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At least 163 records · Page 9

High-Voltage Isolation Transformer

Arcing and field-included surface erosion reduced by electrostatic shields around windings and ferromagnetic core of 80-kilovolt isolation transformer. Fabricated from high-resistivity polyurethane-based material brushed on critical surfaces, shields maintained at approximately half potential difference of windings.

Clatterbuck, C. H.↗

NASA Lunar Surface Innovation Initiative: Ensuring a Cohesive, Executable Strategy for Technology Development

Establishing a sustainable human presence on the Moon allows NASA to develop and test new approaches, technologies, and systems that will enable us to function in other, more challenging environments. The Lunar Surface Innovation Initiative (LSII) was established in 2019 and has evolved into a key agency asset to spur technology development and provide risk reduction for lunar surface system development and flight demonstrations. LSII coordinates activities implemented through a combination of in-house activities, competitive programs, and public-private partnerships to create transformative technologies needed for lunar surface exploration. This paper will outline the LSII model used to develop a technology pipeline that will retire the primary technology hurdles in six capability areas. In-situ resource utilization technologies for collecting, processing, storing, and using material found or manufactured on the Moon. Surface power technologies that provide the capability for sustainable, continuous power throughout the day and night for lunar missions. Dust mitigation strategies that diminish lunar dust hazards on lunar surface systems such as cameras, solar panels, space suits, habitats, and instrumentation. Extreme environments technologies that enable systems to operate throughout the full range of lunar surface conditions, including lunar noon (up to 150 at the equator), night (down to - 180 at the equator), multiple day/night cycles, and in permanently shadowed regions (down to -250). Extreme access technologies that enable humans or robotic systems to access, navigate, and explore previously inaccessible lunar surface or subsurface areas. Excavation and construction technologies that will allow affordable, autonomous manufacturing or construction. We outline key results, including milestones and achievements related to the capability areas and outcomes from partnerships with the commercial sector. A key tenet of the LSII is the Lunar Surface Innovation Consortium (LSIC), a collaboration across industry, academia, and government to successfully develop the transformative capabilities for lunar surface exploration. LSIC provides a forum for NASA to communicate technological requirements, needs, and opportunities and for the community to share existing capabilities and identify critical gaps with NASA. By working side by side with commercial enterprises and our international partners, NASA is able to combine the knowledge and expertise needed to explore the lunar surface and make technical advances that will feed technological and economic growth. Since its inception, LSII has engaged over 600 organizations across the United States and 46 countries to shape the technologies and systems needed to explore the lunar surface and stimulate a lunar surface economy.

lunar, lunar surface, technology development, ISRU↗

NASA Lunar Surface Innovation Initiative: Ensuring a Cohesive, Executable Strategy for Technology

Establishing a sustainable human presence on the Moon allows NASA to develop and test new approaches, technologies, and systems that will enable us to function in other, more challenging environments. The Lunar Surface Innovation Initiative (LSII) was established in 2019 and has evolved into a key agency asset to spur technology development and provide risk reduction for lunar surface system development and flight demonstrations. LSII coordinates activities implemented through a combination of in-house activities, competitive programs, and public-private partnerships to create transformative technologies needed for lunar surface exploration. This paper will outline the LSII model used to develop a technology pipeline that will retire the primary technology hurdles in six capability areas. In-situ resource utilization technologies for collecting, processing, storing, and using material found or manufactured on the Moon. Surface power technologies that provide the capability for sustainable, continuous power throughout the day and night for lunar missions. Dust mitigation strategies that diminish lunar dust hazards on lunar surface systems such as cameras, solar panels, space suits, habitats, and instrumentation. Extreme environments technologies that enable systems to operate throughout the full range of lunar surface conditions, including lunar noon (up to 150 at the equator), night (down to - 180 at the equator), multiple day/night cycles, and in permanently shadowed regions (down to -250). Extreme access technologies that enable humans or robotic systems to access, navigate, and explore previously inaccessible lunar surface or subsurface areas. Excavation and construction technologies that will allow affordable, autonomous manufacturing or construction. We outline key results, including milestones and achievements related to the capability areas and outcomes from partnerships with the commercial sector. A key tenet of the LSII is the Lunar Surface Innovation Consortium (LSIC), a collaboration across industry, academia, and government to successfully develop the transformative capabilities for lunar surface exploration. LSIC provides a forum for NASA to communicate technological requirements, needs, and opportunities and for the community to share existing capabilities and identify critical gaps with NASA. By working side by side with commercial enterprises and our international partners, NASA is able to combine the knowledge and expertise needed to explore the lunar surface and make technical advances that will feed technological and economic growth. Since its inception, LSII has engaged over 600 organizations across the United States and 46 countries to shape the technologies and systems needed to explore the lunar surface and stimulate a lunar surface economy.

