Tropospheric Oxidation Capacity Research Articles

Rapid Atmospheric Reactions between Criegee Intermediates and Hypochlorous Acid.

Hypochlorous acid (HOCl) is a paramount compound in the atmosphere due to its significant contribution to both tropospheric oxidation capacity and ozone depletion. The main removal routes for HOCl are photolysis and the reaction with OH during the daytime, while these processes are unimportant during the nighttime. Here, we report the rapid reactions of Criegee intermediates (CH2OO and anti/syn-CH3CHOO) with HOCl by using high-level quantum chemical methods as the benchmark; their accuracy is close to coupled cluster theory with single, double, and triple excitations and quasiperturbative connected quadruple excitations with a complete basis limit by extrapolation [CCSDT(Q)/CBS]. Their rate constants have been calculated by using a dual-level strategy; this combines conventional transition state theory calculated at the benchmark level with variational transition state theory with small-curvature tunneling by a validated density functional method. We find that the introduction of the methyl group into Criegee intermediates not only affects their reactivities but also exerts a remarkable influence on anharmonicity. The calculated results uncover that anharmonicity increases the rate constants of CH2OO + HOCl by a factor of 18-5, while it is of minor importance in the anti/syn-CH3CHOO + HOCl reaction at 190-350 K. The present findings reveal that the loose transition state for anti-CH3CHOO and HOCl is a rate-determining step at 190-350 K. We also find that the reaction of Criegee intermediates with HOCl contributes significantly to the sink of HOCl during the nighttime in the atmosphere.

Development and application of a nitrogen oxides analyzer based on the cavity attenuated phase shift technique

Nitrogen oxides (NOx) are crucial in tropospheric photochemical ozone (O3) production and oxidation capacity. Currently, the widely used NOx measurement technique is chemiluminescence (CL) (CL-NOx), which tends to overestimate NO2 due to atmospheric oxidation products of NOx (i.e., NOz). We developed and characterized a NOx measurement system using the cavity attenuated phase shift (CAPS) technique (CAPS-NOx), which is free from interferences with nitrogen-containing species. The NOx measured by the CAPS-NOx and CL-NOx analyzers were compared. Results show that both analyzers showed consistent measurement results for NO, but the NO2 measured by the CAPS-NOx analyzer (NO2_CAPS) was mostly lower than that measured by the CL-NOx analyzer (NO2_CL), which led to the deviations in O3 formation sensitivity regime and Ox (= O3 + NO2) sources (i.e., regional background and photochemically produced Ox) determined by the ozone production efficiencies (OPE) calculated from NO2_CL and NO2_CAPS. Overall, OPE_CL exceeded OPE_CAPS by 18.9%, which shifted 3 out of 13 observation days from the VOCs-limited to the transition regime when judging using OPE_CL, as compared to calculations using OPE_CAPS. During the observation period, days dominated by regional background Ox accounted for 46% and 62% when determined using NO2_CL and NO2_CAPS, respectively. These findings suggest that the use of the CL-NOx analyzer tends to underestimate both the VOCs-limited regime and the regional background Ox dominated days. The newly built CAPS-NOx analyzer here can promote the accurate measurement of NO2, which is meaningful for diagnosing O3 formation regimes and Ox sources.

Overlooked Long‐Term Atmospheric Chemical Feedbacks Alter the Impact of Solar Geoengineering: Implications for Tropospheric Oxidative Capacity

AbstractStudies of the impacts of solar geoengineering have mostly ignored tropospheric chemistry. By decreasing the sunlight reaching Earth's surface, geoengineering may help mitigate anthropogenic climate change, but changing sunlight also alters the rates of chemical reactions throughout the troposphere. Using the GEOS‐Chem atmospheric chemistry model, we show that stratospheric aerosol injection (SAI) with sulfate, a frequently studied solar geoengineering method, can perturb tropospheric composition over a span of 10 years, increasing tropospheric oxidative capacity by 9% and reducing methane lifetime. SAI decreases the overall flux of shortwave radiation into the troposphere, but increases flux at certain UV wavelengths due to stratospheric ozone depletion. These radiative changes, in turn, perturb tropospheric photochemistry, driving chemical feedbacks that can substantially influence the seasonal and spatial patterns of radiative forcing beyond what is caused by enhanced stratospheric aerosol concentrations alone. For example, chemical feedbacks decrease the radiative effectiveness of geoengineering in northern high latitude summer by 20%. Atmospheric chemical feedbacks also imply the potential for net global public health benefits associated with stratospheric ozone depletion, as the decreases in mortality resulting from SAI‐induced improvements in air quality outweigh the increases in mortality due to increased UV radiation exposure. Such chemical feedbacks also lead to improved plant growth. Our results show the importance of including fuller representations of atmospheric chemistry in studies of solar geoengineering and underscore the risk of surprises from this technology that could carry unexpected consequences for Earth's climate, the biosphere, and human health.

