Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Reaction Time”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,747 records · Page 97
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Difference in chemical reactions in bulk plasma and sheath regions during surface modification of graphene oxide film using capacitively coupled NH{sub 3} plasma

Reduced graphene oxide (r-GO) films were obtained from capacitively coupled NH{sub 3} plasma treatment of spin-coated graphene oxide (GO) films at room temperature. Variations were evaluated according to the two plasma treatment regions: the bulk plasma region (R{sub bulk}) and the sheath region (R{sub sheath}). Reduction and nitridation of the GO films began as soon as the NH{sub 3} plasma was exposed to both regions. However, with the increase in treatment time, the reduction and nitridation reactions differed in each region. In the R{sub bulk}, NH{sub 3} plasma ions reacted chemically with oxygen functional groups on the GO films, which was highly effective for reduction and nitridation. While in the R{sub sheath}, physical reactions by ion bombardment were dominant because plasma ions were accelerated by the strong electrical field. The accelerated plasma ions reacted not only with the oxygen functional groups but also with the broken carbon chains, which caused the removal of the GO films by the formation of hydrocarbon gas species. These results showed that reduction and nitridation in the R{sub bulk} using capacitively coupled NH{sub 3} plasma were very effective for modifying the properties of r-GO films for application as transparent conductive films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Exponential Time Differencing Schemes for Fuel Depletion and Transport in Molten Salt Reactors: Theory and Implementation

A numerical framework for modeling depletion and mass transport in liquid-fueled molten salt reactions is presented based on exponential time differencing. The solution method involves using the finite volume method to transform the system of partial differential equations (PDEs) into a much larger system of ordinary differential equations. The key part of this method involves solving for the exponential of a matrix. We explore six different algorithms to compute the exponential in a series of progression problems that explore physical transport phenomena in molten salt reactors. This framework shows good results for solving linear parabolic PDEs with each of the six matrix exponential algorithms. For large problems, the series solvers such as Padé and Taylor have large run times, which can be mitigated by using the Krylov subspace.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
NASA NTRS1991

Safety considerations in testing a fuel-rich aeropropulsion gas generator

A catalyst containing reactor is being tested using a fuel-rich mixture of Jet A fuel and hot input air. The reactor product is a gaseous fuel that can be utilized in aeropropulsion gas turbine engines. Because the catalyst material is susceptible to damage from high temperature conditions, fuel-rich operating conditions are attained by introducing the fuel first into an inert gas stream in the reactor and then displacing the inert gas with reaction air. Once a desired fuel-to-air ratio is attained, only limited time is allowed for a catalyst induced reaction to occur; otherwise the inert gas is substituted for the air and the fuel flow is terminated. Because there presently is not a gas turbine combustor in which to burn the reactor product gas, the gas is combusted at the outlet of the test facility flare stack. This technique in operations has worked successfully in over 200 tests.

Rollbuhler, R. James↗
DOE OSTI2023

Production and discovery of neutron-rich isotopes by fragmentation of 198 Pt

Production cross sections were measured for fragments produced by an 85 MeV/u 198 Pt beam incident on a beryllium target. Event-by-event particle identification of A, Z, and q for the reaction products was performed by employing energy loss, time-of-flight, magnetic rigidity, and total kinetic energy measurements. Over 70 nuclei in the Hf-Pt region were identified, including three isotopes first observed in this work: 191,192 Hf and 189 Lu. Due to the existence of multiple charge states between H-like and C-like ions, a new analysis method was introduced, incorporating Monte Carlo calculations of charge state fractions for a given charge state of the projectile residue just after the reaction. For the first time, charge-state probability distribution functions after the reaction have been deduced from experimental data. Furthermore, this study provides insight into how to produce key nuclides near N = 126 and the ability of a fragmentation residue to retain electrons from the primary beam.

