Solid phase evolution in the Biosphere 2 hillslope experiment as predicted by modeling of hydrologic and geochemical fluxes

A reactive transport geochemical modeling study was conducted to help predict the mineral transformations occurring over a ten year time-scale that are expected to impact soil hydraulic properties in the Biosphere 2 (B2) synthetic hillslope experiment. The modeling sought to predict the rate and extent of weathering of a granular basalt (selected for hillslope construction) as a function of climatic drivers, and to assess the feedback effects of such weathering processes on the hydraulic properties of the hillslope. Flow vectors were imported from HYDRUS into a reactive transport code, CrunchFlow2007, which was then used to model mineral weathering coupled to reactive solute transport. Associated particle size evolution was translated into changes in saturated hydraulic conductivity using Rosetta software. We found that flow characteristics, including velocity and saturation, strongly influenced the predicted extent of incongruent mineral weathering and neo-phase precipitation on the hillslope. Results were also highly sensitive to specific surface areas of the soil media, consistent with surface reaction controls on dissolution. Effects of fluid flow on weathering resulted in significant differences in the prediction of soil particle size distributions, which should feedback to alter hillslope hydraulic conductivities

Ecosystem-bedrock interaction changes nutrient compartmentalization during early oxidative weathering

Ecosystem-bedrock interactions power the biogeochemical cycles of Earth's shallow crust, supporting life, stimulating substrate transformation, and spurring evolutionary innovation. While oxidative processes have dominated half of terrestrial history, the relative contribution of the biosphere and its chemical fingerprints on Earth's developing regolith are still poorly constrained. Here, we report results from a two-year incipient weathering experiment. We found that the mass release and compartmentalization of major elements during weathering of granite, rhyolite, schist and basalt was rock-specific and regulated by ecosystem components. A tight interplay between physiological needs of different biota, mineral dissolution rates, and substrate nutrient availability resulted in intricate elemental distribution patterns. Biota accelerated CO2 mineralization over abiotic controls as ecosystem complexity increased, and significantly modified stoichiometry of mobilized elements. Microbial and fungal components inhibited element leaching (23.4% and 7%), while plants increased leaching and biomass retention by 63.4%. All biota left comparable biosignatures in the dissolved weathering products. Nevertheless, the magnitude and allocation of weathered fractions under abiotic and biotic treatments provide quantitative evidence for the role of major biosphere components in the evolution of upper continental crust, presenting critical information for large-scale biogeochemical models and for the search for stable in situ biosignatures beyond Earth.Comment: 41 pages (MS, SI and Data), 16 figures (MS and SI), 6 tables (SI and Data). Journal article manuscrip

Silk as a Multifunctional Biomaterial Substrate for Reduced Glial Scarring around Brain‐Penetrating Electrodes

The reliability of chronic, brain‐penetrating electrodes must be improved for these ‐neural recording technologies to be viable in widespread clinical applications. One approach to improving electrode reliability is to reduce the foreign body response at the probe‐tissue interface. In this work, silk fibroin is investigated as a candidate material for fabricating mechanically dynamic neural probes with enhanced biocompatibility compared to traditional electrode materials. Silk coatings are applied to flexible cortical electrodes to produce devices that transition from stiff to flexible upon hydration. Theoretical modeling and in vitro testing show that the silk coatings impart mechanical properties sufficient for the electrodes to penetrate brain tissue. Further, it is demonstrated that silk coatings may reduce some markers of gliosis in an in vitro model and that silk can encapsulate and release the gliosis‐modifying enzyme chondroitinase ABC. This work establishes a basis for future in vivo studies of silk‐based brain‐penetrating electrodes, as well as the use of silk materials for other applications in the central nervous system where gliosis must be controlled. Silk fibroin is investigated as a novel material for fabricating brain‐penetrating electrodes with dynamic mechanical properties and the capacity to deliver sensitive therapeutics. Silk coatings are shown to natively reduce some markers of gliosis in vitro, and a further reduction is demonstrated by encapsulation and release of the enzyme chondroitinase ABC.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/98822/1/3185_ftp.pd

