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Molecular-Scale Understanding of Sulfate Exchange from Schwertmannite by Chromate Versus Arsenate

Schwertmannite effectively sorbs chromate (Cr(VI)), yet the sorption mechanisms remain elusive. We determined the Cr(VI) sorption mechanisms on schwertmannite at pH 3.2 and 5 using combined macroscopic sorption experiments with molecularscale characterization and by comparing them to arsenate (As(V)) sorption. Cr(VI) adsorbs as bidentate-binuclear (BB) inner-sphere complexes through exchanging more sulfate and less >Fe–OH/OH 2 , with 0.59–0.71 sulfate released per Cr(VI) sorbed. While As(V) also forms BB complexes, it exchanges sulfate and >Fe–OH/OH 2 equally with 0.49–0.52 sulfate released per As(V) sorbed. At high As(V) loadings, As(V) precipitates as amorphous FeAsO 4 , particularly at low pH. The abovementioned differences between Cr(VI) and As(V) can be related to their different ionic radii and binding strength. Moreover, Cr(VI) and As(V) preferentially exchange sulfate innersphere complexes, increasing the proportion of sulfate outer-sphere complexes in schwertmannite. In turn, the concentration of sulfate outer-sphere complexes increases and then decreases with increasing Cr(VI) loading. Results suggest that an oxyanion, which would form inner-sphere complexes on a mineral surface, preferentially exchanges inner-spherically bound oxyanions than outerspherically bound ones on the surface, even though both are exchanged. Furthermore, this study improves our understanding of the sorption of oxyanions on schwertmannite and their capabilities to template schwertmannite formation and stabilize its structure.

54 ENVIRONMENTAL SCIENCES↗

Degradation of Carbon Fiber Microstructures Due to Oxidative Etch Pitting

In order to understand the influence of etch pits on the material properties of carbon fiber microstructures, we use the Porous Microstructure Analysis (PuMA) software to create realistic pitted structures from virgin fiber structures and then analyze their degradation as the degree of pitting increases. For that purpose, we developed a pitting module within PuMA that creates pits with user-defined geometry (shape, size) and distribution (defect density) on the surface of arbitrary microstructures. In this work, we consider FiberForm microstructures, which are commonly used as the base material for ablative thermal protection systems (TPS). Using the new pitting module, we mimic the evolution of etch pits on FiberForm as it occurs from oxidation in ablative heating environments, by first importing the virgin FiberForm structure from a micrograph scan and then imposing different pitting conditions by varying pit radii and defect densities. We then leverage PuMA’s capabilities to calculate material properties for each structure. The results clearly show the degradation of thermal conductivity and structural integrity as etch pits grow, and furthermore highlight the complex evolution of the surface topology, which results in significant changes of the flowgeometry and chemical gas-surface interactions. Furthermore, a comparison of these changes with the case of shrinking fibers, which has heretofore been the standard for modelling ablation of carbon structures, yields significant differences. For example, we observe the formation of small chunks of fibers as pits grow in size, which could be released into the surrounding flow environment as spallation particles. This motivates us to continue our efforts of modelling pitting as an integral part of the structural degradation of carbon fiber structures in oxidation environments, which will ultimately improve our understanding of failure mechanisms in those materials.