190 ≤ A ≤ 219↗
DOE OSTI2017

Functional Enzyme-Based Approach for Linking Microbial Community Functions with Biogeochemical Process Kinetics

The kinetics of biogeochemical processes in natural and engineered environmental systems are typically described using Monod-type or modified Monod-type models. These models rely on biomass as surrogates for functional enzymes in microbial community that catalyze biogeochemical reactions. A major challenge to apply such models is the difficulty to quantitatively measure functional biomass for constraining and validating the models. On the other hand, omics-based approaches have been increasingly used to characterize microbial community structure, functions, and metabolites. Here we proposed an enzyme-based model that can incorporate omics-data to link microbial community functions with biogeochemical process kinetics. The model treats enzymes as time-variable catalysts for biogeochemical reactions and applies biogeochemical reaction network to incorporate intermediate metabolites. The sequences of genes and proteins from metagenomes, as well as those from the UniProt database, were used for targeted enzyme quantification and to provide insights into the dynamic linkage among functional genes, enzymes, and metabolites that are necessary to be incorporated in the model. The application of the model was demonstrated using denitrification as an example by comparing model-simulated with measured functional enzymes, genes, denitrification substrates and intermediates

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Shock compression response of highly reactive Ni + Al multilayered thin foils

The shock-compression response of Ni + Al multilayered thin foils is investigated using laser-accelerated thin-foil plate-impact experiments over the pressure range of 2 to 11 GPa. The foils contain alternating Ni and Al layers (parallel but not flat) of nominally 50 nm bilayer spacing. The goal is to determine the equation of state and shock-induced reactivity of these highly reactive fully dense thin-foil materials. The laser-accelerated thin-foil impact set-up involved combined use of photon-doppler-velocimetry to monitor the acceleration and impact velocity of an aluminum flyer, and VISAR interferometry was used to monitor the back free-surface velocity of the impacted Ni + Al multilayered target. The shock-compression response of the Ni + Al target foils was determined using experimentally measured parameters and impedance matching approach, with error bars identified considering systematic and experimental errors. Meso-scale CTH shock simulations were performed using real imported microstructures of the cross-sections of the multilayered Ni + Al foils to compute the Hugoniot response (assuming no reaction) for correlation with their experimentally determined equation of state. It was observed that at particle velocities below ∼150 m/s, the experimentally determined equation of state trend matches the CTH-predicted inert response and is consistent with the observed unreacted state of the recovered Ni + Al target foils from this velocity regime. At higher particle velocities, the experimentally determined equation of state deviates from the CTH-predicted inert response. A complete and self-sustained reaction is also seen in targets recovered from experiments performed at these higher particle velocities. The deviation in the measured equation of state, to higher shock speeds and expanded volumes, combined with the observation of complete reaction in the recovered multilayered foils, confirmed via microstructure characterization, is indicative of the occurrence of shock-induced chemical reaction occurring in the time-scale of the high-pressure state. TEM characterization of recovered shock-compressed (unreacted) Ni + Al multilayered foils exhibits distinct features of constituent mixing revealing jetted layers and inter-mixed regions. These features were primarily observed in the proximity of the undulations present in the alternating layers of the Ni + Al starting foils, suggesting the important role of such instabilities in promoting shock-induced intermetallic-forming reactions in the fully dense highly exothermic multilayered thin foils.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2013

A (S)TEM Gas Cell Holder with Localized Laser Heating for In Situ Experiments

The advent of aberration correction for transmission electron microscopy has transformed atomic resolution imaging into a nearly routine technique for structural analysis. Now an emerging frontier in electron microscopy is the development of in situ capabilities to observe reactions at atomic resolution in real time and within realistic environments. Here we present a new in situ gas cell holder that is designed for compatibility with a wide variety of sample type (i.e., dimpled 3-mm discs, standard mesh grids, various types of focused ion beam lamellae attached to half grids). Its capabilities include localized heating and precise control of the gas pressure and composition while simultaneously allowing atomic resolution imaging at ambient pressure. The results show that 0.25-nm lattice fringes are directly visible for nanoparticles imaged at ambient pressure with gas path lengths up to 20 μm. Additionally, we quantitatively demonstrate that while the attainable contrast and resolution decrease with increasing pressure and gas path length, resolutions better than 0.2 nm should be accessible at ambient pressure with gas path lengths less than the 15 μm utilized for these experiments.

