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Atmospheric ozone (O3) is a pollutant produced through chemical chain reactions where volatile organic compounds (VOCs), carbon monoxide and methane are oxidized in the presence of oxides of nitrogen (NOx). For decades, the controlling chain termination step has been used to separate regions into either ‘NOx limited’ (peroxyl-radical self-reactions dominate) or ‘VOC limited’ (hydroxyl radical (OH) + nitrogen dioxide (NO2) reaction dominates). The controlling regime would then guide policies for reducing emissions and so O3 concentrations. Using a chemical transport model, we show that a third ‘aerosol inhibited’ regime exists, where reactive uptake of hydroperoxyl radicals (HO2) onto aerosol particles dominates. In 1970, 2% of the Northern Hemisphere population lived in an aerosol-inhibited regime, but by 2014 this had increased to 21%; 60% more than lived in a VOC-limited regime. Aerosol-inhibited chemistry suppressed surface O3 concentrations in North America and Europe in the 1970s and is currently suppressing surface O3 over Asia. This third photochemical O3 regime leads to potential trade-off tensions between reducing particle pollution in Asia (a key current health policy and priority) and increasing surface O3, should O3 precursors emissions not be reduced in tandem.

Studies of wintertime air quality in the North China Plain (NCP) show that particulate-nitrate pollution persists despite rapid reduction in NOx emissions. This intriguing NOx-nitrate relationship may originate from non-linear nitrate-formation chemistry, but it is unclear which feedback mechanisms dominate in NCP. In this study, we re-interpret the wintertime observations of 17O excess of nitrate (∆17O(NO3−)) in Beijing using the GEOS-Chem (GC) chemical transport model to estimate the importance of various nitrate-production pathways and how their contributions change with the intensity of haze events. We also analyze the relationships between other metrics of NOy chemistry and [PM2.5] in observations and model simulations. We find that the model on average has a negative bias of −0.9‰ and −3617O(NO3−) and [Ox,major] (≡ [O3] + [NO2] + [p-NO3−]), respectively, while overestimating the nitrogen oxidation ratio ([NO3−]/([NO3−] + [NO2])) by +0.12 in intense haze. The discrepancies become larger in more intense haze. We attribute the model biases to an overestimate of NO2-uptake on aerosols and an underestimate in wintertime O3 concentrations. Our findings highlight a need to address uncertainties related to heterogeneous chemistry of NO2 in air-quality models. The combined assessment of observations and model results suggest that N2O5 uptake in aerosols and clouds is the dominant nitrate-production pathway in wintertime Beijing, but its rate is limited by ozone under high-NOx-high-PM2.5 conditions. Nitrate production rates may continue to increase as long as [O3] increases despite reduction in [NOx], creating a negative feedback that reduces the effectiveness of air pollution mitigation.

Effective mitigation of surface ozone pollution entails detailed knowledge of the contributing precursors' sources. We use the GEOS-Chem adjoint model to analyze the precursors contributing to surface ozone in the Beijing-Tianjin-Hebei area (BTH) of China on days of different ozone pollution severities in June 2019. We find that BTH ozone on heavily polluted days is sensitive to local emissions, as well as to precursors emitted from the provinces south of BTH (Shandong, Henan, and Jiangsu, collectively the SHJ area). Heavy ozone pollution in BTH can be mitigated effectively by reducing NOx (from industrial processes and transportation), ≥C3 alkenes (from on-road gasoline vehicles and industrial processes), and xylenes (from paint use) emitted from both BTH and SHJ, as well as by reducing CO (from industrial processes, transportation, and power generation) and ≥C4 alkanes (from industrial processes, paint and solvent use, and on-road gasoline vehicles) emissions from SHJ. In addition, reduction of NOx, xylene, and ≥C3 alkene emissions within BTH would effectively decrease the number of BTH ozone-exceedance days. Our analysis pinpoint the key areas and activities for locally and regionally coordinated emission control efforts to improve surface ozone air quality in BTH.

In assessments of cancer risk from atmospheric polycyclic aromatic hydrocarbons (PAHs), scientists and regulators rarely consider the complex mixture of emitted compounds and degradation products, and they often represent the entire mixture using a single emitted compound—benzo[a]pyrene. Here, we show that benzo[a]pyrene is a poor indicator of PAH risk distribution and management: nearly 90% of cancer risk worldwide results from other PAHs, including unregulated degradation products of emitted PAHs. We develop and apply a global‐scale atmospheric model and conduct health impact analyses to estimate human cancer risk from 16 PAHs and several of their N‐PAH degradation products. We find that benzo[a]pyrene is a minor contributor to the total cancer risks of PAHs (11%); the remaining risk comes from other directly emitted PAHs (72%) and N‐PAHs (17%). We show that assessment and policy‐making that relies solely on benzo[a]pyrene exposure provides misleading estimates of risk distribution, the importance of chemical processes, and the prospects for risk mitigation. We conclude that researchers and decision‐makers should consider additional PAHs as well as degradation products., Key Points Benzo[a]pyrene is a small contributor to human cancer risk of polycyclic aromatic hydrocarbons (PAHs) worldwide (11%)Using benzo[a]pyrene as a surrogate compound leads to erroneous conclusions about high‐risk populations and the importance of uncertain chemical processesScience and policy could be improved by considering a wider group of both emitted PAHs as well as their degradation products

Graph theoretical methods have revolutionized the exploration of complex systems across scientific disciplines. Here, we demonstrate their applicability to the investigation and comparison of three widely-used atmospheric chemical mechanisms of varying complexity: the Master Chemical Mechanism v3.3, GEOS-Chem v12.6, and the Super-Fast chemical mechanism. We investigate these mechanisms using a class of graphical models known as species-reaction graphs and find similarities between these chemical reaction systems and other systems arising in nature. Several graph theoretical properties are consistent across mechanisms, including strong dynamical system disequilibrium and clustering of chemically-related species. This formalism also reveals key differences between the mechanisms, some of which have characteristics inconsistent with domain knowledge; for example, isoprene and peroxy radical chemistry exhibit substantially different graph properties in each mechanism. Graph theoretical methods provide a promising set of tools for investigating atmospheric chemical mechanisms, complementing existing computational approaches, and potentially opening new avenues for scientific discovery.