A considerable fraction of soil-respired CO2 is not emitted directly to the atmosphere

All data used in this study are freely available (http://criticalzone.org/ catalina-jemez/data/datasets/). The authors wish to thank Rebecca Larkin Minor and Nate Abramson for their careful operation and maintenance of the field measurement devices. The program “Unidades de Excelencia Científica del Plan Propio de Investigación de la Universidad de Granada” funded the cost of this publicationSoil CO2 efflux (Fsoil) is commonly considered equal to soil CO2 production (Rsoil), and both terms are used interchangeably. However, a non-negligible fraction of Rsoil can be consumed in the subsurface due to a host of disparate, yet simultaneous processes. The ratio between CO2 efflux/O2 influx, known as the apparent respiratory quotient (ARQ), enables new insights into CO2 losses from Rsoil not previously captured by Fsoil. We present the first study using continuous ARQ estimates to evaluate annual CO2 losses of carbon produced from Rsoil. We found that up to 1/3 of Rsoil was emitted directly to the atmosphere, whereas 2/3 of Rsoil was removed by subsurface processes. These subsurface losses are attributable to dissolution in water, biological activities and chemical reactions. Having better estimates of Rsoil is key to understanding the true influence of ecosystem production on Rsoil, as well as the role of soil CO2 production in other connected processes within the critical zoneThis project and data were supported by NSF awards 1417101 and 1331408, as well as by the European Commission project DIESEL (FP7-PEOPLE-2013-IOF, 625988) and the Spanish Ministry of Economy and Competitiveness (IJCI-2016-30822)

Sorptive stabilization of organic matter by amorphous Al hydroxide

Amorphous Al hydroxides (am-Al(OH)3) strongly sorb and by this means likely protect dissolved organic matter (OM) against microbial decay in soils. We carried out batch sorption experiments (pH 4.5; 40 mg organic C L-1) with OM extracted from organic horizons under a Norway spruce and a European beech forest. The stabilization of OM by sorption was analyzed by comparing the CO2 mineralized during the incubation of sorbed and non-sorbed OM. The mineralization of OM was evaluated based in terms of (i) the availability of the am-Al(OH)3, thus surface OM loadings, (ii) spectral properties of OM, and (iii) the presence of phosphate as a competitor for OM. This was done by varying the solid-to-solution ratio (SSR = 0.02-1.2 g L-1) during sorption. At low SSRs, hence limited am-Al(OH)3 availability, only small portions of dissolved OM were sorbed; for OM from Oa horizons, the mineralization of the sorbed fraction exceeded that of the original dissolved OM. The likely reason is competition with phosphate for sorption sites favouring the formation of weak mineral-organic bindings and the surface accumulation of N-rich, less aromatic and less complex OM. This small fraction controlled the mineralization of sorbed OM even at higher SSRs. At higher SSRs, i.e., with am-Al(OH)3 more available, competition of phosphate decreased and aromatic compounds were sorbed selectively, which resulted in pronounced resistance of sorbed OM against decay. The combined OC mineralization of sorbed and non-sorbed OM was 12-65% less than that of the original DOM. Sorbed OM contributed only little to the overall OC mineralization. Stabilization of OC increased in direct proportion to am-Al(OH)3 availability, despite constant aromatic C (~30%). The strong stabilization at higher mineral availability is primarily governed by strong Al-OM bonds formed under less competitive conditions. Due to these strong bonds and the resulting strong stabilization, the surface loading, a proxy for the mineral's occupation by OM, was not a factor in the mineralization of sorbed OM over a wide range of C sorption (0.2-1.1 mg C m-2). This study demonstrates that sorption to am-Al(OH)3 results in stabilization of OM. The mineral availability as well as the inorganic solution chemistry control sorptive interactions, thereby the properties of sorbed OM, and the stability of OM against microbial decay

Hydrological Partitioning in the Critical Zone: Recent Advances and Opportunities for Developing Transferable Understanding of Water Cycle Dynamics

