Tropospheric OH Research Articles

Inverse modeling of 2010–2022 satellite observations shows that inundation of the wet tropics drove the 2020–2022 methane surge

Atmospheric methane concentrations rose rapidly over the past decade and surged in 2020-2022 but the causes have been unclear. We find from inverse analysis of GOSAT satellite observations that emissions from the wet tropics drove the 2010-2019 increase and the subsequent 2020-2022 surge, while emissions from northern mid-latitudes decreased. The 2020-2022 surge is principally contributed by emissions in Equatorial Asia (43%) and Africa (30%). Wetlands are the major drivers of the 2020-2022 emission increases in Africa and Equatorial Asia because of tropical inundation associated with La Niña conditions, consistent with trends in the GRACE terrestrial water storage data. In contrast, emissions from major anthropogenic emitters such as the United States, Russia, and China are relatively flat over 2010-2022. Concentrations of tropospheric OH (the main methane sink) show no long-term trend over 2010-2022 but a decrease over 2020-2022 that contributed to the methane surge.

An improved estimate of inorganic iodine emissions from the ocean using a coupled surface microlayer box model

Abstract. Iodine at the ocean's surface impacts climate and health by removing ozone (O3) from the troposphere both directly via ozone deposition to seawater and indirectly via the formation of iodine gases that are released into the atmosphere. Here we present a new box model of the ocean surface microlayer that couples oceanic O3 dry deposition to inorganic chemistry to predict inorganic iodine emissions. This model builds on the previous work of Carpenter et al. (2013), improving both chemical and physical processes. This new box model predicts iodide depletion in the top few micrometres of the ocean surface due to rapid chemical loss to ozone competing with replenishment from underlying water. From this box model, we produce parameterized equations for HOI and I2 emissions, which are implemented into the global chemical transport model GEOS-Chem along with an updated sea surface iodide climatology. Compared to the previous model, inorganic iodine emissions from some tropical waters decrease by as much as half, while higher-latitude emissions increase by a factor of ≫10. With these large local changes, global total inorganic iodine emissions increased by ∼49 % (2.99 to 4.48 Tg) compared to the previous parameterization. This results in a negligible change in average tropospheric OH (<0.2 %) and tropospheric methane lifetime (<0.2 %). The annual mean tropospheric O3 burden decreases (−1.5 % to 325 Tg); however, higher-latitude surface O3 concentrations decrease by as much as 20 %.

Revising VOC emissions speciation improves the simulation of global background ethane and propane.

Non-Methane Volatile Organic Compounds (NMVOCs) generate ozone (O3) when they are oxidized in the presence of oxides of nitrogen, modulate the oxidative capacity of the atmosphere and can lead to the formation of aerosol. Here, we assess the capability of a chemical transport model (GEOS-Chem) to simulate NMVOC concentrations by comparing ethane, propane and higher alkane observations in remote regions from the NOAA Flask Network and the World Meteorological Organization's Global Atmosphere Watch (GAW) network. Using the Community Emissions Data System (CEDS) inventory we find a significant underestimate in the simulated concentration of both ethane (35%) and propane (64%), consistent with previous studies. We run a new simulation where the total mass of anthropogenic NMVOC emitted in a grid box is the same as that used in CEDS, but with the NMVOC speciation derived from regional inventories. For US emissions we use the National Emissions Inventory (NEI), for Europe we use the UK National Atmospheric Emissions Inventory (NAEI), and for China, the Multi-resolution Emission Inventory for China (MEIC). These changes lead to a large increase in the modelled concentrations of ethane, improving the mean model bias from -35% to -4%. Simulated propane also improves (from -64% to -48% mean model bias), but there remains a substantial model underestimate. There were relatively minor changes to other NMVOCs. The low bias in simulated global ethane concentration is essentially removed, resolving one long-term issue in global simulations. Propane concentrations are improved but remain significantly underestimated, suggesting the potential for a missing global propane source. The change in the NMVOC emission speciation results in only minor changes in tropospheric O3 and OH concentrations.

