Global Three-dimensional Chemical Transport Model Research Articles

Socioeconomic disparities in aerosol pollutant exposure may be amplified by ultrafine particles despite declining PM2.5

BACKGROUND AND AIM: No study has investigated the spatiotemporal race-ethnicity and income disparities in ultrafine particles (UFP; ≤0.1µm) exposure, which is increasingly identified as a key subcomponent of PM₂.₅-related health effects. This study aims to establish the importance of distinguishing UFP from PM₂.₅ and quantify their race-ethnicity and income disparities in New York State (NYS). METHODS: Exposure disparities among seven race-ethnicity groups (Hispanics of any race, non-Hispanic Asian, Black, Native, Pacific& White alone, and Other/Mixed) and by household income across spatial scales (state, county, county subdivision, NCHS urban levels) during the period 2013–2020 for UFP and PM₂.₅, were quantified using Census data. A global three-dimensional chemical transport model with state-of-the-science aerosol microphysical processes were used to estimate UFP/PM₂.₅ that have been validated extensively with observations. RESULTS: The average New Yorker was exposed to 5171#·cm⁻³ UFP and 8.2µg·m⁻³ PM₂.₅ in 2013–2020. Minority race-ethnicity groups were invariably exposed to greater daily aerosol pollution in NYS (+51–104% UFP & +1.9–32% PM₂.₅). Race-ethnicity exposure disparities for PM₂.₅ exposure have declined over time; by −6% from 2013–2017 and plateauing thereafter despite increasing PM₂.₅. Crucially and in contrast, these disparities have persisted (+10%) for UFP exposure and even widened in periods of declining UFP. Economic status (median household income) by itself does not reveal significant exposure disparities. However, in tandem with race-ethnicity it uncovers these disparities as disproportionately magnified for socioeconomically disadvantaged subgroups. CONCLUSIONS: PM₂.₅ decline was associated with decline in race-ethnicity exposure disparities. which continued despite a post-2018 reversal in PM₂.₅ trends. However, race-ethnicity UFP exposure disparities were much larger, more disproportionate, and increased or remained constant across various income strata and levels of urbanicity. The need to distinguish ultrafine (UFP) from fine (PM₂.₅) aerosols is established through microphysical, geostatistical, and exposure assessment perspectives. KEYWORDS: air pollution, ultrafine particles, particulate matter, environmental justice, socioeconomic status

Investigation of the Production of Trifluoroacetic Acid from Two Halocarbons, HFC-134a and HFO-1234yf and Its Fates Using a Global Three-Dimensional Chemical Transport Model

Trifluoroacetic acid (TFA), a highly soluble and stable organic acid, is photochemically produced by certain anthropogenically emitted halocarbons such as HFC-134a and HFO-1234yf. Both these haloca...

Atmospheric-methane source and sink sensitivity analysis using Gaussian process emulation

Abstract. We present a method to efficiently approximate the response of atmospheric-methane mole fraction and δ13C–CH4 to changes in uncertain emission and loss parameters in a three-dimensional global chemical transport model. Our approach, based on Gaussian process emulation, allows relationships between inputs and outputs in the model to be efficiently explored. The presented emulator successfully reproduces the chemical transport model output with a root-mean-square error of 1.0 ppb and 0.05 ‰ for hemispheric-methane mole fraction and δ13C–CH4, respectively, for 28 uncertain model inputs. The method is shown to outperform multiple linear regression because it captures non-linear relationships between inputs and outputs as well as the interaction between model input parameters. The emulator was used to determine how sensitive methane mole fraction and δ13C–CH4 are to the major source and sink components of the atmospheric budget given current estimates of their uncertainty. We find that our current knowledge of the methane budget, as inferred through hemispheric mole fraction observations, is limited primarily by uncertainty in the global mean hydroxyl radical concentration and freshwater emissions. Our work quantitatively determines the added value of measurements of δ13C–CH4, which are sensitive to some uncertain parameters to which mole fraction observations on their own are not. However, we demonstrate the critical importance of constraining isotopic initial conditions and isotopic source signatures, small uncertainties in which strongly influence long-term δ13C–CH4 trends because of the long timescales over which transient perturbations propagate through the atmosphere. Our results also demonstrate that the magnitude and trend of methane mole fraction and δ13C–CH4 can be strongly influenced by the combined uncertainty in more minor components of the atmospheric budget, which are often fixed and assumed to be well-known in inverse-modelling studies (e.g. emissions from termites, hydrates, and oceans). Overall, our work provides an overview of the sensitivity of atmospheric observations to budget uncertainties and outlines a method which could be employed to account for these uncertainties in future inverse-modelling systems.

