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Marjorie S. Schulz

Publications and source records attributed to Marjorie S. Schulz.

At least 19 recordsLinked to original sources

Biofilms in the Critical Zone: Distribution and mediation of processes

Microbial biofilms occur in all levels of the Critical Zone (CZ); they are on and in the vegetation, throughout the soil-saprolite zone, and along fractures in deep subsurface. Here we discuss biofilms in each level of the CZ with a focus in the soil-saprolite continuum. We show how scanning electron microscope (SEM) images provide an appropriate scale to explore microbe mineral interactions in the CZ and can be used without extensive sample preparation. Through SEM imaging, we show that biofilms weather primary minerals, that macropores and fractures are hotspots of biofilm development, that biologic precipitation of short-range-order minerals (SROs) occurs in biofilms, and that biofilms are important in the process of organic matter stabilization.

Book chapter

Mechanisms for retention of low molecular weight organic carbon varies with soil depth at a coastal prairie ecosystem

Though primary sources of carbon (C) to soil are plant inputs (e.g., rhizodeposits), the role of microorganisms as mediators of soil organic carbon (SOC) retention is increasingly recognized. Yet, insufficient knowledge of sub-soil processes complicates attempts to describe microbial-driven C cycling at depth as most studies of microbial-mineral-C interactions focus on surface horizons. We leveraged a well-studied paleo-marine terrace (90 ka) located near Santa Cruz, CA, to characterize the short-term (days to weeks) and intermediate-term (months to years) fate of two low molecular weight organic carbon. compounds at three depths in the soil profile (∼25 cm, A horizon; ∼75 cm A/B transition; and ∼125 cm, B horizon). We employed isotopically-labeled glucose (GLU) and oxalic acid (OXA) to represent two common classes of rhizodeposits: carbohydrates and organic acids. Using a combination of laboratory (9 d) and field (490 d) incubations, we traced the fate of GLU-C and OXA-C through dissolved-, metal-associated-, and microbially-respired CO2 and bulk SOC pools. Our results suggest new SOC retention (i.e., defined as 13C label identified in solid or aqueous fractions) over intermediate time frames (490 d) is correlated with patterns in short-term (9 d) cycling dynamics, which in turn is related to the theoretical efficiency by which microorganisms process each substrate. For all horizons (A, A/B, and B) GLU-C was converted to CO2 more quickly than OXA-C with modeled decomposition rates ∼2–4 times faster for GLU depending on microbial density (higher in A than B horizon). The faster decomposition rates of GLU-C increased fractional recovery (0.399 ± 0.026 to 0.504 ± 0.030 for GLU-C) compared to OXA-C (0.035 ± 0.003 to 0.127 ± 0.010) among all horizons in our field experiment (490 d). Though the overall proportion of GLU-C recovered in solid fractions did not vary significantly with horizon, based on 13C recovered in aqueous fractions the apparent mechanism for retention did. After the 9-d laboratory incubation, fractional recovery for GLU-C among C pools associated with microbial biomass was almost 20× higher than OXA-C (0.192 versus 0.010, respectively across all horizons). More than a year later, 43–46% of GLU-C retained in the field incubation was extractable with a neutral salt (representing a pool of soil C residing within or available to microbial biomass) among A and A/B horizons, while only 6% of retained GLU-C was similarly extractable in the B horizon. Thus, it appears among depths with higher microbial density (A, A/B horizons), anabolic recycling is the most likely process contributing to the persistence of glucose C, whereas abiotic sinks contributed more to intermediate-term stability for GLU-C in the B horizon. By contrast, most OXA-C was lost, presumably as CO2, over the short-term from the A and A/B horizons (fractional recovery: 0.136 ± 0.011 and 0.091 ± 0.002, respectively). However, though substantially lower than GLU-C recovered at the conclusion of our field experiment, the fraction of oxalic acid C retained in the B horizon over both short- (0.72 ± 0.037) and intermediate-time (0.127 ± 0.010) frames was several-fold higher than for overlying horizons. The specific process(es) (e.g., more efficient microbial utilization, metal-organic complexation, direct adsorption to the mineral matrix, etc.) contributing to higher retention for OXA-C at depth are discussed but remain unresolved.