Resetting tropospheric OH and CH4 lifetime with ultraviolet H2O absorption.

The decay of methyl chloroform, a banned ozone-depleting substance, has provided a clear observational metric of mean tropospheric hydroxyl radical (OH) abundance. Almost all current global chemistry models calculate about 15% too much OH and thus too rapid methane loss. Methane is a short-lived climate forcer, critical to achieving global warming targets, and this error affects our model projections of climate change. New observations of water vapor absorption in the ultraviolet region (290 to 350 nanometers) imply reductions in sunlight with key photolysis rates decreasing by 8 to 12% in the near-surface tropical atmosphere. Incorporation of this new mechanism in a chemistry-transport model reduces OH and methane loss by only 4%, but combined with other proposed mechanisms, such as tropospheric halogen chemistry (7%), we may be able to resolve this conundrum.

Environmental implications of oxalic and malonic acids with tropospheric oxidants

AbstractDicarboxylic acids (DCAs) are major players in the formation of secondary organic aerosols (SOAs) and climate change. DCAs have potential impact on human health and environmental issues ranging from local scale to global scale participate mainly in the cloud condensation. In this context, oxalic acid (OA) and malonic acid (MA) are the most dominant DCAs in the atmosphere. A full atmospheric degradation mechanism of OA and MA with the most reactive tropospheric oxidants, namely, OH, Cl and NO3 radicals, were studied using M06‐2X, ωB97XD/cc‐pVTZ and 6‐311++G(2df,2p) level of theories. To evaluate the atmospheric influence, this study enables us to deep investigation of fate of OA and MA with respect to the mentioned radicals and their subsequent secondary reactions. The latter result in the formation of carbon dioxide (CO2), formic acid (HCOOH), which contributes to the formation of SOA and climate change. The reaction mechanism in this study was initiated through H‐abstraction reaction, followed by dehydrogenation and decarboxylation reaction of both DCAs. The rate coefficients of OA, MA with OH, Cl and NO3 radicals are determined theoretically using variational transition state theory (VTST) with Eckart tunnelling method in the temperature range of 278–1000 K. At 298 K, the rate coefficient of OA with OH, Cl and NO3 are 2.48 × 10−15, 2.37 × 10−20, 6.16 × 10−23 in cm3 molecule−1 s−1, whereas MA with OH, Cl and NO3 are 9.76 × 10−14, 1.01 × 10−12 and 5.89 × 10−18 in cm3 molecule−1 s−1, respectively. Our present results shed light on the atmospheric implications of two DCAs and provide the significant insight for the atmospheric pathways.

The impact of internal climate variability on OH trends between 2005 and 2014

The hydroxyl radical (OH) lies at the nexus of climate and air quality as the primary oxidant for both reactive greenhouse gases and many hazardous air pollutants. To better understand the role of climate variability on spatiotemporal patterns of OH, we utilize a 13-member ensemble of the Community Earth System Model version 2-Whole Atmosphere Community Climate Model version 6 (CESM2-WACCM6), a fully coupled chemistry-climate model, spanning the years 1950–2014. Ensemble members vary only in their initial conditions of the climate state in 1950. We focus on the final decade of the simulation, 2005–2014, when prior studies disagree on the signs of the global OH trends. The ensemble mean global airmass-weighted mean tropospheric column OH ( ΩTOH ), which is an estimate of the forced signal, increases by 0.06%/year between 2005 and 2014 while regional ΩTOH trends range from −0.56%/year over Southern Europe to +0.64%/year over South America. We show that ten-year ΩTOH trends are strongly affected by internal climate variability, as the spread of ΩTOH trends across the ensemble varies between 0.23%/year in Asia and 1.53%/year in South America. We train a fully connected neural network to emulate the ΩTOH simulated by the CESM2-WACCM6 model and combine it with satellite observations to interpret the role of OH chemical proxies. While the OH chemical proxies are subject to internal variability, the impact of internal variability on ΩTOH trends is primarily due to the meteorological parameters except for South America. Forced trends in global mean ΩTOH do not unambiguously emerge from trends driven by internal variability over the 2005–2014 period. The observation-constrained ΩTOH presents opposite trends due to climate variability, resulting in varying conclusions on the attribution of OH to CH4 trends.