The impact of volatile organic compound (VOC) emissions to the atmosphere on the production of secondary pollutants, such as ozone and secondary organic aerosol (SOA), is mediated by the concentration of nitric oxide (NO). Polluted urban atmospheres are typically considered to be high-NO environments, while remote regions such as rainforests, with minimal anthropogenic influences, are considered to be low-NO. Policy to reduce urban air pollution is typically developed assuming that the chemistry is controlled by the high-NO regime. However, our observations from central Beijing show that this simplistic separation of regimes is flawed. Despite being in one of the largest megacities in the world, we observe significant formation of gas and aerosol phase oxidation products associated with the low-NO rainforest-like regime during the afternoon. This is caused by a surprisingly low concentration of NO, coupled with high concentrations of VOCs and of the atmospheric oxidant hydroxyl (OH). Box model calculations suggest that during the morning high-NO chemistry predominates (95 %) but in the afternoon low-NO chemistry plays a greater role (30 %). With increasing global emphasis on reducing air pollution, the modelling tools used to develop urban air quality policy need to adequately represent both high- and low-NO regimes if they are to have utility.

The chemistry of the halogen species bromine and iodine has a range of impacts on tropospheric composition, and can affect oxidising capacity in a number of ways. However, recent studies disagree on the overall sign of the impacts of halogens on the oxidising capacity of the troposphere. We present simulations of OH and HO2 radicals for comparison with observations made in the remote tropical ocean boundary layer during the Seasonal Oxidant Study at the Cape Verde Atmospheric Observatory in 2009. We use both a constrained box model, using detailed chemistry derived from the Master Chemical Mechanism (v3.2), and the three-dimensional global chemistry transport model GEOS-Chem. Both model approaches reproduce the diurnal trends in OH and HO2. Absolute observed concentrations are well reproduced by the box model but are overpredicted by the global model, potentially owing to incomplete consideration of oceanic sourced radical sinks. The two models, however, differ in the impacts of halogen chemistry. In the box model, halogen chemistry acts to increase OH concentrations (by 9.8 % at midday at the Cape Verde Atmospheric Observatory), while the global model exhibits a small increase in OH at the Cape Verde Atmospheric Observatory (by 0.6 % at midday) but overall shows a decrease in the global annual mass-weighted mean OH of 4.5 %. These differences reflect the variety of timescales through which the halogens impact the chemical system. On short timescales, photolysis of HOBr and HOI, produced by reactions of HO2 with BrO and IO, respectively, increases the OH concentration. On longer timescales, halogen-catalysed ozone destruction cycles lead to lower primary production of OH radicals through ozone photolysis, and thus to lower OH concentrations. The global model includes more of the longer timescale responses than the constrained box model, and overall the global impact of the longer timescale response (reduced primary production due to lower O3 concentrations) overwhelms the shorter timescale response (enhanced cycling from HO2 to OH), and thus the global OH concentration decreases. The Earth system contains many such responses on a large range of timescales. This work highlights the care that needs to be taken to understand the full impact of any one process on the system as a whole.

We report measurements of bromine monoxide (BrO) and use an observationally constrained chemical box model to infer total gas-phase inorganic bromine (Bry) over the tropical western Pacific Ocean (tWPO) during the CONTRAST field campaign (January–February 2014). The observed BrO and inferred Bry profiles peak in the marine boundary layer (MBL), suggesting the need for a bromine source from sea-salt aerosol (SSA), in addition to organic bromine (CBry). Both profiles are found to be C-shaped with local maxima in the upper free troposphere (FT). The median tropospheric BrO vertical column density (VCD) was measured as 1.6×1013 molec cm−2, compared to model predictions of 0.9×1013 molec cm−2 in GEOS-Chem (CBry but no SSA source), 0.4×1013 molec cm−2 in CAM-Chem (CBry and SSA), and 2.1×1013 molec cm−2 in GEOS-Chem (CBry and SSA). Neither global model fully captures the C-shape of the Bry profile. A local Bry maximum of 3.6 ppt (2.9–4.4 ppt; 95 % confidence interval, CI) is inferred between 9.5 and 13.5 km in air masses influenced by recent convective outflow. Unlike BrO, which increases from the convective tropical tropopause layer (TTL) to the aged TTL, gas-phase Bry decreases from the convective TTL to the aged TTL. Analysis of gas-phase Bry against multiple tracers (CFC-11, H2O ∕ O3 ratio, and potential temperature) reveals a Bry minimum of 2.7 ppt (2.3–3.1 ppt; 95 % CI) in the aged TTL, which agrees closely with a stratospheric injection of 2.6 ± 0.6 ppt of inorganic Bry (estimated from CFC-11 correlations), and is remarkably insensitive to assumptions about heterogeneous chemistry. Bry increases to 6.3 ppt (5.6–7.0 ppt; 95 % CI) in the stratospheric "middleworld" and 6.9 ppt (6.5–7.3 ppt; 95 % CI) in the stratospheric "overworld". The local Bry minimum in the aged TTL is qualitatively (but not quantitatively) captured by CAM-Chem, and suggests a more complex partitioning of gas-phase and aerosol Bry species than previously recognized. Our data provide corroborating evidence that inorganic bromine sources (e.g., SSA-derived gas-phase Bry) are needed to explain the gas-phase Bry budget in the upper free troposphere and TTL. They are also consistent with observations of significant bromide in Upper Troposphere–Lower Stratosphere aerosols. The total Bry budget in the TTL is currently not closed, because of the lack of concurrent quantitative measurements of gas-phase Bry species (i.e., BrO, HOBr, HBr, etc.) and aerosol bromide. Such simultaneous measurements are needed to (1) quantify SSA-derived Bry in the upper FT, (2) test Bry partitioning, and possibly explain the gas-phase Bry minimum in the aged TTL, (3) constrain heterogeneous reaction rates of bromine, and (4) account for all of the sources of Bry to the lower stratosphere.