Lunar↗

Characterization of the surfaces of platinum/tin oxide based catalysts by Fourier transform spectroscopy (FTIR)

The Laser Atmospheric Wind Sounder (LAWS) Program has as one of its goals the development of a satellite based carbon dioxide laser for making wind velocity measurements. The specifications for this laser include the requirement that the laser operate at a repetition rate of 10 Hertz continuously for three years. Earth-based carbon dioxide lasers can operate for only a short time on a single charge of gas because the lasing action causes the CO2 to break down into CO and O2. Therefore, earth-based CO2 lasers are generally operated in a flow through mode in which the spent gas is continually exhausted and fresh gas is continually added. For a satellite based system, however, a recirculation system is desired because it is not practical to send up extra tanks of CO2. A catalyst which could enable a recirculating CO2 laser to function continuously for three years needs to be developed. In the development of a catalyst system there are many variables. Obviously, not all possible formulations can be tested for three years, therefore, an accurate model which is based on the reaction mechanism is needed. The construction of a multistep reaction mechanism is similar to the construction of a jigsaw puzzle. Different techniques each supply a piece of the puzzle and the researcher must put the pieces together. Transmission infrared spectroscopy was shown to be very useful in supplying some of the information needed to elucidate reaction mechanisms. The purpose was to see what kind of information might be obtained about the NASA catalyst using infrared absorption spectroscopy. Approximately 200 infrared spectra of the prototype Pt/tin oxide catalyst and its precursor components are observed under a variety of different conditions. The most significant observations are summarized.

Keiser, Joseph T.↗

Assimilation of Satellite Sea Surface Temperature and Salinity Using the Local Ensemble Transform Kalman Filter Applied to the NASA GEOS Earth System Model

The NASA GEOS-S2S-2 system (Molod et al., 2020) uses the SST relaxation with the Level-4 SST products while the latest GEOS GEOS-S2S-3 system directly assimilates the Level-4 SST in the data assimilation step, yet no study has been conducted to understand the impact of this switch on the GEOS coupled analysis and short-range forecast. In addition, the GEOS-S2S-2/3 systems use the ocean model MOM5. Recently, the ocean model MOM6 is added to the GEOS ESM. This poster presents results of the first coupling of the ensemble data assimilation system to the GEOS MOM6.

Cheng Da↗

Morphological Degradation of Oxygen Evolution Reaction-Electrocatalyzing Nickel Selenides at Industrially Relevant Current Densities