Trends and Interannual Variability of the Hydroxyl Radical in the Remote Tropics During Boreal Autumn Inferred From Satellite Proxy Data

AbstractDespite its importance for the global oxidative capacity, spatially resolved trends and variability of the hydroxyl radical (OH) are poorly constrained. We demonstrate the utility of a tropospheric column OH (TCOH) product, created from machine learning and satellite proxy data, in determining the spatial variability in trends of tropical OH over the oceans during September through November. While OH increases domain‐wide by 2.1%/decade from 2005–2019, we find significant spatial heterogeneity in regional trends, with decreases in some areas of 2.5%/decade. Our analysis of the trends in the proxy data indicate anthropogenic‐driven changes in emissions of OH drivers as well as increasing temperatures cause these trends. This OH product is potentially a significant advance in constraining OH spatial variability and serves as a useful complement to existing tools in understanding the atmospheric oxidative capacity. Comprehensive observations of TCOH are required to assess the fidelity of this method.

Impacts of updated reaction kinetics on the global GEOS-Chem simulation of atmospheric chemistry.

We updated the chemical mechanism of the GEOS-Chem global 3-D model of atmospheric chemistry to include new recommendations from the NASA Jet Propulsion Laboratory (JPL) chemical kinetics Data Evaluation 19-5 and from the International Union of Pure and Applied Chemistry (IUPAC) and to balance carbon and nitrogen. We examined the impact of these updates on the GEOS-Chem version 14.0.1 simulation. Notable changes include 11 updates to reactions of reactive nitrogen species, resulting in a 7% net increase in the stratospheric NOx (NO + NO2) burden; an updated CO + OH rate formula leading to a 2.7% reduction in total tropospheric CO; adjustments to the rate coefficient and branching ratios of propane + OH, leading to reduced tropospheric propane (-17%) and increased acetone (+3.5%) burdens; a 41% increase in the tropospheric burden of peroxyacetic acid due to a decrease in the rate coefficient for its reaction with OH, further contributing to reductions in peroxyacetyl nitrate (PAN; -3.8%) and acetic acid (-3.4%); and a number of minor adjustments to halogen radical cycling. Changes to the global tropospheric burdens of other species include -0.7% for ozone, +0.3% for OH (-0.4% for methane lifetime against oxidation by tropospheric OH), +0.8% for formaldehyde, and -1.7% for NOx. The updated mechanism reflects the current state of the science, including complex chemical dependencies of key atmospheric species on temperature, pressure, and concentrations of other compounds. The improved conservation of carbon and nitrogen will facilitate future studies of their overall atmospheric budgets.

An observation-based, reduced-form model for oxidation in the remote marine troposphere

The hydroxyl radical (OH) fuels atmospheric chemical cycling as the main sink for methane and a driver of the formation and loss of many air pollutants, but direct OH observations are sparse. We develop and evaluate an observation-based proxy for short-term, spatial variations in OH (ProxyOH) in the remote marine troposphere using comprehensive measurements from the NASA Atmospheric Tomography (ATom) airborne campaign. ProxyOH is a reduced form of the OH steady-state equation representing the dominant OH production and loss pathways in the remote marine troposphere, according to box model simulations of OH constrained with ATom observations. ProxyOH comprises only eight variables that are generally observed by routine ground- or satellite-based instruments. ProxyOH scales linearly with in situ [OH] spatial variations along the ATom flight tracks (median r2 = 0.90, interquartile range = 0.80 to 0.94 across 2-km altitude by 20° latitudinal regions). We deconstruct spatial variations in ProxyOH as a first-order approximation of the sensitivity of OH variations to individual terms. Two terms modulate within-region ProxyOH variations-water vapor (H2O) and, to a lesser extent, nitric oxide (NO). This implies that a limited set of observations could offer an avenue for observation-based mapping of OH spatial variations over much of the remote marine troposphere. Both H2O and NO are expected to change with climate, while NO also varies strongly with human activities. We also illustrate the utility of ProxyOH as a process-based approach for evaluating intermodel differences in remote marine tropospheric OH.