PuMA↗

Degradation of Carbon Fiber Microstructures Due to Oxidative Etch Pitting

In order to understand the influence of etch pits on the material properties of carbon fiber microstructures, we use the Porous Microstructure Analysis (PuMA) software to create realistic pitted structures from virgin fiber structures and then analyze their degradation as the degree of pitting increases. For that purpose, we developed a pitting module within PuMA that creates pits with user-defined geometry (shape, size) and distribution (defect density) on the surface of arbitrary microstructures. In this work, we consider FiberForm microstructures, which are commonly used as the base material for ablative thermal protection systems (TPS). Using the new pitting module, we mimic the evolution of etch pits on FiberForm as it occurs from oxidation in ablative heating environments, by first importing the virgin FiberForm structure from a micrograph scan and then imposing different pitting conditions by varying pit radii and defect densities. We then leverage PuMA’s capabilities to calculate material properties for each structure. The results clearly show the degradation of thermal conductivity and structural integrity as etch pits grow, and furthermore highlight the complex evolution of the surface topology, which results in significant changes of the flowgeometry and chemical gas-surface interactions. Furthermore, a comparison of these changes with the case of shrinking fibers, which has heretofore been the standard for modelling ablation of carbon structures, yields significant differences. For example, we observe the formation of small chunks of fibers as pits grow in size, which could be released into the surrounding flow environment as spallation particles. This motivates us to continue our efforts of modelling pitting as an integral part of the structural degradation of carbon fiber structures in oxidation environments, which will ultimately improve our understanding of failure mechanisms in those materials.

PuMA↗

Multicritical Fermi Surface Topological Transitions

A wide variety of complex phases in quantum materials are driven by electron-electron interactions, which are enhanced through density of states peaks. A well-known example occurs at van Hove singularities where the Fermi surface undergoes a topological transition. Here we show that higher order singularities, where multiple disconnected leaves of Fermi surface touch all at once, naturally occur at points of high symmetry in the Brillouin zone. Such multicritical singularities can lead to stronger divergences in the density of states than canonical van Hove singularities, and critically boost the formation of complex quantum phases via interactions. Further, as a concrete example of the power of these Fermi surface topological transitions, we demonstrate how they can be used in the analysis of experimental data on Sr 3 Ru 2 O 7 . Understanding the related mechanisms opens up new avenues in material design of complex quantum phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis, characterization and crystal structure determination of Mn (II) ion based 1D polymer constructed from 2, 2′ bipyridyl and azide group, its thermal stability, magnetic properties and Hirshfeld surface analysis

The 1-D polymeric complex (I) is having formula [Mn(2,2′-BP).(N{sub 3}){sub 2}]{sub n}, which has been crystallized in distilled water and characterized by elemental analyses, FT-IR spectrum, powder X-ray diffraction analyses and single-crystal diffraction analysis. This polymer possesses 1D helical chains or coils where Mn–azide–Mn forms the base of the coil which is alternatively garlanded by rigid bi-pyridine rings, where coordinates are in anti-fashion. The Mn (II) ions in the repeating units are linked by two end-on azide groups which extend through the two end-to-end azide ligands to the next unit forming a 1-D polymeric chain. The present study suggests that the use of this rigid and neutral building block leads to give better arrangement of the polymeric motif with [010] chains in 2-c uninodal net. During investigation of strong or weak intermolecular interactions, X-ray diffraction analysis and Hirshfeld surface analysis give rise to comparable results but in Hirshfeld surface analysis, two-third times more results of close contacts are obtained. The fingerprint plots demonstrate that these weak non-bonding interactions are important for stabilizing the crystal packing. Magnetic properties of the complex (I) were analyzed on the basis of an alternating ferro- and antiferromagnetic Heisenberg chain of Mn (II) ions. The J-exchange parameters found are J{sub 1}=64.3 K (45.3 cm{sup −1}), and J{sub 2}=−75.7 K (−53.3 cm{sup −1}). Magnetic properties are discussed in comparison with those of other similar molecular magnets of [Mn(L–L)(N{sub 3}){sub 2}]{sub n} type. - - Highlights: • Synthesized 1-D polymeric complex of Mn (II) ions with 2, 2′ bipyridyl and azide group. • X-ray data of complex (I) is in a good agreement with TGA and other spectroscopic techniques. • DFT calculations were done and compared with the parameter of experimental and theoretical data. • Intermolecular interactions calculated by Hirshfeld surface analysis compared with X-ray data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spray Combustion Modeling with VOF and Finite-Rate Chemistry