Bromine chemistry, particularly in the tropics, has been suggested to play an important role in tropospheric ozone loss (Theys et al., 2011) although a lack of measurements of active bromine species impedes a quantitative understanding of its impacts. Recent modelling and measurements of bromine monoxide (BrO) by Wang et al. (2015) have shown current models under predict BrO concentrations over the Pacific Ocean and allude to a missing source of BrO. Here, we present the first simultaneous aircraft measurements of atmospheric bromine monoxide, BrO (a radical that along with atomic Br catalytically destroys ozone) and the inorganic Br precursor compounds HOBr, BrCl and Br2 over the Western Pacific Ocean from 0.5 to 7 km. The presence of 0.17-€“1.64 pptv BrO and 3.6-8 pptv total inorganic Br from these four species throughout the troposphere causes 10-20% of total ozone loss, and confirms the importance of bromine chemistry in the tropical troposphere; contributing to a 6 ppb decrease in ozone levels due to halogen chemistry. Observations are compared with a global chemical transport model and find that the observed high levels of BrO, BrCl and HOBr can be reconciled by active multiphase oxidation of halide (Br- and Cl-ˆ’) by HOBr and ozone in cloud droplets and aerosols. Measurements indicate that 99% of the instantaneous free Br in the troposphere up to 8 km originates from inorganic halogen photolysis rather than from photolysis of organobromine species.

From 17–22 August 2017 simultaneous enhancements of ammonia (NH3), carbon monoxide (CO), hydrogen cyanide (HCN), and ethane (C2H6) were detected from ground-based solar absorption Fourier transform infrared (FTIR) spectroscopic measurements at two high-Arctic sites: Eureka (80.05°N, 86.42°W) Nunavut, Canada, and Thule (76.53°N, 68.74°W), Greenland. These enhancements were attributed to wildfires in British Columbia and the Northwest Territories of Canada using FLEXPART back-trajectories and fire locations from Moderate Resolution Imaging Spectroradiometer (MODIS) and found to be the greatest observed enhancements in more than a decade of measurements at Eureka (2006–2017) and Thule (1999–2017). Observations of gas-phase NH3 from these wildfires illustrate that boreal wildfires may be a considerable episodic source of NH3 in the summertime high Arctic. Comparisons of GEOS-Chem model simulations using the Global Fire Assimilation System (GFASv1.2) biomass burning emissions to FTIR measurements and Infrared Atmospheric Sounding Interferometer (IASI) measurements showed that the transport of wildfire emissions to the Arctic was underestimated in GEOS-Chem. However, GEOS-Chem simulations showed that these wildfires contributed to surface layer NH3 and NH4 + enhancements of 0.01–0.11 ppbv and 0.05–1.07 ppbv, respectively, over the Canadian Archipelago from 15–23 August 2017., SCOPUS: ar.j, info:eu-repo/semantics/published

For the first time, a plume-in-grid approach is implemented in a chemical transport model (CTM) to parameterize the effects of the nonlinear reactions occurring within high concentrated NOx plumes from lightning NOx emissions (LNOx) in the upper troposphere. It is characterized by a set of parameters including the plume lifetime, the effective reaction rate constant related to NOx–O3 chemical interactions, and the fractions of NOx conversion into HNO3 within the plume. Parameter estimates were made using the Dynamical Simple Model of Atmospheric Chemical Complexity (DSMACC) box model, simple plume dispersion simulations, and the 3-D Meso-NH (non-hydrostatic mesoscale atmospheric model). In order to assess the impact of the LNOx plume approach on the NOx and O3 distributions on a large scale, simulations for the year 2006 were performed using the GEOS-Chem global model with a horizontal resolution of 2° × 2.5°. The implementation of the LNOx parameterization implies an NOx and O3 decrease on a large scale over the region characterized by a strong lightning activity (up to 25 and 8 %, respectively, over central Africa in July) and a relative increase downwind of LNOx emissions (up to 18 and 2 % for NOx and O3, respectively, in July). The calculated variability in NOx and O3 mixing ratios around the mean value according to the known uncertainties in the parameter estimates is at a maximum over continental tropical regions with ΔNOx [−33.1, +29.7] ppt and ΔO3 [−1.56, +2.16] ppb, in January, and ΔNOx [−14.3, +21] ppt and ΔO3 [−1.18, +1.93] ppb, in July, mainly depending on the determination of the diffusion properties of the atmosphere and the initial NO mixing ratio injected by lightning. This approach allows us (i) to reproduce a more realistic lightning NOx chemistry leading to better NOx and O3 distributions on the large scale and (ii) to focus on other improvements to reduce remaining uncertainties from processes related to NOx chemistry in CTM.