Technical note: Constraining the hydroxyl (OH) radical in the tropics with satellite observations of its drivers – first steps toward assessing the feasibility of a global observation strategy

Abstract. Despite its importance in controlling the abundance of methane (CH4) and a myriad of other tropospheric species, the hydroxyl radical (OH) is poorly constrained due to its large spatial heterogeneity and the inability to measure tropospheric OH with satellites. Here, we present a methodology to infer tropospheric column OH (TCOH) in the tropics over the open oceans using a combination of a machine learning model, output from a simulation of the GEOS model, and satellite observations. Our overall goals are to assess the feasibility of our methodology, to identify potential limitations, and to suggest areas of improvement in the current observational network. The methodology reproduces the variability of TCOH from independent 3D model output and of observations from the Atmospheric Tomography mission (ATom). While the methodology also reproduces the magnitude of the 3D model validation set, the accuracy of the magnitude when applied to observations is uncertain because current observations are insufficient to fully evaluate the machine learning model. Despite large uncertainties in some of the satellite retrievals necessary to infer OH, particularly for NO2 and formaldehyde (HCHO), current satellite observations are of sufficient quality to apply the machine learning methodology, resulting in an error comparable to that of in situ OH observations. Finally, the methodology is not limited to a specific suite of satellite retrievals. Comparison of TCOH determined from two sets of retrievals does show, however, that systematic biases in NO2, resulting both from retrieval algorithm and instrumental differences, lead to relative biases in the calculated TCOH. Further evaluation of NO2 retrievals in the remote atmosphere is needed to determine their accuracy. With slight modifications, a similar methodology could likely be expanded to the extratropics and over land, with the benefits of increasing our understanding of the atmospheric oxidation capacity and, for instance, informing understanding of recent CH4 trends.

Comparison between ozone column depths and methane lifetimes computed by one- and three-dimensional models at different atmospheric O2 levels.

Recently, Cooke et al. (Cooke et al. 2022 R. Soc. Open Sci. 9, 211165. (doi:10.1098/rsos.211165)) used a three-dimensional coupled chemistry-climate model (WACCM6) to calculate ozone column depths at varied atmospheric O2 levels. They argued that previous one-dimensional (1-D) photochemical model studies, e.g. Segura et al. (Segura et al. 2003 Astrobiology 3, 689-708. (doi:10.1089/153110703322736024)), may have overestimated the ozone column depth at low pO2, and hence also overestimated the lifetime of methane. We have compared new simulations from an updated version of the Segura et al. model with those from WACCM6, together with some results from a second three-dimensional model. The discrepancy in ozone column depths is probably due to multiple interacting parameters, including H2O in the upper troposphere, lower boundary conditions, vertical and meridional transport rates, and different chemical mechanisms, especially the treatment of O2 photolysis in the Schumann-Runge (SR) bands (175-205 nm). The discrepancy in tropospheric OH concentrations and methane lifetime between WACCM6 and the 1-D model at low pO2 is reduced when absorption from CO2 and H2O in this wavelength region is included in WACCM6. Including scattering in the SR bands may further reduce this difference. Resolving these issues can be accomplished by developing an accurate parametrization for O2 photolysis in the SR bands and then repeating these calculations in the various models.