Investigating the Impacts of Nonacyl Peroxy Nitrates on the Global Composition of the Troposphere Using a 3-D Chemical Transport Model, STOCHEM-CRI

Nonacyl peroxy nitrates, RO2NO2, act as a reservoir species for NOx in the upper troposphere. The low thermal stability of these compounds means that they only become a significant sink of NOx at the low temperatures observed in the upper troposphere. The chemical processes involved with the formation and degradation of methyl peroxy nitrate (CH3O2NO2) and an additional 44 RO2NO2 have been incorporated into the global three-dimensional chemical transport model, STOCHEM-CRI. The study investigates the effect of the addition of RO2NO2 chemistry on the budget of NOx, which in turn impacts the ozone, hydroxyl radical (OH), and nitrate radical (NO3) formation. This investigation found that the addition of CH3O2NO2 led to an increase in the tropospheric burdens of NOx (+3.0%), ozone (+2.0%), OH (+4.0%), and NO3 (+8.8%). However, the other 44 RO2NO2 contribute a significant increment of tropospheric global burdens of NOx (+4.4%), ozone (+3.4%), OH (+5.5%), and NO3 (+11.1%) with the largest mixing ratios of NOx of up to 25%, ozone up to 14%, OH up to 20%, and NO3 up to 50%. The increase in the global burden of oxidizing species such as OH due to the addition of 44 other RO2NO2 led to a significant decrease in the lifetimes of greenhouse gases such as methane (∼6%). The modeled mixing ratios of CH3O2NO2 were in reasonable agreement with measurements, the only extensive data set available.

Tropospheric ozone over the Indian subcontinent from 2000 to 2015: Data set and simulation using GEOS-Chem chemical transport model

The Indian subcontinent (IS) is a region of increasing economic growth, urbanization, and consequently, anthropogenic emissions, altering tropospheric ozone (O3) over the region with impacts on the lives and health of 1.3 billion people. We have developed a comprehensive data set of the tropospheric O3 for 16 years (2000–2015) for the region between 50-115°E and 0–45°N, focusing on the IS. The data set included available balloon-borne, aircraft, and satellite-based measurements. We used a global three-dimensional chemical transport model, GEOS-Chem, at a 2° × 2.5° resolution to calculate daily tropospheric O3 over the region. The simulated O3 abundances in the boundary layer and lower, mid, and upper troposphere were compared with ozonesonde, aircraft, and satellite observations. The statistical analyses indicate that the model simulated boundary layer and lower, mid, and upper tropospheric O3 column abundances reasonably well with a mean bias ~1–3 DU in comparison to observations, but within the uncertainties of the observations. The model reproduced the vertical profiles of O3 and CO with a bias of less than 20% over different regions in the IS. The simulated tropospheric column NO2 was higher by a factor of ~1.5 compared to satellite observations. The model reproduced the regional difference in seasonal variations of tropospheric column O3 as observed by the Ozone Monitoring Instrument. We conclude that the CO emissions from the IS are underestimated while those of NOx are overestimated, both by around 20–30%.

Impacts of the Degradation of 2,3,3,3-Tetrafluoropropene into Trifluoroacetic Acid from Its Application in Automobile Air Conditioners in China, the United States, and Europe.

