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Johnson, Matthew S.

Publications and source records attributed to Johnson, Matthew S..

At least 19 records

Global Methane Budget 2000–2020

Abstract. Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. CH4 is the second most important human-influenced greenhouse gas in terms of climate forcing after carbon dioxide (CO2), and both emissions and atmospheric concentrations of CH4 have continued to increase since 2007 after a temporary pause. The relative importance of CH4 emissions compared to those of CO2 for temperature change is related to its shorter atmospheric lifetime, stronger radiative effect, and acceleration in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in quantifying the factors responsible for the observed atmospheric growth rate arise from diverse, geographically overlapping CH4 sources and from the uncertain magnitude and temporal change in the destruction of CH4 by short-lived and highly variable hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to improve, synthesise, and update the global CH4 budget regularly and to stimulate new research on the methane cycle. Following Saunois et al. (2016, 2020), we present here the third version of the living review paper dedicated to the decadal CH4 budget, integrating results of top-down CH4 emission estimates (based on in situ and Greenhouse Gases Observing SATellite (GOSAT) atmospheric observations and an ensemble of atmospheric inverse-model results) and bottom-up estimates (based on process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations). We present a budget for the most recent 2010–2019 calendar decade (the latest period for which full data sets are available), for the previous decade of 2000–2009 and for the year 2020. The revision of the bottom-up budget in this 2025 edition benefits from important progress in estimating inland freshwater emissions, with better counting of emissions from lakes and ponds, reservoirs, and streams and rivers. This budget also reduces double counting across freshwater and wetland emissions and, for the first time, includes an estimate of the potential double counting that may exist (average of 23 Tg CH4 yr−1). Bottom-up approaches show that the combined wetland and inland freshwater emissions average 248 [159–369] Tg CH4 yr−1 for the 2010–2019 decade. Natural fluxes are perturbed by human activities through climate, eutrophication, and land use. In this budget, we also estimate, for the first time, this anthropogenic component contributing to wetland and inland freshwater emissions. Newly available gridded products also allowed us to derive an almost complete latitudinal and regional budget based on bottom-up approaches. For the 2010–2019 decade, global CH4 emissions are estimated by atmospheric inversions (top-down) to be 575 Tg CH4 yr−1 (range 553–586, corresponding to the minimum and maximum estimates of the model ensemble). Of this amount, 369 Tg CH4 yr−1 or ∼ 65 % is attributed to direct anthropogenic sources in the fossil, agriculture, and waste and anthropogenic biomass burning (range 350–391 Tg CH4 yr−1 or 63 %–68 %). For the 2000–2009 period, the atmospheric inversions give a slightly lower total emission than for 2010–2019, by 32 Tg CH4 yr−1 (range 9–40). The 2020 emission rate is the highest of the period and reaches 608 Tg CH4 yr−1 (range 581–627), which is 12 % higher than the average emissions in the 2000s. Since 2012, global direct anthropogenic CH4 emission trends have been tracking scenarios that assume no or minimal climate mitigation policies proposed by the Intergovernmental Panel on Climate Change (shared socio-economic pathways SSP5 and SSP3). Bottom-up methods suggest 16 % (94 Tg CH4 yr−1) larger global emissions (669 Tg CH4 yr−1, range 512–849) than top-down inversion methods for the 2010–2019 period. The discrepancy between the bottom-up and the top-down budgets has been greatly reduced compared to the previous differences (167 and 156 Tg CH4 yr−1 in Saunois et al. (2016, 2020) respectively), and for the first time uncertainties in bottom-up and top-down budgets overlap. Although differences have been reduced between inversions and bottom-up, the most important source of uncertainty in the global CH4 budget is still attributable to natural emissions, especially those from wetlands and inland freshwaters. The tropospheric loss of methane, as the main contributor to methane lifetime, has been estimated at 563 [510–663] Tg CH4 yr−1 based on chemistry–climate models. These values are slightly larger than for 2000–2009 due to the impact of the rise in atmospheric methane and remaining large uncertainty (∼ 25 %). The total sink of CH4 is estimated at 633 [507–796] Tg CH4 yr−1 by the bottom-up approaches and at 554 [550–567] Tg CH4 yr−1 by top-down approaches. However, most of the top-down models use the same OH distribution, which introduces less uncertainty to the global budget than is likely justified. For 2010–2019, agriculture and waste contributed an estimated 228 [213–242] Tg CH4 yr−1 in the top-down budget and 211 [195–231] Tg CH4 yr−1 in the bottom-up budget. Fossil fuel emissions contributed 115 [100–124] Tg CH4 yr−1 in the top-down budget and 120 [117–125] Tg CH4 yr−1 in the bottom-up budget. Biomass and biofuel burning contributed 27 [26–27] Tg CH4 yr−1 in the top-down budget and 28 [21–39] Tg CH4 yr−1 in the bottom-up budget. We identify five major priorities for improving the CH4 budget: (i) producing a global, high-resolution map of water-saturated soils and inundated areas emitting CH4 based on a robust classification of different types of emitting ecosystems; (ii) further development of process-based models for inland-water emissions; (iii) intensification of CH4 observations at local (e.g. FLUXNET-CH4 measurements, urban-scale monitoring, satellite imagery with pointing capabilities) to regional scales (surface networks and global remote sensing measurements from satellites) to constrain both bottom-up models and atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) integration of 3D variational inversion systems using isotopic and/or co-emitted species such as ethane as well as information in the bottom-up inventories on anthropogenic super-emitters detected by remote sensing (mainly oil and gas sector but also coal, agriculture, and landfills) to improve source partitioning. The data presented here can be downloaded from https://doi.org/10.18160/GKQ9-2RHT (Martinez et al., 2024).