Methane emissions are predominantly responsible for record-breaking atmospheric methane growth rates in 2020 and 2021

Abstract. The global atmospheric methane growth rates reported by NOAA for 2020 and 2021 are the largest since systematic measurements began in 1983. To explore the underlying reasons for these anomalous growth rates, we use newly available methane data from the Japanese Greenhouse gases Observing SATellite (GOSAT) to estimate methane surface emissions. Relative to baseline values in 2019, we find that a significant global increase in methane emissions of 27.0 ± 11.3 and 20.8 ± 11.4 Tg is needed to reproduce observed atmospheric methane in 2020 and 2021, respectively, assuming fixed climatological values for OH. We see the largest annual increases in methane emissions during 2020 over Eastern Africa (14 ± 3 Tg), tropical Asia (3 ± 4 Tg), tropical South America (5 ± 4 Tg), and temperate Eurasia (3 ± 3 Tg), and the largest reductions are observed over China (−6 ± 3 Tg) and India (−2 ± 3 Tg). We find comparable emission changes in 2021, relative to 2019, except for tropical and temperate South America where emissions increased by 9 ± 4 and 4 ± 3 Tg, respectively, and for temperate North America where emissions increased by 5 ± 2 Tg. The elevated contributions we saw in 2020 over the western half of Africa (−5 ± 3 Tg) are substantially reduced in 2021, compared to our 2019 baseline. We find statistically significant positive correlations between anomalies of tropical methane emissions and groundwater, consistent with recent studies that have highlighted a growing role for microbial sources over the tropics. Emission reductions over India and China are expected in 2020 due to the Covid-19 lockdown but continued in 2021, which we do not currently understand. To investigate the role of reduced OH concentrations during the Covid-19 lockdown in 2020 on the elevated atmospheric methane growth in 2020–2021, we extended our inversion state vector to include monthly scaling factors for OH concentrations over six latitude bands. During 2020, we find that tropospheric OH is reduced by 1.4 ± 1.7 % relative to the corresponding 2019 baseline value. The corresponding revised global growth of a posteriori methane emissions in 2020 decreased by 34 % to 17.9 ± 13.2 Tg, relative to the a posteriori value that we inferred using fixed climatological OH values, consistent with sensitivity tests using the OH climatology inversion using reduced values for OH. The counter statement is that 66 % of the global increase in atmospheric methane during 2020 was due to increased emissions, particularly from tropical regions. Regional flux differences between the joint methane–OH inversion and the OH climatology inversion in 2020 are typically much smaller than 10 %. We find that OH is reduced by a much smaller amount during 2021 than in 2020, representing about 10 % of the growth of atmospheric methane in that year. Therefore, we conclude that most of the observed increase in atmospheric methane during 2020 and 2021 is due to increased emissions, with a significant contribution from reduced levels of OH.

Nitrogen oxides in the free troposphere: implications for tropospheric oxidants and the interpretation of satellite NO2 measurements