We investigated electrodeposited nanoparticulate nickel selenide (pre)catalysts that transform into nickel oxides/ oxyhydroxides under oxygen evolution reaction conditions in alkaline solutions. Previous studies of this transformation were conducted at lower current densities than those of industrial relevance (≥1 A cm −2 ). We used ultramicroelectrodes (UMEs) to achieve such current densities, benefiting from their small size, ensuring low absolute currents and low ohmic drop but high current densities. Morphological degradation of the catalyst material was only observed at current densities exceeding 1 A cm −2 but not for smaller ones. Using X-ray absorption, Xray photoemission spectroscopy, and X-ray diffraction, we confirmed that the degradation was accompanied by the literature-known transformation of nanoparticulate Ni 3 Se 2 (bulk)/NiSe (surface) into nickel oxyhydroxide. The transformation of the precatalyst goes along with a significant improvement in the charge transfer kinetics observed by decreasing Tafel slopes with ongoing experimental time extracted from cyclic voltammetry (CV) experiments and electrochemical impedance spectroscopy (EIS) in the high-frequency range. However, these kinetic improvements are accompanied by limitations in mass transport concluded from decreasing current responses at high overpotentials in CVs and increasing impedance in the low-frequency range of the EIS spectra after extended CV cycling. These mass transport limitations originated from morphological degradations at the UME exceeding 1 A cm −2 which we proved by applying identical location scanning electron microscopy. This has not been reported in studies that have been limited to lower current densities before. Our findings showcase how UMEs can be used to study (pre)catalysts (herein nickel selenides) under current densities of industrial relevance in the absence of ohmic drop-related ambiguities, combined with in-depth materials characterization studies, e.g., identical location microscopy and advanced spectroscopic methods. This approach enables direct evaluation and comparison of catalyst materials and thus demonstrates how to overcome long-standing limitations of electrocatalyst design and testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The 3-D unstructured mesh generation using local transformations

The topics are presented in viewgraph form and include the following: 3D combinatorial edge swapping; 3D incremental triangulation via local transformations; a new approach to multigrid for unstructured meshes; surface mesh generation using local transforms; volume triangulations; viscous mesh generation; and future directions.

Timothy J Barth↗

Strain-driven surface reconstruction and cation segregation in layered Li(Ni 1– x – y Mn x Co y )O 2 (NMC) cathode materials

The composition, structure and phase transformations occurring on cathode surfaces greatly affect the performance of Li-ion batteries. Li-Ion diffusion and surface–electrolyte interaction are two major phenomena that impact the capacity and cell impedance. The effects of surface reconstruction (SR) of cathode materials on the performance of Li-ion batteries are of current interest. However, the origin and evolution of the SR are still not well understood. In this work, density functional theory (DFT) calculations are used to investigate the processes taking place during surface segregation and reconstruction. Facet dependent segregation was found in Li(Ni 1– x – y Mn x Co y )O 2 (NMC) cathodes. Specifically, Co tends to segregate to the (104) surface of the primary particles within the transition metal layer, while Ni ions tend to segregate to the (012) surface in the Li layer, forming a SR. Experimental evidence shows the SR to be epitaxial with the bulk of the as-synthesized material, and the new SR phase is pinned to the NMC unit cell leading to a strained SR. Here, we demonstrate that strain can stabilize a spinel structure of the SR layers. Understanding the effects of surface strain opens a new avenue for the design of cathode materials with enhanced surface properties.

25 ENERGY STORAGE↗

Investigation of N 2 /O 2 plasma interaction with Pt-catalyst: effect of metastable adsorbates on product hysteresis