A spray atomization and combustion model is developed based on the volume-of-fluid (VOF) transport equation with finite-rate chemistry model. The gas-liquid interface mass, momentum and energy conservation laws are modeled by continuum surface force mechanisms. A new solution method is developed such that the present VOF model can be applied for all-speed range flows. The objectives of the present study are: (1) to develop and verify the fractional volume-of-fluid (VOF) cell partitioning approach into a predictor-corrector algorithm to deal with multiphase (gas-liquid) free surface flow problems; (2) to implement the developed unified algorithm in a general purpose computational fluid dynamics (CFD) code, Finite Difference Navier-Stokes (FDNS), with droplet dynamics and finite-rate chemistry models; and (3) to demonstrate the effectiveness of the present approach by simulating benchmark problems of jet breakup/spray atomization and combustion. Modeling multiphase fluid flows poses a significant challenge because a required boundary must be applied to a transient, irregular surface that is discontinuous, and the flow regimes considered can range from incompressible to highspeed compressible flows. The flow-process modeling is further complicated by surface tension, interfacial heat and mass transfer, spray formation and turbulence, and their interactions. The major contribution of the present method is to combine the novel feature of the Volume of Fluid (VOF) method and the Eulerian/Lagrangian method into a unified algorithm for efficient noniterative, time-accurate calculations of multiphase free surface flows valid at all speeds. The proposed method reformulated the VOF equation to strongly couple two distinct phases (liquid and gas), and tracks droplets on a Lagrangian frame when spray model is required, using a unified predictor-corrector technique to account for the non-linear linkages through the convective contributions of VOF. The discontinuities within the sharp interface will be modeled as a volume force to avoid stiffness. Formations of droplets, tracking of droplet dynamics and modeling of the droplet breakup/evaporation, are handled through the same unified predictor-corrector procedure. Thus the new algorithm is non-iterative and is flexible for general geometries with arbitrarily complex topology in free surfaces. The FDNS finite-difference Navier-Stokes code is employed as the baseline of the current development. Benchmark test cases of shear coaxial LOX/H2 liquid jet with atomization/combustion and impinging jet test cases are investigated in the present work. Preliminary data comparisons show good qualitative agreement between data and the present analysis. It is indicative from these results that the present method has great potential to become a general engineering design analysis and diagnostics tool for problems involving spray combustion.

Chen, Yen-Sen↗

Uncrewed Lunar Surface Operations and Support Activities

This presentation summarizes the contents of the uncrewed lunar surface operations and support activities paper. It outlines the functions, features, and capabilities that support sustained human and robotic surface operations. It summarizes the complexities associated with the development and operation of autonomous systems and discusses a simulation tool for integrated surface operations planning.

Lunar↗

Fast Ultrasonic Imaging with Total Focusing Method (TFM) for Inspection of Additively Manufactured Polymer Composite Component

Ultrasonic adaptive imaging based on the phased-array technology and the synthetic focusing algorithm Total Focusing Method (TFM) is proposed for fast ultrasonic nondestructive evaluation of additively manufactured composite materials. Nondestructive evaluation and inspection of additively manufactured parts and components are necessary for quality assurance of the materials. Effective detection of defects and anomalies in manufactured parts prevents extra cost and production time. However, there are several limitations encountered when using conventional methods of nondestructive inspection for as built additively manufactured parts due to surface conditions and geometrical complexity. Post-processing operations, such as machining, are usually needed to detect possible defects such as layer disband, micro-cracks, and voids in the composite parts. The capability of aperture focusing in phased array ultrasonic methods provides the opportunity for the adjustment of the delay laws in ultrasonic beams and reduces the noise and beam distortion for better imaging. An additively manufactured carbon fiber reinforced Acrylonitrile Butadiene Styrene (ABS) composite sample with artificial side and bottom-drilled holes of different sizes, used to represent defects, was successfully inspected using the Total Focusing Method (TFM). Unlike conventional ultrasonic techniques, results show a promising way to provide inspection of as built additively manufactured composite parts with rough surface finishes. The proposed method helps to decrease inspection time and eliminate extra machining and preparation costs.