54 ENVIRONMENTAL SCIENCES↗

Estimating Carbon Dioxide Emissions in Two California Cities Using Bayesian Inversion and Satellite Measurements

NASA's Orbiting Carbon Observatories (OCO-2 and OCO-3) provide measurements of column-averaged carbon dioxide concentrations (XCO 2 ) with sufficient spatial resolution and precision to constrain bottom-up estimates of CO 2 fluxes at regional scales. We use Bayesian inversion methods assimilating satellite retrievals to improve estimates of CO 2 fluxes in the South Coast Air Basin (SoCAB) which surrounds Los Angeles, and in the San Francisco Bay Area Air Basin (SFBA). We study 2020 to understand the impact of the COVID-19 lockdowns and an active wildfire season. Our results indicated that a 50% (30%) reduction in CO 2 emissions relative to 2015 during the COVID-19 lockdown period was consistent with OCO measurements for SFBA (SoCAB). We find that posterior wildfire emissions differed significantly from the prior at the scale of individual wildfires, though with large uncertainties, and that wildfire emissions in SFBA are significant, attributing 72% of the region's CO 2 emissions during August 2020 to wildfires.

54 ENVIRONMENTAL SCIENCES↗

Transitory sensitivity in automatic chemical kinetic mechanism analysis

Abstract Detailed chemical kinetic mechanisms are necessary for resolving many important chemical processes. As the chemistry of smaller molecules has become better grounded and quantum chemistry calculations have become cheaper, kineticists have become interested in constructing progressively larger kinetic mechanisms to model increasingly complex chemical processes. These large kinetic mechanisms prove incredibly difficult to refine and time‐consuming to interpret. Traditional sensitivity analysis on a large mechanism can range from inconvenient to practically impossible without special techniques to reduce the computational cost. We first present a new time‐local sensitivity analysis we term transitory sensitivity analysis. Transitory sensitivity analysis is demonstrated in an example to accurately identify traditionally sensitive reactions at an 18,000x speed up over traditional sensitivities. By fusing transitory sensitivity analysis with more traditional time‐local branching, pathway, and cluster analyses, we develop an algorithm for efficient automatic mechanism analysis. This automatic mechanism analysis at a time point is able to identify the reactions a target is most sensitive to using transitory sensitivity analysis and then propose hypotheses why the reaction might be sensitive using branching, pathway, and cluster analyses. We implement these algorithms within the reaction mechanism simulator (RMS) package, which enables us to report the automatic mechanism analysis results in highly readable text formats and in molecular flux diagrams.