Application of Satellite‐Based Detections of Arctic Bromine Explosion Events Within GEOS‐Chem

AbstractDuring polar spring, periods of elevated tropospheric bromine drive near complete removal of surface ozone. These events impact the tropospheric oxidative capacity and are an area of active research with multiple approaches for representing the underlying processes in global models. We present a method for parameterizing emissions of molecular bromine (Br2) over the Arctic using satellite retrievals of bromine monoxide (BrO) from the Ozone Monitoring Instrument (OMI). OMI retrieves column BrO with daily near global coverage, and we use the GEOS‐Chem chemical mechanism, run online within the Goddard Earth Observing System Earth System Model to identify hotspots of BrO likely associated with polar processes. To account for uncertainties in modeling background BrO, hotspots are only identified where the difference between OMI and modeled columns exceeds a statistical threshold. The resulting hotspot columns are a lower‐limit for the portion of OMI BrO attributable to bromine explosion events. While these hotspots are correlated with BrO measured in the lower troposphere over the Arctic Ocean, a case study of missing detections of near‐surface BrO is identified. Daily flux of Br2 is estimated from hotspot columns of BrO using internal model parameters. When the emissions are applied, BrO hotspots are modeled with a 5% low bias. The sensitivity of the resulting ozone simulations to the treatment of background uncertainties in the BrO column is demonstrated. While periods of isolated, large (>50%) decreases in surface ozone are modeled, this technique does not simulate the low ozone observed at coastal stations and consistently underestimates ozone loss during March.

Development of an enhanced method for atmospheric carbonyls and characterizing their roles in photochemistry in subtropical Hong Kong

Carbonyl compounds are ubiquitous and play vital roles in tropospheric photochemistry and oxidation capacity, particularly affecting radical cycling and ozone formation. An enhanced method based on ultra-high-performance liquid chromatography and electrospray ionization tandem mass spectrometry was developed to simultaneously quantify 47 carbonyl compounds with carbon (C) numbers from 1 to 13. Applying this new method to samples collected at ground and ship-borne field campaigns, we investigated the abundance, characteristic distribution, and photochemical activity of carbonyl species in the coastal atmosphere of Hong Kong. The total concentration of detected carbonyls ranged from 9.1 to 32.7 ppbv and exhibited distinct spatial variability. In addition to the usual abundant carbonyl species (formaldehyde, acetaldehyde, and acetone), aliphatic saturated aldehydes with C ≥ 5 (particularly hexaldehyde and nonanaldehyde), and di‑carbonyls, exhibit significant abundance and photochemical reactivity in the coastal site and on the sea. The measured carbonyls could contribute to an estimated peroxyl radical formation rate of 1.88–8.43 ppb/h via OH oxidation and photolysis, greatly enhancing oxidation capacity and radical cycling. The ozone formation potential (OFP) estimated from the maximum incremental reactivity (MIR) was dominated (69 %–82 %) by formaldehyde and acetaldehyde, with significant contribution (4 %–13 %) from di‑carbonyls. Furthermore, another dozens of long-chain carbonyls without MIR values, which were typically below detection or not included in the conventional analytical method, would increase the ozone formation rate by an additional 2 %–33 %. Additionally, the glyoxal, methylglyoxal, benzaldehyde and other α, β-unsaturated aldehydes also exhibited considerable contribution to secondary organic aerosol (SOA) formation potential. This study highlights the importance of various reactive carbonyls in the atmospheric chemistry of urban and coastal regions. The newly developed method can effectively characterize more carbonyl compounds and advance our understanding of their roles in photochemical air pollution.

