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At least 307 records · Page 17

Reduced Complexity Model Intercomparison Project Phase 2: Synthesizing Earth System Knowledge for Probabilistic Climate Projections

Over the last decades, climate science has evolved rapidly across multiple expert domains. Our best tools to capture state-of-the-art knowledge in an internally self-consistent modelling framework are the increasingly complex fully coupled Earth System Models (ESMs). However, computational limitations and the structural rigidity of ESMs mean that the full range of uncertainties across multiple domains are difficult to capture with ESMs alone. The tools of choice are instead more computationally efficient reduced complexity models (RCMs), which are structurally flexible and can span the response dynamics across a range of domain-specific models and ESM experiments. Here we present Phase 2 of the Reduced Complexity Model Intercomparison Project (RCMIP Phase 2), the first comprehensive intercomparison of RCMs that are probabilistically calibrated with key benchmark ranges from specialized research communities. Unsurprisingly, but crucially, we find that models which have been constrained to reflect the key benchmarks better reflect the key benchmarks. Under the low-emissions SSP1-1.9 scenario, across the RCMs, median peak warming projections range from 1.3 to 1.7°C (relative to 1850-1900, using an observationally-based historical warming estimate of 0.8°C between 1850-1900 and 1995-2014). Further developing methodologies to constrain these projection uncertainties seems paramount given the international community's goal to contain warming to below 1.5°C above pre-industrial in the long-term. Our findings suggest that users of RCMs should carefully evaluate their RCM, specifically its skill against key benchmarks and consider the need to include projections benchmarks either from ESM results or other assessments to reduce divergence in future projections.

Climate↗

A Data-Driven Reduced Order Model of an Isolated Rotor

There are numerous conceptual design stage rotorcraft analysis tasks which demand a high-fidelity and low cost method for rotor load distribution predictions. Considering Urban Air Mobility (UAM) vehicles aim to operate in close proximity to buildings and with unique rotor configurations, there is a significant challenge in quickly and accurately modeling rotors operating in complex, turbulent flow fields. One potential path for deriving a high-fidelity, low cost rotor model is with data-driven surrogate modeling. In this study, an initial investigation is taken to apply a proper orthogonal decomposition (POD) based reduced order model (ROM) for the purpose of pressure distribution prediction. In this study, a POD ROM was derived to produce distributed pressure predictions on rotor blades subjected to topology change due to variation in twist and taper ratio. Rotor twist was varied between 0◦, 10◦, 20◦, and 30◦ while taper ratio was varied between 1.0, 0.9, 0.8, and 0.7. All rotors consisted of a single blade. The POD ROM was validated for three demonstration cases; a high thrust rotor in hover, a low thrust rotor in hover, and a rotor in forward flight with a flight speed of M = 0.1. Results showed highly accurate distributed load predictions could be achieved at minimal computational cost. Computational cost for hovering blade surface pressure modeling was reduced from 12 hours on 440 cores to 10−5 seconds on a single core. For blade in forward flight cost was reduced from 20 hours on 440 cores to 0.6 seconds on a single core. For cases of high thrust and low thrust rotors, POD ROM was used to undergo a design optimization of the rotor such that figure of merit was maximized. Total optimization time for each case was 1 minute.

Data-Driven↗

A REDUCED ORDER MODELING APPROACH TO PROBABILISTIC CREEP-DAMAGE PREDICTIONS IN FINITE ELEMENT ANALYSIS

This paper introduces a computationally efficient Reduced Order Modeling (ROM) approach for the probabilistic prediction of creep-damage failure. Component-level probabilistic simulations are needed to assess the reliability and safety of high-temperature components. Full-scale probabilistic creep-damage modeling in finite element (FE) approach is computationally expensive requiring many hundreds of simulations to replicate the uncertainty of component failure. To that end, ROM is proposed to minimize the elevated computational cost while controlling the loss of accuracy. It is proposed that full-scale probabilistic simulations can be completed in 1D at a reduced cost, the extremum conditions extracted, and those conditions applied for lower-cost 2D/3D probabilistic simulations of components that capture the mean and uncertainty of failure. The probabilistic Sine-hyperbolic (Sinh) model is selected which in previous work was calibrated to alloy 304 stainless steel. The Sinh model includes probability density functions (pdfs) for test condition (stress and temperature), initial damage (i.e. microstructure), and material properties uncertainty. The Sinh model is programmed into ANSYS finite element software using the USERCREEP.F material subroutine. First, the Sinh model and FE code are subject to verification and validation to ensure the accuracy of the simulations. Numerous Monte Carlo simulations are executed in a 1D model to generate probabilistic creep deformation, damage, and rupture data. This data is analyzed and the probabilistic parameters corresponding to extreme creep response are extracted. The ROM concept is applied where only the extreme conditions are applied in the 2D probabilistic prediction of a component. The probabilistic predictions between the 1D and 2D geometry is compared to assess ROM for creep. The accuracy of the probabilistic prediction employing the ROM approach will potentially reduce the time and cost of simulating complex engineering systems. Future studies will introduce multi-stage Sinh, stochasticity, and spatial uncertainty for improved prediction.

