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Global stratospheric chlorine inventories for 2004–2009 from Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) measurements

We present chlorine budgets calculated between 2004 and 2009 for four latitude bands (70° N–30° N, 30° N–0° N, 0° N–30° S, and 30° S–70° S). The budgets were calculated using ACE-FTS version 3.0 retrievals of the volume mixing ratios (VMRs) of 9 chlorine-containing species: CCl4, CFC-12 (CCl2F2), CFC-11 (CCl3F), COCl2, COClF, HCFC-22 (CHF2Cl), CH3Cl, HCl and ClONO2. These data were supplemented with calculated VMRs from the SLIMCAT 3-D chemical transport model (CFC-113, CFC-114, CFC-115, H-1211, H-1301, HCFC-141b, HCFC-142b, ClO and HOCl). The total chlorine profiles are dominated by chlorofluorocarbons (CFCs) and halons up to 24 km in the tropics and 19 km in the extra-tropics. In this altitude range CFCs and halons account for 58% of the total chlorine VMR. Above this altitude HCl increasingly dominates the total chlorine profile, reaching a maximum of 95% of total chlorine at 54 km. All total chlorine profiles exhibit a positive slope with altitude, suggesting that the total chlorine VMR is now decreasing with time. This conclusion is supported by the time series of the mean stratospheric total chlorine budgets which show mean decreases in total stratospheric chlorine of 0.38 ± 0.03% per year in the Northern Hemisphere extra-tropics, 0.35 ± 0.07% per year in the Northern Hemisphere tropical stratosphere, 0.54 ± 0.16% per year in the Southern Hemisphere tropics and 0.53 ± 0.12% per year in the Southern Hemisphere extra-tropical stratosphere for 2004–2009. Globally stratospheric chlorine is decreasing by 0.46 ± 0.02% per year. Both global warming potential-weighted chlorine and ozone depletion potential-weighted chlorine are decreasing at all latitudes. These results show that the Montreal Protocol has had a significant effect in reducing emissions of both ozone-depleting substances and greenhouse gases.
Aerosol extinction-to-backscatter ratio derived from passive satellite measurements

Spaceborne reflectance measurements from the POLDER instrument are used to study the specific directional signature close to the backscatter direction. The data analysis makes it possible to derive the extinction-to-backscatter ratio (EBR), which is related to the inverse of the scattering phase function for an angle of 180° and is needed for a quantitative interpretation of lidar observations (active measurements). In addition, the multidirectional measurements are used to quantify the scattering phase function variations close to backscatter, which also provide some indication of the aerosol particle size and shape. The spatial distributions of both parameters show consistent patterns that are consistent with the aerosol type distributions. Pollution aerosols have an EBR close to 70, desert dust values are on the order of 50 and EBR of marine aerosols is close to 25. The scattering phase function shows an increase with the scattering angle close to backscatter. The relative increase ∂lnP/∂γ is close to 0.01 for dust and pollution type aerosols and 0.06 for marine type aerosols. These values are consistent with those retrieved from Mie simulations.
Ozone photochemistry in an oil and natural gas extraction region during winter: simulations of a snow-free season in the Uintah Basin, Utah

The Uintah Basin in northeastern Utah, a region of intense oil and gas extraction, experienced ozone (O3) concentrations above levels harmful to human health for multiple days during the winters of 2009–2010 and 2010–2011. These wintertime O3 pollution episodes occur during cold, stable periods when the ground is snow-covered, and have been linked to emissions from the oil and gas extraction process. The Uintah Basin Winter Ozone Study (UBWOS) was a field intensive in early 2012, whose goal was to address current uncertainties in the chemical and physical processes that drive wintertime O3 production in regions of oil and gas development. Although elevated O3 concentrations were not observed during the winter of 2011–2012, the comprehensive set of observations tests our understanding of O3 photochemistry in this unusual emissions environment. A box model, constrained to the observations and using the near-explicit Master Chemical Mechanism (MCM) v3.2 chemistry scheme, has been used to investigate the sensitivities of O3 production during UBWOS 2012. Simulations identify the O3 production photochemistry to be highly radical limited (with a radical production rate significantly smaller than the NOx emission rate). Production of OH from O3 photolysis (through reaction of O(1D) with water vapor) contributed only 170 pptv day−1, 8% of the total primary radical source on average (primary radicals being those produced from non-radical precursors). Other radical sources, including the photolysis of formaldehyde (HCHO, 52%), nitrous acid (HONO, 26%), and nitryl chloride (ClNO2, 13%) were larger. O3 production was also found to be highly sensitive to aromatic volatile organic compound (VOC) concentrations, due to radical amplification reactions in the oxidation scheme of these species. Radical production was shown to be small in comparison to the emissions of nitrogen oxides (NOx), such that NOx acted as the primary radical sink. Consequently, the system was highly VOC sensitive, despite the much larger mixing ratio of total non-methane hydrocarbons (230 ppbv (2080 ppbC), 6 week average) relative to NOx (5.6 ppbv average). However, the importance of radical sources which are themselves derived from NOx emissions and chemistry, such as ClNO2 and HONO, make the response of the system to changes in NOx emissions uncertain. Model simulations attempting to reproduce conditions expected during snow-covered cold-pool conditions show a significant increase in O3 production, although calculated concentrations do not achieve the highest seen during the 2010–2011 O3 pollution events in the Uintah Basin. These box model simulations provide useful insight into the chemistry controlling winter O3 production in regions of oil and gas extraction.
Formulation and test of an ice aggregation scheme for two-moment bulk microphysics schemes