Soil Biology and Biochemistry

The influence of soil development on the depth distribution and structure of soil microbial communities.

Although it has been shown that the interaction of climate and time shape the dynamics of soil organic matter (SOM) storage and preservation in soil, the role of soil microbial communities in this dynamic remains unclear. Microbial communities are present throughout soil profiles and likely play critical roles in SOM and nutrient cycling, however the influence of other factors such as soil development (i.e., age) and the composition SOM on microbial community variation with depth has yet to be quantified. Improving our understanding of the relationship between soil development, soil depth, and microbial communities may provide insight to the critical role they play in cycling and preservation of SOM, as well as more mechanistic predictions of the response of soil communities to change, such as landscape-scale changes in available moisture or temperature regimes. Here we compare soils spanning a soil age by climate gradient (i.e., climo-chronosequence) to better understand the mechanisms which influence soil microbial community structure and the molecular composition of SOM. While we observed little depth-dependence in metrics of microbial community structure (i.e., composition, diversity, dissimilarity) across the range of soil development under a wetter climate, we found significant depth-dependent changes in community metrics under a drier climate, which became more pronounced as soils became older. This shift in bacterial and archaeal community structure and diversity is most apparent below a clay-rich argillic horizon formed in the older, drier soils. The molecular composition of SOM as measured by high resolution mass spectrometry (i.e., FTICR MS) also exhibited similar shifts in composition with soil depth and age. Our results highlight how soil moisture shapes the interaction of soil development, SOM, and microbial community composition. Differences in the moisture regime between our two study sites drives differences in biogeochemical depth gradients and subsequent variation in soil microbes and SOM. This suggests that knowledge of not just the pedogenic trajectory of soil development, but also the spatial position relative to distinct pedogenic features, are important for explaining variations in the depth-dependencies of microbial communities and associated SOM.

California

Response to ‘Stochastic and deterministic interpretation of pool models’

We concur with Azizi‐Rad et al. (2021) that it is vital to critically evaluate and compare different soil carbon models, and we welcome the opportunity to further describe the unique contribution of the PROMISE model (Waring et al. 2020) to this literature. The PROMISE framework does share many features with established biogeochemical models, as our original manuscript highlighted in Table 1, and our work builds upon model innovations developed by many different groups, including that of Azizi‐Rad and colleagues. Yet, the PROMISE framework is distinctive due to where it places mechanistic emphasis, and how these mechanisms are formalized in the mathematical model structure.

Global Change Biology

The trajectory of soil development and its relationship to soil carbon dynamics

It has been postulated that the amount of soil organic carbon (SOC) associated with soil minerals exhibits a threshold relationship in response to effective soil moisture (estimated as precipitation less evapotranspiration). To better characterize the role of moisture in influencing mechanisms of SOC storage during pedogenesis, we compare soils from two different chronosequence sites: the Santa Cruz and Mattole River marine terraces that together form a soil age-by-climate gradient (i.e., climo-chronosequence). Our results demonstrate how variation in the effective soil moisture may drive soil development along divergent pedogenic trajectories, resulting in variations in the form and depth distribution of secondary weathering products. In particular, the residual metals Fe and Al are directly related to the type of secondary minerals that accumulate during weathering, and these variations are coupled to differences in the storage and long-term preservation of SOC both within and between soils. Over time, these differences in soil development may lead to ‘pedogenic thresholds’ that further differentiate soil characteristics and influence SOC dynamics. In this case, the pedogenic threshold takes the form of clay-rich argillic horizons that once formed, inhibit aqueous transport, decouple shallow and deep soil environments, and potentially limit SOC inputs and increase microbial recycling in deep soils. Our data suggest argillic horizon development is favorable in the drier Santa Cruz soils, where kaolinite is the dominant secondary weathering product. In contrast, greater available moisture in soils of the Mattole chronosequence drive a different weathering trajectory characterized by the accumulation of more amorphous secondary minerals. As a result, the Mattole soils and do not exhibit argillic horizon development but are instead characterized by greater accumulation of SOC across all depths sampled. Overall, our results illustrate how the interaction of climate (i.e., moisture) and time may shape the trajectory of soil development and the dynamics of SOC storage and preservation.