36 MATERIALS SCIENCE↗

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↗

Highly Efficient Layer-by-Layer Processed Quaternary Organic Solar Cells with Improved Charge Transport and Reduced Energy Loss

We report how to improve charge transport properties and reduce energy losses are the two main challenges of organic solar cells (OSCs). Herein, a new device fabrication strategy that combines the layer-by-layer (LBL) method and a quaternary active layer is demonstrated to realize highly efficient photovoltaic performance of the OSCs based on PM6:PM7/Y6:O1-2F. The introduction of the second donor, PM7,forms a cascade energy-level alignment with PM6 that facilitates effective charge transfer. The second acceptor, O1-2F, which is poorly miscible with the donors, helps to reduce the miscibility between the donors and acceptors, and thus delivers a more desirable vertical phase separation of the active layer. Furthermore, the alloy acceptor of O1-2F and Y6 can optimize the horizontal and vertical morphology of the active layer, forming an effective charge separation and continuous charge transport channel. As a result, the PM6:PM7/Y6:O1-2F system shows a distinct increase in charge mobility and a reduced nonradiative lossΔVnrof 0.231 V compared to the PM6/Y6 system, achieving a high-power conversion efficiency of18.23%. The results indicate that the quaternary LBL OSCs are promising for future large-scale and industrial manufacture of the OSCs.

14 SOLAR ENERGY↗

Reduced-order modeling of near-field THMC coupled processes for nuclear waste repositories in shale

Performance assessment (PA) of geologic radioactive waste repositories requires three-dimensional simulation of highly nonlinear, thermo-hydro-mechanical-chemical (THMC), multiphase flow and transport processes across many kilometers and over tens to hundreds of thousands of years. Integrating the effects of a near-field geomechanical process (i.e. buffer swelling) into coupled THC simulations through reduced-order modeling, rather than through fully coupled geomechanics, can reduce the dimensionality of the problem and improve computational efficiency. In this study, PFLOTRAN simulations model a single waste package in a shale host rock repository, where re-saturation of a bentonite buffer causes the buffer to swell and exert stress on a highly fractured disturbed rock zone (DRZ). Three types of stress-dependent permeability functions (exponential, modified cubic, and Two-part Hooke’s law models) are implemented to describe mechanical characteristics of the system. Overall, our modeling study suggests that compressing fractures reduces DRZ permeability, which could influence the rate of radionuclide transport and exchange with corrosive species in host rock groundwater that could accelerate waste package degradation. Less permeable shale host rock delays buffer swelling, consequently retarding DRZ permeability reduction as well as chemical transport within the barrier system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Reducing the complexity of finite-temperature auxiliary-field quantum Monte Carlo

The auxiliary-field quantum Monte Carlo (AFMC) method is a powerful and widely used technique for ground-state and finite-temperature simulations of quantum many-body systems. Here we introduce several algorithmic improvements for finite-temperature AFMC calculations of dilute fermionic systems that reduce the computational complexity of most parts of the algorithm. This is principally achieved by reducing the number of single-particle states that contribute at each configuration of the auxiliary fields to a number that is of the order of the number of fermions. Our methods are applicable for both the canonical and grand-canonical ensembles. We demonstrate the reduced computational complexity of the methods for the homogeneous unitary Fermi gas.