aberration correction↗
DOE OSTI2020

Exploration of Electrochemical Reactions at Organic–Inorganic Halide Perovskite Interfaces via Machine Learning in In Situ Time-of-Flight Secondary Ion Mass Spectrometry

The instability of hybrid organic–inorganic perovskite (HOIP) devices is one of the significant challenges preventing commercialization. Exploring these phenomena is severely limited by the complexity of the intrinsic electrochemistry of HOIPs, the presence of multiple volatile and mobile ionic species, and the possible role of environmentally induced reactions at surfaces and triple-phase junctions. Here, in situ studies of the electrochemistry of methylammonium lead bromide perovskite with the Au electrode interface are reported via light- and voltage-dependent time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging of lateral perovskite heterostructures. While ToF-SIMS allows for the visualization of the chemical composition along the surface and its evolution with light and electrical bias, the interpretation of the multidimensional data obtained is often limited due to strong correlations between chemical signatures and the need to track multiple peaks at once. Here, a machine learning workflow combining the Hough transform and non-negative matrix factorization and no-negative tensor decomposition is developed to avoid this limitation and extract salient features of associated chemical changes and to separate the light- and voltage-dependent dynamics. Finally, combining these in situ characterizations and the machine learning workflow provides comprehensive information on the chemical nature of moving species, ion accumulation, and interfacial electrochemical reactions in HOIP devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Bayesian estimation of the $S$ factor and thermonuclear reaction rate for 16 O(p, γ) 17 F

The 16 O(p, γ) 17 F reaction is the slowest hydrogen-burning process in the CNO mass region. Its thermonuclear rate sensitively impacts predictions of oxygen isotopic ratios in a number of astrophysical sites, including AGB stars. The reaction has been measured several times at low bombarding energies using a variety of techniques. The most recent evaluated experimental rates have a reported uncertainty of about 7.5% below 1 GK. However, the previous rate estimate represents a best guess only and was not based on rigorous statistical methods. We apply a Bayesian model to fit all reliable 16 O(p, γ) 17 F cross section data, and take into account independent contributions of statistical and systematic uncertainties. The nuclear reaction model employed is a single-particle potential model involving a Woods-Saxon potential for generating the radial bound state wave function. The model has three physical parameters, the radius and diffuseness of the Woods-Saxon potential, and the asymptotic normalization coefficients (ANCs) of the final bound state in 17 F. Here, we find that performing the Bayesian S -factor fit using ANCs as scaling parameters has a distinct advantage over adopting spectroscopic factors instead. Based on these results, we present the first statistically rigorous estimation of experimental 16 O(p, γ) 17 F reaction rates, with uncertainties (±4.2%) of about half the previously reported values.

6 ≤ A ≤ 19↗
DOE OSTI2014

Core-to-valence spectroscopic detection of the CH{sub 2}Br radical and element-specific femtosecond photodissociation dynamics of CH{sub 2}IBr

Element-specific single photon photodissociation dynamics of CH{sub 2}IBr and core-to-valence absorption spectroscopy of CH{sub 2}Br radicals are investigated using femtosecond high-harmonic extreme ultraviolet (XUV) transient absorption spectroscopy. Photodissociation of CH{sub 2}IBr along both the C–I or C–Br reaction coordinates is observed in real-time following excitation at 266 nm. At this wavelength, C–I dissociation is the dominant reaction channel and C–Br dissociation is observed as a minor pathway. Both photodissociation pathways are probed simultaneously through individual 4d(I) N{sub 4/5} and 3d(Br) M{sub 4/5} core-to-valence transitions. The 3d(Br) M{sub 4/5} pre-edge absorption spectrum of the CH{sub 2}Br radical photoproduct corresponding to the C–I dissociation channel is characterized for the first time. Although the radical's singly occupied molecular orbital (SOMO) is mostly localized on the central carbon atom, the 3d(Br) → π{sup *}(SOMO) resonances at 68.5 eV and 69.5 eV are detected 2 eV below the parent molecule 3d(Br) → σ{sup *}(LUMO) transitions. Core-to-valence XUV absorption spectroscopy provides a unique probe of the local electronic structure of the radical species in reference to the Br reporter atom. The measured times for C–I dissociation leading to I and I{sup *} atomic products are 48 ± 12 fs and 44 ± 4 fs, respectively, while the measured C–Br dissociation time leading to atomic Br is 114 ± 17 fs. The investigation performed here demonstrates the capability of femtosecond time-resolved core-level spectroscopy utilizing multiple reporter atoms simultaneously.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Direct observation of bimolecular reactions of ultracold KRb molecules