Johnson, Matthew S.↗

ReactionMechanismSimulator.jl: A modern approach to chemical kinetic mechanism simulation and analysis

Abstract We present ReactionMechanismSimulator.jl (RMS), a modern differentiable software for the simulation and analysis of chemical kinetic mechanisms, including multiphase systems. RMS has already been applied to problems in combustion, pyrolysis, polymers, pharmaceuticals, catalysis, and electrocatalysis. RMS is written in Julia, making it easy to develop and allowing it to take advantage of Julia's extensive numerical computing ecosystem. In addition to its extensive library of optimized analytic Jacobians, RMS can generate and use Jacobians computed using automatic differentiation and symbolically generated analytic Jacobians. RMS is demonstrated to be faster than Cantera and Chemkin in several benchmarks. RMS also implements an extensive set of features for analyzing chemical mechanisms, including a library of easy‐to‐call plotting functions, molecular structure resolved flux diagram generation, crash analysis, traditional sensitivity analysis, transitory sensitivity analysis, and an automatic mechanism analysis toolkit. RMS implements efficient adjoint and parallel forward sensitivity analyses. We also demonstrate the ease of adding new features to RMS.

Johnson, Matthew S.↗

Automated reaction kinetics and network exploration (Arkane): A statistical mechanics, thermodynamics, transition state theory, and master equation software

The open-source statistical mechanics software described here, Arkane–Automated Reaction Kinetics and Network Exploration–facilitates computations of thermodynamic properties of chemical species, high-pressure limit reaction rate coefficients, and pressure-dependent rate coefficient over multi-well molecular potential energy surfaces (PES) including the effects of collisional energy transfer on phenomenological kinetics. Arkane can use estimates to fill in information for molecules or reactions where quantum chemistry information is missing. The software solves the internal energy master equation for complex unimolecular reaction systems. Inputs to the software include converged electronic structure computations performed by the user using a variety of supported software packages (Gaussian, Molpro, Orca, TeraChem, Q-Chem, Psi4). The software outputs high-pressure limit rate coefficients and pressure-dependent phenomenological rate coefficients, as well as computed thermodynamic properties (enthalpy, entropy, and constant pressure heat capacity) with added energy corrections. Some of the key features of Arkane include treatment of 1D, 2D or ND hindered internal rotation modes, treatment of free internal rotation modes, quantum tunneling effect consideration, transition state theory (TST) and Rice-Ramsperger-Kassel-Marcus (RRKM) rate coefficient computations, master equation solution with four implemented methods, inverse-Laplace transform of high-pressure limit rate coefficients into the energy domain, energy corrections based on bond-additivity or isodesmic reactions, automated and efficient PES exploration, and PES sensitivity analysis. The present work describes the design of Arkane, how it should be used, and refers to the theory that it employs. Arkane is distributed via the RMG-Py software suite (https://github.com/ReactionMechanismGenerator/RMG-Py).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

National CO 2 budgets (2015–2020) inferred from atmospheric CO 2 observations in support of the global stocktake

Accurate accounting of emissions and removals of CO 2 is critical for the planning and verification of emission reduction targets in support of the Paris Agreement. Here, we present a pilot dataset of country-specific net carbon exchange (NCE; fossil plus terrestrial ecosystem fluxes) and terrestrial carbon stock changes aimed at informing countries' carbon budgets. These estimates are based on “top-down” NCE outputs from the v10 Orbiting Carbon Observatory (OCO-2) modeling intercomparison project (MIP), wherein an ensemble of inverse modeling groups conducted standardized experiments assimilating OCO-2 column-averaged dry-air mole fraction (X CO 2 ) retrievals (ACOS v10), in situ CO 2 measurements or combinations of these data. The v10 OCO-2 MIP NCE estimates are combined with “bottom-up” estimates of fossil fuel emissions and lateral carbon fluxes to estimate changes in terrestrial carbon stocks, which are impacted by anthropogenic and natural drivers. These flux and stock change estimates are reported annually (2015–2020) as both a global 1° x 1° gridded dataset and a country-level dataset and are available for download from the Committee on Earth Observation Satellites' (CEOS) website. Across the v10 OCO-2 MIP experiments, we obtain increases in the ensemble median terrestrial carbon stocks of 3.29–4.58 Pg CO2 yr -1 (0.90–1.25 Pg C yr -1 ). This is a result of broad increases in terrestrial carbon stocks across the northern extratropics, while the tropics generally have stock losses but with considerable regional variability and differences between v10 OCO-2 MIP experiments. We discuss the state of the science for tracking emissions and removals using top-down methods, including current limitations and future developments towards top-down monitoring and verification systems.