A Computational Perspective on the Chemical Reaction of HFO-1234zc with the OH Radical in the Gas Phase and in the Presence of Mineral Dust.

The gas phase and heterogeneous reaction on mineral dust aerosols of trace gases could significantly affect the tropospheric oxidation capacity and aerosol composition of the atmosphere. In this work, the OH radical-initiated oxidation of a hydrofluoroolefin, HFO-1234zc, and subsequent reaction of favorable intermediates with other reactive species, such as O2, HO2, and NOx (x = 1-2) radicals, were studied, and the role of mineral dust in the form of silicate clusters on the reaction mechanism and rate constant was studied. In the gas phase, OH radical addition to HFO-1234zc is kinetically more favorable than the H-atom abstraction reaction. The calculated reaction energy barrier and thermochemical parameters show that both the initial reactions are more feasible on silicate clusters. Thus, silicates can act as chemical sinks for trapping of hydrofluoroolefins (HFOs). It is found that both gas-phase and heterogeneous reactions are responsible for the transformation of HFOs into fluorinated compounds in the atmosphere. Further, the results show that the ozone creation potential of HFO-1234zc is low, and few of the products are harmful to aquatic organisms. This study provides new insights on the formation of toxic pollutants from the oxidation of HFO-1234zc, which may have significant implications in the troposphere.

Stratosphere‐Troposphere Exchanges of Air Mass and Ozone Concentration in the Last Glacial Maximum

AbstractStratosphere‐troposphere exchange (STE) of ozone represents a significant source term in the tropospheric ozone budget and can impact surface ozone concentrations, tropospheric oxidation capacity, and methane lifetime. Using the Whole Atmosphere Community Climate Model 6, changes in the air mass and ozone STEs in the Last Glacial Maximum (LGM) as compared with preindustrial (PI) climate are investigated. We use dynamic isentropic surfaces that are determined by fitting to the tropical tropopauses as the upper boundary of the lowermost stratosphere in a mass budget approach, a method particularly suitable for estimating air mass and ozone STEs across different climates. Relative to the PI, the magnitude of ozone STE in the LGM is decreased by 14%–19%, 18%–24%, 18%–23%, 16%–21%, and 15%–21% over the Northern hemisphere extratropics, Southern hemisphere extratropics, the tropics, the extratropics, and the globe, respectively. The extratropical and global decreases are mainly caused by decreased ozone in the extratropical lower stratosphere associated with a weakening of Brewer‐Dobson circulation, while changes in air mass fluxes play a minor role because the effects of weakening Brewer‐Dobson circulation and increased isentropic density partly cancel each other. Analysis of the modeled tropospheric ozone budget indicates that the ozone STE in the LGM is 28% of the tropospheric ozone production rate, as compared to about 9% in the modern climate (year 2000) and 19% in the PI.

Global Emissions of Hydrogen Chloride and Particulate Chloride from Continental Sources.

Gaseous and particulate chlorine species play an important role in modulating tropospheric oxidation capacity, aerosol water uptake, visibility degradation, and human health. The lack of recent global continental chlorine emissions has hindered modeling studies of the role of chlorine in the atmosphere. Here, we develop a comprehensive global emission inventory of gaseous HCl and particulate Cl- (pCl), including 35 sources categorized in six source sectors based on published up-to-date activity data and emission factors. These emissions are gridded at a spatial resolution of 0.1° × 0.1° for the years 1960 to 2014. The estimated emissions of HCl and pCl in 2014 are 2354 (1661-3201) and 2321 (930-3264) Gg Cl a-1, respectively. Emissions of HCl are mostly from open waste burning (38%), open biomass burning (19%), energy (19%), and residential (13%) sectors, and the major sources classified by fuel type are combustion of waste (43%), biomass (32%), and coal (25%). Emissions of pCl are mostly from biofuel (29%) and open biomass burning processes (44%). The sectoral and spatial distributions of HCl and pCl emissions are very heterogeneous along the study period, and the temporal trends are mainly driven by the changes in emission factors, energy intensity, economy, and population.

