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At least 451 records · Page 25

Peatland microbial community responses to plant functional group and drought are depth-dependent

Peatlands store one-third of Earth's soil carbon, the stability of which is uncertain due to climate change-driven shifts in hydrology and vegetation, and consequent impacts on microbial communities that mediate decomposition. Peatland carbon cycling varies over steep physicochemical gradients characterizing vertical peat profiles. However, it is unclear how drought-mediated changes in plant functional groups (PFGs) and water table (WT) levels affect microbial communities at different depths. We combined a multiyear mesocosm experiment with community sequencing across a 70-cm depth gradient, to test the hypotheses that vascular PFGs (Ericaceae vs. sedges) and WT (high vs. low) structure peatland microbial communities in depth-dependent ways. Several key results emerged. (i) Both fungal and prokaryote (bacteria and archaea) community structure shifted with WT and PFG manipulation, but fungi were much more sensitive to PFG whereas prokaryotes were much more sensitive to WT. (ii) PFG effects were largely driven by Ericaceae, although sedge effects were evident in specific cases (e.g., methanotrophs). (iii) Treatment effects varied with depth: the influence of PFG was strongest in shallow peat (0-10, 10-20 cm), whereas WT effects were strongest at the surface and middle depths (0-10, 30-40 cm), and all treatment effects waned in the deepest peat (60-70 cm). Furthermore, our results underline the depth-dependent and taxon-specific ways that plant communities and hydrologic variability shape peatland microbial communities, pointing to the importance of understanding how these factors integrate across soil profiles when examining peatland responses to climate change.

59 BASIC BIOLOGICAL SCIENCES↗

Surface Hydration of Porous Nickel Hydroxides Facilitates the Reversible Adsorption of CO 2 from Ambient Air

Direct air capture (DAC) under humid ambient conditions typically requires the use of organic components, with sorbents that are purely inorganic in composition for the most part operating hundreds of degrees above room temperature. In this work, we report porous metal hydroxides as a novel class of water-tolerant, oxidatively and hydrothermally stable low-temperature sorbents that exhibit competitive DAC working capacities of 1.25 mmol/g over 5 consecutive temperature swing adsorption–desorption cycles in the presence of steam and oxygen. Aqueous miscible organic solvent treatments are used to create highly porous structures with surface areas exceeding 700 m 2 /g that capture CO 2 in the form of bicarbonates under dry conditions, and carbonates under wet conditions. Water exerts a facilitative rather than an inhibiting effect on CO 2 binding, and the presence of hydrating multilayers serves to stabilize carbonate species akin to moisture swing adsorbents except for the fact that solvation results in a remarkable (upto 10-fold) increase, not decrease, in DAC capacity. High-valent doping with cerium is used to improve DAC capacities by amplifying surface basicity, evidencing porous nickel hydroxides specifically (and porous metal hydroxides more generally) as a novel class of robust, earth-abundant DAC sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Utilization of Ultrasonication as a Method of Reducing Organic and Inorganic Contamination in Post‐Consumer Plastic Film Waste

Post-consumer plastic film waste often carries organic and inorganic contaminants that challenge recycling processes and affect the quality of recycled products. An effective contaminant removal procedure through washing such single-used plastic films (SUPFs) can address environmental and waste management concerns. This study compares the efficiency of different washing techniques in reducing SUPF contamination. To evaluate the efficacy of each washing technique, film samples collected from material recovery facilities are individually exposed to friction, ultrasonic-assisted, and a combination of both washes. Thermal analysis indicates that the polymers' melting temperature, crystallization temperature, and crystallinity remain unaffected by the washing methods, demonstrating method aptness. Confocal laser scanning microscope images show that washing results in a cleaner sample surface. 91% ash reduction during the combined wash treatment indicates a high method efficiency compared to the individual friction and ultrasonic wash procedures. This is further validated by reducing characteristic contaminant IR bands (3600–3000, 1750–1600, and 1100–1000 cm −1 ). Elements of concern such as Cd, Cr, Hg, and Pb in SUPFs after each washing technique applied conform with regulations (<100 ppm) for packaging products. This research shows the novel ultrasonic washing reduces more contamination than friction with shorter wash times and no surfactants.