Abstract. Satellite-based retrievals of tropospheric NO2 columns are widely used to infer NOx (≡ NO + NO2) emissions. These retrievals rely on model information for the vertical distribution of NO2. The free tropospheric background above 2 km is particularly important because the sensitivity of the retrievals increases with altitude. Free tropospheric NOx also has a strong effect on tropospheric OH and ozone concentrations. Here we use observations from three aircraft campaigns (SEAC4RS, DC3, and ATom) and four atmospheric chemistry models (GEOS-Chem, GMI, TM5, and CAMS) to evaluate the model capabilities for simulating NOx in the free troposphere and attribute it to sources. NO2 measurements during the Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS) and Deep Convective Clouds and Chemistry (DC3) campaigns over the southeastern U.S. in summer show increasing concentrations in the upper troposphere above 10 km, which are not replicated by the GEOS-Chem, although the model is consistent with the NO measurements. Using concurrent NO, NO2, and ozone observations from a DC3 flight in a thunderstorm outflow, we show that the NO2 measurements in the upper troposphere are biased high, plausibly due to interference from thermally labile NO2 reservoirs such as peroxynitric acid (HNO4) and methyl peroxy nitrate (MPN). We find that NO2 concentrations calculated from the NO measurements and NO–NO2 photochemical steady state (PSS) are more reliable to evaluate the vertical profiles of NO2 in models. GEOS-Chem reproduces the shape of the PSS-inferred NO2 profiles throughout the troposphere for SEAC4RS and DC3 but overestimates NO2 concentrations by about a factor of 2. The model underestimates MPN and alkyl nitrate concentrations, suggesting missing organic NOx chemistry. On the other hand, the standard GEOS-Chem model underestimates NO observations from the Atmospheric Tomography Mission (ATom) campaigns over the Pacific and Atlantic oceans, indicating a missing NOx source over the oceans. We find that we can account for this missing source by including in the model the photolysis of particulate nitrate on sea salt aerosols at rates inferred from laboratory studies and field observations of nitrous acid (HONO) over the Atlantic. The median PSS-inferred tropospheric NO2 column density for the ATom campaign is 1.7 ± 0.44 × 1014 molec. cm−2, and the NO2 column density simulated by the four models is in the range of 1.4–2.4 × 1014 molec. cm−2, implying that the uncertainty from using modeled NO2 tropospheric columns over clean areas in the retrievals for stratosphere–troposphere separation is about 1 × 1014 molec. cm−2. We find from GEOS-Chem that lightning is the main primary NOx source in the free troposphere over the tropics and southern midlatitudes, but aircraft emissions dominate at northern midlatitudes in winter and in summer over the oceans. Particulate nitrate photolysis increases ozone concentrations by up to 5 ppbv (parts per billion by volume) in the free troposphere in the northern extratropics in the model, which would largely correct the low model bias relative to ozonesonde observations. Global tropospheric OH concentrations increase by 19 %. The contribution of the free tropospheric background to the tropospheric NO2 columns observed by satellites over the contiguous U.S. increases from 25 ± 11 % in winter to 65 ± 9 % in summer, according to the GEOS-Chem vertical profiles. This needs to be accounted for when deriving NOx emissions from satellite NO2 column measurements.

Extensive field evidence for the release of HONO from the photolysis of nitrate aerosols.

Particulate nitrate ([Formula: see text]) has long been considered a permanent sink for NOx (NO and NO2), removing a gaseous pollutant that is central to air quality and that influences the global self-cleansing capacity of the atmosphere. Evidence is emerging that photolysis of [Formula: see text] can recycle HONO and NOx back to the gas phase with potentially important implications for tropospheric ozone and OH budgets; however, there are substantial discrepancies in "renoxification" photolysis rate constants. Using aircraft and ground-based HONO observations in the remote Atlantic troposphere, we show evidence for renoxification occurring on mixed marine aerosols with an efficiency that increases with relative humidity and decreases with the concentration of [Formula: see text], thus largely reconciling the very large discrepancies in renoxification photolysis rate constants found across multiple laboratory and field studies. Active release of HONO from aerosol has important implications for atmospheric oxidants such as OH and O3 in both polluted and clean environments.

Reconciling the bottom-up and top-down estimates of the methane chemical sink using multiple observations

Abstract. The methane chemical sink estimated by atmospheric chemistry models (bottom-up method) is significantly larger than estimates based on methyl chloroform (MCF) inversions (top-down method). The difference is partly attributable to large uncertainties in hydroxyl radical (OH) concentrations simulated by the atmospheric chemistry models used to derive the bottom-up estimates. In this study, we propose a new approach based on OH precursor observations and a chemical box model. This approach contributes to improving the 3D distributions of tropospheric OH radicals obtained from atmospheric chemistry models and reconciling bottom-up and top-down estimates of the chemical loss of atmospheric methane. By constraining simulated OH precursors with observations, the global mean tropospheric column-averaged air-mass-weighted OH concentration ([OH]trop-M) is ∼10×105 molec. cm−3 (which is 2×105 molec. cm−3 lower than the original model-simulated global [OH]trop-M) and agrees with that obtained by the top-down method based on MCF inversions. With OH constrained by precursor observations, the methane chemical loss is 471–508 Tg yr−1, averaged from 2000 to 2009. The new adjusted estimate is in the range of the latest top-down estimate of the Global Carbon Project (GCP) (459–516 Tg yr−1), contrary to the bottom-up estimates that use the original model-simulated OH fields (577–612 Tg yr−1). The overestimation of global [OH]trop-M and methane chemical loss simulated by the atmospheric chemistry models is caused primarily by the models' underestimation of carbon monoxide and total ozone column, and overestimation of nitrogen dioxide. Our results highlight that constraining the model-simulated OH fields with available OH precursor observations can help improve bottom-up estimates of the global methane sink.