Enhanced stratospheric intrusion at Lulin Mountain, Taiwan inferred from beryllium-7 activity

Beryllium-7 (7Be), produced by the interaction of cosmic radiation with atoms and molecules primarily in the upper troposphere and lower stratosphere, provides a useful tracer of cross-tropopause transport and vertical mixing in the troposphere. In the western Pacific subtropical region, the interaction of the subtropical jet stream with monsoon systems potentially enhances the transport. Here, we report one year of 7Be measurements at daily resolution during 2010, at Mt. Lulin (2862 m above mean sea level; NOAA code: LLN), along with other gaseous compounds such as O3 and CO and meteorological information, to assess processes that affect the variability of 7Be. The 7Be concentrations are of the order 1 mBq/m3 or less. The 7Be activity is generally low during summer, largely due to precipitation and unfavorable conditions of atmospheric dynamics (i.e., prevalence of upward motion), but it is occasionally high because of the influence of typhoons. In winter and spring, stratospheric effects observed at the surface were frequent and significant, thereby directly affecting the strength of stratospheric effects on the troposphere, such as the tropospheric oxidation capacity. The effects of the stratospheric intrusions are seen by negative and positive correlations of 7Be with relative humidity and concentration of O3, respectively. The stratospheric effect is further supported by the presence of downwelling transport in this region in the European Centre for Medium-Range Weather Forecasts-Atmospheric Composition Reanalysis Version 4 CO, O3, and relative humidity data.

First retrievals of peroxyacetyl nitrate (PAN) from ground-based FTIR solar spectra recorded at remote sites, comparison with model and satellite data

Peroxyacetyl nitrate (PAN) is the main tropospheric reservoir of NOx (NO + NO2). Its lifetime can reach several months in the upper cold troposphere. This enables the long-range transport of NOx radicals, under the form of PAN, far from the regions of emission. The subsequent release of NOx through the PAN thermal decomposition leads to the efficient formation of tropospheric ozone (O3), with important consequences for tropospheric oxidative capacity and air quality. The chemical properties of PAN have stimulated the progressive development of remote-sensing products by the satellite community, and recent additions open the prospect for the production of decadal and near-global time series. These products will provide new constraints on the distribution and evolution of this key trace gas in the Earth’s atmosphere, but they will also require reliable measurements for validation and characterization of performance. We present an approach that has been developed to retrieve PAN total columns from ground-based high-resolution solar absorption Fourier transform infrared (FTIR) spectra. This strategy is applied to observations recorded at remote FTIR stations of the Network for the Detection of Atmospheric Composition Change (NDACC). The resulting data sets are compared with total column time series derived from IASI (Infrared Atmospheric Sounding Interferometer) satellite observations and to a global chemical transport model. The results are discussed in terms of their overall consistency, mutual agreement, and seasonal cycles. Noticeable is the fact that the FTIR data point to substantial deficiencies in the global model simulation over high latitudes, a poorly sampled region, with an underestimation of the PAN columns during spring, at the peak of the seasonal cycle. Finally, we suggest avenues for development that should make it possible to limit intra- or intersite biases and extend the retrieval of PAN to other NDACC stations that are more affected by water vapor interferences.

Overlooked organic vapor emissions from thawing Arctic permafrost

Volatile organic compounds (VOCs) play an essential role in climate change and air pollution by modulating tropospheric oxidation capacity and providing precursors for ozone and aerosol formation. Arctic permafrost buries large quantities of frozen soil carbon, which could be released as VOCs with permafrost thawing or collapsing as a consequence of global warming. However, due to the lack of reported studies in this field and the limited capability of the conventional measurement techniques, it is poorly understood how much VOCs could be emitted from thawing permafrost and the chemical speciation of the released VOCs. Here we apply a Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF) in laboratory incubations for the first time to examine the release of VOCs from thawing permafrost peatland soils sampled from Finnish Lapland. The warming-induced rapid VOC emissions from the thawing soils were mainly attributed to the direct release of old, trapped gases from the permafrost. The average VOC fluxes from thawing permafrost were four times as high as those from the active layer (the top layer of soil in permafrost terrain). The emissions of less volatile compounds, i.e. sesquiterpenes and diterpenes, increased substantially with rising temperatures. Results in this study demonstrate the potential for substantive VOC releases from thawing permafrost. We anticipate that future global warming could stimulate VOC emissions from the Arctic permafrost, which may significantly influence the Arctic atmospheric chemistry and climate change.