California

From pools to flow: The PROMISE framework for new insights on soil carbon cycling in a changing world

Soils represent the largest terrestrial reservoir of organic carbon, and the balance between soil organic carbon (SOC) formation and loss will drive powerful carbon‐climate feedbacks over the coming century. To date, efforts to predict SOC dynamics have rested on pool‐based models, which assume classes of SOC with internally homogenous physicochemical properties. However, emerging evidence suggests that soil carbon turnover is not dominantly controlled by the chemistry of carbon inputs, but rather by restrictions on microbial access to organic matter in the spatially heterogeneous soil environment. The dynamic processes that control the physicochemical protection of carbon translate poorly to pool‐based SOC models; as a result, we are challenged to mechanistically predict how environmental change will impact movement of carbon between soils and the atmosphere. Here, we propose a novel conceptual framework to explore controls on belowground carbon cycling: P robabilistic R epresentation of O rganic M atter I nteractions within the S oil E nvironment (PROMISE). In contrast to traditional model frameworks, PROMISE does not attempt to define carbon pools united by common thermodynamic or functional attributes. Rather, the PROMISE concept considers how SOC cycling rates are governed by the stochastic processes that influence the proximity between microbial decomposers and organic matter, with emphasis on their physical location in the soil matrix. We illustrate the applications of this framework with a new biogeochemical simulation model that traces the fate of individual carbon atoms as they interact with their environment, undergoing biochemical transformations and moving through the soil pore space. We also discuss how the PROMISE framework reshapes dialogue around issues related to SOC management in a changing world. We intend the PROMISE framework to spur the development of new hypotheses, analytical tools, and model structures across disciplines that will illuminate mechanistic controls on the flow of carbon between plant, soil, and atmospheric pools.

Global Change Biology

Mineralogy dictates the initial mechanism of microbial necromass association

Soil organic matter (SOM) improves soil fertility and mitigates disturbance related to climate and land use change. Microbial necromass (the accumulated cellular residues of microorganisms) comprises the majority of soil C, yet the formation and persistence of necromass in relation to mineralogy is poorly understood. We tested whether soil minerals had different microbial necromass association mechanisms. Specifically, we tested whether microbial necromass directly sorbed to mineral surfaces or was consumed by live microorganisms prior to mineral association. Applying Raman microspectroscopy with 13 C enriched microbial necromass to quantify microbe-mineral interactions, we show that mineralogy alters the initial mechanism of microbial necromass association. In the presence of K-feldspar (lower abiotic C preservation potential), microbial necromass required assimilation by live microorganisms for mineral retention. In contrast, with amorphous aluminum hydroxide (higher abiotic C preservation potential) microbial necromass was retained predominately through abiotic sorption, and was subsequently protected from microbial decomposition. Despite different mechanisms, both minerals retained similar quantities of microbial necromass under biotic conditions. Mineralogy determined not only the quantity of mineral-associated C, but the distinct pathway of microbial necromass association. These findings show the utility of Raman microspectroscopy as a technique to study microbe-mineral interactions, and imply that heterogeneity in mineral-organic interactions could result in gradients of organic matter stability.

Geochimica et Cosmochimica Acta

Root-driven weathering impacts on mineral-organic associations in deep soils over pedogenic time scales