42 ENGINEERING↗

Electrical passivation of III-V multijunction solar cells with luminescent coupling effect

Perimeter recombination is one of the causes identified for having a nonuniform luminescent coupling effect in III-V multijunction solar cells. A potential solution could be the electrical passivation of the multijunction solar cell perimeter. To test this hypothesis, electrical passivation of InGaP/GaAs/Ge 3-junction solar cells was done by the atomic layer deposition of thin Al2O3 films. Further, perimeter passivation of a 3-junction solar cell relatively increased current collection measured at luminescent coupling and direct subcell excitation by as much as 11.4% and 29.8%, respectively. Meanwhile, the current homogeneity improved relatively by as much as 7.9% after electrical passivation. At 1-sun global standard illumination (AM 1.5G), 0.2% absolute conversion efficiency increase was achieved. Therefore, electrical passivation of fully working III-V multijunction solar cells is a non-invasive, post-treatment process that can recover losses due to surface defects caused by oxidation.

14 SOLAR ENERGY↗

Impact of sodium vanadium oxide (NaV 3 O 8 , NVO) material synthesis conditions on charge storage mechanism in Zn-ion aqueous batteries

The electrochemical charge storage of sodium vanadate (NaV 3 O 8 or NVO) cathodes in aqueous Zn-ion batteries has been hypothesized to be influenced by the inclusion of structural water for facilitating ion transfer in the material. Materials properties considered important (morphology, crystallite and particle size, surface area) are systematically studied herein through investigation of two NVO materials, NaV 3 O 8 ·0.34H 2 O [NVO(300)] and NaV 3 O 8 ·0.05H 2 O [NVO(500)], with different water content, acicular morphologies with different size and surface area achieved via post-synthesis heat treatment. The electrochemistry of the two materials was evaluated in aqueous Zn-ion cells with 2 M ZnSO 4 electrolyte using cyclic voltammetry, galvanostatic cycling, and rate capability testing. Furthermore, the thinner NVO(300) nanobelts (0.13 μm) demonstrate greater specific capacities and higher effective diffusion coefficients relative to the thicker NVO(500) nanorods. Notably however, while cells containing NVO(500) deliver lower specific capacity, they demonstrate enhanced capacity retention with cycling. The structural changes accompanying oxidation and reduction are elucidated via ex situ X-ray diffraction, transmission electron microscopy, and operando V K-edge X-ray absorption spectroscopy (XAS), where NVO material properties are shown to influence the ion insertion. Operando XAS verified that electron transfer corresponds directly to change in vanadium oxidation state, affirming vanadium redox as the governing electrochemical process.

25 ENERGY STORAGE↗

Fundamental data for modeling electron-induced processes in plasma remediation of perfluoroalkyl substances

Plasma treatment of per- and polyfluoroalkyl substances (PFAS) contaminated water is a potentially energy efficient remediation method. In this treatment, an atmospheric pressure plasma interacts with surface-resident PFAS molecules. Developing a reaction mechanism and modeling of plasma–PFAS interactions requires fundamental data for electron–molecule reactions. In this paper, we present results of electron scattering calculations, potential energy landscapes and their implications for plasma modelling of a dielectric barrier discharge in PFAS contaminated gases, a first step towards modelling of plasma–water–PFAS intereactions. It is found that the plasma degradation of PFAS is dominated by dissociative electron attachment with the importance of other contributing processes varying depending on the molecule. All molecules posses a large number of shape resonances – transient negative ion states – from near-threshold up to ionization threshold. These states lie in the region of the most probable electron energies in the plasma (4–5 eV) and consequently are expected to further enhance the fragmentation dynamics in both dissociative attachment and dissociative excitation.