The coupling of catalysts and atmospheric-pressure plasma has the potential to improve the efficiency of certain catalytic reactions. Understanding the changes that the catalyst surface undergoes during exposure to plasma is key to improving plasma–catalytic performance. In this work, long term exposure of Pt–Al 2 O 3 powder catalyst to an Ar/N 2 /O 2 non-equilibrium atmospheric-pressure plasma-jet was investigated. Products produced by the interaction were analyzed downstream with Fourier-transform infrared spectroscopy while surface species were analyzed operandi with diffuse reflectance infrared Fourier transform spectroscopy. During exposure, the catalyst temperature was ramped cyclically between 100 °C and 350 °C to understand how substrate temperature affects the plasma–catalyst interaction. Long-lasting changes were revealed to take place on the catalyst surface during plasma exposure. At low temperatures, Pt–O and Pt–NO accumulate on the surface which react at elevated temperatures to form NO 2 . NO 2 initially appears to spill on to the Al 2 O 3 support as nitrites and nitrates instead of desorbing. Stable surface conditions are only achieved after prolonged plasma exposure, when nitrate sites on the Al 2 O 3 support are filled. By changing the catalyst temperature at various rates, the impact of total plasma species flux to the surface was analyzed. It was found that decreasing the heating rate increased the hysteresis in the pattern of NO 2 formation during thermal cycling. The variation with temperature demonstrates that plasma exposure results in a buildup of surface NO x and oxygen species which react or desorb at high temperatures. The observed changes are discussed from the generic viewpoint that a non-equilibrium plasma interacting with a catalyst at low temperature introduces metastable steady-state surface conditions. Upon heating above a threshold temperature, the introduced surface modifications can change either due to thermal effects, or, for a plasma environment, by additional interaction with the incident plasma species flux. The surface/material changes take place in a highly predictable fashion and after sufficient time above the threshold temperature reach a steady-state condition that is different from the transient behavior that is observed during initial heating. During cooling the plasma-surface interaction exhibits a different behavior than during heating, and this results in hysteresis of diverse observables. The metastability/hysteresis description appears quite generic and analogous to hysteresis behavior seen for different systems. Furthermore, it is expected to be useful for understanding the consequences of plasma–catalyst surface interactions for various systems.

36 MATERIALS SCIENCE↗

Roles of Carburization and Oxidation on Transition-Metal Catalyzed Surface Reactions

Many industrial chemical transformation processes are based on reactions catalyzed by transition metals. In some cases the nano-size particles used as catalysts are synthesized simultaneously or right before the initiation of the main catalytic reaction. Synthesis treatments involve complex processes such as reductions followed by calcinations in oxygenated environments coupled to the presence of gases used for the main reaction. Synthesis details are crucial because they have important consequences on the catalyst shape, size, and chemical composition, and may also affect the structure and composition of the catalyst support. All these effects may alter the main catalyzed reaction in unexpected ways. This work focuses on the synthesis of the overall catalytic system that includes catalyst and support taking place in parallel with the initial stages of the main catalyzed reaction. Two important processes are characterized: carburization and oxidation of the transition metal catalyst during synthesis or initial stages of the main reaction. The objective is to understand how the coking mechanism coupled to surface oxidation and changes in the substrate influence the dry reforming of methane taken as a model reaction. The approach uses first principles computational methods to investigate the catalyst synthesis and characterization and catalytic reaction mechanisms. These studies are complemented with experimental characterization done by the group of Dr. Renu Sharma at the National Institute of Standards and Technology (unfunded collaborator) using high resolution transmission electron microscopy. Specific goals are to identify the role of the synthesis process on the initial nanocatalyst structure and composition, and to determine how that structure and composition may evolve after being exposed to the reactants atmosphere. These studies facilitate a systematic analysis of conditions where the nanoparticle composition can be optimized regarding activity and stability. Moreover, the fundamental study of catalyst/support interactions yields valuable insights for other catalytic processes and is a first step toward controlled nanocatalyst synthesis.

36 MATERIALS SCIENCE↗

Development of Aeroservoelastic Analytical Models and Gust Load Alleviation Control Laws of a SensorCraft Wind-Tunnel Model Using Measured Data

Aeroservoelastic (ASE) analytical models of a SensorCraft wind-tunnel model are generated using measured data. The data was acquired during the ASE wind-tunnel test of the HiLDA (High Lift-to-Drag Active) Wing model, tested in the NASA Langley Transonic Dynamics Tunnel (TDT) in late 2004. Two time-domain system identification techniques are applied to the development of the ASE analytical models: impulse response (IR) method and the Generalized Predictive Control (GPC) method. Using measured control surface inputs (frequency sweeps) and associated sensor responses, the IR method is used to extract corresponding input/output impulse response pairs. These impulse responses are then transformed into state-space models for use in ASE analyses. Similarly, the GPC method transforms measured random control surface inputs and associated sensor responses into an AutoRegressive with eXogenous input (ARX) model. The ARX model is then used to develop the gust load alleviation (GLA) control law. For the IR method, comparison of measured with simulated responses are presented to investigate the accuracy of the ASE analytical models developed. For the GPC method, comparison of simulated open-loop and closed-loop (GLA) time histories are presented.