Plant roots are critical weathering agents in deep soils, yet the impact of resulting mineral transformations on the vast deep soil carbon (C) reservoir are largely unknown. Root-driven weathering of primary minerals may cause the formation of reactive secondary minerals, which protect mineral-organic associations (MOAs) for centuries or millennia. Conversely, root-driven weathering may also transform secondary minerals, potentially enhancing the bioavailability of C previously protected in MOAs. Here we examined the impact of root-driven weathering on MOAs and their capacity to store C over pedogenic time scales. To accomplish this, we examined deep horizons (100-160 cm) that experienced root-driven weathering in four soils of increasing ages (65-226 kyr) of the Santa Cruz Marine Terrace chronosequence. Specifically, we compared discrete rhizosphere zones subject to root-driven weathering, with adjacent zones that experienced no root growth. Using a combination of radiocarbon, mass spectrometry, 57Fe Mössbauer spectroscopy, high-resolution mass spectrometry, and X-ray spectromicroscopy approaches, we characterized transformations of MOAs in relation to changes in C content, Δ14C values, and chemistry across the chronosequence. We found that the onset of root-driven weathering (65-90kyr) increased the amount of C associated with poorly crystalline iron (Fe) and aluminum (Al) phases, particularly highly disordered nano-particulate goethite (np-goethite). This increase coincided with greater C concentrations, lower Δ14C values, and greater abundance of what is likely microbially-derived C. Continued root-driven weathering (137-226kyr) did not significantly change the amount of C associated with crystalline Fe and Al phases, but resulted in a decline in the amount of C associated with poorly crystalline Fe and Al phases. This decline coincided with a decrease in C concentrations, an increase in 14C values, and a shift toward plant-derived C. In contrast, soil not affected by root-driven weathering showed comparatively low amounts of C bound to poorly crystalline Fe and Al phases regardless of soil age and, correspondingly, lower C concentrations. Our results demonstrate that root-driven formation and disruption of MOAs are direct controls on both C accrual and loss in deep soil. This finding suggests that root impacts on soil C storage are dependent on soil weathering stage, a consideration that is critical for future predictions of the vulnerability of deep soil C to global change.

California

Geochemistry and microbiology of groundwater and solids from extraction and monitoring wells and their relation to well efficiency at a Federally operated confined disposal facility, East Chicago, Indiana

In cooperation with the U.S. Army Corps of Engineers, Chicago District, the U.S. Geological Survey investigated the processes affecting water quality, geochemistry, and microbiology in representative extraction and monitoring wells at a confined disposal facility (CDF) in East Chicago, Indiana. The CDF is a 140-acre Federally-managed facility that was the former location of an oil refinery and is now used for the long-term disposal and storage of dredge material from the Indiana Harbor and Indiana Harbor Canal. Residual petroleum hydrocarbons and leachate from the CDF are contained within the facility by use of a groundwater cutoff wall. The wall consists of a soil-bentonite slurry and a gradient control system made up of an automated network of 96 extraction wells, 42 monitoring wells, and 2 ultrasonic sensors that maintain an inward hydraulic gradient at the site. The pumps in the extraction wells require vigilant maintenance and must be replaced when unable to withdraw water at a rate sufficient to maintain the required inward gradient. The wells are screened in the Calumet aquifer, a coarse-grained sand and gravel unit that extends approximately 35 feet below the land surface and is not utilized for drinking-water supply at the CDF or in the surrounding area. This study was initiated to identify the cause of decreased pump discharges and to identify potential mitigation strategies. For this study, the U.S. Geological Survey collected groundwater and solids from monitoring and extraction wells. Groundwater samples were collected during June 2014 for precautionary health screening and on four occasions during September 2014 through November 2014. Groundwater samples collected from two extraction wells during June 2014 were analyzed for concentrations of anthropogenic organic constituents. During September through November 2014, groundwater samples were collected from one additional extraction well, and samples from three monitoring wells were analyzed for concentrations of inorganic and organic constituents, dissolved gases, and bacterial abundance and diversity. Solid samples were collected during April 2014, during September 2014 through November 2014, and during November 2016. Solid samples were collected from the exterior of extraction-well pumps and as flocculent from water samples. Solid samples were collected from 10 wells, including 1 extraction well and 3 monitoring wells sampled for water quality. Solid samples were analyzed for mineralogy, solid-phase habit, geochemistry, and organic composition. The following is a list of observations that were made during this study: (1) the water quality is substantially variable among the six well locations sampled as part of this study—lower (more negative) redox values and higher concentrations of many constituents (including calcium, magnesium, sodium, and sulfate) and properties (including dissolved solids, hardness, and turbidity) were detected in sampled wells located near the extraction wells with the highest frequency of failure; (2) water-level drawdown is variable between extraction wells—wells with the greatest drawdown may pull deeper groundwater into the borehole; (3) dissolved gas results indicate reducing oxidation-reduction processes in the aquifer material that can feasibly contribute iron, carbon dioxide, and other byproducts from hydrocarbon degradation to precipitates and solids that accumulate on and impair pump operation; (4) crystalline and amorphous solid-phase minerals are precipitating in the borehole; (5) several types of bacteria are present in water pumped from extraction wells and are likely responsible for bonding mineral and microbiologic matter to the pump (and other well components); and (6) bacteria may create microenvironments that facilitate precipitation of solids or inhibit dissolution of unstable minerals once the bacteria adhere to biofilm attached to the pump. Results of the study indicate that bacteria may be accumulating and entrapping solid material on the exterior of pumps. This accumulation reduces heat transfer and water discharge from the pump and may lead to decreased efficiency or mechanical failure. Observations could not be made on the well screen, gravel pack, or surrounding geologic formation; therefore, mitigating measures in the borehole may not solve well-productivity issues. Remedies for the pump fouling problems were derived from the review and interpretation of data collected during this study and from information documented in other sources about groundwater well fouling. Potential remedies to problems associated with pump fouling at the CDF may include the following: (1) reducing attractiveness of the extraction wells for microbiological growth by modifying the chemical or physical environment of the well, (2) modifying the pump exterior to decrease microbiological adherence, (3) changing the pumping regime to control the chemistry of water entering the well from the surrounding aquifer material, (4) modifying the pumps to be less physically and thermally attractive, and (5) removing hydrocarbons from groundwater and the aquifer material surrounding the wells or adding surfactants to make them more mobile. Pilot scale testing may be necessary to identify the most effective treatment or combination of treatments.