54 ENVIRONMENTAL SCIENCES↗

Effect of Carbon Support Heat Treatment on the Performance of Ion-Pair High-Temperature PEM Fuel Cells

Heat treatment can significantly alter the physical and chemical properties of carbon supports, thereby influencing the performance of proton exchange membrane (PEM) fuel cells. This study explores how varying carbon heat treatment temperatures—from 1,000 °C to 2,200 °C—affect the structure and performance of platinum-based catalysts in high-temperature PEM fuel cells. Increasing the heat treatment temperature led to a notable decrease in surface area, along with increases in carbon grain size and hydrophobicity. Although the catalyst supported on carbon treated at 1,000 °C exhibited the highest catalyst activity, the MEA using carbon treated at 1,500 °C delivered the best overall fuel cell performance. This is attributed to an optimized balance between hydrophobicity and accessible surface area, which enhances water management and catalyst utilization. These findings underscore the importance of carbon support engineering in improving the efficiency of ion-pair high-temperature PEM fuel cells.

08 HYDROGEN↗

Study of unripe and inferior banana flours pre-gelatinized by four different physical methods

This study aimed to prepare the pre-gelatinized banana flours and compare the effects of four physical treatment methods (autoclaving, microwave, ultrasound, and heat-moisture) on the digestive and structural characteristics of unripe and inferior banana flours. After the four physical treatments, the resistant starch (RS) content values of unripe and inferior banana flours were decreased from 96.85% (RS2) to 28.99–48.37% (RS2 + RS3), while C∞ and k values were increased from 5.90% and 0.039 min −1 to 56.22–74.58% and 0.040–0.059 min −1 , respectively. The gelatinization enthalpy (ΔHg) and I 1047/1022 ratio (short-range ordered crystalline structures) were decreased from 15.19 J/g and 1.0139 to 12.01–13.72 J/g, 0.9275–0.9811, respectively. The relative crystallinity decreased from 36.25% to 21.69–26.30%, and the XRD patterns of ultrasound (UT) and heat-moisture (HMT) treatment flours maintained the C-type, but those samples pre-gelatinized by autoclave (AT) and microwave (MT) treatment were changed to C + V-type, and heat-moisture (HMT) treatment was changed to A-type. The surface of pre-gelatinized samples was rough, and MT and HMT showed large amorphous holes. The above changes in structure further confirmed the results of digestibility. According to the experimental results, UT was more suitable for processing unripe and inferior banana flours as UT had a higher RS content and thermal gelatinization temperatures, a lower degree and rate of hydrolysis, and a more crystalline structure. The study can provide a theoretical basis for developing and utilizing unripe and inferior banana flours.

Zhang, Siwei↗

Mechanical Behavior Assessment of Ti-6Al-4V ELI Alloy Produced by Laser Powder Bed Fusion

The present work correlates the quasi-static, tensile mechanical properties of additively manufactured Ti-6Al-4V extra low interstitial (ELI, Grade 23) alloy to the phase constituents, microstructure, and fracture surface characteristics that changed with post-heat treatment of stress relief (670 °C for 5 h) and hot isostatic pressing (HIP with 100 MPa at 920 °C for 2 h under an Ar atmosphere). Ti-6Al-4V ELI alloy tensile specimens in both the horizontal (i.e., X and Y) and vertical (Z) directions were produced by the laser powder bed fusion (LPBF) technique. Higher yield strength (1141 MPa), higher tensile strength (1190 MPa), but lower elongation at fracture (6.9%), along with mechanical anisotropy were observed for as-stress-relieved (ASR) samples. However, after HIP, consistent and isotropic mechanical behaviors were observed with a slight reduction in yield strength (928 MPa) and tensile strength (1003 MPa), but with a significant improvement in elongation at fracture (16.1%). Phase constituents of acicular α' phase in ASR and lamellar α + β phases in HIP samples were observed and quantified to corroborate the reduction in strength and increase in ductility. The anisotropic variation in elongation at fracture observed for the ASR samples, particularly built in the build (Z) direction, was related to the presence of “keyhole” porosity.