Silva, Walter A.↗

Development of Aeroservoelastic Analytical Models and Gust Load Alleviation Control Laws of a SensorCraft Wind-Tunnel Model Using Measured Data

Aeroservoelastic (ASE) analytical models of a SensorCraft wind-tunnel model are generated using measured data. The data was acquired during the ASE wind-tunnel test of the HiLDA (High Lift-to-Drag Active) Wing model, tested in the NASA Langley Transonic Dynamics Tunnel (TDT) in late 2004. Two time-domain system identification techniques are applied to the development of the ASE analytical models: impulse response (IR) method and the Generalized Predictive Control (GPC) method. Using measured control surface inputs (frequency sweeps) and associated sensor responses, the IR method is used to extract corresponding input/output impulse response pairs. These impulse responses are then transformed into state-space models for use in ASE analyses. Similarly, the GPC method transforms measured random control surface inputs and associated sensor responses into an AutoRegressive with eXogenous input (ARX) model. The ARX model is then used to develop the gust load alleviation (GLA) control law. For the IR method, comparison of measured with simulated responses are presented to investigate the accuracy of the ASE analytical models developed. For the GPC method, comparison of simulated open-loop and closed-loop (GLA) time histories are presented.

Walter A. Silva↗

Dataset from: "Adjoint methods for quasisymmetry of vacuum fields on a surface"

Adjoint methods can speed up stellarator optimisation by providing gradient information more efficiently compared to finite-difference evaluations. Adjoint methods are herein applied to vacuum magnetic fields, with objective functions targeting quasisymmetry and a rotational transform value on a surface. To measure quasisymmetry, a novel way of evaluating approximate flux coordinates on a single flux surface without the assumption of a neighbourhood of flux surfaces is proposed. The shape gradients obtained from the adjoint formalism are evaluated numerically and verified against finite-difference evaluations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Corn stover‐derived porous carbon for asymmetric supercapacitors

In this investigation, hydrothermal liquefaction‐derived hydrochar from pulverized corn stover (avg. particle size 1.12 mm and ash content 6.75 wt%) is chemically activated with aqueous KOH in the presence of Pluronic F127 surfactant and thermally treated further up to 800°C to generate porous carbon (POC) with higher specific surface area and porosity. POC obtained under different processing conditions is thoroughly characterized by Brunauer‐Emmett‐Teller surface area analyzer, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. Metallic impurity present in POC is characterized by inductively coupled plasma mass spectrometry. Higher specific surface area POC is observed with the use of the surfactant during the activation process. Fully characterized POC is used with (Mn, Ti)‐mixed oxide electrode to fabricate asymmetric supercapacitor (ASC). Specific capacitance of ASC is measured by cyclic voltammetry (CV) technique using Gamry G‐300 potentiostat/galvanostat/ZRA. CV plots are obtained with different voltage scan rates whereas galvanostatic charge‐discharge plots are studied by varying the current density. Renewable corn stover‐derived POC prepared using Pluronic F127/KOH activation method is found to be highly suitable as an electrode material because of higher capacitance and electrochemical stability over 100 charging‐discharging cycles.