Indiana

Landscapes from the waves—Marine terraces of California

Many coastlines around the world have stair-step landforms, known as marine terraces. Marine terraces make up a large part of coastal California’s landscape—from San Diego to Crescent City. Find out how these landscapes form, why marine terraces are of interest to scientists, and where you can explore these landscapes.

California

Lithological influences on contemporary and long-term regolith weathering at the Luquillo Critical Zone Observatory

Lithologic differences give rise to the differential weatherability of the Earth’s surface and globally variable silicate weathering fluxes, which provide an important negative feedback on climate over geologic timescales. To isolate the influence of lithology on weathering rates and mechanisms, we compare two nearby catchments in the Luquillo Critical Zone Observatory in Puerto Rico, which have similar climate history, relief and vegetation, but differ in bedrock lithology. Regolith and pore water samples with depth were collected from two ridgetops and at three sites along a slope transect in the volcaniclastic Bisley catchment and compared to existing data from the granitic Río Icacos catchment. The depth variations of solid-state and pore water chemistry and quantitative mineralogy were used to calculate mass transfer (tau) and weathering solute profiles, which in turn were used to determine weathering mechanisms and to estimate weathering rates. Regolith formed on both lithologies is highly leached of most labile elements, although Mg and K are less depleted in the granitic than in the volcaniclastic profiles, reflecting residual biotite in the granitic regolith not present in the volcaniclastics. Profiles of both lithologies that terminate at bedrock corestones are less weathered at depth, near the rock-regolith interfaces. Mg fluxes in the volcaniclastics derive primarily from dissolution of chlorite near the rock-regolith interface and from dissolution of illite and secondary phases in the upper regolith, whereas in the granitic profile, Mg and K fluxes derive from biotite dissolution. Long-term mineral dissolution rates and weathering fluxes were determined by integrating mass losses over the thickness of solid-state weathering fronts, and are therefore averages over the timescale of regolith development. Resulting long-term dissolution rates for minerals in the volcaniclastic regolith include chlorite: 8.9 × 10 −14 mol m −2 s −1 , illite: 2.1 × 10 −14 mol m −2 s −1 and kaolinite: 4.0 × 10 −14 mol m −2 s −1 . Long-term weathering fluxes are several orders of magnitude lower in the granitic regolith than in the volcaniclastic, despite higher abundances of several elements in the granitic regolith. Contemporary weathering fluxes were determined from net (rain-corrected) solute profiles and thus represent rates over the residence time of water in the regolith. Contemporary weathering fluxes within the granitic regolith are similar to the long-term fluxes. In contrast, the long-term fluxes are faster than the contemporary fluxes in the volcaniclastic regolith. Contemporary fluxes in the granitic regolith are generally also slightly faster than in the volcaniclastic. The differences in weathering fluxes over space and time between these two watersheds indicate significant lithologic control of chemical weathering mechanisms and rates.