Hydrology is an integrative discipline linking the broad array of water-related research with physical, ecological, and social sciences. The increasing breadth of hydrological research, often where subdisciplines of hydrology partner with related sciences, reflects the central importance of water to environmental science, while highlighting the fractured nature of the discipline itself. This lack of coordination among hydrologic subdisciplines has hindered the development of hydrologic theory and integrated models capable of predicting hydrologic partitioning across time and space. The recent development of the concept of the critical zone (CZ), an open system extending from the top of the canopy to the base of groundwater, brings together multiple hydrological subdisciplines with related physical and ecological sciences. Observations obtained by CZ researchers provide a diverse range of complementary process and structural data to evaluate both conceptual and numerical models. Consequently, a cross-site focus on ‘‘critical zone hydrology’’ has potential to advance the discipline of hydrology and to facilitate the transition of CZ observatories into a research network with immediate societal relevance. Here we review recent work in catchment hydrology and hydrochemistry, hydrogeology, and ecohydrology that highlights a common knowledge gap in how precipitation is partitioned in the critical zone: ‘‘how is the amount, routing, and residence time of water in the subsurface related to the biogeophysical structure of the CZ?’’ Addressing this question will require coordination among hydrologic subdisciplines and interfacing sciences, and catalyze rapid progress in understanding current CZ structure and predicting how climate and land cover changes will affect hydrologic partitioning

Effect of Re-acidification on Buffalo Grass Rhizosphere and Bulk Microbial Communities During Phytostabilization of Metalliferous Mine Tailings

Phytostabilized highly acidic, pyritic mine tailings are susceptible to re-acidification over time despite initial addition of neutralizing amendments. Studies examining plant-associated microbial dynamics during re-acidification of phytostabilized regions are sparse. To address this, we characterized the rhizosphere and bulk bacterial communities of buffalo grass used in the phytostabilization of metalliferous, pyritic mine tailings undergoing re-acidification at the Iron King Mine and Humboldt Smelter Superfund Site in Dewey-Humboldt, AZ. Plant-associated substrates representing a broad pH range (2.35-7.76) were sampled to (1) compare the microbial diversity and community composition of rhizosphere and bulk compartments across a pH gradient, and (2) characterize how re-acidification affects the abundance and activity of the most abundant plant growth-promoting bacteria (PGPB; including N2-fixing) versus acid-generating bacteria (AGB; including Fe-cycling/S-oxidizing). Results indicated that a shift in microbial diversity and community composition occurred at around pH 4. At higher pH (>4) the species richness and community composition of the rhizosphere and bulk compartments were similar, and PGPB, such as Pseudomonas, Arthrobacter, Devosia, Phyllobacterium, Sinorhizobium, and Hyphomicrobium, were present and active in both compartments with minimal presence of AGB. In comparison, at lower pH (<4) the rhizosphere had a significantly higher number of species than the bulk (p < 0.05) and the compartments had significantly different community composition (unweighted UniFrac; PERMANOVA, p < 0.05). Whereas some PGPB persisted in the rhizosphere at lower pH, including Arthrobacter and Devosia, they were absent from the bulk. Meanwhile, AGB dominated in both compartments; the most abundant were the Fe-oxidizer Leptospirillum and Fe-reducers Acidibacter and Acidiphilium, and the most active was the Fe-reducer Aciditerrimonas. This predominance of AGB at lower pH, and even their minimal presence at higher pH, contributes to acidifying conditions and poses a significant threat to sustainable plant establishment. These findings have implications for phytostabilization field site management and suggest re-application of compost or an alternate buffering material may be required in regions susceptible to re-acidification to maintain a beneficial bacterial community conducive to long-term plant establishment.National Institute of Environmental and Health Sciences (NIEHS) Superfund Research Program (SRP) [P42 ES004940]; National Science Foundation Graduate Research Fellowhip Program (NSF GRFP) [DGE-1143953]Open access journalThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Coupling Sorption to Soil Weathering during Reactive Transport: Impacts of Mineral Transformation and Sorbate Aging on Contaminant Speciation and Mobility