42 ENGINEERING↗

LIBS Applications to Liquids and Solids in Liquids

In this chapter, LIBS instrumentation and data collection system used for the analysis of liquids and solids in liquids are discussed. LIBS measurements of bulk liquid samples and solids submerged in aqueous media, measurements made by focusing laser pulses on liquid surfaces, and measurements of liquids after various sample treatments are presented. In addition, the working mechanism of NETL‐developed field‐deployable LIBS sensor and its preliminary performance in field measurements are also reported.

atomic emission spectroscopy↗

Reformed Mesoporous Ge for Substrate Reuse in III-V Solar Cells

Mesoporous Ge was generated by bipolar electrochemical etching of (100) Ge. Through high-temperature annealing experiments, we found that the mesoporous Ge microstructure produces pore coalescence deep in the structure rather than at the surface. III-V epitaxy on annealed porous Ge with subsurface coalescence and coral-like structures on the surface produced shunted photovoltaic devices. The roughness of the annealed porous Ge film was reduced by a pre-annealing HBr treatment and a post-annealing ultrasonic DI water dip. A smoother reformed surface was obtained, on which a GaInAs upright device with an efficiency of 5.7% was grown, demonstrating a first step towards technical viability.

14 SOLAR ENERGY↗

Resource Recovery and Environmental Protection in Wyoming’s Greater Green River Basin Using Selective Nanostructured Membranes (Final Report)

Produced water (PW) represents a sizable waste stream that is co-generated with oil and natural gas production. In 2021 Wyoming ranked 8th and 9th, respectively in domestic oil and natural gas production. In 2017 Wyoming ranked as the 4th highest generator of PW in the U.S, accounting for 7% of the total volume generated. In the context of being the 3rd most arid state in the U.S., the value of water reuse becomes obvious. PW reuse, and resource recovery, in any form requires some level of treatment to remove particulates, residual (free, dispersed) hydrocarbons, organics, and salts. The level of treatment depends on the requirements of the reuse, or resource recovery, application. PW management systems in Wyoming employ in order of volume of PW managed the following management strategies: reinjection for enhanced oil recovery, surface discharge, deep well injection, evaporation ponds (impoundments), and commercial management/treatment. Complicating treatment efforts are the relatively high concentrations of organics (natural and synthetic), dispersed/free hydrocarbons, benzene-toluene-ethylbenzene, and xylenes (BTEX) compounds, biologicals, salts, and minerals. Hydrocarbons (dispersed/dissolved crude oils) and BTEX compounds, as well as synthetic organics, present economic and environmental concerns. The former represents lost revenue, while the latter results in negative environmental impacts like emissions from surface impoundments. The overall objective of this proposal was to synthesize superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes for selectively concentrating and then separating BTEX compounds and oil and grease (O&G) from PW originating from the Greater Green River Basin (GGRB) in Wyoming. Three specific research aims were pursued to accomplish this overall objective. This final report details the development of the superhydrophobic and superhydrophilic membranes, as well as the design of the membrane module prototypes specifically. The technoeconomic assessment is separately reported in another document. 1. Aim #1 – Material optimization and performance evaluation of superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes made by electrospinning/spraying. 2. Aim #2 – Design and construction of cross-flow membrane modules for selectively concentrating and then separating BTEX/oil from GGRB produced water. 3. Aim #3 – Techno-economic assessment of BTEX/oil recovery, and clean water production, using superhydrophilic/oleophobic and superhydrophobic/oleophilic membrane separation for GGRB PW. Superhydrophobic membranes were synthesized by electrospinning poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers onto polyester (PET) substrates and electrospraying nano-carbon black/PVDF-HFP onto the nanofibrous layer. These membranes were characterized by high (>8000 liters per square meter per hour per bar (LMH/bar)) permeance values for pure hydrocarbon phases and a high hydrocarbon selectivity (>96%) when treating GGRB PW. All results were obtained when operating the membrane in a crossflow configuration representative of actual field operating conditions. Solvent/oil properties, specifically viscosity and total surface energy/tension, affected permeance across the membrane, which resulted in light mineral oil (394 LMH/bar) and o-xylene (1834 LMH/bar) being characterized by lower permeance values in the pure phase tests. Mixed phase fluxes between 40 to 80 LMH were obtained for the PW when operating the membrane at a feed pressure of 0.3 bar. Flux decreased as the mixed phase concentration in the feed decreased pointing to the importance of maximizing the collision efficiency between the emulsion and the membrane surface and maximizing the emulsion concentration in the feed and the turbulence within the feed channel. These tests demonstrated that the superhydrophobic membranes developed here are a viable hydrocarbon recovery method for GGRB PWs and should be pursued for testing in pilot-scale trials. Superhydrophilic membranes were successfully synthesized via electrospinning/spraying using polyacrylonitrile (PAN) nanofibers as a base nanofibrous matrix. Integration of polyaniline (PANI) into the nanofibrous matrix produced a superior membrane, for water filtration applications, relative to PAN alone and reduced graphene oxide (RGO) when integrated into the nanofibrous matrix. This conclusion was based on the PANI-PAN resistance to flux loss (fouling) when treating model solvent/oil solutions representative of GGRB PWs and field collected PW from the GGRB. The synthesized PAN membranes outperformed a commercially available PAN membrane designed for oil/water separation. This finding indicates that the surface chemical and physical characteristics of the electrospun membranes presents improved properties for filtration of challenging waters like GGRB PWs. The electrospun membranes therefore show promise overall as a substitute for conventionally polymerized membranes in PW treatment applications. The PANI-PAN membrane specifically presents superior performance characteristics for concentration O&G prior to treatment by the hydrocarbon recovery membrane and producing high-quality filtrate for reuse and/or additional treatment (desalination).