67.85.Lm↗

Phosphate-modulated transformation of Sb(V)-bearing ferrihydrite under microbial iron- and sulfate-reducing conditions

Antimony (Sb) is a toxic metalloid that poses environmental risks in terrestrial and aquatic systems. The fate of the Sb(V) oxyanion, Sb(OH) 6 − , is governed by complex biogeochemical processes, including immobilization by ferric (Fe(III)) oxides, reduction by sulfide, and the less-explored competitive adsorption with other anions such as phosphate (PO 4 3− ). Here, this study investigates the interplay between such mechanisms in controlling the behavior of Sb(V) associated with ferrihydrite (Fh) under Fe(III)- and sulfate-reducing conditions, with a particular emphasis on the role of phosphate in influencing Sb(V) mobility and transformation. Anoxic reactors that contained Sb(V)-coprecipitated Fh, varying PO 4 3− concentrations (0, 0.2, and 2 mM), and sulfate, were inoculated with a microbial community sourced from Sb-contaminated soil. Additionally, abiotic reactors with either Sb(V)-adsorbed or Sb(V)-coprecipitated Fh and different PO 4 3− loadings (0–100 mM) were created to investigate the competitive adsorption mechanisms in the absence of microbial activity. Results from the abiotic reactors suggest that Sb(V) is likely incorporated into the Fh structure, with only minor amounts remaining surface-bound and extractable by PO 4 3− . In the biotic reactors, microbial Fe(III) and sulfate reduction were more extensive in the presence of PO 4 3− . At 0.2 mM PO 4 3− , microbial activity transformed Fh into siderite and led to the complete reduction of Sb(V) to Sb(III) as stibnite (Sb 2 S 3 ). At 2 mM PO 4 3− , the greater coverage by PO 4 3− stabilized Fh and decreased the extent of both Fe(III) and Sb(V) reduction, and shifted the reduced products to mackinawite and Sb(III) adsorbed onto Fh, in addition to stibnite formation. This study demonstrates that while PO 4 3− may not directly compete with Sb(V) for sorption sites, it can influence Sb mobility in Fe(III)- and sulfate-reducing environments by enhancing microbial activity and altering the mineralization pathways.

Microbial Fe(III) and sulfate reduction↗

Weight function procedure for reduced order fracture analysis of arbitrary flaws in cylindrical pressure vessels

Fracture mechanics calculations using the finite element method can be computationally expensive, which makes them challenging to use in engineering evaluations of flaws in pressure vessels. The weight function (WF) technique is a reduced order fracture modeling method that is widely used to greatly reduce these computational costs. Its computational efficiency is essential for use in probabilistic fracture mechanics evaluations of embrittled nuclear reactor pressure vessels (RPVs), due to the large number of sampled flaws that must be evaluated. Although the WF technique is general, it is typically used only for axis-aligned flaws. Recent discoveries of off-axis flaws in operating nuclear reactors have necessitated detailed simulations of such flaws and the interactions between neighboring flaws. This paper presents a generalized WF approach applicable for analyzing arbitrary flaw geometries in thick-walled cylindrical vessels, including surface-breaking and subsurface flaws, which can either axis-aligned or off-axis, and can account for interactions with other flaws. Herein, this approach is demonstrated on representative simulations of multiple flaw geometries in a RPV subjected to transient loading conditions. In all cases, the WF technique gives good comparison with benchmark results from direct simulation with greatly reduced computational effort.

42 ENGINEERING↗

Effects of transient thermal shock on the microstructures and corrosion properties of a reduced activation high-entropy alloy

The devices would subject transient thermal shocks (TTS) during operation under extremely harsh conditions of nuclear fusion reactors, which inevitably exert significant impact on the microstructure and performance of structural materials. Here, a reduced activation VCrFeTa 0.2 W 0.2 high-entropy alloy (HEA) was developed by vacuum arc melting. The effects of electron beam induced TTS on its microstructure, microhardness, and corrosion properties were investigated. The results indicate that the weight fraction of each phase changes after TTS, showing a significant decrease in the content of BCC1 phase and an increase in the content of BCC2 and Laves phases. The content of BCC1 phase continues to decrease slightly with increasing the power of TTS. Besides, the microhardness of the alloy increases from ~673 HV to ~714 HV after TTS treatments. In the reduced activation HEA, TTS results in a relatively low corrosion current density of ~0.472 μA/cm 2 in 3.5 wt% NaCl solution, around one-third of the current density observed in the as-cast sample. Furthermore, the VCrFeTa 0.2 W 0.2 HEA after TTS exhibits a pitting potential of ~1.165 V SCE , which is much higher than that of the as-cast sample. The refined composite multiscale entropy method is employed to analyze the influence of TTS on current fluctuation behavior during the corrosion process. The reduced activation VCrFeTa 0.2 W 0.2 HEA exhibits excellent properties in harsh environments after TTS, thereby showing advantageous property in the field of nuclear structural materials. Furthermore, TTS is an efficient and controllable strategy for the improvement of the HEAs’ microstructures and performances.