Bisley watersheds

Long-term flow-through column experiments and their relevance to natural granitoid weathering rates

Four pairs of fresh and partly-weathered granitoids, obtained from well-characterized watersheds—Merced River, CA, USA; Panola, GA, USA; Loch Vale, CO, USA, and Rio Icacos, Puerto Rico—were reacted in columns under ambient laboratory conditions for 13.8 yrs, the longest running experimental weathering study to date. Low total column mass losses (<1 wt. %), correlated with the absence of pitting or surface roughening of primary silicate grains. BET surface area (S BET ) increased, primarily due to Fe-oxyhydroxide precipitation. Surface areas returned to within factors of 2 to 3 of their original values after dithionite extraction. Miscible displacement experiments indicated homogeneous plug flow with negligible immobile water, commonly cited for column experiments. Fresh granitoid effluent solute concentrations initially declined rapidly, followed by much slower decreases over the next decade. Weathered granitoid effluent concentrations increased modestly over the same time period, indicating losses of natural Fe-oxide and/or clay coatings and the increased exposure of primary mineral surfaces. Corresponding (fresh and weathered) elemental effluent concentrations trended toward convergence during the last decade of reaction. NETPATH/PHREEQC code simulations indicated non-stoichiometric dissolution involving Ca release from disseminated calcite and excess K release from interlayer biotite. Effluent 87 Sr/ 85 Sr ratios reflected a progressive weathering sequence beginning and ending with 87 Sr/ 85 Sr values of plagioclase with an additional calcite input and a radiogenic biotite excursion proportional to the granitoid ages. Effluents became thermodynamically saturated with goethite and gibbsite, slightly under-saturated with kaolinite and strongly under-saturated with plagioclase, consistent with kinetically-limited weathering in which solutes such as Na varied with column flow rates. Effluent Na concentrations showed no clear trend with time during the last decade of reaction (fresh granitoids) or increased slowly with time (weathered granitoids). Analysis of cumulative Na release indicated that plagioclase dissolution achieved steady state in 3 of the 4 fresh granitoids during the last decade of reaction. Surface-area normalized plagioclase dissolution rates exhibited a narrow range (0.95 to 1.26 10 -13 moles m -2 s -1 ), in spite of significant stoichiometric differences (An 0.21 to An 0.50 ). Rates were an order of magnitude slower than previously reported in shorter duration experiments but generally 2 to 3 orders of magnitude faster than corresponding natural analogs. CrunchFlow simulations indicated that more than a hundredfold decrease in column flow rates would be required to produce near-saturation reaction affinities that would start to slow plagioclase weathering to real-world levels. Extending simulations to approximate long term weathering in naturally weathered profiles required additional decreases in the intrinsic plagioclase dissolution and kaolinite precipitation rates and relatively large decreases in the fluid flow rate, implying that exposure to reactive mineral surfaces is significantly limited in the natural environment compared to column experiments.