02 PETROLEUM↗

Challenges in atomic layer etching of gallium nitride using surface oxidation and ligand-exchange

Two atomic layer etching (ALE) methods were studied for crystalline GaN, based on oxidation, fluorination, and ligand exchange. Etching was performed on unintentionally doped GaN grown by hydride vapor phase epitaxy. For the first step, the GaN surfaces were oxidized using either water vapor or remote O 2 -plasma exposure to produce a thin oxide layer. Removal of the surface oxide was addressed using alternating exposures of hydrogen fluoride (HF) and trimethylgallium (TMG) via fluorination and ligand exchange, respectively. Several HF and TMG super cycles were implemented to remove the surface oxide. Each ALE process was monitored in situ using multiwavelength ellipsometry. X-ray photoelectron spectroscopy was employed for the characterization of surface composition and impurity states. Additionally, the thermal and plasma-enhanced ALE methods were performed on patterned wafers and transmission electron microscopy (TEM) was used to measure the surface change. The x-ray photoelectron spectroscopy measurements indicated that F and O impurities remained on etched surfaces for both ALE processes. Ellipsometry indicated a slight reduction in thickness. TEM indicated a removal rate that was less than predicted. In conclusion, we suggest that the etch rates were reduced due to the ordered structure of the oxide formed on crystalline GaN surfaces.

36 MATERIALS SCIENCE↗

Design and Assessment of a Novel Approach for Ecosystem Warming Experiments in High‐Energy Tidal Wetlands