Femtochemistry techniques have been instrumental in accessing the short time scales necessary to probe transient intermediates in chemical reactions. In this study, we took the contrasting approach of prolonging the lifetime of an intermediate by preparing reactant molecules in their lowest rovibronic quantum state at ultralow temperatures, thereby markedly reducing the number of exit channels accessible upon their mutual collision. Using ionization spectroscopy and velocity-map imaging of a trapped gas of potassium-rubidium (KRb) molecules at a temperature of 500 nanokelvin, we directly observed reactants, intermediates, and products of the reaction 40 K 87 Rb + 40 K 87 Rb → K 2 Rb 2 * → K 2 + Rb 2 . Beyond observation of a long-lived, energy-rich intermediate complex, this technique opens the door to further studies of quantum-state–resolved reaction dynamics in the ultracold regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solutions based upon mixed quantum-classical approximation. I. Proton transfer reaction in water

In order to investigate proton transfer reaction in solution, mixed quantum-classical molecular dynamics calculations have been carried out based on our previously proposed quantum equation of motion for the reacting system [A. Yamada and S. Okazaki, J. Chem. Phys. 128, 044507 (2008)]. Surface hopping method was applied to describe forces acting on the solvent classical degrees of freedom. In a series of our studies, quantum and solvent effects on the reaction dynamics in solutions have been analysed in detail. Here, we report our mixed quantum-classical molecular dynamics calculations for intramolecular proton transfer of malonaldehyde in water. Thermally activated proton transfer process, i.e., vibrational excitation in the reactant state followed by transition to the product state and vibrational relaxation in the product state, as well as tunneling reaction can be described by solving the equation of motion. Zero point energy is, of course, included, too. The quantum simulation in water has been compared with the fully classical one and the wave packet calculation in vacuum. The calculated quantum reaction rate in water was 0.70 ps{sup −1}, which is about 2.5 times faster than that in vacuum, 0.27 ps{sup −1}. This indicates that the solvent water accelerates the reaction. Further, the quantum calculation resulted in the reaction rate about 2 times faster than the fully classical calculation, which indicates that quantum effect enhances the reaction rate, too. Contribution from three reaction mechanisms, i.e., tunneling, thermal activation, and barrier vanishing reactions, is 33:46:21 in the mixed quantum-classical calculations. This clearly shows that the tunneling effect is important in the reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Transitioning NWChem to the Next Generation of Manycore Machines

The NorthWest chemistry (NWChem) modeling software is a popular molecular chemistry simulation software that was designed from the start to work on massively parallel processing supercomputers [1-3]. It contains an umbrella of modules that today includes self-consistent eld (SCF), second order Møller-Plesset perturbation theory (MP2), coupled cluster (CC), multiconguration self-consistent eld (MCSCF), selected conguration interaction (CI), tensor contraction engine (TCE) many body methods, density functional theory (DFT), time-dependent density functional theory (TDDFT), real-time time-dependent density functional theory, pseudopotential plane-wave density functional theory (PSPW), band structure (BAND), ab initio molecular dynamics (AIMD), Car-Parrinello molecular dynamics (MD), classical MD, hybrid quantum mechanics molecular mechanics (QM/MM), hybrid ab initio molecular dynamics molecular mechanics (AIMD/MM), gauge independent atomic orbital nuclear magnetic resonance (GIAO NMR), conductor like screening solvation model (COSMO), conductor-like screening solvation model based on density (COSMO-SMD), and reference interaction site model (RISM) solvation models, free energy simulations, reaction path optimization, parallel in time, among other capabilities [4]. Moreover, new capabilities continue to be added with each new release.