Measurement of NO2 at low concentrations (tens of ppts) is non-trivial. A variety of techniques exist, with the conversion of NO2 into NO followed by chemiluminescent detection of NO being prevalent. Historically this conversion has used a catalytic approach (molybdenum); however, this has been plagued with interferences. More recently, photolytic conversion based on UV-LED irradiation of a reaction cell has been used. Although this appears to be robust there have been a range of observations in low-NOx environments which have measured higher NO2 concentrations than might be expected from steady-state analysis of simultaneously measured NO, O3, jNO2, etc. A range of explanations exist in the literature, most of which focus on an unknown and unmeasured “compound X” that is able to convert NO to NO2 selectively. Here we explore in the laboratory the interference on the photolytic NO2 measurements from the thermal decomposition of peroxyacetyl nitrate (PAN) within the photolysis cell. We find that approximately 5 % of the PAN decomposes within the instrument, providing a potentially significant interference. We parameterize the decomposition in terms of the temperature of the light source, the ambient temperature, and a mixing timescale ( ∼ 0.4 s for our instrument) and expand the parametric analysis to other atmospheric compounds that decompose readily to NO2 (HO2NO2, N2O5, CH3O2NO2, IONO2, BrONO2, higher PANs). We apply these parameters to the output of a global atmospheric model (GEOS-Chem) to investigate the global impact of this interference on (1) the NO2 measurements and (2) the NO2 : NO ratio, i.e. the Leighton relationship. We find that there are significant interferences in cold regions with low NOx concentrations such as the Antarctic, the remote Southern Hemisphere, and the upper troposphere. Although this interference is likely instrument-specific, the thermal decomposition to NO2 within the instrument's photolysis cell could give an at least partial explanation for the anomalously high NO2 that has been reported in remote regions. The interference can be minimized by better instrument characterization, coupled to instrumental designs which reduce the heating within the cell, thus simplifying interpretation of data from remote locations.

The reaction CH3C(O)O2 + HO2 → CH3C(O)OOH + O2 (Reaction R5a), CH3C(O)OH + O3 (Reaction R5b), CH3 + CO2 + OH + O2 (Reaction R5c) was studied in a series of experiments conducted at 1000 mbar and (293 ± 2) K in the HIRAC simulation chamber. For the first time, products, (CH3C(O)OOH, CH3C(O)OH, O3 and OH) from all three branching pathways of the reaction have been detected directly and simultaneously. Measurements of radical precursors (CH3OH, CH3CHO), HO2 and some secondary products HCHO and HCOOH further constrained the system. Fitting a comprehensive model to the experimental data, obtained over a range of conditions, determined the branching ratios α(R5a) = 0.37 ± 0.10, α(R5b) = 0.12 ± 0.04 and α(R5c) = 0.51 ± 0.12 (errors at 2σ level). Improved measurement/model agreement was achieved using k(R5) = (2.4 ± 0.4) × 10−11 cm3 molecule−1 s−1, which is within the large uncertainty of the current IUPAC and JPL recommended rate coefficients for the title reaction. The rate coefficient and branching ratios are in good agreement with a recent study performed by Groß et al. (2014b); taken together, these two studies show that the rate of OH regeneration through Reaction (R5) is more rapid than previously thought. GEOS-Chem has been used to assess the implications of the revised rate coefficients and branching ratios; the modelling shows an enhancement of up to 5 % in OH concentrations in tropical rainforest areas and increases of up to 10 % at altitudes of 6–8 km above the equator, compared to calculations based on the IUPAC recommended rate coefficient and yield. The enhanced rate of acetylperoxy consumption significantly reduces PAN in remote regions (up to 30 %) with commensurate reductions in background NOx.

Air parcels with mixing ratios of high O3 and low H2O (HOLW) are common features in the tropical western Pacific (TWP) mid-troposphere (300–700 hPa). Here, using data collected during aircraft sampling of the TWP in winter 2014, we find strong, positive correlations of O3 with multiple biomass burning tracers in these HOLW structures. Ozone levels in these structures are about a factor of three larger than background. Models, satellite data and aircraft observations are used to show fires in tropical Africa and Southeast Asia are the dominant source of high O3 and that low H2O results from large-scale descent within the tropical troposphere. Previous explanations that attribute HOLW structures to transport from the stratosphere or mid-latitude troposphere are inconsistent with our observations. This study suggest a larger role for biomass burning in the radiative forcing of climate in the remote TWP than is commonly appreciated., High ozone and low water structures in the tropical western Pacific are commonly attributed to transport from the stratosphere or mid-latitudes. Here, Anderson et al. show these structures actually result from ozone production in biomass burning plumes and large-scale descent of air within the tropics.

There is growing global consumption of non-fossil fuels such as ethanol made from renewable biomass. Previous studies have shown that one of the main air quality disadvantages of using ethanol blended fuels is a significant increase in the production of acetaldehyde, an unregulated and toxic pollutant. Most studies on the impacts of ethanol blended gasoline have been carried out in the US and Brazil, with much less focus on the UK and Europe. We report time resolved measurements of ethanol in London during the winter and summer of 2012. In both seasons the mean mixing ratio of ethanol was around 5 ppb, with maximum values over 30 ppb, making ethanol currently the most abundant VOC in London air. We identify a road transport related source, with ‘rush-hour’ peaks observed. Ethanol is strongly correlated with other road transport-related emissions, such as small aromatics and light alkanes, and has no relationship to summer biogenic emissions. To determine the impact of road transport-related ethanol emission on secondary species (i.e. acetaldehyde and ozone), we use both a chemically detailed box model (incorporating the Master Chemical Mechanism, MCM) and a global and nested regional scale chemical transport model (GEOS-Chem), on various processing time scales. Using the MCM model, only 16% of the modelled acetaldehyde was formed from ethanol oxidation. However, the model significantly underpredicts the total levels of acetaldehyde, indicating a missing primary emission source, that appears to be traffic-related. Further support for a primary emission source comes from the regional scale model simulations, where the observed concentrations of ethanol and acetaldehyde can only be reconciled with the inclusion of large primary emissions. Although only constrained by one set of observations, the regional modelling suggests a European ethanol source similar in magnitude to that of ethane (∼60 Gg per year) and greater than that of acetaldehyde (∼10 Gg per year). The increased concentrations of ethanol and acetaldehyde from primary emissions impacts both radical and NOx cycling over Europe, resulting in significant regional impacts on NOy speciation and O3 concentrations, with potential changes to human exposure to air pollutants.