Wetland emission and atmospheric sink changes explain methane growth in 2020.

Atmospheric methane growth reached an exceptionally high rate of 15.1 ± 0.4 parts per billion per year in 2020 despite a probable decrease in anthropogenic methane emissions during COVID-19 lockdowns1. Here we quantify changes in methane sources and in its atmospheric sink in 2020 compared with 2019. We find that, globally, total anthropogenic emissions decreased by 1.2 ± 0.1 teragrams of methane per year (Tg CH4 yr-1), fire emissions decreased by 6.5 ± 0.1 Tg CH4 yr-1 and wetland emissions increased by 6.0 ± 2.3 Tg CH4 yr-1. Tropospheric OH concentration decreased by 1.6 ± 0.2 per cent relative to 2019, mainly as a result of lower anthropogenic nitrogen oxide(NOx) emissions and associated lower free tropospheric ozone during pandemic lockdowns2. From atmospheric inversions,we also infer that global net emissions increased by 6.9 ± 2.1 Tg CH4 yr-1 in 2020 relative to 2019, and global methane removal from reaction with OH decreased by 7.5 ± 0.8 Tg CH4 yr-1. Therefore, we attribute the methane growth rate anomaly in 2020 relative to 2019 to lower OH sink (53 ± 10 per cent) and higher natural emissions (47 ± 16 per cent), mostly from wetlands. In line with previous findings3,4, our results imply that wetland methane emissions are sensitive to a warmer and wetter climate and could act as a positive feedback mechanism inthe future. Our study also suggests that nitrogen oxide emission trends need to be taken into account when implementing the global anthropogenic methane emissions reduction pledge5.

Observed versus simulated OH reactivity during KORUS-AQ campaign: Implications for emission inventory and chemical environment in East Asia

We present a holistic examination of tropospheric OH reactivity (OHR) in South Korea using comprehensive NASA DC-8 airborne measurements collected during the Korea–United States Air Quality field study and chemical transport models. The observed total OHR (tOHR) averaged in the planetary boundary layer (PBL, <2.0 km) and free troposphere was 5.2 s−1 and 2.0 s−1 during the campaign, respectively. These values were higher than the calculated OHR (cOHR, 3.4 s−1, 1.0 s−1) derived from trace-gas observations, indicating missing OHR fractions in the PBL and free troposphere of 35% and 50%, respectively. Incorporating nonobserved secondary species from the observationally constrained box model increased cOHR to 4.0 s−1 in the PBL and 1.3 s−1 in the free troposphere. Simulated OHR (sOHR, 2.7 s−1, 0.8 s−1) was substantially lower than both tOHR and cOHR by as much as 60%. This underestimate was substantial in the free troposphere and marine boundary layer of the marginal sea (Yellow Sea). We then discuss the potential causes of unaccounted OHR. First, we suggest improving the accuracy of tropospheric reaction kinetics, which vary significantly in the available literature. Second, underestimated emissions of anthropogenic CO and oxygenated volatile organic compounds in East Asia contributed to the discrepancy between tOHR and sOHR. In addition, oxygenated and biogenic volatile organic compounds emitted from the marginal sea may contribute substantially to the regional OHR. Typical chemical transport models underestimate these sources, leading to a large missing OHR fraction. Despite this discrepancy, we found that simulated OH concentrations were comparable with those observed during the campaign because of slow OH recycling rates in the models; therefore, the models predicted less formation of photochemical oxidation products such as ozone.