36 MATERIALS SCIENCE↗

Optimizing $\mathrm{ACRT}$ to reduce inclusion formation during the $\mathrm{VGF}$ growth of cadmium zinc telluride: II. Application to experiments

Here two different accelerated crucible rotation technique (ACRT) rotation schedules are assessed, via theoretical computations and growth experiments, according to their ability to reduce tellurium-rich inclusions during the vertical gradient freeze (VGF) of cadmium zinc telluride (CZT). A vigorous rotation schedule based on classical ACRT guidelines produces a well-mixed melt that is expected to reduce tellurium inclusions compared to growth without crucible rotation. In contrast, a new ACRT schedule, derived from model-based optimization for interface stability, employs slower rotation with longer periods and is predicted to further reduce inclusions. Growth experiments corroborate these expectations. Namely, both ACRT schedules result in crystals with inclusion size and volume significantly decreased from levels found in material grown with no rotation, and material grown using the computationally optimized ACRT parameters exhibits a median inclusion size that is smaller and with a sharper distribution than in material grown via classical ACRT.

36 MATERIALS SCIENCE↗

SWAT model application for evaluating agricultural conservation practice effectiveness in reducing phosphorous loss from the Western Lake Erie Basin

Lake Erie is threatened by eutrophication and harmful algal blooms due to excess nutrient loading from agricultural sources. Agricultural conservation practices (ACPs) have been developed and implemented to reduce nutrient losses but estimating ACP effectiveness is challenging. The Soil and Water Assessment Tool (SWAT) has been used to investigate ACP effectiveness for water quality improvement. Many SWAT applications have been developed by different investigators to evaluate ACP effectiveness for reducing nutrient, particularly phosphorus (P), loading in the agriculturally-dominated Western Lake Erie Basin (WLEB). Our objective is to establish what has been achieved by past modeling research and make suggestions for future applications and improvements. We synthesized the findings of 28 SWAT modeling studies within the WLEB. Models generally performed satisfactorily against accepted criteria for streamflow and sediment, but performance for P loads, like soluble reactive P, was mostly “unsatisfactory”. The “unsatisfactory” performance maybe due to imperfections and idealizations in model formulations and/or parameterization. Thus, simulations of P transport and transformation processes need improvement. In addition, model parameter selection is the key part of model set-up. Most SWAT modeling studies used default values during initial set-up, then performed calibration and validation. It was found that the calibrated P related parameter values varied widely across different studies, even within the same watershed with some values unrealistic for the study areas. The phenomena of different combinations of model parameters producing similar outputs indicates equifinality. Equifinality in the baseline model may impact results when ACPs are incorporated. Furthermore, the unrealistic values used in ACP assessment undermine the credibility of ACP effectiveness. Future model applications should try to re-examine the calibrated P parameters and make sure they are realistic for the study area as well as reduce equifinality by constraining the model with characterization of watershed conditions, better understanding of hydrologic processes, and parameter values based on real-world observations. As a result, future model applications should focus on improving P transport and transformation processes, using measured watershed characteristics for parameterization, and improving reflections of climate change, which could result in more accurate assessments of ACP effectiveness to meet targeted goals.

54 ENVIRONMENTAL SCIENCES↗

The effectiveness of D 2 pellet and gas injection in reducing intra-ELM tungsten erosion and heat flux in the DIII-D small angle slot divertor