We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant-aerosol-halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea-salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are small in comparison. Reactive gas-phase chlorine Cl*, including Cl, ClO, Cl2, BrCl, ICl, HOCl, ClNO3, ClNO2, and minor species, is produced by the HCl + OH reaction and by heterogeneous conversion of sea-salt aerosol chloride to BrCl, ClNO2, Cl2, and ICl. The model simulates successfully the observed mixing ratios of HCl in marine air (highest at northern mid-latitudes) and the associated HNO3 decrease from acid displacement. It captures the high ClNO2 mixing ratios observed in continental surface air at night with chlorine of sea salt origin transported inland as HCl and fine aerosol. It simulates successfully the vertical profiles of HCl measured from aircraft, where enhancements in the continental boundary layer can again be explained by transport inland of the marine source. It does not reproduce the boundary layer Cl2 mixing ratios measured in the WINTER aircraft campaign (1–5 ppt in the daytime, low at night); the model is too high at night compared to WINTER observations, which could be due to uncertainty in the rate of the ClNO2 + Cl− reaction, but we have no explanation for the daytime observations. The global mean tropospheric concentration of Cl atoms in the model is 620 cm−3 and contributes 1.0 % of the global oxidation of methane, 20 % of ethane, 14 % of propane, and 4 % of methanol. Chlorine chemistry increases global mean tropospheric BrO by 85 %, mainly through the HOBr + Cl− reaction, and decreases global burdens of tropospheric ozone by 7 % and OH by 3 % through the associated bromine radical chemistry. ClNO2 chemistry drives increases in ozone of up to 8 ppb over polluted continents in winter.

Terrestrial vegetation releases large quantities of plant volatiles into the atmosphere that can then oxidize to form secondary organic aerosol. These particles affect plant productivity through the diffuse radiation fertilization effect by altering the balance between direct and diffuse radiation reaching the Earth’s surface. Here, using a suite of models describing relevant coupled components of the Earth system, we quantify the impacts of biogenic secondary organic aerosol on plant photosynthesis through this fertilization effect. We show that this leads to a net primary productivity enhancement of 1.23 Pg C yr−1 (range 0.76–1.61 Pg C yr−1 due to uncertainty in biogenic secondary organic aerosol formation). Notably, this productivity enhancement is twice the mass of biogenic volatile organic compound emissions (and ~30 times larger than the mass of carbon in biogenic secondary organic aerosol) causing it. Hence, our simulations indicate that there is a strong positive ecosystem feedback between biogenic volatile organic compound emissions and plant productivity through plant-canopy light-use efficiency. We estimate a gain of 1.07 in global biogenic volatile organic compound emissions resulting from this feedback.

Recent field studies have suggested that sea-salt particulate nitrate (NITs) photolysis may act as a significant local source of nitrogen oxides (NOx) over oceans. We present a study of the global impact of this process on oxidant concentrations in the marine boundary layer using the GEOS-Chem model, after first updating the model to better simulate observed gas/particle phase partitioning of nitrate in the marine boundary layer. Model comparisons with long-term measurements of NOx from the Cape Verde Atmospheric Observatory (CVAO) in the eastern tropical North Atlantic provide support for an in situ source of NOx from NITs photolysis, with NITs photolysis coefficients about 25–50 times larger than corresponding HNO3 photolysis coefficients. Short-term measurement of nitrous acid (HONO) at this location show a clear daytime peak, with average peak mixing ratios ranging from 3 to 6 pptv. The model reproduces the general shape of the diurnal HONO profile only when NITs photolysis is included, but the magnitude of the daytime peak mixing ratio is under-predicted. This under-prediction is somewhat reduced if HONO yields from NITs photolysis are assumed to be close to unity. The combined NOx and HONO analysis suggests that the upper limit of the ratio of NITs : HNO3 photolysis coefficients is about 100. The largest simulated relative impact of NITs photolysis is in the tropical and subtropical marine boundary layer, with peak local enhancements ranging from factors of 5–20 for NOx, 1.2–1.6 for OH, and 1.1–1.3 for ozone. Since the spatial extent of the sea-salt aerosol impact is limited, global impacts on NOx, ozone and OH mass burdens are small (~ 1–3 %). We also present preliminary analysis showing that particulate nitrate photolysis in accumulation-mode aerosols (predominantly over continental regions) could lead to ppbv-level increases in ozone in the continental boundary layer. Our results highlight the need for more comprehensive long-term measurements of NOx, and related species like HONO and sea-salt particulate nitrate, to better constrain the impact of particulate nitrate photolysis on marine boundary layer oxidant chemistry. Further field and laboratory studies on particulate nitrate photolysis in other aerosol types are also needed to better understand the impact of this process on continental boundary layer oxidant chemistry.

Measurements of atmospheric ozone levels taken during the nineteenth century cast doubt on the computational models used today to simulate the atmosphere. An independent proxy of past ozone levels offers reassurance. A new constraint on atmospheric levels of ozone.