HFO-1234yf (2,3,3,3-tetrafluoropropene) was proposed as an automobile air conditioner (MAC) refrigerant worldwide. However, its atmospheric degradation product is the highly soluble and phytotoxic trifluoroacetic acid (TFA), which persists in aquatic environments. We used a global three-dimensional chemical transport model to assess the potential environmental effects resulting from complete future conversion of the refrigerant in all MAC to HFO-1234yf in China, the United States, and Europe. The annual mean atmospheric concentrations of HFO-1234yf were 2.62, 2.20, and 2.73 pptv, and the mean deposition rates of TFA were 0.96, 0.45, and 0.52 kg km-2 yr-1, in three regions. The regional TFA deposition sources mainly came from emissions within the same region. The annual TFA deposition in the North Pole region was lower than the global average and mainly originated from European emissions. A potential doubling in the future HFO-1234yf emissions in China mainly affected the local TFA depositions. The TFA concentrations in rainwater were strongly affected by the regional precipitation rates. North Africa and the Middle East, regions with scant rainfall, had extremely high TFA concentrations. The rainwater concentrations of TFA during individual rain events can exceed the level considered to be safe, indicating substantial potential regional risks from future HFO-1234yf use.

Comparisons of a Chemical Transport Model with a Four-Year (April to September) Analysis of Fine- and Coarse-Mode Aerosol Optical Depth Retrievals Over the Canadian Arctic

ABSTRACTWe compared April to September retrievals of total, fine-mode (sub-micron), and coarse-mode (super-micron) aerosol optical depth (AOD) from the Aerosol Robotic Network (AERONET) with simulations from a global three-dimensional chemical transport model, the Goddard Earth Observing System (GEOS-Chem), across five Arctic stations and a four-year sampling period. It was determined that the AOD histograms of both the retrievals and the simulations were better represented by a lognormal distribution and that the successful simulation of this empirical feature as well as its consequences (including a better model versus retrieval coefficient of determination in log-log AOD space) represented a general indicator of model evaluation success. Seasonal (monthly averaged) AOD retrievals were sensitive to the way in which the averaging was performed; this was ascribed to the presence of highly variable fine-mode smoke in the western Arctic. The retrieved and modelled station-by-station fine-mode AOD averages showed a peak in April/May that decreased over the summer, while the model underestimated the fine-mode AOD by an average of about 0.004 (∼6%). Both the retrievals and simulations showed seasonal coarse-mode AOD variations with a peak in April/May that was attributed to Asian and/or Saharan dust. The model's success in capturing such weak seasonal events helps to confirm the relevance of the separation of the fine and coarse modes and the general validity of model estimates in the Arctic.

Impacts of East Asian summer and winter monsoons on interannual variations of mass concentrations and direct radiative forcing of black carbon over eastern China

Abstract. We applied a global three-dimensional chemical transport model (GEOS-Chem) to examine the impacts of the East Asian monsoon on the interannual variations of mass concentrations and direct radiative forcing (DRF) of black carbon (BC) over eastern China (110–125° E, 20–45° N). With emissions fixed at the year 2010 levels, model simulations were driven by the Goddard Earth Observing System (GEOS-4) meteorological fields for 1986–2006 and the Modern Era Retrospective-analysis for Research and Applications (MERRA) meteorological fields for 1980–2010. During the period of 1986–2006, simulated June–July–August (JJA) and December–January–February (DJF) surface BC concentrations were higher in MERRA than in GEOS-4 by 0.30 µg m−3 (44 %) and 0.77 µg m−3 (54 %), respectively, because of the generally weaker precipitation in MERRA. We found that the strength of the East Asian summer monsoon (EASM; East Asian winter monsoon, EAWM) negatively correlated with simulated JJA (DJF) surface BC concentrations (r = −0. 7 (−0.7) in GEOS-4 and −0.4 (−0.7) in MERRA), mainly by the changes in atmospheric circulation. Relative to the 5 strongest EASM years, simulated JJA surface BC concentrations in the 5 weakest monsoon years were higher over northern China (110–125° E, 28–45° N) by 0.04–0.09 µg m−3 (3–11 %), but lower over southern China (110–125° E, 20–27° N) by 0.03–0.04 µg m−3 (10–11 %). Compared to the 5 strongest EAWM years, simulated DJF surface BC concentrations in the 5 weakest monsoon years were higher by 0.13–0.15 µg m−3 (5–8 %) in northern China and by 0.04–0.10 µg m−3 (3–12 %) in southern China. The resulting JJA (DJF) mean all-sky DRF of BC at the top of the atmosphere was 0.04 W m−2 (3 %; 0.03 W m−2, 2 %) higher in northern China but 0.06 W m−2 (14 %; 0.03 W m−2, 3 %) lower in southern China. In the weakest monsoon years, the weaker vertical convection at the elevated altitudes led to the lower BC concentrations above 1–2 km in southern China, and therefore the lower BC DRF in the region. The differences in vertical profiles of BC between the weakest and strongest EASM years (1998–1997) and EAWM years (1990–1996) reached up to −0.09 µg m−3 (−46 %) and −0.08 µg m−3 (−11 %) at 1–2 km in eastern China.