Bylaska, Eric J.↗
DOE OSTI2021

An experimental and kinetic modeling study of NO x sensitization on methane autoignition and oxidation

An experimental and kinetic modeling study of the influence of NO x (i.e. NO 2 , NO and N 2 O) addition on the ignition behavior of methane/‘air’ mixtures is performed. Ignition delay time measurements are taken in a rapid compression machine (RCM) and in a shock tube (ST) at temperatures and pressures ranging from 900–1500 K and 1.5–3.0 MPa, respectively for equivalence ratios of 0.5–2.0 in ‘air’. The conditions chosen are relevant to spark ignition and homogeneous charge compression ignition engine operating conditions where exhaust gas recirculation can potentially add NO x to the premixed charge. The RCM measurements show that the addition of 200 ppm NO 2 to the stoichiometric CH 4 /oxidizer mixture results in a factor of three increase in reactivity compared to the baseline case without NOx for temperatures in the range 600–1000 K. However, adding up to 1000 ppm N 2 O does not show any appreciable effect on the measurements. The promoting effect of NO 2 was found to increase with temperature in the range 950–1150 K, while the sensitization effect decreases at higher pressures. The experimental results measured are simulated using NUIGMech1.2 comprising an updated NO x sub-chemistry in this work. A kinetic analysis indicates that the competition between the reactions ĊH 3 + NO 2 ↔ CH 3 Ȯ + NO and ĊH 3 + NO 2 (+M) ↔ CH 3 NO 2 (+M), the former being a propagation reaction and the latter being a termination reaction governs NO x sensitization on CH 4 ignition. Recent calculations by Matsugi and Shiina (A. Matsugi, H. Shiina, J. Phys. Chem. A. 121 (2017) 4218–4224) for the nitromethane formation reaction CH 3 + NO 2 (+M) ↔ CH 3 NO 2 (+M), together with the recently calculated rate constants for HONO/HNO 2 reactions significantly improve ignition delay time predictions in the temperature range 600–1000 K. Furthermore, the experiments with NO addition reveal a non-monotonous sensitization impact on CH 4 ignition at lower temperatures with NO initially acting as an inhibitor at low NO concentrations and then as a promoter as NO concentrations increase in the mixture. This non-monotonous trend is attributed to the role of the chain-termination reaction ĊH 3 + NO 2 (+M) ↔ CH 3 NO 2 (+M) and the impact of NO on the transition to the chain-branching steps CH 2 O + HȮ 2 ↔ HĊO + H 2 O 2 , H 2 O 2 (+M) ↔ ȮH + ȮH (+M), HĊO ↔ CO + Ḣ followed by CO + O 2 ↔ CO 2 + Ö and Ḣ + O 2 ↔ Ö + ȮH. NUIGMech1.2 is systematically validated against the new ignition delay measurements taken here together with species measurements and high temperature ignition delay time data available in the literature for CH 4 /oxidizer mixtures diluted with NO 2 /N 2 O/NO and is observed to accurately capture the sensitization trends.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Functional Connectivity of Red Chlorophylls in Cyanobacterial Photosystem I Revealed by Fluence-Dependent Transient Absorption

External stressors modulate the oligomerization state of photosystem I (PSI) in cyanobacteria. The number of red chlorophylls (Chls), pigments lower in energy than the P700 reaction center, depends on the oligomerization state of PSI. Here, we use ultrafast transient absorption spectroscopy to interrogate the effective connectivity of the red Chls in excitonic energy pathways in trimeric PSI in native thylakoid membranes of the model cyanobacterium Synechocystis sp. PCC 6803, including emergent dynamics, as red Chls increase in number and proximity. Fluence-dependent dynamics indicate singlet–singlet annihilation within energetically connected red Chl sites in the PSI antenna but not within bulk Chl sites on the picosecond time scale. These data support picosecond energy transfer between energetically connected red Chl sites as the physical basis of singlet–singlet annihilation. The time scale of this energy transfer is faster than predicted by Förster resonance energy transfer calculations, raising questions about the physical mechanism of the process. Our results indicate distinct strategies to steer excitations through the PSI antenna; the red Chls present a shallow reservoir that direct excitations away from P 700 , extending the time to trapping by the reaction center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Real-time observation of X-ray-induced intramolecular and interatomic electronic decay in CH 2 I 2