Taheri, Hossein↗

Interparticle Interactions in Dilute Solutions of Polyelectrolyte Complex Micelles.

The application of dilute solutions of poly electrolyte complex (PEC) micelles for delivering therapeutic nucleic acids into disease sites has gained momentum. This Letter reports a detailed characterization of PEC micelles in dilute solutions including their internal structures and the determination of the interparticle interactions. The polymer concentration ranges from 0.1 to 0.5 wt %, a regime where micelle-micelle interactions are infrequent. We employ synchrotron small-angle X-ray scattering (SAXS) to simultaneously probe the morphology, internal structure, and radius of gyration (R-g) of the self-assemblies formed by charged diblock polyelectrolytes and homopolyelectrolytes. The emerging appearance of the structure factor in SAXS profiles with the increasing polymer concentration demonstrates the presence of the repulsive intermicellar correlations, which is further confirmed by the differences between the "reciprocal R-g" estimated by Guinier approximation and the "real space R-g" determined by pair distribution functions. We find that the soft corona chains tethered on the surface of phase-separated complex domains are compressed when micelles come close to the point where a hard-sphere interaction takes over. These findings contribute to the fundamental understanding of the structure and space-filling constraints in the complexation-driven self-assemblies and advance the rational design of cationic polymer-based nonviral gene delivery vectors.

Wu, Hao↗

Probing the Dissociation of Protein Complexes by Means of Gas-Phase H/D Exchange Mass Spectrometry

Gas-phase hydrogen/deuterium exchange measured by mass spectrometry (gas-phase HDX-MS) is a fast method to probe the conformation of protein ions. The use of gas-phase HDX-MS to investigate the structure and interactions of protein complexes is however mostly unharnessed. Ionizing proteins under conditions that maximize preservation of their native structure (native MS) enables the study of solution-like conformation for milliseconds after electrospray ionization (ESI), which enables the use of ND{sub 3}-gas inside the mass spectrometer to rapidly deuterate heteroatom-bound non-amide hydrogens. Here, we explored the utility of gas-phase HDX-MS to examine protein-protein complexes and inform on their binding surface and the structural consequences of gas-phase dissociation. Protein complexes ranging from 24 kDa dimers to 395 kDa 24mers were analyzed by gas-phase HDX-MS with subsequent collision-induced dissociation (CID). The number of exchangeable sites involved in complex formation could, therefore, be estimated. For instance, dimers of cytochrome c or α-lactalbumin incorporated less deuterium/subunit than their unbound monomer counterparts, providing a measure of the number of heteroatom-bound side-chain hydrogens involved in complex formation. We furthermore studied if asymmetric charge-partitioning upon dissociation of protein complexes caused intermolecular H/D migration. In larger multimeric protein complexes, the dissociated monomer showed a significant increase in deuterium. This indicates that intermolecular H/D migration occurs as part of the asymmetric partitioning of charge during CID. We discuss several models that may explain this increase deuterium content and find that a model where only deuterium involved in migrating charge can account for most of the deuterium enrichment observed on the ejected monomer. In summary, the deuterium content of the ejected subunit can be used to estimate that of the intact complex with deviations observed for large complexes accounted for by charge migration. .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Probabilistic Thermal Analysis During Mars Reconnaissance Orbiter Aerobraking

A method for performing a probabilistic thermal analysis during aerobraking has been developed. The analysis is performed on the Mars Reconnaissance Orbiter solar array during aerobraking. The methodology makes use of a response surface model derived from a more complex finite element thermal model of the solar array. The response surface is a quadratic equation which calculates the peak temperature for a given orbit drag pass at a specific location on the solar panel. Five different response surface equations are used, one of which predicts the overall maximum solar panel temperature, and the remaining four predict the temperatures of the solar panel thermal sensors. The variables used to define the response surface can be characterized as either environmental, material property, or modeling variables. Response surface variables are statistically varied in a Monte Carlo simulation. The Monte Carlo simulation produces mean temperatures and 3 sigma bounds as well as the probability of exceeding the designated flight allowable temperature for a given orbit. Response surface temperature predictions are compared with the Mars Reconnaissance Orbiter flight temperature data.