54 ENVIRONMENTAL SCIENCES↗

A workflow for automatic generation and efficient refinement of individual pressure-dependent networks

Manual chemical kinetic model construction often requires modelists to at least implicitly guess all possible decay pathways and their relative fluxes for all important species. We present a workflow and associated tool for automatic generation and re finement of pressure-dependent networks that should enable modelists to efficiently and comprehensively identify decay pathways and estimate respective parameters for chemical species. This tool combines the capabilities of the Reaction Mechanism Generator (RMG) software to generate possible reaction paths, determine thermochemistry, approximate rate coefficients and estimate frequencies with the capabilities of the Arkane software to use quantum chemical parameters to compute thermochemistry and pressure dependent rates. A flux-based algorithm is used to decide which isomers to add to the network. Isomers added to the network are reacted to form other channels. When enough of the flux is accounted for by the isomers and bimolecular product channels, the generation process terminates to yield a comprehensive network. Network sensitivity analysis is applied to the network to identify the most important wells and barriers that can be refined using quantum chemistry calculations. Iterative refinement can then be used to achieve accuracy. The comprehensive network can be easily reduced using energy and flux-based algorithms to the most important channels and isomers in the network.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reaction Mechanism Generator v3.0: Advances in Automatic Mechanism Generation

In chemical kinetics research, kinetic models containing hundreds of species and tens of thousands of elementary reactions are commonly used to understand and predict the behavior of reactive chemical systems. Reaction Mechanism Generator (RMG) is a software suite developed to automatically generate such models by incorporating and extrapolating from a database of known thermochemical and kinetic parameters. Here, we present the recent version 3 release of RMG and highlight improvements since the previously published description of RMG v1.0. Most notably, RMG can now generate heterogeneous catalysis models in addition to the previously available gas- and liquid-phase capabilities. For model analysis, new methods for local and global uncertainty analysis have been implemented to supplement first-order sensitivity analysis. The RMG database of thermochemical and kinetic parameters has been significantly expanded to cover more types of chemistry. The present release includes parallelization for faster model generation and a new molecule isomorphism approach to improve computational performance. RMG has also been updated to use Python 3, ensuring compatibility with the latest cheminformatics and machine learning packages. Overall, RMG v3.0 includes many changes which improve the accuracy of the generated chemical mechanisms and allow for exploration of a wider range of chemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidation and pyrolysis of methyl propyl ether

The ignition, oxidation, and pyrolysis chemistry of methyl propyl ether (MPE) was probed experimentally at several different conditions, and a comprehensive chemical kinetic model was constructed to help understand the observations, with many of the key parameters computed using quantum chemistry and transition state theory. Experiments were carried out in a shock tube measuring time variation of CO concentrations, in a flow tube measuring product concentrations, and in a rapid compression machine (RCM) measuring ignition delay times. The detailed reaction mechanism was constructed using the Reaction Mechanism Generator software. Sensitivity and flux analyses were used to identify key rate and thermochemical parameters, which were then computed using quantum chemistry to improve the mechanism. Validation of the final model against the 1-20 bar 600-1500 K experimental data is presented with a discussion of the kinetics. The model is in excellent agreement with most of the shock tube and RCM data. Strong non-monotonic variation in conversion and product distribution is observed in the flow-tube experiments as the temperature is increased, and unusually strong pressure dependence and significant heat release during the compression stroke is observed in the RCM experiments. These observations are largely explained by a close competition between radical decomposition and addition to O2 at different sites in MPE; this causes small shifts in conditions to lead to big shifts in the dominant reaction pathways. The validated mechanism was used to study the chemistry occurring during ignition in a diesel engine, simulated using Ignition Quality Test (IQT) conditions. At the IQT conditions, where the MPE concentration is higher, bimolecular reactions of peroxy radicals are much more important than in the RCM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