The gas-phase reaction of alkenes with ozone is known to produce stabilised Criegee intermediates (SCIs). These biradical/zwitterionic species have the potential to act as atmospheric oxidants for trace pollutants such as SO2, enhancing the formation of sulfate aerosol with impacts on air quality and health, radiative transfer and climate. However, the importance of this chemistry is uncertain as a consequence of limited understanding of the abundance and atmospheric fate of SCIs. In this work we apply experimental, theoretical and numerical modelling methods to quantify the atmospheric impacts, abundance, and fate, of the structurally diverse SCIs derived from the ozonolysis of monoterpenes, the second most abundant group of unsaturated hydrocarbons in the atmosphere. We have investigated the removal of SO2 by SCI formed from the ozonolysis of three monoterpenes (-pinene, -pinene and limonene) in the presence of varying amounts of water vapour in large-scale simulation chamber experiments. The SO2 removal displays a clear dependence on water vapour concentration, but this dependence is not linear across the range of [H2O] explored. At low [H2O] a strong dependence of SO2 removal on [H2O] is observed, while at higher [H2O] this dependence becomes much weaker. This is interpreted as being caused by the production of a variety of structurally (and hence chemically) different SCI in each of the systems studied, each displaying different rates of reaction with water and of unimolecular rearrangement/decomposition. The determined rate constants, k(SCI+H2O), for those SCI that react primarily with H2O range from 4–310 × 10−15 cm3 s−1. For those SCI that predominantly react unimolecularly, determined rates range from 130–240 s−1. These values are in line with previous results for the (analogous) stereo-specific SCI system of syn/anti-CH3CHOO. The experimental results are interpreted through theoretical studies of the SCI unimolecular reactions and bimolecular reactions with H2O, characterised for -pinene and -pinene at the M06-2X/aug-cc-pVTZ level of theory. The theoretically derived rates agree with the experimental results within the uncertainties. A global modelling study, applying the experimental results within the GEOS-Chem chemical transport model, suggests that > 98 % of the total monoterpene derived global SCI burden is comprised of SCI whose structure determines that they react slowly with water, and whose atmospheric fate is dominated by unimolecular reactions. Seasonally averaged boundary layer concentrations of monoterpene-derived SCI reach up to 1.2 × 104 cm−3 in regions of elevated monoterpene emissions in the tropics. Reactions of monoterpene derived SCI with SO2 account for

Air quality models are limited by the computational costs associated with the simulation of the complex chemical and dynamical processes of reactive pollutants in the atmosphere. We discuss here the potential usage of machine learning and reduced-order modeling techniques to mitigate some of these limitations. We first give an overview of three new methods emerging from the field of signal processing — sparse sampling, randomized matrix decompositions and the construction of reduced order models — and discuss them in the context of air quality modeling. In the second part we discuss the substitution of the standard chemical solver of the chemistry model with a random forest regression model trained through machine learning. We find that this approach shows promising initial results for important air pollutants such as ozone (O 3 ), predicting concentrations that deviate less than 10% from the values computed by the traditional model. The here highlighted methods all have the potential to significantly reduce the computational burden of air quality models while maintaining the model's capability to capture all features relevant to air quality. Such lightweight air quality models offer new opportunities for air quality forecasting and to assimilate the rapidly increasing array of air quality observations.

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10 °N to 40 °S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (∼ 3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.

Tropospheric ozone is important for the Earth’s climate and air quality. It is produced during the oxidation of organics in the presence of nitrogen oxides. Due to the range of organic species emitted and the chain like nature of their oxidation, this chemistry is complex and understanding the role of different processes (emission, deposition, chemistry) is difficult. We demonstrate a new methodology for diagnosing ozone production based on the processing of bonds contained within emitted molecules, the fate of which is determined by the conservation of spin of the bonding electrons. Using this methodology to diagnose ozone production in the GEOS-Chem chemical transport model, we demonstrate its advantages over the standard diagnostic. We show that the number of bonds emitted, their chemistry and lifetime, and feedbacks on OH are all important in determining the ozone production within the model and its sensitivity to changes. This insight may allow future model-model comparisons to better identify the root causes of model differences.

We report measurements of bromine monoxide (BrO) and use an observationally constrained chemical box-model to infer total gas phase inorganic bromine (Bry) over the tropical Western Pacific Ocean (tWPO) during the CONTRAST field campaign (January–February 2014). The median tropospheric BrO Vertical Column Density (VCD) over the tWPO was measured as 1.6 × 1013 molec cm−2, compared to model predictions of 0.4 × 1013 in CAM-Chem, 0.9 × 1013 in GEOS-Chem, and 2.1 × 1013 in GEOS-Chem with a sea-salt aerosol (SSA) bromine source. The observed BrO and inferred Bry profiles is found to be C-shaped in the troposphere, with local maxima in the marine boundary layer (MBL) and in the upper free troposphere. Neither global model fully captures this profile shape. Between 6 and 13.5 km, the inferred Bry is highly sensitive to assumptions about the rate of heterogeneous bromine recycling (depends on the surface area of ice/aerosols), and the inclusion of a SSA bromine source. A local Bry maximum of 3.6 ppt (2.3–11.1 ppt, 95 % CI) is observed between 9.5 and 13.5 km in air masses influenced by recent convective outflow. Unlike BrO, which increases from the convective TTL to the aged TTL, gas phase Bry decreases from the convective TTL to the aged TTL. Analysis of gas phase Bry against multiple tracers (CFC-11, H2O / O3 ratio, and θ) reveals a Bry minimum of 2.7 ppt (2.4–3.0 ppt, 95 % CI) in the aged TTL, which is remarkably insensitive to assumptions about heterogeneous chemistry. Bry increases to 6.3 ppt (5.9–6.7 ppt, 95 % CI) in the stratospheric middleworld, and 6.9 ppt (6.7–7.1 ppt, 95 % CI) in the stratospheric overworld. The local Bry minimum in the aged TTL is qualitatively (but not quantitatively) captured by CAM-chem, and suggests a more complex partitioning of gas phase and aerosol Bry species than previously recognized. Our data provide corroborating evidence that inorganic bromine sources (e.g., SSA derived gas phase Bry) are needed to explain the gas phase Bry budget in the TTL. They are also consistent with observations of significant bromide in UTLS aerosols. The total Bry budget in the TTL is currently not closed, because of the lack of concurrent quantitative measurements of gas phase Bry species (i.e., BrO, HOBr, HBr, etc.) and aerosol bromide. These simultaneous measurements are needed 1) to quantify SSA derived Bry aloft, 2) to test Bry partitioning, and explain the gas phase Bry minimum in the aged TTL, 3) to constrain heterogeneous reaction rates of bromine, and 4) to account for all of the sources of Bry to the lower stratosphere.