Factors controlling black carbon distribution in the Arctic

Abstract. We investigate the sensitivity of black carbon (BC) in the Arctic, including BC concentration in snow (BCsnow, ng g−1) and surface air (BCair, ng m−3), as well as emissions, dry deposition, and wet scavenging using the global three-dimensional (3-D) chemical transport model (CTM) GEOS-Chem. We find that the model underestimates BCsnow in the Arctic by 40 % on average (median = 11.8 ng g−1). Natural gas flaring substantially increases total BC emissions in the Arctic (by ∼ 70 %). The flaring emissions lead to up to 49 % increases (0.1–8.5 ng g−1) in Arctic BCsnow, dramatically improving model comparison with observations (50 % reduction in discrepancy) near flaring source regions (the western side of the extreme north of Russia). Ample observations suggest that BC dry deposition velocities over snow and ice in current CTMs (0.03 cm s−1 in the GEOS-Chem) are too small. We apply the resistance-in-series method to compute a dry deposition velocity (vd) that varies with local meteorological and surface conditions. The resulting velocity is significantly larger and varies by a factor of 8 in the Arctic (0.03–0.24 cm s−1), which increases the fraction of dry to total BC deposition (16 to 25 %) yet leaves the total BC deposition and BCsnow in the Arctic unchanged. This is largely explained by the offsetting higher dry and lower wet deposition fluxes. Additionally, we account for the effect of the Wegener–Bergeron–Findeisen (WBF) process in mixed-phase clouds, which releases BC particles from condensed phases (water drops and ice crystals) back to the interstitial air and thereby substantially reduces the scavenging efficiency of clouds for BC (by 43–76 % in the Arctic). The resulting BCsnow is up to 80 % higher, BC loading is considerably larger (from 0.25 to 0.43 mg m−2), and BC lifetime is markedly prolonged (from 9 to 16 days) in the Arctic. Overall, flaring emissions increase BCair in the Arctic (by ∼ 20 ng m−3), the updated vd more than halves BCair (by ∼ 20 ng m−3), and the WBF effect increases BCair by 25–70 % during winter and early spring. The resulting model simulation of BCsnow is substantially improved (within 10 % of the observations) and the discrepancies of BCair are much smaller during the snow season at Barrow, Alert, and Summit (from −67–−47 % to −46–3 %). Our results point toward an urgent need for better characterization of flaring emissions of BC (e.g., the emission factors, temporal, and spatial distribution), extensive measurements of both the dry deposition of BC over snow and ice, and the scavenging efficiency of BC in mixed-phase clouds. In addition, we find that the poorly constrained precipitation in the Arctic may introduce large uncertainties in estimating BCsnow. Doubling precipitation introduces a positive bias approximately as large as the overall effects of flaring emissions and the WBF effect; halving precipitation produces a similarly large negative bias.

A modelling study of the atmospheric chemistry of DMS using the global model, STOCHEM-CRI

The tropospheric chemistry of dimethylsulfide (DMS) is investigated using a global three-dimensional chemical transport model, STOCHEM with the CRIv2-R5 chemistry scheme. The tropospheric distribution of DMS and its removal at the surface by OH abstraction, OH addition, NO3 oxidation, and BrO oxidation is modelled. The study shows that the lifetime and global burden of DMS is ca. 1.2 days and 98 Gg S, respectively. Inclusion of BrO oxidation resulted in a reduction of the lifetime (1.0 day) and global burden (83 Gg S) of DMS showing that this reaction is important in the DMS budget. The percentage contribution of BrO oxidation to the total removal of DMS is found to be only 7.9% that is considered a lower limit because the study does not include an inorganic source of bromine from sea-salt. BrO oxidation contributed significantly in the high latitudes of the southern hemisphere (SH). Inclusion of DMS removal by Cl2 showed that potentially a large amount of DMS is removed via this reaction specifically in the remote SH oceans, depending on the flux of Cl2 from the Southern Ocean. Model DMS levels are evaluated against measurement data from six different sites around the globe. The model predicted the correct seasonal cycle for DMS at all locations and correlated well with measurement data for most of the periods.