Geochimica et Cosmochimica Acta

Structured heterogeneity in a marine terrace chronosequence: Upland mottling

Soil mottles generally are interpreted as a product of reducing conditions during periods of water saturation. The upland soils of the Santa Cruz, CA, marine terrace chronosequence display an evolving sequence of reticulate mottling from the youngest soil (65 ka) without mottles to the oldest soil (225 ka) with well-developed mottles. The mottles consist of an interconnected network of clay and C-enriched regions (gray, 2.5Y 6/1) bordered by leached parent material (white, 2.5Y 8/1) within a diminishing matrix of oxidized parent material (orange, 7.5YR 5/8). The mottles develop in soils that formed from relatively uniform nearshore sediments and occur below the depth of soil bioturbation. To explore how a presumably wetland feature occurs in an unsaturated upland soil, physical and chemical characteristics of mottle separates (orange, gray, and white) were compared through the deep time represented by the soil chronosequence. Mineralogical, isotopic, and surface-area differences among mottle separates indicate that rhizogenic centimeter-scale mass transfer acting across millennia is an integral part of weathering, pedogenesis, and C and nutrient transfer. Elemental analysis, electron microscopy, and Fe-isotope systematics indicate that mottle development is driven by deep roots together with their fungal and microbial symbionts. Taken together, these data suggest that deep soil horizons on old stable landforms can develop reticulate mottling as the long-term imprint of rhizospheric processes. The processes of rhizogenic mottle formation appear to regulate pedogenesis, nutrients, and C sequestration at depth in unsaturated zones.

California

Long-term controls of soil organic carbon with depth and time: a case study from the Cowlitz River Chronosequence, WA USA

Over timescales of soil development (millennia), the capacity of soils to stabilize soil organic carbon (SOC) is linked to soil development through changes in soil mineralogy and other soil properties. In this study, an extensive dataset of soil profile chemistry and mineralogy is compiled from the Cowlitz River Chronosequence (CRC), WA USA. The CRC soils range in age from 0.25 to 1200 kyr, spanning a developmental gradient encompassing clear changes in soil mineralogy, chemistry, and surface area. Comparison of these and other metrics of soil development with SOC properties reveal several relationships that may be diagnostic of the long-term coupling of soil development and C cycling. Specifically, SOC content was significantly correlated with sodium pyrophosphate extractable metals emphasizing the relevance of organo-metal complexes in volcanic soils. The depth distributions of organo-metals and other secondary weathering products, including the kaolin and short-range order (SRO) minerals, support the so-called &ldquo;binary composition&rdquo; of volcanic soils. The formation of organo-metal complexes limits the accumulation of secondary minerals in shallow soils, whereas in deep soils with lower SOC content, secondary minerals accumulate. In the CRC soils, secondary minerals formed in deep soils (below 50 cm) including smectite, allophane, Fe-oxides and dominated by the kaolin mineral halloysite. The abundance of halloysite was significantly correlated with bulk soil surface area and 14 C content (a proxy for the mean age of SOC), implying enhanced stability of C in deep soils. Allophane, an SRO mineral commonly associated with SOC storage, was not correlated with SOC content or 14 C values in CRC soils. We propose conceptual framework to describe these observations based on a general understanding of pedogenesis in volcanic soils, where SOC cycling is coupled with soil development through the formation of and fate of organo-metal or other mobile weathering products. This framework highlights interactions between SOC and soil development, which may be applicable to other soils where organic inputs interact with the products of chemical weathering.

Washington

Probing the deep critical zone beneath the Luquillo Experimental Forest, Puerto Rico

Recent work has suggested that weathering processes occurring in the subsurface produce the majority of silicate weathering products discharged to the world's oceans, thereby exerting a primary control on global temperature via the well-known positive feedback between silicate weathering and CO 2 . In addition, chemical and physical weathering processes deep within the critical zone create aquifers and control groundwater chemistry, watershed geometry and regolith formation rates. Despite this, most weathering studies are restricted to the shallow critical zone (e.g. soils, outcrops). Here we investigate the chemical weathering, fracturing and geomorphology of the deep critical zone in the Bisley watershed in the Luquillo Critical Zone Observatory, Puerto Rico, from two boreholes drilled to 37.2 and 27.0 m depth, from which continuous core samples were taken. Corestones exposed aboveground were also sampled. Weathered rinds developed on exposed corestones and along fracture surfaces on subsurface rocks slough off of exposed corestones once rinds attain a thickness up to ~1 cm, preventing the corestones from rounding due to diffusion limitation. Such corestones at the land surface are assumed to be what remains after exhumation of similar, fractured bedrock pieces that were observed in the drilled cores between thick layers of regolith. Some of these subsurface corestones are massive and others are highly fractured, whereas aboveground corestones are generally massive with little to no apparent fracturing. Subsurface corestones are larger and less fractured in the borehole drilled on a road where it crosses a ridge compared with the borehole drilled where the road crosses the stream channel. Both borehole profiles indicate that the weathering zone extends to well below the stream channel in this upland catchment; hence weathering depth is not controlled by the stream level within the catchment and not all of the water in the watershed is discharged to the stream