Dec, John A.↗

Role of Dynamic Polarization Interactions in the Electrical Double Layer at Calcite (104) Interfaces with Aqueous Solutions

Reactions at mineral interfaces with aqueous solutions control many geochemical and biogeochemical processes in the Earth’s critical zone. At the molecular level, insights into important properties such as the structure of the electrical double layer (EDL) at specific mineral interfaces continue to improve due to the increasing fidelity of laboratory instrumentation and computational approaches. However, molecular simulation approaches suffer from limited reach into relevant scales of time, length, and system complexity. To span this gap, a novel hybrid approach that couples first principle plane-wave density functional theory (DFT) with classical DFT (cDFT) is demonstrated and applied to calcite (104) interfaces with various electrolytes. In this approach, a region of interest described using DFT interacts with the surrounding medium described using cDFT to arrive at a self-consistent ground state. Benchmarking against experimental observations and entirely first principle DFT simulations demonstrates that this hybrid model efficiently encompasses the key short-range and collective interactions in the EDL. Simulations of calcite (104)/solution interfaces reveal the key static and dynamic polarization interactions that give rise to structuring of ions and water. Ion hydration interactions have the strongest effect on the depth of the first minimum in the density distribution of counterions at the surface, and the position and width of the first density peak is largely determined by the strength of ion-correlation forces. Finer details of ion distributions are controlled by mutual polarization of the calcite surface and interfacial electrolyte. Finally, this new ability to efficiently and rigorously predict EDL structure at mineral surfaces in contact with complex solutions paves the way to accurately modeling sorption, nucleation, dissolution, and growth in realistic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recovery of Rare Earth Elements from Geothermal Fluids through Bacterial Cell Surface Adsorption

The increasing demand for rare earth elements (REEs) in the modern economy motivates the development of novel strategies for cost-effective REE recovery from nontraditional feedstocks. We previously engineered E. coli to express lanthanide binding tags on the cell surface, which increased the REE biosorption capacity and selectivity. Here we examined how REE adsorption by the engineered E. coli is affected by various geochemical factors relevant to geothermal fluids, including total dissolved solids (TDS), temperature, pH, and the presence of specific competing metals. REE biosorption is robust to TDS, with high REE recovery efficiency and selectivity observed with TDS as high as 165,000 ppm. Among several metals tested, U, Al, and Pb were found to be the most competitive, causing >25% reduction in REE biosorption when present at concentrations ~3- to 11-fold higher than the REEs. Optimal REE biosorption occurred between pH 5-6, and sorption capacity was reduced by ~65% at pH 2. REE recovery efficiency and selectivity increased as a function of temperature up to ~70 °C due to the thermodynamic properties of metal complexation on the bacterial surface. Ultimately, these data define the optimal and boundary conditions for biosorption and demonstrate its potential utility for selective REE recovery from geofluids.

58 GEOSCIENCES↗

A Versatile Platform for Nanotechnology Based on Circular Permutation of a Chaperonin Protein

A number of protein complexes have been developed as nanoscale templates. These templates can be functionalized using the peptide sequences that bind inorganic materials. However, it is difficult to integrate peptides into a specific position within a protein template. Integrating intact proteins with desirable binding or catalytic activities is an even greater challenge. We present a general method for modifying protein templates using circular permutation so that additional peptide sequence can be added in a wide variety of specific locations. Circular permutation is a reordering of the polypeptide chain such that the original termini are joined and new termini are created elsewhere in the protein. New sequence can be joined to the protein termini without perturbing the protein structure and with minimal limitation on the size and conformation of the added sequence. We have used this approach to modify a chaperonin protein template, placing termini at five different locations distributed across the surface of the protein complex. These permutants are competent to form the double-ring structures typical of chaperonin proteins. The permuted double-rings also form the same assemblies as the unmodified protein. We fused a fluorescent protein to two representative permutants and demonstrated that it assumes its active structure and does not interfere with assembly of chaperonin double-rings.