Aerosol radiative effects on tropospheric photochemistry with GEOS-Chem simulations

Through scattering or absorbing radiation, aerosols have important impacts on tropospheric photochemistry and oxidation capacity. In this study, we systematically evaluate the radiative impacts of aerosols on the tropospheric actinic flux, photolysis rates (J(NO2) and J(O3)) and oxidants such as OH radicals and ozone (O3) from a global and seasonal perspective. Sensitivity simulations for year 2013 are conducted by the global chemical transport model GEOS-Chem to quantify the photochemical effects of aerosols, including sulfate-nitrate-ammonium (SNA), organic carbon (OC), black carbon (BC), dust and sea salt. The results suggest that aerosols can enhance or reduce the actinic flux by scattering and absorbing ultraviolet (UV) radiation. It is found that the surface actinic flux can be reduced by over 30% in January over eastern China due to aerosol radiative effects, which leads to maximum reductions of approximately 30% in photolysis rates and OH production. The largest regional-averaged reduction of surface actinic flux is found over eastern China (12%), followed by India (9%) and North Africa (8%). The impacts over other regions are generally less than 5%. The aerosols have a slight positive impact on surface O3 over some regions, possibly due to the dependence of O3 production on NOx/VOCs ratio. The impacts on surface O3 vary from −16% to 2%, with the largest reduction occurring in China during wintertime. The effects of aerosols on tropospheric chemistry are sensitive not only to Aerosol optical depth (AOD) but also to the vertical structure and chemical components of aerosols. The vertical profiles of the impacts over eastern China indicate that the radiative effect of aerosols can reduce the actinic flux in the lower troposphere by approximately 18%, while above the boundary layer, the actinic flux is increased (maximum of 7% approximately 2 km) because of scattering aerosols. In turn, changes in the actinic flux induce changes in photolysis rates (ranging from −17% to 8%), OH production (ranging from −15% to 6%) and O3 concentrations (ranging from −3% to 1%) over eastern China. This study highlights the different roles of each aerosol type in atmospheric photochemistry. The scattering aerosols (SNA and OC) weaken photochemistry in the lower layer and enhance in the upper troposphere, while the absorbing aerosols (BC and dust) slightly weaken the photochemistry throughout the troposphere. Globally, the impact induced by SNA is the most significant, followed by dust and BC.

Global tropospheric effects of aromatic chemistry with the SAPRC-11 mechanism implemented in GEOS-Chem version 9-02.

The Goddard Earth Observing System with chemistry (GEOS-Chem) model has been updated with the Statewide Air Pollution Research Center version 11 (SAPRC-11) aromatics chemical mechanism, with the purpose of evaluating global and regional effects of the most abundant aromatics (benzene, toluene, xylenes) on the chemical species important for tropospheric oxidation capacity. The model evaluation based on surface and aircraft observations indicates good agreement for aromatics and ozone. A comparison between scenarios in GEOS-Chem with simplified aromatic chemistry (as in the standard setup, with no ozone formation from related peroxy radicals or recycling of NOx) and with the SAPRC-11 scheme reveals relatively slight changes in ozone, the hydroxyl radical, and nitrogen oxides on a global mean basis (1 %–4 %), although remarkable regional differences (5 %–20 %) exist near the source regions. NOx decreases over the source regions and increases in the remote troposphere, due mainly to more efficient transport of peroxyacetyl nitrate (PAN), which is increased with the SAPRC aromatic chemistry. Model ozone mixing ratios with the updated aromatic chemistry increase by up to 5 ppb (more than 10 %), especially in industrially polluted regions. The ozone change is partly due to the direct influence of aromatic oxidation products on ozone production rates, and in part to the altered spatial distribution of NOx that enhances the tropospheric ozone production efficiency. Improved representation of aromatics is important to simulate the tropospheric oxidation.

Heterogeneous reactions of mineral dust aerosol: implications for tropospheric oxidation capacity

Abstract. Heterogeneous reactions of mineral dust aerosol with trace gases in the atmosphere could directly and indirectly affect tropospheric oxidation capacity, in addition to aerosol composition and physicochemical properties. In this article we provide a comprehensive and critical review of laboratory studies of heterogeneous uptake of OH, NO3, O3, and their directly related species as well (including HO2, H2O2, HCHO, HONO, and N2O5) by mineral dust particles. The atmospheric importance of heterogeneous uptake as sinks for these species is assessed (i) by comparing their lifetimes with respect to heterogeneous reactions with mineral dust to lifetimes with respect to other major loss processes and (ii) by discussing relevant field and modeling studies. We have also outlined major open questions and challenges in laboratory studies of heterogeneous uptake by mineral dust and discussed research strategies to address them in order to better understand the effects of heterogeneous reactions with mineral dust on tropospheric oxidation capacity.