25 ENERGY STORAGE↗

Adjoint methods for quasi-symmetry of vacuum fields on a surface

Adjoint methods can speed up stellarator optimisation by providing gradient information more efficiently compared with finite-difference evaluations. Adjoint methods are herein applied to vacuum magnetic fields, with objective functions targeting quasi-symmetry and a rotational transform value on a surface. Here to measure quasi-symmetry, a novel way of evaluating approximate flux coordinates on a single flux surface without the assumption of a neighbourhood of flux surfaces is proposed. The shape gradients obtained from the adjoint formalism are evaluated numerically and verified against finite-difference evaluations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Extending a transonic small disturbance code to treat swept vertical surfaces

A flexible-swept vertical surface capability has been developed and implemented within the CAP-TSD transonic small disturbance (TSD) code. The new capability required a modification to the TSD equation and a grid transformation for swept vertical surfaces. Modifications to the vertical surface boundary conditions allow it to be treated as a flexible surface. The new capability extends the range of problems which the code can treat. In order to assess the accuracy of the modifications, calculations were performed for a rectangular T-tail configuration and an AGARD T-tail configuration. Unsteady forces and moments are presented for the rectangular T-tail oscillating in yaw for a range of reduced frequencies. Comparisons are presented with linear theory and experiment. Steady and unsteady surface pressures are presented for the AGARD T-tail along with generalized aerodynamic forces. Comparisons are made with linear theory. The comparisons demonstrate the accuracy of the vertical surface modifications.

Gibbons, Michael D.↗

The evolution and growth of Al2O3 scales on beta-NiAl

The formation and growth of Al2O3 scales on (beta)-NiAl were studied using electron microscopy and other analytical techniques to gain an understanding of the oxidation properties of (beta)-NiAl and of alumina-forming alloys, in general. The transient and mature stages of oxidation were studied as well as the transformation stage during which the oxide scale transforms from metastable Al2O3 phases to the thermodynamically stable alpha-Al2O3 phase. The transient oxidation stages were studied at 800 deg C and for short times at 1100C. At 800C, the scales consist predominantly of delta-Al2O3 which forms by cation vacancy ordering in the defective spinel lattice of gamma-Al2O3. At 1100C, a fast-growth morphology of theta-Al2O3 forms as a surface layer over delta-Al2O3. For both oxidation temperatures, the scales are often epitaxially oriented with respect to the metal. The transient scales grow by outward cation diffusion as evidenced by surface growth morphologies. The transformation to alpha-Al2O3 occurs within 1 hour at 1100C by a nucleation and radial growth process. The large volume decrease associated with the transformation results in a highly strained alpha-Al2O3 microstructure. A change in scale growth mechanism from outward cation to inward anion diffusion allows transient surface morphologies to be smoothed by surface diffusion. The mature stage of oxidation involves the growth of an alpha-Al2O3 scale having the lacey morphology formed as a result of the gamma yields alpha transformation. Growth of the scale occurs by counterdiffusion along grain boundaries resulting in ridges formed by impingement of alpha-Al2O3 nuclei during the transformation stage. Also scale growth occurs by inward oxygen diffusion through healed cracks; the cracks result from transformation stresses. The measured growth rates of scales having the lacey morphology are an order of magnitude less than fine-grained alpha-Al2O3 scales. Metal orientations were found to have a large effect on oxide morpholoies during all stages of oxidation.

Doychak, J. K.↗

Integration of Omics into a New Comprehensive Rate Law for Competitive Terminal Electron-Accepting Processes in Reactive Transport Models: Application to N, Fe, S, and Contaminant Transformations in Stream and Wetland Sediments