Edge localized modes (ELMs) in H-mode plasmas can melt and erode plasma-facing components (PFCs) and lead to impurities in the core, reducing confinement. This study analyzes the use of D 2 pellet and gas injection for ELM mitigation on the DIII-D tokamak during the 2022 Small Angle Slot V-shaped Tungsten (W) (SAS-VW) divertor campaign, reducing W erosion and heat flux during ELMs. D α (656 nm) and WI (400.9 nm) filterscopes and Langmuir probes provide photon emission and electron density/temperature to estimate W atom erosion using the S/XB method, while surface eroding thermocouples measured ELM peak heat flux at the outer strike point (OSP). Thomson Scattering measurements of pedestal T e and n e provided input to predict W divertor erosion and heat flux during ELMs via the Free-Streaming plus Recycling Model (FSRM). While a greater D 2 mass injection rate decreased the ELM peak heat flux, the impact on W erosion was not monotonic. The average ‘large’ intra-ELM W erosion was lower for plasma shots with D 2 mass injection compared to the plasma shots without any D 2 mass injection in the SAS-VW divertor. However, plasma shots did not see significant changes in ‘large’ intra-ELM W divertor erosion as the D 2 mass injection rate increased. On average, the FSRM overestimated SAS-VW experimental intra-ELM W erosion by a factor of 6.9, but the overestimation is reduced to a factor of 3.6 with the implication of C deposition effects. Generally, experimentally measured and predicted quantities were worse for plasma shots with a lower D 2 mass injection rate and corresponding higher plasma carbon (C) impurity percentage (f C ). The discrepancies are postulated to be due to C/W material mixing, for which a simple analytic mixed-material model is presented. These results highlight the importance of incorporating and improving the robustness of a mixed-material layer model in the analysis of PFC erosion on present and future tokamak devices.

Carbon (C)↗

Toward reducing uncertainty quantification costs in DEM models of particulate flow: Testing simple, sensitivity-based, forward uncertainty propagation techniques

The performance of two conceptually-simple uncertainty quantification techniques are tested against the rigorous nested-loop sampling technique of Roy and Oberkampf (Comput Methods Appl Mech Eng, 200: 2131–2144, 2011) (herein called full-sampling) using two very small-scale DEM-based models of particulate flow (one gas-solid flow and one granular flow). The first simplified forward uncertainty propagation technique, reduced-sampling, uses a sensitivity analysis to eliminate uncertain inputs that have little impact on the model output prior to nested-loop sampling. The second technique, boundary-sampling, uses a sensitivity analysis to inform the selection of two bounding cases for each key model output. In conclusion, the uncertainties in the model outputs obtained via the reduced- and boundary-sampling methods agree well with those from full-sampling for both the gas-solid and granular flow models while yielding computational savings of 65–75% (reduced sampling) and 94–97% (boundary sampling).

42 ENGINEERING↗

Oxidation of biogenic U(IV) mediated by iron-bearing clay minerals, iron-reducing bacteria, and organic ligands

Bioreduction of hexavalent uranium (U(VI)) to tetravalent uranium (U(IV)) by dissimilatory metal-reducing bacteria (DMRB) is considered an effective strategy for uranium immobilization in contaminated environments. However, U(IV) can be reoxidized to U(VI) under fluctuating redox conditions and remobilized. This work investigates the oxidation behavior of biogenic U(IV) in the presence of bioreduced iron-bearing clay minerals (rNAu-2), iron-reducing bacteria (Shewanella putrefaciens CN32), and organic ligands (ethylenediaminetetraacetic acid (EDTA) and citrate). Results demonstrate that the presence of CN32 significantly inhibits U(IV) oxidation. rNAu-2 exerted a context-dependent influence on U(IV) oxidation: its effect was masked by bicarbonate-promoted U(VI) mobilization in the absence of active CN32, but became detectable when CN32-mediated microbial protection slowed U(IV) oxidation. EDTA and citrate markedly accelerate U(IV) oxidation via formation of soluble U(IV)-ligand complexes, changing U(IV) redox potentials, and by promoting clay mineral dissolution that enhances Fe(II)/Fe(III) redox cycling. Collectively, our findings constrain the roles that clay minerals, iron-reducing bacteria, and organic ligands play in governing U(IV) stability, emphasizing the need to account for these factors in developing robust bioremediation strategies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Dexamethasone reduces the formation of thoracic aortic aneurysm and dissection in a murine model

