams with resistivity inversions. Structure beneath the streambed was particularly noisy for the seismic surveys due to the flow of stream water. This study demonstrates that an accurate critical zone model, especially at urban sites, must rely on in situ investigation of hydrologic parameters based on land use, rather than assumptions of parameter values based on the underlying geology or soil type. / Geology

This study turns to what is for many an everyday item – yogurt – as a critical zone observatory, a synergistic, place-based laboratory which aims to integrate heterogenous representations of planetary phenomena as they are registered at a common surface. Yogurt has an impressive cultural endurance largely derived from its prominence in various paradigms of health. The product has culturally endured in another sense: as a common cultural medium where humans and microbes have met for generations. This study begins with a profile of yogurt as most encounter it today to consider how normative notions of health interface with the temporal and spatial imaginaries entailed in commodity geographies. Commoditized yogurt is characterized by a low and limited microbial biodiversity compared to yogurts produced outside of the commodity context. Yogurt is therefore presented as a micro case study to consider modes by which we sense and valuate ecological phenomena beyond the perceptible surface, how such sens-abilities intersect models of health, and to what effect. To trace a history of yogurt along these contours, I introduce it as a particular kind of artefact: a global object. As an object of environmental history, I define a global object as a global commodity with a high potential to be re-localized, and therefore with a high potential to re-shape commodity geographies. However, this trajectory is contingent upon framing yogurt as a critical zone observatory – a site where global phenomena like human-microbial interaction may become familiar and intimate. Guided by new materialist theory, I weave together historical and ethnographic case studies from the following consortium: resident yogurt bacteria, artisanal yogurt producers and home fermenters, a mystical immunologist, and an 11th century linguistic scholar. Through these perspectives, I both sketch and apply a framework for de-centered, interspecies histories of cultural (re)production through an extended metaphor of biofilm: the coagulative bacterial structure giving yogurt its characteristic texture. In so doing I provide a re-articulation of “the probiotic” as an integrative case of human and more-than-human health. The study concludes by directing these implications towards a consideration of aesthetic engagement by displaying how fermentation practice may enliven matters of re-diversification and re-localization.