Low cost air pollution sensors have substantial potential for atmospheric research and for the applied control of pollution in the urban environment, including more localized warnings to the public. The current generation of single-chemical gas sensors experience degrees of interference from other co-pollutants and have sensitivity to environmental factors such as temperature, wind speed and supply voltage. There are uncertainties introduced also because of sensor-to-sensor response variability, although this is less well reported. The sensitivity of Metal Oxide Sensors (MOS) to volatile organic compounds (VOCs) changed with relative humidity (RH) by up to a factor of five over the range of 19–90% RH and with an uncertainty in the correction of a factor of two at any given RH. The short-term (second to minute) stabilities of MOS and electrochemical CO sensor responses were reasonable. During more extended use, inter-sensor quantitative comparability was degraded due to unpredictable variability in individual sensor responses (to either measurand or interference or both) drifting over timescales of several hours to days. For timescales longer than a week identical sensors showed slow, often downwards, drifts in their responses which diverged across six CO sensors by up to 30% after two weeks. The measurement derived from the median sensor within clusters of 6, 8 and up to 21 sensors was evaluated against individual sensor performance and external reference values. The clustered approach maintained the cost competitiveness of a sensor device, but the median concentration from the ensemble of sensor signals largely eliminated the randomised hour-to-day response drift seen in individual sensors and excluded the effects of small numbers of poorly performing sensors that drifted significantly over longer time periods. The results demonstrate that for individual sensors to be optimally comparable to one another, and to reference instruments, they would likely require frequent calibration. The use of a cluster median value eliminates unpredictable medium term response changes, and other longer term outlier behaviours, extending the likely period needed between calibration and making a linear interpolation between calibrations more appropriate. Through the use of sensor clusters rather than individual sensors, existing low cost technologies could deliver significantly improved quality of observations.

We present two years of NOx observations from the Cape Verde Atmospheric Observatory located in the tropical Atlantic boundary layer. We find NOx mixing ratios peak around solar noon (at 20–30 pptV depending on season), which is counter to box model simulations that show a midday minimum due to OH conversion of NO2 to HNO3. Production of NOx via decomposition of organic nitrogen species and the photolysis of HNO3 appear insufficient to provide the observed noon-time maximum. A rapid photolysis of nitrate aerosol to produce HONO and NO2, however, is able to simulate the observed diurnal cycle. This would make it the dominant source of NOx at this remote marine boundary layer site overturning the previous paradigm of transport of organic nitrogen species such as PAN being the dominant source. We show that observed mixing ratios (Nov–Dec 2015) of HONO at Cape Verde (~ 2.5 pptV peak at solar noon) are consistent with this route for NOx production. Reactions between the nitrate radical and halogen hydroxides which have been postulated in the literature appear to improve the box model simulation. This rapid conversion of aerosol phase nitrate to NOx changes our perspective of the NOx cycling chemistry in the tropical marine boundary layer, suggesting a more chemically complex environment than previously thought.

International audience

[1] Simulating the emission of mineral dust and sea-salt aerosol is nonlinear with surface winds and therefore requires accurate representation of surface winds. Consequently, the resolution of a simulation affects emission and is often corrected with nonphysical scaling in coarse resolution global models. We examine the resolution dependence of emissions in the GEOS-Chem model and find that globally, annual emissions at 4° × 5° resolution are 59% of those simulated at 2° × 2.5° and only 33% of emissions at 0.25° × 0.3125°. The spatial and seasonal distribution of dust emissions vary substantially, indicating that applying a uniform scaling is inappropriate. We demonstrate the benefit of characterizing the subgrid surface wind as a Weibull probability distribution, reconciling much of the difference in emissions between resolutions for dust. Such a representation is shown to have little impact on sea-salt emissions.

Forests fires are a significant source of chemicals to the atmosphere including numerous non-methane organic compounds (NMOCs). We report airborne measurement of hydrocarbons, acetone and methanol from >500 whole air samples collected over Eastern Canada, including interceptions of several different boreal biomass burning plumes. From these and concurrent measurements of carbon monoxide (CO) we derive fire emission ratios for 29 different organic species relative to the emission of CO. These range from 8.9 ± 3.2 ppt ppb−1 CO for methanol to 0.007 ± 0.004 ppt ppb−1 CO for cyclopentane. The ratios are in good to excellent agreement with literature values. Using the GEOS-Chem global 3-D chemical transport model (CTM) we show the influence of biomass burning on the global distributions of benzene, toluene, ethene and propene (species which are controlled for air quality purposes and sometimes used as indicative tracers of anthropogenic activity). Using our observationally derived emission ratios and the GEOS-Chem CTM, we show that biomass burning can be the largest fractional contributor to observed benzene, toluene, ethene and propene levels in many global locations. The widespread biomass burning contribution to atmospheric benzene, a heavily regulated air pollutant, suggests that pragmatic approaches are needed when setting air quality targets as tailpipe and solvent emissions decline in developed countries. We subsequently determine the extent to which the 28 global-status World Meteorological Organisation – Global Atmosphere Watch stations worldwide are influenced by biomass burning sourced benzene, toluene, ethene and propene as compared to their exposure to anthropogenic emissions.