Highlights: • Dexamethasone attenuated thoracic aortic aneurysm and dissection in a mouse model. • Dexamethasone reduced infiltration of inflammatory cell and apoptosis of vascular smooth muscle cell and fibroblast. • Dexamethasone partly alleviated degradation of collagen and phenotype switch. • DEX might ameliorate thoracic aortic aneurysm and dissection by suppressing NF-κB signaling pathway. Thoracic aortic aneurysm and dissection (TAAD) is a life-threatening vascular disease with no effective pharmaceutical therapies currently available. Inflammation plays a key role in the progression of aneurysms. Dexamethasone (DEX), a synthetic glucocorticoid, has showed alleviating effects on cells in vitro from TAAD patients. Here we performed a study aiming at investigating the protective role of DEX in a β-aminopropionitrile monofumarate (BAPN)-induced TAAD mouse model. DEX (dose: 0.04 mg/kg/day) treatment significantly reduced the aortic diameter and inhibited TAAD formation. DEX reduced infiltration of macrophages and neutrophils, apoptosis of vascular smooth muscle cells (VSMCs), expression of metalloproteinase 2/9, and extracellular matrix degradation in BAPN-treated TAAD mice. Furthermore, DEX therapy downregulated the expression of p-p65 in macrophages and VSMCs, which suggested that DEX might ameliorate BAPN-induced TAAD by suppressing NF-κB signaling. Therefore, DEX therapy attenuates the progression of BAPN-induced TAAD murine model and could be used as an effective adjuvant therapy for treating TAAD.

60 APPLIED LIFE SCIENCES↗

Co-Hydrotreatment of Yellow Greases and the Water-Insoluble Fraction of Pyrolysis Oil. Part I: Experimental Design to Increase Kerosene Yield and Reduce Coke Formation

Here, this paper reports the co-hydrotreatment of Biomass Technology Group commercial pyrolysis oil water-insoluble (WIS) phase (also known as pyrolytic lignin) and yellow greases (waste cooking oil), aiming to produce sustainable aviation fuels (SAFs). We use a sulfided NiMo/Al 2 O 3 blend with 16 wt % WIS and a central composite experimental design to identify processing conditions increasing kerosene yield and reducing coke formation. The input variables were: (1) reaction temperature (320, 350, and 380 °C), (2) initial hydrogen pressure (5, 6, and 7 MPa), and (3) amount of catalyst (0.7, 1.0, and 1.3 g). The hydrotreated oily phases were distilled to obtain gasoline (<150 °C), kerosene (150–250 °C), diesel (250–350 °C), and residual oil (>350 °C). The reaction temperature is the main factor affecting the yield of gaseous, solid, and liquid products. Meanwhile, a higher initial hydrogen pressure and catalyst loading increased the yield of kerosene and other distillates and decreased the coke formation. A high temperature correlated with a lower content of oxygenates in kerosene cuts. Based on our experimental results, we propose to conduct hydrotreatment studies at 380 °C, initial H 2 pressure of 7 MPa, and 1.3 g of catalyst. Under the identified conditions, it was possible to improve the kerosene yield to more than 20 wt % and reduce the yield of coke to close to 2.0 wt %. The chemical composition and fuel properties of the gasoline, kerosene, and diesel cuts were thoroughly analyzed. The content of aromatics and phenols in the kerosene fraction produced at the conditions identified in this project exceeded the recommended values for SAFs. New strategies (such as blending and more intense hydrotreatment to remove oxygenated compounds) need to be implemented to reduce the content of these molecules in our final product.

09 BIOMASS FUELS↗

Inhibition of Extracellular Enzyme Activity by Reactive Oxygen Species upon Oxygenation of Reduced Iron-Bearing Minerals

The dual roles of minerals in inhibiting and prolonging extracellular enzyme activity in soils and sediments are governed by enzyme adsorption to mineral surface. Oxigenation of mineral-bound Fe(II) generates reactive oxygen species (ROS), yet it is unknown whether and how this process alters the activity and functional lifespan of extracellular enzymes. Here, the effect of mineral-bound Fe(II) oxidation on the hydrolytic activity of a cellulose-degrading enzyme ß-glucosidase (BG) was studied using two pre-reduced Fe-bearing clay minerals (nontronite and montmorillonite) and one pre-reduced iron oxide (magnetite) at pH 5 and 7. Under anoxic condition, BG adsorption to mineral surface decreased its activity but prolonged its lifespan. Under oxic condition, ROS was produced, with the amount of •OH, the most abundant ROS, being positively correlated with the extent of structural Fe(II) oxidation in reduced minerals. •OH decreased BG activity and shortened its lifespan via conformational change and structural decomposition of BG. These results suggest that under oxic condition the ROS-induced inhibitory role of Fe(II)-bearing minerals outweighed their adsorption-induced protective role in controlling enzyme activity. These results disclose a previously unknown mechanism of extracellular enzyme inactivation, which have pivotal implications for predicting the active enzyme pool in redox-oscillating environments.

58 GEOSCIENCES↗