A simple formulation of aggregation for two-moment bulk microphysical models is derived. The solution involves the evaluation of a double integral of the collection kernel weighted with the crystal size (or mass) distribution. This quantity is to be inserted into the differential equation for the crystal number concentration which has classical Smoluchowski form. The double integrals are evaluated numerically for log-normal size distributions over a large range of geometric mean masses. A polynomial fit of the results is given that yields good accuracy. Various tests of the new parameterisation are described: aggregation as stand-alone process, in a box-model, and in 2-D simulations of a cirrostratus cloud. These tests suggest that aggregation can become important for warm cirrus, leading even to higher and longer-lasting in-cloud supersaturation. Cold cirrus clouds are hardly affected by aggregation. The collection efficiency is taken from a parameterisation that assumes a dependence on temperature, a situation that might be improved when reliable measurements from cloud chambers suggests the necessary constraints for the choice of this parameter.
Laboratory studies of immersion and deposition mode ice nucleation of ozone aged mineral dust particles

Ice nucleation in the atmosphere is central to the understanding the microphysical properties of mixed-phase and cirrus clouds. Ambient conditions such as temperature (T) and relative humidity (RH), as well as aerosol properties such as chemical composition and mixing state play an important role in predicting ice formation in the troposphere. Previous field studies have reported the absence of sulfate and organic compounds on mineral dust ice crystal residuals sampled at mountain top stations or aircraft based measurements despite the long-range transport mineral dust is subjected to. We present laboratory studies of ice nucleation for immersion and deposition mode on ozone aged mineral dust particles for 233 < T < 263 K. Heterogeneous ice nucleation of untreated kaolinite (Ka) and Arizona Test Dust (ATD) particles is compared to corresponding aged particles that are subjected to ozone concentrations of 0.4–4.3 ppmv in a stainless steel aerosol tank. The portable ice nucleation counter (PINC) and immersion chamber combined with the Zurich ice nucleation chamber (IMCA-ZINC) are used to conduct deposition and immersion mode measurements, respectively. Ice active fractions as well as ice active surface site densities (ns) are reported and observed to increase as a function of decreasing temperature. We present first results that demonstrate enhancement of the ice nucleation ability of aged mineral dust particles in both the deposition and immersion mode due to ageing. We also present the first results to show a suppression of heterogeneous ice nucleation activity without the condensation of a coating of (in)organic material. In immersion mode, low ozone exposed Ka particles showed enhanced ice activity requiring a median freezing temperature of 1.5 K warmer than that of untreated Ka, whereas high ozone exposed ATD particles showed suppressed ice nucleation requiring a median freezing temperature of 3 K colder than that of untreated ATD. In deposition mode, low exposure Ka had ice active fractions of an order of magnitude higher than untreated Ka, whereas high ozone exposed ATD had ice active fractions up to a factor of 4 lower than untreated ATD. From our results, we derive and present parameterizations in terms of ns(T) that can be used in models to predict ice nuclei concentrations based on available aerosol surface area.
Present and future nitrogen deposition to national parks in the United States: critical load exceedances