The increasing availability of X-ray free-electron lasers (XFELs) has catalyzed the development of single-object structural determination and of structural dynamics tracking in real-time. Disentangling the molecular-level reactions triggered by the interaction with an XFEL pulse is a fundamental step towards developing such applications. Here we report real-time observations of XFEL-induced electronic decay via short-lived transient electronic states in the diiodomethane molecule, using a femtosecond near-infrared probe laser. We determine the lifetimes of the transient states populated during the XFEL-induced Auger cascades and find that multiply charged iodine ions are issued from short-lived (~20 fs) transient states, whereas the singly charged ones originate from significantly longer-lived states (~100 fs). We identify the mechanisms behind these different time scales: contrary to the short-lived transient states which relax by molecular Auger decay, the long-lived ones decay by an interatomic Coulombic decay between two iodine atoms, during the molecular fragmentation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Reaction Rate Sensitivity of the Production of γ-Ray Emitting Isotopes in Core-collapse Supernovae

Radioactive isotopes produced in core-collapse supernovae (CCSNe) provide useful insights into the underlying processes driving the collapse mechanism and the origins of elemental abundances. Their study generates a confluence of major physics research, including experimental measurements of nuclear reaction rates, astrophysical modeling, and γ-ray observations. Here we identify the key nuclear reaction rates to the nucleosynthesis of observable radioactive isotopes in explosive silicon burning during CCSNe. Using the nuclear reaction network calculator SkyNet and current REACLIB reaction rates, we evolve temperature–density–time profiles of the innermost 0.45 M⊙ ejecta from the core collapse and explosion of a 12 M⊙ star. Individually varying 3403 reaction rates by factors of 100, we identify 141 reactions that cause significant differences in the isotopes of interest, namely, 43 K, 47 Ca, 44,47 Sc, 44 Ti, 48,51 Cr, 48,49 V, 52,53 Mn, 55,59 Fe, 56,57 Co, and 56,57,59 Ni. For each of these reactions, we present a novel method to extract the temperature range pertinent to the nucleosynthesis of the relevant isotope; the resulting temperatures lie within the range T = 0.47–6.15 GK. Limiting the variations to within 1σ of STARLIB reaction rate uncertainties further reduces the identified reactions to 48 key rates, which can be used to guide future experimental research. Complete results are presented in tabular form.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

Modeling the formation of methane hydrate-bearing intervals in fine-grained sediments

Sediment grain size exerts a fundamental control on how methane hydrates are distributed within the pore space. Fine-grained muds are the predominant sediments in continental margins, and hydrates in these sediments have often been observed in semi-vertical veins and fractures. In several instances, these hydrate veins/fractures are found in discrete depth intervals a few tens meters thick within the gas hydrate stability zone (GHSZ) surrounded by hydrate-free sediments above and below. As they are not obviously connected with free gas occurring beneath the base of the GHSZ, these isolated hydrate-bearing intervals have been interpreted as formed by microbial methane generated in situ. To investigate further the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, solute diffusion, and microbial methane generation. The microbial methane generation term depends on the amount of metabolizable organic carbon deposited at the seafloor, which is degraded at a prescribed rate resulting in methane formation beneath the sulfate reduction zone. In the model, methane hydrate precipitates once the dissolved methane concentration is greater than solubility, or hydrate dissolves if concentration goes below solubility. If the deposition of organic carbon at the seafloor is kept constant in time, we found that the predicted amounts of hydrate formed in discrete intervals within the GHSZ are much less than those estimated from observations. We then investigated the effect of temporal variations in the deposition of organic carbon. If greater amounts of organic carbon are deposited during some time interval, methane generation is enhanced during burial in the corresponding sediment interval. With variations in organic carbon deposition that are consistent with observations in continental margin sediments, we were able to reproduce the methane hydrate contents estimated in discrete depth intervals. Our results support the suggestion that in situ microbial methane generation is the source for hydrates within fine-grained sediments.

Malinverno, Alberto↗