The 1-way on-line coupled model system MECO(n) – Part 4: Chemical evaluation (based on MESSy v2.52)

Abstract. For the first time, a simulation incorporating tropospheric and stratospheric chemistry using the newly developed MECO(n) model system is performed. MECO(n) is short for MESSy-fied ECHAM and COSMO models nested n times. It features an online coupling of the COSMO-CLM model, equipped with the Modular Earth Submodel System (MESSy) interface (called COSMO/MESSy), with the global atmospheric chemistry model ECHAM5/MESSy for Atmospheric Chemistry (EMAC). This online coupling allows a consistent model chain with respect to chemical and meteorological boundary conditions from the global scale down to the regional kilometre scale. A MECO(2) simulation incorporating one regional instance over Europe with 50 km resolution and one instance over Germany with 12 km resolution is conducted for the evaluation of MECO(n) with respect to tropospheric gas-phase chemistry. The main goal of this evaluation is to ensure that the chemistry-related MESSy submodels and the online coupling with respect to the chemistry are correctly implemented. This evaluation is a prerequisite for the further usage of MECO(n) in atmospheric chemistry-related studies. Results of EMAC and the two COSMO/MESSy instances are compared with satellite, ground-based and aircraft in situ observations, focusing on ozone, carbon monoxide and nitrogen dioxide. Further, the methane lifetimes in EMAC and the two COSMO/MESSy instances are analysed in view of the tropospheric oxidation capacity. From this evaluation, we conclude that the chemistry-related submodels and the online coupling with respect to the chemistry are correctly implemented. In comparison with observations, both EMAC and COSMO/MESSy show strengths and weaknesses. Especially in comparison to aircraft in situ observations, COSMO/MESSy shows very promising results. However, the amplitude of the diurnal cycle of ground-level ozone measurements is underestimated. Most of the differences between COSMO/MESSy and EMAC can be attributed to differences in the dynamics of both models, which are subject to further model developments.

Historical Trends of Biogenic SOA Tracers in an Ice Core from Kamchatka Peninsula

Biogenic secondary organic aerosol (SOA) is ubiquitous in the Earth’s atmosphere, influencing climate and air quality. However, the historical trend of biogenic SOA is not well known. Here, we report for the first time the major isoprene- and monoterpene-derived SOA tracers preserved in an ice core from the Kamchatka Peninsula. Significant variations are recorded during the past 300 years with lower concentrations in the early-to-middle 19th century and higher concentrations in the preindustrial period and the present day. We discovered that isoprene SOA tracers were more abundant in the preindustrial period than the present day, while monoterpene SOA tracers stay almost unchanged. The causes of the observed variability are complex, depending on atmospheric circulation, changes in emissions, and other factors such as tropospheric oxidative capacity. Our data presents an unprecedented opportunity to shed light on the formation, evolution, and fate of atmospheric aerosols and to constrain the uncertainties ...

Uncertainties in isoprene photochemistry and emissions: implications for the oxidative capacity of past and present atmospheres and for climate forcing agents

Abstract. Isoprene and its oxidation products are major players in the oxidative chemistry of the troposphere. Current understanding of the factors controlling biogenic isoprene emissions and of the fate of isoprene oxidation products in the atmosphere has been evolving rapidly. We use a climate–biosphere–chemistry modeling framework to evaluate the sensitivity of estimates of the tropospheric oxidative capacity to uncertainties in isoprene emissions and photochemistry. Our work focuses on two climate transitions: from the Last Glacial Maximum (LGM, 19 000–23 000 years BP) to the preindustrial (1770s) and from the preindustrial to the present day (1990s). We find that different oxidants have different sensitivities to the uncertainties tested in this study. Ozone is relatively insensitive, whereas OH is the most sensitive: changes in the global mean OH levels for the LGM-to-preindustrial transition range between −29 and +7 % and those for the preindustrial-to-present-day transition range between −8 and +17 % across our simulations. We find little variability in the implied relative LGM–preindustrial difference in methane emissions with respect to the uncertainties tested in this study. Conversely, estimates of the preindustrial-to-present-day and LGM-to-preindustrial changes in the global burden of secondary organic aerosol (SOA) are highly sensitive. We show that the linear relationship between tropospheric mean OH and tropospheric mean ozone photolysis rates, water vapor, and total emissions of NOx and reactive carbon – first reported in Murray et al. (2014) – does not hold across all periods with the new isoprene photochemistry mechanism. This study demonstrates how inadequacies in our current understanding of isoprene emissions and photochemistry impede our ability to constrain the oxidative capacities of the present and past atmospheres, its controlling factors, and the radiative forcing of some short-lived species such as SOA over time.