The Hanford subsurface has become contaminated with highly alkaline, radioactive waste generated as a result of weapons production. The radioactive brine was stored in underground storage tanks, a number of which developed leaks and contaminated the surrounding subsurface. The high pH and ionic strength of these wastes has been predicted to accelerate the degree of soil weathering to produce new mineral phases--cancrinite and sodalite among the most abundant. Previous work has demonstrated that Cs and Sr, which along with I represent the most radioactive components in the waste, are sequestered by these neo-formed solids. The present work is aimed at assessing the stability of these neo-formed solids, with special emphasis on the degree of Cs, Sr and I release under ambient (neutral pH, low ionic strength) conditions expected to return to the Hanford area after the caustic radioactive brine waste is removed

Soil Microbiome Dynamics During Pyritic Mine Tailing Phytostabilization: Understanding Microbial Bioindicators of Soil Acidification

Challenges to the reclamation of pyritic mine tailings arise from in situ acid generation that severely constrains the growth of natural revegetation. While acid mine drainage (AMD) microbial communities are well-studied under highly acidic conditions, fewer studies document the dynamics of microbial communities that generate acid from pyritic material under less acidic conditions that can allow establishment and support of plant growth. This research characterizes the taxonomic composition dynamics of microbial communities present during a 6-year compost-assisted phytostabilization field study in extremely acidic pyritic mine tailings. A complementary microcosm experiment was performed to identify successional community populations that enable the acidification process across a pH gradient. Taxonomic profiles of the microbial populations in both the field study and microcosms reveal shifts in microbial communities that play pivotal roles in facilitating acidification during the transition between moderately and highly acidic conditions. The potential co-occurrence of organoheterotrophic and lithoautotrophic energy metabolisms during acid generation suggests the importance of both groups in facilitating acidification. Taken together, this research suggests that key microbial populations associated with pH transitions could be used as bioindicators for either sustained future plant growth or for acid generation conditions that inhibit further plant growth.National Institute of Environmental and Health Sciences (NIEHS) Superfund Research Program (SRP) [P42 ES004940]Open access journalThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Final Report: Caustic Waste-Soil Weathering Reactions and Their Impacts on Trace Contaminant Migration and Sequestration

The principal goal of this project was to assess the molecular nature and stability of radionuclide (137-Cs, 90-Sr, and 129-I) immobilization during weathering reactions in bulk Hanford sediments and their high surface area clay mineral constituents. We focused on the unique aqueous geochemical conditions that are representative of waste-impacted locations in the Hanford site vadose zone: high ionic strength, high pH and high Al concentrations. The specific objectives of the work were to (i) measure the coupling of clay mineral weathering and contaminant uptake kinetics of Cs+, Sr2+ and I-; (ii) determine the molecular structure of contaminant binding sites and their change with weathering time during and after exposure to synthetic tank waste leachate (STWL); (iii) establish the stability of neoformed weathering products and their sequestered contaminants upon exposure of the solids to more “natural” soil solutions (i.e., after removal of the caustic waste source); and (iv) integrate macroscopic, microscopic and spectroscopic data to distinguish labile from non-labile contaminant binding environments, including their dependence on system composition and weathering time. During this funding period, we completed a large set of bench-scale collaborative experiments and product characterization aimed at elucidating the coupling between mineral transformation reactions and contaminant sequestration/stabilization. Our experiments included three representative Hanford sediments: course and fine sediments collected from the Hanford Formation and Ringold Silt, in addition to investigations with specimen clay minerals illite, vermiculite, smectite and kaolinite. These experiments combined macroscopic measurements of element release, contaminant uptake and subsequent neoformed mineral dissolution behavior, with detailed studies of solid phase products using SEM and TEM microscopy, NMR, XAS and FTIR spectroscopy. Our studies have shown direct coupling between mineral transformation reactions and contaminant sequestration/stabilization