Global modeling of the C1–C3 alkyl nitrates using STOCHEM-CRI

The atmospheric global budget and distribution of C1–C3 alkyl nitrates have been investigated using a global three-dimensional chemistry transport model, STOCHEM-CRI. Alkyl nitrates (RONO2) are significant NOx reservoir species and the more detailed VOC oxidation mechanism (CRI v2-R5) leads to greater photochemical production. RONO2 are significant sources of NOx in regions remote from NOx sources. The study shows that the global burden and the atmospheric life-time of C1–C3 alkyl nitrates are 113 Gg and 9–10 days, respectively, which are in excellent agreement with estimates established by previous studies. The abundance of alkyl nitrates have been found to be higher in the continental atmosphere, with CH3ONO2 mixing ratios up to 20 ppt over the Amazon rainforest. Up to 15, 10, 2, and 5 ppt of modelled CH3ONO2, C2H5ONO2, n-C3H7ONO2 and i-C3H7ONO2 have been found in the northern hemisphere over regions with large anthropogenic emissions of NOx and VOCs. The combination of atmospheric production and long-range transport led to high alkyl nitrate levels at high latitudes. The model performance for C1–C3 alkyl nitrates was established using observations from nine flights and nine field campaigns. The comparison shows a tendency towards model under-prediction of the observations, particularly in the southern hemispheric marine boundary layer, possibly due to the absence of oceanic production mechanisms and air-sea exchange processes in the model. The discrepancies between model and observed seasonal cycles, especially of CH3ONO2, in both hemispheres are discussed.

Verifying Fossil-Fuel Carbon Dioxide Emissions Forecasted by an Artificial Neural Network with the GEOS-Chem Model

In this study, the authors developed an en- semble of Elman neural networks to forecast the spatial and temporal distribution of fossil-fuel emissions (ff) in 2009. The authors built and trained 29 Elman neural net- works based on the monthly average grid emission data (1979-2008) from different geographical regions. A three-dimensional global chemical transport model, God- dard Earth Observing System (GEOS)-Chem, was applied to verify the effectiveness of the networks. The results showed that the networks captured the annual increasing trend and interannual variation of ff well. The difference between the simulations with the original and predicted ff ranged from −1 ppmv to 1 ppmv globally. Meanwhile, the authors evaluated the observed and simulated north-south gradient of the atmospheric CO2 concentrations near the surface. The two simulated gradients appeared to have a similar changing pattern to the observations, with a slightly higher background CO2 concentration, ~ 1 ppmv. The results indicate that the Elman neural network is a useful tool for better understanding the spatial and tem- poral distribution of the atmospheric CO2 concentration and ff.

Reassessing the photochemical production of methanol from peroxy radical self and cross reactions using the STOCHEM-CRI global chemistry and transport model

Methanol (CH3OH) is an oxygenated volatile organic compound (VOC) and one of the most abundant species present in the troposphere. The mass of CH3OH in the atmospheric reservoir, its annual mass flux from sources to sinks, and its global budget have been investigated using STOCHEM-CRI, a global three-dimensional chemistry transport model. Our study shows that the global burden of methanol is 5 Tg. The atmospheric life-time of CH3OH is found to be 6.1 days which falls within the range of previous modelling studies. The impact of peroxy radicals on the photochemical production of CH3OH has been studied and suggests that NMVOCs (non-methane Volatile Organic Compounds) are an important source of both peroxy radicals and CH3OH. The photochemical production routes of CH3OH are found to be 48 Tg/yr, which are higher than the previous studies and contributes significantly to the total global methanol sources of 287 Tg/yr. An additional CH3OH production of 8.2 Tg/yr from the reaction of methyl peroxy radicals (CH3O2) with hydroxyl radicals (OH) could be a significant additional source of CH3OH particularly over the tropical oceans which would lead to a revision of the global sources and life cycle of CH3OH.