Aircraft and satellite observations indicate the presence of ppt (pptpmol/mol) levels of BrO in the free troposphere with important implications for the tropospheric budgets of ozone, OH, and mercury. We can reproduce these observations with the GEOS-Chem global tropospheric chemistry model by including a broader consideration of multiphase halogen (Br-Cl) chemistry than has been done in the past. Important reactions for regenerating BrO from its nonradical reservoirs include HOBr+Br-/Cl- in both aerosols and clouds, and oxidation of Br- by ClNO3 and ozone. Most tropospheric BrO in the model is in the free troposphere, consistent with observations and originates mainly from the photolysis and oxidation of ocean-emitted CHBr3. Stratospheric input is also important in the upper troposphere. Including production of gas phase inorganic bromine from debromination of acidified sea salt aerosol increases free tropospheric Br-y by about 30%. We find HOBr to be the dominant gas-phase reservoir of inorganic bromine. Halogen (Br-Cl) radical chemistry as implemented here in GEOS-Chem drives 14% and 11% decreases in the global burdens of tropospheric ozone and OH, respectively, a 16% increase in the atmospheric lifetime of methane, and an atmospheric lifetime of 6months for elemental mercury. The dominant mechanism for the Br-Cl driven tropospheric ozone decrease is oxidation of NOx by formation and hydrolysis of BrNO3 and ClNO3.

Models of atmospheric composition play an essential role in our scientific understanding of atmospheric processes and in providing policy strategies to deal with societally relevant problems such as climate change, air quality and ecosystem degradation. The fidelity of these models needs to be assessed against observations to ensure that errors in model formulations are found and that model limitations are understood. A range of approaches are necessary for these comparisons. Here, we apply a spectral analysis methodology for this comparison. We use the Lomb-Scargle Periodogram, a method similar to a Fourier transform, but better suited to dealing with the gapped datasets typical of observational data. We apply this methodology to long-term hourly ozone observations and the equivalent model (GEOS-Chem) output. We show that the spectrally transformed observational data shows a distinct power spectrum with regimes indicative of meteorological processes (weather, macroweather) and specific peaks observed at the daily and annual timescales together with corresponding harmonic peaks at half, third etc. of these frequencies. Model output shows corresponding features. A comparison between the amplitude and phase of these peaks introduces a new comparison methodology between model and measurements.We focus on the amplitude and phase of diurnal and seasonal cycles and present observational/model comparisons and discuss model performance. We find large biases notably for the seasonal cycle in the mid-latitude northern hemisphere where the amplitudes are generally overestimated by up to 16 ppb, and phases are too late on the order of 1–5 months. This spectral methodology can be applied to a range of model-measurement applications and is highly suitable for Multimodel Intercomparison Projects (MIPs).

We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by −1 (6.5% globally), with the largest effects in the northern extratropics in spring. The global mean tropospheric OH concentration decreases by 4%. Inclusion of bromine chemistry improves the ability of global models (GEOS-Chem and p-TOMCAT) to simulate observed 19th-century ozone and its seasonality. Bromine effects on tropospheric ozone are comparable in the present-day and pre-industrial atmospheres so that estimates of anthropogenic radiative forcing are minimally affected. Br atom concentrations are 40% higher in the pre-industrial atmosphere due to lower ozone, which would decrease by a factor of 2 the atmospheric lifetime of elemental mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.

Field measurements of the hydroxyl radical, OH, are crucial for our understanding of tropospheric chemistry. However, observations of this key atmospheric species in the tropical marine boundary layer, where the warm, humid conditions and high solar irradiance lend themselves favourably to production, are sparse. The Seasonal Oxidant Study at the Cape Verde Atmospheric Observatory in 2009 allowed, for the first time, seasonal measurements of both OH and HO2 in a clean (i.e. low NOx), tropical marine environment. It was found that concentrations of OH and HO2 were typically higher in the summer months (June, September), with maximum daytime concentrations of ~9 × 106 and 4 × 108 molecule cm−3, respectively – almost double the values in winter (late February, early March). HO2 was observed to persist at ~107 molecule cm−3 through the night, but there was no strong evidence of nighttime OH, consistent with previous measurements at the site in 2007. HO2 was shown to have excellent correlations (R2 ~ 0.90) with both the photolysis rate of ozone, J(O1D), and the primary production rate of OH, P(OH), from the reaction of O(1D) with water vapour. The analogous relations of OH were not so strong (R2 ~ 0.6), but the coefficients of the linear correlation with J(O1D) in this study were close to those yielded from previous works in this region, suggesting that the chemical regimes have similar impacts on the concentration of OH. Analysis of the variance of OH and HO2 across the Seasonal Oxidant Study suggested that ~70% of the total variance could be explained by diurnal behaviour, with ~30% of the total variance being due to changes in air mass.

NOx measurements were conducted at the Halley Research Station, coastal Antarctica, during the austral summer period 1 January–10 February 2005. A clear NOx diurnal cycle was observed with minimum concentrations close to instrumental detection limit (5 pptv) measured between 04:00–05:00 GMT. NOx concentrations peaked (24 pptv) between 19:00–20:00 GMT, approximately 5 h after local solar noon. An optimised box model of NOx concentrations based on production from in-snow nitrate photolysis and chemical loss derives a mean noon emission rate of 3.48 × 108 molec cm−2 s−1, assuming a 100 m boundary layer mixing height, and a relatively short NOx lifetime of ~6.4 h. This emission rate compares to directly measured values ranging from 2.1 to 12.6 × 108 molec cm−2 s−1 made on 3 days at the end of the study period. Calculations of the maximum rate of NO2 loss via a variety of conventional HOx and halogen oxidation processes show that the lifetime of NOx is predominantly controlled by halogen processing, namely BrNO3 and INO3 gas-phase formation and their subsequent heterogeneous uptake. Furthermore the presence of halogen oxides is shown to significantly perturb NOx concentrations by decreasing the NO/NO2 ratio. We conclude that in coastal Antarctica, the potential ozone production efficiency of NOx emitted from the snowpack is mitigated by the more rapid NOx loss due to halogen nitrate hydrolysis.