Paavola, Chad↗

Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH{sub 3}COO){sub 2}Cr{sup +} ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. {sup 13}C, {sup 29}Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level.

36 MATERIALS SCIENCE↗

A Subsurface Soil Composition and Physical Properties Experiment to Address Mars Regolith Stratigraphy

Previous in-situ measurements of soil-like materials on the surface of Mars, in particular during the on-going Mars Exploration Rover missions, have shown complex relationships between composition, exposure to the surface environment, texture, and local rocks. In particular, a diversity in both compositional and physical properties could be established that is interpreted to be diagnostic of the complex geologic history of the martian surface layer. Physical and chemical properties vary laterally and vertically, providing insight into the composition of rocks from which soils derive, and environmental conditions that led to soil formation. They are central to understanding whether habitable environments existed on Mars in the distant past. An instrument the Mole for Soil Compositional Studies and Sampling (MOCSS) - is proposed to allow repeated access to subsurface regolith on Mars to depths of up to 1.5 meters for in-situ measurements of elemental composition and of physical and thermophysical properties, as well as for subsurface sample acquisition. MOCSS is based on the compact PLUTO (PLanetary Underground TOol) Mole system developed for the Beagle 2 lander and incorporates a small X-ray fluorescence spectrometer within the Mole which is a new development. Overall MOCSS mass is approximately 1.4 kilograms. Taken together, the MOCSS science data support to decipher the geologic history at the landing site as compositional and textural stratigraphy if they exist - can be detected at a number of places if the MOCSS were accommodated on a rover such as MSL. Based on uncovered stratigraphy, the regional sequence of depositional and erosional styles can be constrained which has an impact on understanding the ancient history of the Martian near-surface layer, considering estimates of Mars soil production rates of 0.5... 1.0 meters per billion years on the one hand and Mole subsurface access capability of approximately 1.5 meters. An overview of the MOCSS, XRS instrument accomodation and the impact that these instruments have on Mars science is discussed.

Richter, L.↗

Comparison of Mesoscale Model Setups for Offshore Wind Resource Assessment: A New Jersey Case Study