Abstract Coastal salt marshes have an important role in climate change adaptation and mitigation. Direct and indirect responses to warming are expected to vary along the marsh elevation gradient, making ecosystem responses to warming at this marine‐terrestrial ecotone uncertain. The Marsh Ecosystem Response to Increased Temperatures (MERIT) experiment was established in 2018 on the North Sea coast of Germany. Experimental plots are evenly distributed over three elevational marsh zones (pioneer, low marsh, and high marsh) and include three temperature treatments (ambient, +1.5°C, +3.0°C). MERIT's novel design combines active warming (horizontal surface warming cables and vertical soil warming pins) with passive, partially covered domes. For performance assessment, temperature deltas between ambient and warmed plots were calculated and evaluated at seasonal, daily, and diurnal timescales. We used Linear Mixed Models with Residual Maximum Likelihood for evaluating warming treatment effects and constraining environmental factors. MERIT was effective at ecosystem warming in this high‐energy environment both above‐ and belowground. Mixed models show that warming treatment dominates temperature differences belowground and at the soil surface, along with factors such as wind speed, flooding duration, and solar radiation. Aboveground warming was lower than belowground warming, but the dome design minimized issues seen in other open‐top chamber experiments. The combination of passive aboveground warming with feedback‐controlled active surface and belowground heating provides a setup for understanding warming effects on tidal ecosystems without altering the natural impacts of wind, radiation, and tidal inundations at high‐energy coastlines. Our design creates opportunities to expand future warming experiments to remote locations and technically challenging environments.

Environmental Sciences & Ecology↗

Steam‐Induced Coarsening of Single‐Unit‐Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis

Abstract Commonly used methods to assess crystallinity, micro‐/mesoporosity, Brønsted acid site density and distribution (in micro‐ vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two‐dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro‐ and mesoporosity, and micropore reaction rates.

Guefrachi, Yasmine↗

Assessment of Combustion Residual Leachate Volume, Composition, and Treatment Costs

Combustion residuals and the resulting leachate from storage sites represent a large volume of wastewater in the United States (U.S.) that has not been quantified. Here this work estimates the constituents present, volume of wastewater, and costs of treatment for both combustion residual landfill leachate and the leachate from surface impoundment closures. Combustion residual landfill leachate produced from contact with bituminous coal combustion byproducts is generally predicted to be higher in lithium and manganese, whereas landfill leachate produced from contact with subbituminous coal combustion byproducts is generally predicted to be higher in mercury and vanadium. The annual volume of a single landfill with combustion residual leachate can reach more than 800,000 cubic meters. This leachate represents an annual volume of 26.8–42.8 million cubic meters nationally. Closing surface impoundments can yield between 830 and 1040 cubic meters of leachate nationally for a three-year closure period. Costs as low as $1.5/m 3 or as high as $95/m 3 are observed. Treatment trains will need to remove 72% of total suspended solids (TSS), 87% of arsenic, and 64% of mercury from landfill leachate. When applied to impoundments, these treatment trains would need to remove 97% of arsenic.

01 COAL, LIGNITE, AND PEAT↗

TiO 2 Nanocoatings with Controllable Crystal Type and Nanoscale Topography on Zirconia Implants to Accelerate Bone Formation

In dentistry, zirconia implants have emerged as a promising alternative for replacing missing teeth due to their superior aesthetic performance and chemical stability. To improve the osseointegration of zirconia implants, modifying their surface with hierarchical micro/nanotopography and bioactive chemical composition are two effective ways. In this work, a microscale topography was prepared on a zirconia surface using hydrofluoric acid etching, and then a 50 nm TiO 2 nanocoating was deposited via atomic layer deposition (ALD). Subsequently, an annealing treatment was used to transform the TiO 2 from amorphous to anatase and simultaneously generate nanoscale topography. Various investigations into the coating surface morphology, topography, wettability, and chemical composition were carried out using scanning electron microscopy, white light interferometry, contact‐angle measurement, X‐ray diffraction, and X‐ray photoelectron spectroscopy. In addition, in vitro cytocompatibility and osteogenic potential performance of the coatings were evaluated by human bone marrow mesenchymal stem cells (hBMSCs), and in vivo osseointegration performance was assessed in a rat femoral condyle model. Moreover, the possible mechanism was also investigated. The deposition of TiO 2 film with/without annealing treatment did not alter the microscale roughness of the zirconia surface, whereas the nanotopography changed significantly after annealing. The in vitro studies revealed that the anatase TiO 2 coating with regular wavelike nanostructure could promote the adhesion and proliferation of osteoblasts and further improve the osteogenic potential in vitro and osseointegration in vivo. These positive effects may be caused by nanoscale topography via the canonical Wnt/ β ‐catenin pathway. The results suggest that using ALD in combination with annealing treatment to fabricate a nanotopographic TiO 2 coating is a promising way to improve the osteogenic properties of zirconia implants.