Earth Surface Processes and Landforms

The impact of biotic/abiotic interfaces in mineral nutrient cycling: A study of soils of the Santa Cruz chronosequence, California

Biotic/abiotic interactions between soil mineral nutrients and annual grassland vegetation are characterized for five soils in a marine terrace chronosequence near Santa Cruz, California. A Mediterranean climate, with wet winters and dry summers, controls the annual cycle of plant growth and litter decomposition, resulting in net above-ground productivities of 280–600 g m −2 yr −1 . The biotic/abiotic (A/B) interface separates seasonally reversible nutrient gradients, reflecting biological cycling in the shallower soils, from downward chemical weathering gradients in the deeper soils. The A/B interface is pedologically defined by argillic clay horizons centered at soil depths of about one meter which intensify with soil age. Below these horizons, elevated solute Na/Ca, Mg/Ca and Sr/Ca ratios reflect plagioclase and smectite weathering along pore water flow paths. Above the A/B interface, lower cation ratios denote temporal variability due to seasonal plant nutrient uptake and litter leaching. Potassium and Ca exhibit no seasonal variability beneath the A/B interface, indicating closed nutrient cycling within the root zone, whereas Mg variability below the A/B interface denotes downward leakage resulting from higher inputs of marine aerosols and lower plant nutrient requirements. The fraction of a mineral nutrient annually cycled through the plants, compared to that lost from pore water discharge, is defined their respective fluxes F j,plants = q j,plants /( q j,plants + q j,discharge ) with average values for K and Ca ( F K,plants = 0.99; F Ca,plants = 0.93) much higher than for Mg and Na ( F Mg,plants 0.64; F Na,plants = 0.28). The discrimination against Rb and Sr by plants is described by fractionation factors ( K Sr/Ca = 0.86; K Rb/K = 0.83) which are used in Rayleigh fractionation-mixing calculations to fit seasonal patterns in solute K and Ca cycling. K Rb/K and K 24 Mg / 22 Mg "> K24Mg/22Mg values (derived from isotope data in the literature) fall within fractionation envelopes bounded by inputs from rainfall and mineral weathering. K Sr/Ca and K 44 Ca / 40 Ca "> K44Ca/40Ca fractionation factors fall outside these envelopes indicating that Ca nutrient cycling is closed to these external inputs. Small net positive K and Ca fluxes (6–14 mol m −2 yr −1 ), based on annual mass balances, indicate that the soils are accumulating mineral nutrients, probably as a result of long-term environmental disequilibrium.

California

Vadose zone controls on weathering intensity and depth: Observations from grussic saprolites

An investigation of vadose zone weathering processes has been undertaken on grussic saprolites developed on Californian granitoids. Preliminary results indicate strong climatic control, through infiltration, on the depth and intensity of weathering. At sites with higher infiltration, the vadose zone is comprehensively altered to grussic saprolite and saprock. Conversely, lower infiltration sites display only thin grussic saprolites, strongly influenced by rock texture. Both vadose zone and weathering depth appear to be governed by local base level, and vadose zone hydrology exerts a fundamental control on the effective operation and relative dominance of the key weathering reactions. In zones of matrix permeability, oxidation of biotite comprehensively disaggregates the rock but results in little mass loss and clay mineral formation. Conversely, the higher transient flow rates that characterize zones of fracture permeability result in plagioclase hydrolysis, significant mass losses and accompanying clay mineral formation. A variable hydrological regime may also contribute to high partial pressures of O 2 in vadose zone pore waters and pore spaces, thereby enhancing the oxidative environment and further predisposing grussic saprolite formation.

Applied Geochemistry