As the offshore wind energy industry begins to emerge on the U.S. northeast coast, there is an urgent need for an accurate characterization of the offshore wind resource. The offshore regime features various resource characteristics not seen onshore, including frequent coastal low-level jets, non-steady surface conditions (e.g. waves), complex air-sea and land-sea interactions, and coastal mesoscale circulations (e.g. sea breeze). An accurate characterization of these phenomena in mesoscale models is critical to support accurate energy production estimates and forecasting for future offshore wind farms. However, a robust validation of mesoscale model performance in the offshore U.S. has been limited due to sparse data and difficulty obtaining offshore measurements. Consequently, it is unclear how mesoscale models perform offshore and which suite of parameterizations and input data are best suited for accurate resource characterization. To begin addressing this knowledge gap, the National Renewable Energy Laboratory, in collaboration with the Rutgers Center for Ocean Observing Leadership, conducted a mesoscale model validation campaign in the offshore environment. The Weather Research and Forecasting (WRF) model was assessed and the New Jersey offshore coastal area served as the validation domain. An ensemble of WRF simulations conducted over a one-year period sampled from a range of model setups, including different reanalysis and forecast data inputs, sea surface temperature data inputs, planetary boundary layer parameterizations, and WRF versions. The performance of each ensemble member was validated against a network of observations including offshore floating lidars, coastal met towers, offshore platform measurements, and offshore buoys. Model performance was assessed on annual, seasonal, and diurnal scales with particular emphasis on the vertical wind speed profile and temperature stratification. Preliminary results from this validation work will be presented here. The key WRF inputs and parameters driving changes in the modeled wind resource will be discussed and preliminary recommendations on WRF setups for offshore wind resource modeling will be proposed. The application of this validation exercise to other proposed offshore wind energy areas in the U.S. will also be discussed. mesoscale circulations (e.g. sea breeze). An accurate characterization of these phenomena in mesoscale models is critical to support accurate energy production estimates and forecasting for future offshore wind farms. However, a robust validation of mesoscale model performance in the offshore U.S. has been limited due to sparse data and difficulty obtaining offshore measurements. Consequently, it is unclear how mesoscale models perform offshore and which suite of parameterizations and input data are best suited for accurate resource characterization. To begin addressing this knowledge gap, the National Renewable Energy Laboratory, in collaboration with the Rutgers Center for Ocean Observing Leadership, conducted a mesoscale model validation campaign in the offshore environment. The Weather Research and Forecasting (WRF) model was assessed and the New Jersey offshore coastal area served as the validation domain. An ensemble of WRF simulations conducted over a one-year period sampled from a range of model setups, including different reanalysis and forecast data inputs, sea surface temperature data inputs, planetary boundary layer parameterizations, and WRF versions. The performance of each ensemble member was validated against a network of observations including offshore floating lidars, coastal met towers, offshore platform measurements, and offshore buoys. Model performance was assessed on annual, seasonal, and diurnal scales with particular emphasis on the vertical wind speed profile and temperature stratification. Preliminary results from this validation work will be presented here. The key WRF inputs and parameters driving changes in the modeled wind resource will be discussed and preliminary recommendations on WRF setups for offshore wind resource modeling will be proposed. The application of this validation exercise to other proposed offshore wind energy areas in the U.S. will also be discussed.

17 WIND ENERGY↗

Effect of Anions on the Changes in the Structure and Adsorption Mechanism of Zirconium Species at the Muscovite (001)–Water Interface

Multivalent cations primarily exist as polynuclear hydroxo and oxyhydroxo clusters and/or nanoparticles (NPs) in aqueous environments, where their interactions with mineral surfaces can be influenced by complexing anions. In this work, we explored the distribution of tetravalent Zr adsorbed on the negatively charged basal surface of muscovite mica in four background electrolytes (0.1 M NaClO 4 , 0.1 M NaCl, 0.04 M Na 2 SO 4 , and 0.045 M Na 2 HPO 4 ) at constant pH (= 3), total Zr(IV) concentration (= 0.1 mM), and ionic strength (= 0.1 M). The results show that aqueous Zr speciation determined by reactions with anions controls the formation and structure of Zr-containing adsorbates on the mica surface. The Zr coverages measured by X-ray fluorescence (XRF) in ClO 4 - and Cl - systems were 1.3 and 2.1 Zr/A UC (where A UC = 46.72 Å 2 is the area of the unit cell of the mica (001) surface), respectively, and mostly remained unchanged during the reaction time from 6 to 50 h. In these conditions, Zr adsorption occurred both as small NPs (with an average height of ~4 nm observed by ex situ atomic force microscopy, AFM) and in a ~2 nm-thick molecular layer (observed by in situ resonant anomalous X-ray reflectivity, RAXR). In comparison, higher Zr coverages that increased with reaction time (i.e., from ~4 to ~7 Zr/A UC from 6 to 50 h reactions) were observed in the SO 4 2- system. Ex situ AFM showed that the Zr uptake in this system occurred predominantly as NPs that were ~5 to 15 nm tall and 20 to 40 nm wide, but no evidence of the interfacial molecular-layer formation was observed by RAXR. In the HPO 4 2– solution, all measurements unequivocally showed no significant Zr sorption, in stark contrast to the observations in the other solutions. Details of the Zr surface coverage and sorption modes are consistent with the known clustering of tetravalent Zr in solutions in the presence of these anions. These results reveal the critical impact of anions on the adsorption affinity and mechanism of Zr on the negatively charged mica surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