Observed and simulated features of the CO2 diurnal cycle in the boundary layer at Beijing and Hefei, China

The mechanism of the CO2 diurnal cycle is a basis for investigating the carbon budget and its impacts on climate and environment change. Regional diurnal variations in CO2 concentration based on observations and modeling have been studied widely. However, few studies have focused on the pattern of the CO2 diurnal cycle in China. In this study, a three-dimensional global chemical transport model, Goddard Earth Observing System (GEOS)-Chem, was applied to simulate the CO2 concentration and its variation over China from 2004 to 2012. Meanwhile, we also analyzed the CO2 concentration as observed by two eddy covariance flux observation towers, one located in Beijing (39°58′N, 116°22′E) and one in Hefei (31°55′N, 117°10′E), using LI-COR 7500A infrared gas analyzers. Observations showed the amplitude of the CO2 diurnal cycle at Hefei to be larger than at Beijing, due to stronger ecological activities. GEOS-Chem successfully captured the main aspects of the diurnal cycle of the CO2 concentration in the boundary layer observed at both Beijing and Hefei. However, some discrepancies between the model and observations did exist; specifically, the model tended to underestimate the amplitude of the CO2 diurnal cycle. The data also showed that traffic emissions significantly enhanced the CO2 concentration in the boundary layer.

Dust vertical profile impact on global radiative forcing estimation using a coupled chemical-transport–radiative-transfer model

Abstract. Atmospheric mineral dust particles exert significant direct radiative forcings and are important drivers of climate and climate change. We used the GEOS-Chem global three-dimensional chemical transport model (CTM) coupled with the Fu-Liou-Gu (FLG) radiative transfer model (RTM) to investigate the dust radiative forcing and heating rate based on different vertical profiles for April 2006. We attempt to actually quantify the sensitivities of radiative forcing to dust vertical profiles, especially the discrepancies between using realistic and climatological vertical profiles. In these calculations, dust emissions were constrained by observations of aerosol optical depth (AOD). The coupled calculations utilizing a more realistic dust vertical profile simulated by GEOS-Chem minimize the physical inconsistencies between 3-D CTM aerosol fields and the RTM. The use of GEOS-Chem simulated vertical profile of dust extinction, as opposed to the FLG prescribed vertical profile, leads to greater and more spatially heterogeneous changes in the estimated radiative forcing and heating rate produced by dust. Both changes can be attributed to a different vertical structure between dust and non-dust source regions. Values of the dust vertically resolved AOD per grid level (VRAOD) are much larger in the middle troposphere, though smaller at the surface when the GEOS-Chem simulated vertical profile is used, which leads to a much stronger heating rate in the middle troposphere. Compared to the FLG vertical profile, the use of GEOS-Chem vertical profile reduces the solar radiative forcing at the top of atmosphere (TOA) by approximately 0.2–0.25 W m−2 over the African and Asian dust source regions. While the Infrared (IR) radiative forcing decreases 0.2 W m−2 over African dust belt, it increases 0.06 W m−2 over the Asian dust belt when the GEOS-Chem vertical profile is used. Differences in the solar radiative forcing at the surface between the use of the GEOS-Chem and FLG vertical profiles are most significant over the Gobi desert with a value of about 1.1 W m−2. The radiative forcing effect of dust particles is more pronounced at the surface over the Sahara and Gobi deserts by using FLG vertical profile, while it is less significant over the downwind area of Eastern Asia.

The contribution of natural and anthropogenic very short-lived species to stratospheric bromine

Abstract. We have used a global three-dimensional chemical transport model to quantify the impact of the very short-lived substances (VSLS) CHBr3, CH2Br2, CHBr2Cl, CHBrCl2, CH2BrCl and C2H5-Br on the bromine budget of the stratosphere. Atmospheric observations of these gases allow constraints on surface mixing ratios that, when incorporated into our model, contribute ~4.9–5.2 parts per trillion (ppt) of inorganic bromine (Bry) to the stratosphere. Of this total, ~76 % comes from naturally-emitted CHBr3 and CH2Br2. The remaining species individually contribute modest amounts. However, their accumulated total accounts for up to ~1.2 ppt of the supply and thus should not be ignored. We have compared modelled tropical profiles of a range of VSLS with observations from the recent 2009 NSF HIPPO-1 aircraft campaign. Modelled profiles agree reasonably well with observations from the surface to the lower tropical tropopause layer. We have also considered the poorly studied anthropogenic VSLS, C2H5Br, CH2BrCH2Br, n-C3H7Br and i-C3H7Br. We find the local atmospheric lifetime of these species in the tropical tropopause layer are ~183, 603, 39 and 49 days, respectively. These species, particularly C2H5Br and CH2BrCH2Br, would thus be important carriers of bromine to the stratosphere if emissions were to increase substantially. Our model shows ~70–73 % and ~80–85 % of bromine from these species in the tropical boundary layer can reach the lower stratosphere.