What can we learn from N 2 O isotope data? – Analytics, processes and modelling

The isotopic composition of nitrous oxide (N 2 O) provides useful information for evaluating N 2 O sources and budgets. Due to the co–occurrence of multiple N 2 O transformation pathways, it is, however, challenging to use isotopic information to quantify the contribution of distinct processes across variable spatiotemporal scales. Here, we present an overview of recent progress in N 2 O isotopic studies and provide suggestions for future research, mainly focusing on: analytical techniques; production and consumption processes; and interpretation and modelling approaches. Comparing isotope–ratio mass spectrometry (IRMS) with laser absorption spectroscopy (LAS), we conclude that IRMS is a precise technique for laboratory analysis of N 2 O isotopes, while LAS is more suitable for in situ/inline studies and offers advantages for site–specific analyses. When reviewing the link between the N 2 O isotopic composition and underlying mechanisms/processes, we find that, at the molecular scale, the specific enzymes and mechanisms involved determine isotopic fractionation effects. In contrast, at plot–to–global scales, mixing of N 2 O derived from different processes and their isotopic variability must be considered. We also find that dual isotope plots are effective for semi–quantitative attribution of co–occurring N 2 O production and reduction processes. More recently, process–based N 2 O isotopic models have been developed for natural abundance and 15 N–tracing studies, and have been shown to be effective, particularly for data with adequate temporal resolution. Here, despite the significant progress made over the last decade, there is still great need and potential for future work, including development of analytical techniques, reference materials and inter–laboratory comparisons, further exploration of N 2 O formation and destruction mechanisms, more observations across scales, and design and validation of interpretation and modelling approaches. Synthesizing all these efforts, we are confident that the N 2 O isotope community will continue to advance our understanding of N 2 O transformation processes in all spheres of the Earth, and in turn to gain improved constraints on regional and global budgets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low Temperature Oxidation of Methylpropyl Ether

Ethers are potential high-performance fuels that can be produced from renewable carbon sources such as biomass, but their combustion properties are not clearly understood. The cetane numbers (CN) for ethers, a measure of autoignition tendency, can range from less than 10 to greater than 100, and predictive tools based upon the molecular structures are desirable in order to focus fuel development research. In this study, we used molecular modeling, chemical kinetic modeling, and experimental measurements to understand the important reactions that lead to the autoignition of methylpropyl ether (MPE), a model for ethers containing alkyl chains long enough for intramolecular hydrogen transfer. These reactions are known to be important in the autoignition of alkanes and ethers and we propose to investigate the relationship between alkyl and ether reaction pathways. A reaction mechanism for MPE was created using MIT's Reaction Mechanism Generator (RMG) and G4 quantum calculation results and models were tested using the ChemKin Pro suite of software. Results from atmospheric pressure, flow tube reactor experiments and rapid compression machine (RCM) experiments were used to test the kinetic model and suggest refinements.

33 ADVANCED PROPULSION SYSTEMS↗

Methyl propyl ether combustion

Ethers are potential diesel blendstocks that have high cetane numbers and identified cost-effective production pathways. Among ethers, methyl propyl ether (MPE) is a small enough molecule to build a good detailed model for and a large enough molecule for studying key intramolecular hydrogen migrations involved in low-temperature feedback loops for larger ethers. In this study, a model was generated for the combustion of MPE from 600-900 K and 10-20 bar using the Reaction Mechanism Generator (RMG) package. Results from rapid compression machine (RCM) experiments were used to validate the kinetic model. At low temperatures, the generated model successfully captured the dominant low-temperature feedback loops. At higher temperatures, propanal is a major combustion intermediate for PME, suggesting that aldehydes likely play a significant role in larger ethers' combustion.

09 BIOMASS FUELS↗

A Decision Tree Based Machine Learning Algorithm for Rate Estimation

A subgraph isomorphic decision tree algorithm was developed for estimating chemical reaction rates. The algorithm essentially associates differences in rate estimation with differences in sub-structures on the reactant or reactants, and the tree splits reactions into groups with similar rates by identifying the substructural differences that affect rate estimation the most. The algorithm was trained on rates from the Reaction Mechanism Generator (RMG) database and compared with a much more traditional rate rule estimator based on the same data. Compared to the previous RMG rate rules, the prediction accuracy of the new algorithm, measured by median absolute error (MAE) factor, root mean squared error (RMSE) factor, and 2-sigma error factor, is consistently improved by a factor of two. Uncertainty estimation was also developed for the decision trees based on fitting a lognormal distribution to the leave-one-out errors at each node. Improvements in accuracy introduced by the algorithm should significantly reduce the amount of effort required to refine models and the need for additional quantum calculations and thus reduce the amount of time and cost required to create and refine biofuel models.

Johnson, Matthew S.↗