Attribution of the 2020 surge in atmospheric methane by inverse analysis of GOSAT observations

Atmospheric methane mixing ratio rose by 15 ppbv between 2019 and 2020, the fastest growth rate on record. We conduct a global inverse analysis of 2019–2020 Greenhouse Gases Observing Satellite observations of atmospheric methane to analyze the combination of sources and sinks driving this surge. The imbalance between sources and sinks of atmospheric methane increased by 31 Tg a−1 from 2019 to 2020, representing a 36 Tg a−1 forcing (direct changes in methane emissions and OH concentrations) on the methane budget away from steady state. 86% of the forcing in the base inversion is from increasing emissions (82 ± 18% in the nine-member inversion ensemble), and only 14% is from decrease in tropospheric OH. Half of the increase in emissions is from Africa (15 Tg a−1) and appears to be driven by wetland inundation. There is also a large relative increase in emissions from Canada and Alaska (4.8 Tg a−1, 24%) that could be driven by temperature sensitivity of boreal wetland emissions.

Reactive halogens increase the global methane lifetime and radiative forcing in the 21st century

CH4 is the most abundant reactive greenhouse gas and a complete understanding of its atmospheric fate is needed to formulate mitigation policies. Current chemistry-climate models tend to underestimate the lifetime of CH4, suggesting uncertainties in its sources and sinks. Reactive halogens substantially perturb the budget of tropospheric OH, the main CH4 loss. However, such an effect of atmospheric halogens is not considered in existing climate projections of CH4 burden and radiative forcing. Here, we demonstrate that reactive halogen chemistry increases the global CH4 lifetime by 6–9% during the 21st century. This effect arises from significant halogen-mediated decrease, mainly by iodine and bromine, in OH-driven CH4 loss that surpasses the direct Cl-induced CH4 sink. This increase in CH4 lifetime helps to reduce the gap between models and observations and results in a greater burden and radiative forcing during this century. The increase in CH4 burden due to halogens (up to 700 Tg or 8% by 2100) is equivalent to the observed atmospheric CH4 growth during the last three to four decades. Notably, the halogen-driven enhancement in CH4 radiative forcing is 0.05 W/m2 at present and is projected to increase in the future (0.06 W/m2 by 2100); such enhancement equals ~10% of present-day CH4 radiative forcing and one-third of N2O radiative forcing, the third-largest well-mixed greenhouse gas. Both direct (Cl-driven) and indirect (via OH) impacts of halogens should be included in future CH4 projections.

Development and evaluation of a new compact mechanism for aromatic oxidation in atmospheric models

Abstract. Aromatic hydrocarbons, including benzene, toluene, and xylenes, play an important role in atmospheric chemistry, but the associated chemical mechanisms are complex and uncertain. Sparing representation of this chemistry in models is needed for computational tractability. Here, we develop a new compact mechanism for aromatic chemistry (GC13) that captures current knowledge from laboratory and computational studies with only 17 unique species and 44 reactions. We compare GC13 to six other currently used mechanisms of varying complexity in box model simulations of environmental chamber data and diurnal boundary layer chemistry, and show that GC13 provides results consistent with or better than more complex mechanisms for oxygenated products (alcohols, carbonyls, dicarbonyls), ozone, and hydrogen oxide (HOx≡OH+HO2) radicals. Specifically, GC13 features increased radical recycling and increased ozone destruction from phenoxy–phenylperoxy radical cycling relative to other mechanisms. We implement GC13 into the GEOS-Chem global chemical transport model and find higher glyoxal yields and net ozone loss from aromatic chemistry compared with other mechanisms. Aromatic oxidation in the model contributes 23 %, 5 %, and 8 % of global glyoxal, methylglyoxal, and formic acid production, respectively, and has mixed effects on formaldehyde. It drives small decreases in global tropospheric OH (−2.2 %), NOx (≡NO+NO2; −3.7 %), and ozone (−0.8 %), but a large increase in NO3 (+22 %) from phenoxy–phenylperoxy radical cycling. Regional effects in polluted environments can be substantially larger, especially from the photolysis of carbonyls produced by aromatic oxidation, which drives large wintertime increases in OH and ozone concentrations.