Surface waters represent important sources of alternate energy and drinking water in the United States, and characterizing the biogeochemical processes that affect surface water quality is relevant to the DOE-BER mission. Sediment biogeochemical processes regulate the release of carbon (C), nutrients, and contaminants to surface waters and thus influence water quality. Sediment biogeochemical processes are dynamic and affected by the deposition and remobilization of solid material and changes in environmental conditions driven by water discharge variations. Wetlands are important natural filters of surface waters which may either trap, metabolize, or mobilize nutrients and contaminants. Despite their importance, biogeochemical processes regulating nutrient and contaminant release and C transformation in stream and wetland sediments cannot be predicted accurately by current mathematical models. These reactive transport models largely rely on detectable changes in geochemical conditions to activate metabolic processes, do not accurately account for the competition between microbial processes, and poorly constrain effects of hydrological perturbations on biogeochemical processes. In this BER-SBR exploratory project, metagenomic and geochemical signatures were combined to identify microbially-mediated redox processes in anaerobic stream and wetland sediments from the Savannah River Site (SRS, ANL SFA) and East Fork Poplar Creek (EFPC, ORNL SFA) that play important roles in C, uranium (U), and mercury (Hg) transformations. In addition, sediment incubations were conducted to examine the competition between anaerobic respiration processes Finally, new rate laws were developed for reactive transport models that rely on complementary metagenomic and geochemical signatures to identify the underlying anaerobic microbial processes in stream and wetland sediments, describe the competition between the dominant metabolic processes involved in nutrient release and U and Hg mobilization, and more accurately quantify carbon transformation and the response of microbial processes to changes in redox conditions associated with hydrological forcing. These rate laws were optimized in batch reactors with SRS wetland sediments, where iron and sulfate reduction dominate. Anaerobic carbon remineralization processes followed the expected thermodynamic sequence of microbial respiration with depth in both sediments, except that geochemical signals indicated that sulfate reduction was inactive in EFPC sediments and moderate in SRS wetland sediments. Estimates indicated that microbial iron reduction contributed to at least half of the production of reduced iron in these sediments. Incubations demonstrated that nitrate reduction, denitrification, and dissimilatory nitrate reduction to ammonium were active in the natural EFPC sediment and activated upon nitrate amendment in these nitrate-rich sediments. In turn, these processes were outcompeted by the addition of either iron oxides or sulfate as alternative terminal electron acceptors. Although geochemical products of sulfate reduction were not detected in the incubations, the abundance of sulfate reduction genes increased with depth in the sediment and was equally more pronounced in treatments amended with either iron oxides or sulfate. Simultaneously, anaerobic sulfide oxidizing bacteria coupling sulfide oxidation to DNRA (and not conventional denitrification) were apparently enriched over time, regardless of the treatments. These findings indicate that sulfate reduction is important in freshwater stream sediments and probably catalyzed by a cryptic sulfur cycle involving nitrogen species, in which the sulfur products from sulfate reduction are immediately removed by side reactions and not detectable by geochemical measurements alone. Similar experiments in SRS sediments, however, demonstrated little interaction between nitrogen and sulfur cycling microorganisms. Sulfate reduction was impacted by the addition of more thermodynamically favorable electron acceptors, suggesting either that iron-reducing microorganisms outcompeted sulfate-reducing microorganisms for organic substrate, depleting the stock of electron donor available for sulfate reduction, or that the cryptic sulfur cycle was shunted by the precipitation of FeS generated as a result of the abiotic reduction of iron oxides by dissolved sulfide. A diagnostic modeling exercise was conducted to further investigate the competition between terminal electron accepting processes. As conventional kinetic models typically do not account for cryptic cycles and used inaccurate formulations to describe competition between microbial communities, new metabolic rate laws were developed that explicitly express the electron acceptor-specific enzyme of each energetically favorable metabolic process based on gene abundance detected in the incubations. The model was tested with the sediment slurry incubation data to determine whether substrate competition could explain the decrease in sulfate reduction observed in the presence of iron oxide competitor. The model was able to reproduce geochemical concentrations really well in each treatment once the model was calibrated with the unamended control, suggesting that microbial competition was indeed driven by thermodynamic considerations. Overall, carbon remineralization processes and rates will be reproduced much more realistically with the new metabolic rate laws.

54 ENVIRONMENTAL SCIENCES↗