Li, Nan (ORCID:0000000255156737)↗

Lime slurry treatment of soils developing on abandoned coal mine spoil: Linking contaminant transport from the micrometer to pedon-scale

Historical and abandoned coal mine spoil continues to generate acid- and metal(loid)-rich porewaters and represents a geographically large and diffuse non-point source of contamination to local watersheds. A potentially inexpensive approach to treat these materials and soils developing on them is through the application of lime slurries, to neutralize acidity and encourage the (co)precipitation of metal(loids) with Fe(III)-(oxy)hydroxides, and potentially other metal-oxides and/or Ca-bearing phases. Here, the efficacy of this approach was evaluated through parallel field application and laboratory-based flow-through column experiments. The field site is Huff Run sub-watershed 25 located in Tuscarawas County, Ohio and was chosen in part because it was previously classified as one of the most highly AMD-impacted sub-watersheds in the region. Two locations with historical spoil were chosen and suction lysimeters were installed at 25 and 75 cm depth to monitor porewater composition on two sides at the base of each pile. Half of each slope received seven lime slurry treatments from June through October of 2017. A suite of aqueous (ICP-OES, IC, and TOC-L) and solid phase geochemical and mineralogical approaches (quantitative SEM-EDS and synchrotron μ-XRF) were used to determine how composition, texture, morphology, and spatial distribution of mineral coatings differ in pre- and post-lime treated soils, and how that impacts the distribution and transport of trace metal(loid)s. Mine spoil porewater at site 1 was slightly less alkaline (pH ranging from 7.04 to 7.37) than at site 2 (ranging from 7.55 to 7.71), and average electrical conductivity values at site 1 (316–405 μS cm —1 ) were slightly lower than at site 2 (358–464 μS cm —1 ), although differences between the sites were not significant. Porewater pH and electrical conductivity in all lysimeters decreased over the course of the field season but there was no obvious response to lime treatment at either site or any depth. At site 1, both treatment and depth were significant factors affecting Ca, K, Ni, SO 4 2— , and DOC concentrations while only treatment effects were significant for dissolved Al and Cu (p < 0.05). For all soils, there were no trends in metal concentration observed over time although DOC and SO 4 2— decreased over the field season. Pedon-scale changes in metal porewater concentrations in response to treatment were linked to micrometer-scale changes in mineral surface coatings; specifically, higher concentrations of Ca, Fe, Mn, and Zn were observed in the coatings and no changes were observed in Fe redox speciation, whereas total S decreased likely due to oxidation of S in coal fragments. In contrast to the field experiment, the column experiments exhibited a much greater response in effluent composition with respect to lime treatment. The untreated columns had approximately an order of magnitude more H + leached over the course of the experiment (p < 0.001) and resulted in greater Ca, Al, Cu, and DIC leached and less Mn, Zn, and SO 4 2— . Soils treated with the lime slurry in the column experiments exhibited larger and thicker secondary Fe-coatings, including the addition of Fe-sulfates. Despite clear trends in the laboratory-based column experiment where the lime-to-soil ratio was higher, the effects were either muted or undetected in the field pilot project, suggesting that a higher application rate of lime in the field is needed to achieve a similar effect. This work provides evidence that a less alkaline lime slurry could be a practical and inexpensive method of treating coal mine spoil-impacted soils and represents an important step in linking laboratory-based remediation studies to implemented field-based studies.

58 GEOSCIENCES↗