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

Abstract. Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NOx, SO2, ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HOx (OH, HO2, and RO2) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HOx distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO2 + HO2 or HO2 + RO2) could be more efficient than radical recycling (RO2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NOx sensitivity and VOC oxidation product formation rates. Overall, the NOx limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO2 levels are positively correlated with oxygenated VOCs (OVOCs) production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher-than-expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.

Production and use of 13N labeled N2O5 to determine gas–aerosol interaction kinetics

Abstract Dinitrogen pentoxide has aroused significant interest in atmospheric chemistry because of its importance in the night time chemistry of nitrogen oxides to influence the tropospheric oxidation capacity. We have used an established method of 13N production to synthesize 13N labeled N2O5 for the first time in order to study N2O5 uptake kinetics on aerosol particles. 13N is produced via the 16O(p, α)13N reaction in a gas target attached to the IP2 endstation of the Injector 2 cyclotron at PSI. The 13NO produced in the gas target is transported to a laboratory where it is mixed, under dry conditions, with non-labeled NO and O3 in a gas reactor, giving 13NNO5. The N2O5 thus produced is fed into an aerosol flow tube together with a humidified aerosol gas flow. The gaseous species present in the resulting gas flow are selectively separated via a narrow parallel plate diffusion denuder system, while aerosol particles can be trapped on a particle filter placed at the end of the denuder system. The activity of the 13N labeled species trapped on the denuder plates and in the particle filter can be monitored via scintillation counters. A system for the routine online production of 13N labeled N2O5 has been assembled and used to assess the conformity of the results by kinetic modeling of gas phase N2O5 chemistry, showing good agreement. A few exemplary experiments of uptake of labelled N2O5 to ammonium sulfate and citric acid particles are presented that are in good agreement with results obtained with other methods reported in the literature.

Factors controlling variability in the oxidative capacity of the troposphere since the Last Glacial Maximum

Abstract. The oxidative capacity of past atmospheres is highly uncertain. We present here a new climate–biosphere–chemistry modeling framework to determine oxidant levels in the present and past troposphere. We use the GEOS-Chem chemical transport model driven by meteorological fields from the NASA Goddard Institute of Space Studies (GISS) ModelE, with land cover and fire emissions from dynamic global vegetation models. We present time-slice simulations for the present day, late preindustrial era (AD 1770), and the Last Glacial Maximum (LGM, 19–23 ka), and we test the sensitivity of model results to uncertainty in lightning and fire emissions. We find that most preindustrial and paleo climate simulations yield reduced oxidant levels relative to the present day. Contrary to prior studies, tropospheric mean OH in our ensemble shows little change at the LGM relative to the preindustrial era (0.5 ± 12 %), despite large reductions in methane concentrations. We find a simple linear relationship between tropospheric mean ozone photolysis rates, water vapor, and total emissions of NOx and reactive carbon that explains 72 % of the variability in global mean OH in 11 different simulations across the last glacial–interglacial time interval and the industrial era. Key parameters controlling the tropospheric oxidative capacity over glacial–interglacial periods include overhead stratospheric ozone, tropospheric water vapor, and lightning NOx emissions. Variability in global mean OH since the LGM is insensitive to fire emissions. Our simulations are broadly consistent with ice-core records of Δ17O in sulfate and nitrate at the LGM, and CO, HCHO, and H2O2 in the preindustrial era. Our results imply that the glacial–interglacial changes in atmospheric methane observed in ice cores are predominantly driven by changes in its sources as opposed to its sink with OH.