The impact of anthropogenic emissions on atmospheric sulfate production pathways, oxidants, and ice core Δ<sup>17</sup>O(SO<sub>4</sub><sup>2–</sup>)

Abstract. We use a global three-dimensional chemical transport model to quantify the influence of anthropogenic emissions on atmospheric sulfate production mechanisms and oxidant concentrations constrained by observations of the oxygen isotopic composition (Δ17O = &delta17O–0.52 × &delta18O) of sulfate in Greenland and Antarctic ice cores and aerosols. The oxygen isotopic composition of non-sea salt sulfate (Δ17O(SO42–)) is a function of the relative importance of each oxidant (e.g. O3, OH, H2O2, and O2) during sulfate formation, and can be used to quantify sulfate production pathways. Due to its dependence on oxidant concentrations, Δ17O(SO42–) has been suggested as a proxy for paleo-oxidant levels. However, the oxygen isotopic composition of sulfate from both Greenland and Antarctic ice cores shows a trend opposite to that expected from the known increase in the concentration of tropospheric O3 since the preindustrial period. The model simulates a significant increase in the fraction of sulfate formed via oxidation by O2 catalyzed by transition metals in the present-day Northern Hemisphere troposphere (from 11% to 22%), offset by decreases in the fractions of sulfate formed by O3 and H2O2. There is little change, globally, in the fraction of tropospheric sulfate produced by gas-phase oxidation (from 23% to 27%). The model-calculated change in Δ17O(SO42–) since preindustrial times (1850 CE) is consistent with Arctic and Antarctic observations. The model simulates a 42% increase in the concentration of global mean tropospheric O3, a 10% decrease in OH, and a 58% increase in H2O2 between the preindustrial period and present. Model results indicate that the observed decrease in the Arctic Δ17O(SO42–) – in spite of increasing tropospheric O3 concentrations – can be explained by the combined effects of increased sulfate formation by O2 catalyzed by anthropogenic transition metals and increased cloud water acidity, rendering Δ17O(SO42–) insensitive to changing oxidant concentrations in the Arctic on this timescale. In Antarctica, the Δ17O(SO42–) is sensitive to relative changes of oxidant concentrations because cloud pH and metal emissions have not varied significantly in the Southern Hemisphere on this timescale, although the response of Δ17O(SO42–) to the modeled changes in oxidants is small. There is little net change in the Δ17O(SO42–) in Antarctica, in spite of increased O3, which can be explained by a compensatory effect from an even larger increase in H2O2. In the model, decreased oxidation by OH (due to lower OH concentrations) and O3 (due to higher H2O2 concentrations) results in little net change in Δ17O(SO42–) due to offsetting effects of Δ17O(OH) and Δ17O(O3). Additional model simulations are conducted to explore the sensitivity of the oxygen isotopic composition of sulfate to uncertainties in the preindustrial emissions of oxidant precursors.

Analysis of a rapid increase of stratospheric ozone during late austral summer 2008 over Kerguelen (49.4° S, 70.3° E)

Abstract. This paper reports on an increase of ozone event observed over Kerguelen (49.4° S, 70.3° E) in relationship with large-scale isentropic transport. This is evidenced by ground-based observations (co-localised radiosonde and SAOZ experiments) together with satellite global observations (Aura/MLS) assimilated into MOCAGE, a Méteo-France model. The study is based on the analyses of the first ozonesonde experiment never recorded at the Kerguelen site within the framework of a French campaign called ROCK that took place from April to August 2008. Comparisons and interpretations of the observed event are supported by co-localised SAOZ observations, by global mapping of tracers (O3, N2O and columns of O3) from Aura/MLS and Aura/OMI experiments, and by model simulations of Ertel Potential Vorticity initialised by the ECMWF (European Centre for Medium-Range Weather Forecasts) data reanalyses. Satellite and ground-based observational data revealed a consistent increase of ozone in the local stratosphere by mid-April 2008. Additionally, Ozone (O3) and nitrous oxide (N2O) profiles obtained during January–May 2008 using the Microwave Limb Sounder (MLS) aboard the Aura satellite are assimilated into MOCAGE (MOdèle de Chimie Atmosphérique à Grande Echelle), a global three-dimensional chemistry transport model of Météo-France. The assimilated total O3 values are consistent with SAOZ ground observations (within ±5%), and isentropic distributions of O3 match well with maps of advected potential vorticity (APV) derived from the MIMOSA model, a high-resolution advection transport model, and from the ECMWF reanalysis. The event studied seems to be related to the isentropic transport of air masses that took place simultaneously in the lower- and middle-stratosphere, respectively from the polar region and from the tropics to the mid-latitudes. In fact, the ozone increase observed by mid April 2008 resulted simultaneously: (1) from an equator-ward departure of polar air masses characterised with a high-ozone layer in the lower stratosphere (near the 475 K isentropic level), and (2) from a reverse isentropic transport from the tropics to mid- and high-latitudes in the upper stratosphere (nearby the 700 K level). The increase of ozone observed over Kerguelen from the 16-April ozonesonde profile is thus attributed to a concomitant isentropic transport of ozone in two stratospheric layers: the tropical air moving southward and reaching over Kerguelen in the upper stratosphere, and the polar air passing over the same area but in the lower stratosphere.

On the effect of a global adoption of various fractions of biodiesel on key species in the troposphere

Biodiesel use is being promoted worldwide as a green alternative to conventional diesel. A global three-dimensional chemistry transport model is employed to investigate the impact on air quality and global tropospheric composition of adopting biodiesel as a fractional component of diesel use. Five global simulations are conducted where emission changes of hydrocarbons and nitrogen oxides were applied within the model to investigate changes in tropospheric pollutants. Hydrocarbon emission reductions lead to an overall improvement in air quality with reductions in ozone, organic aerosol, aromatic species and PAN. However when the increase in NOx, caused by increased exhaust temperature, is included there is negligible difference in ozone production between mineral diesel and biodiesel blends. The cause of these effects is discussed. [Received: September 30, 2009; Accepted: December 12, 2009]

The influence of megacities on global atmospheric chemistry: a modelling study

Environmental context. Over half of the population of the world now live in urban areas, and the number of so-called ‘megacities’, with populations of ~10 million or more, is growing at a tremendous rate. We show how these patterns of urbanisation have the potential to influence the atmospheric chemical environment on a global scale, particularly through the effects of emissions from megacities on the reactive nitrogen cycle. With the growing worldwide interest in the study of the effects of megacities at all spatial scales, such as current European Union projects MEGAPOLI and CityZen, our study represents the first of many future studies that examine the effects of megacities on atmospheric chemistry on the global scale. Abstract. We present the first study of the effects of megacities on global atmospheric chemistry using a global three-dimensional chemical transport model. The effects on air quality, radiative forcing and atmospheric oxidation capacity are disproportionately smaller than the proportion of anthropogenic emissions due to megacities. Disproportionately large effects of megacities are modelled for reactive nitrogen compounds, in particular PAN (peroxy acetyl nitrate), which has increased in abundance globally by 9% due to megacities under year 2000 conditions, with 23% of the Earth experiencing an increase of 10% or more. These influences decrease under two very different future emission scenarios. Under a low-emission future scenario, the influence of megacities is generally reduced, and under a high-emission future scenario, although the local influence of megacities is increased, the geographical extent of the influence becomes smaller. In our model, the individual grid cells that contain megacities respond to the megacity emissions differently depending on their latitude. Tropical megacity grid cells generally show increased ozone year-round, while northern extratropical megacities generally show reduced ozone year-round. Better parameterisation of the sub-grid effects of megacities is an important issue for future work.