National parks in the United States are protected areas wherein the natural habitat is to be conserved for future generations. Deposition of anthropogenic nitrogen (N) transported from areas of human activity (fuel combustion, agriculture) may affect these natural habitats if it exceeds an ecosystem-dependent critical load (CL). We quantify and interpret the deposition to Class I US national parks for present-day and future (2050) conditions using the GEOS-Chem global chemical transport model with 1/2° × 2/3° horizontal resolution over North America. We estimate CL values in the range 2.5–5 kg N ha−1 yr−1 for the different parks to protect the most sensitive ecosystem receptors. For present-day conditions, we find 24 out of 45 parks to be in CL exceedance and 14 more to be marginally so. Many of these are in remote areas of the West. Most (40–85%) of the deposition originates from NOx emissions (fuel combustion). We project future changes in N deposition using representative concentration pathway (RCP) anthropogenic emission scenarios for 2050. These feature 52–73% declines in US NOx emissions relative to present but 19–50% increases in US ammonia (NH3) emissions. Nitrogen deposition at US national parks then becomes dominated by domestic NH3 emissions. While deposition decreases in the East relative to present, there is little progress in the West and increases in some regions. We find that 17–25 US national parks will have CL exceedances in 2050 based on the RCP8.5 and RCP2.6 scenarios. Even in total absence of anthropogenic NOx emissions, 14–18 parks would still have a CL exceedance. Returning all parks to N deposition below CL by 2050 would require at least a 50% decrease in US anthropogenic NH3 emissions relative to RCP-projected 2050 levels.
Key chemical NOx sink uncertainties and how they influence top-down emissions of nitrogen oxides

Triggered by recent developments from laboratory and field studies regarding major NOx sink pathways in the troposphere, this study evaluates the influence of chemical uncertainties in NOx sinks for global NOx distributions calculated by the IMAGESv2 chemistry-transport model, and quantifies their significance for top-down NOx emission estimates. Our study focuses on five key chemical parameters believed to be of primary importance, more specifically, the rate of the reaction of NO2 with OH radicals, the newly identified HNO3-forming channel in the reaction of NO with HO2, the reactive uptake of N2O5 and HO2 by aerosols, and the regeneration of OH in the oxidation of isoprene. Sensitivity simulations are performed to estimate the impact of each source of uncertainty. The model calculations show that, although the NO2+OH reaction is the largest NOx sink globally accounting for ca. 60% of the total sink, the reactions contributing the most to the overall uncertainty are the formation of HNO3 in NO+HO2, leading to NOx column changes exceeding a factor of two over tropical regions, and the uptake of HO2 by aqueous aerosols, in particular over East and South Asia. Emission inversion experiments are carried out using model settings which either minimise (MINLOSS) or maximise (MAXLOSS) the total NOx sink, both constrained by one year of OMI NO2 column data from the DOMINO v2 KNMI algorithm. The choice of the model setup is found to have a major impact on the top-down flux estimates, with 75% higher emissions for MAXLOSS compared to the MINLOSS inversion globally. Even larger departures are found for soil NO (factor of 2) and lightning (1.8). The global anthropogenic source is better constrained (factor of 1.57) than the natural sources, except over South Asia where the combined uncertainty primarily associated to the NO+HO2 reaction in summer and HO2 uptake by aerosol in winter lead to top-down emission differences exceeding a factor of 2. Evaluation of the emission optimisation is performed against independent satellite observations from the SCIAMACHY sensor, with airborne NO2 measurements of the INTEX-A and INTEX-B campaigns, as well as with two new bottom-up inventories of anthropogenic emissions in Asia (REASv2) and China (MEIC). Neither the MINLOSS nor the MAXLOSS setup succeeds in providing the best possible match with all independent datasets. Whereas the minimum sink assumption leads to better agreement with aircraft NO2 profile measurements, consistent with the results of a previous analysis (Henderson et al., 2012), the same assumption leads to unrealistic features in the inferred distribution of emissions over China. Clearly, although our study addresses an important issue which was largely overlooked in previous inversion exercises, and demonstrates the strong influence of NOx loss uncertainties on top-down emission fluxes, additional processes need to be considered which could also influence the inferred source.
The sensitivity of global climate to the episodicity of fire aerosol emissions

One of the major ways in which forest and grass fires have an impact on global climate is through the release of aerosols. Most studies focusing on calculating the radiative forcing and other climate impacts of fire aerosols use monthly mean emissions derived from the Global Fire Emissions Database that captures only the seasonal cycle of fire aerosol emissions. Here we present the results of a sensitivity study that investigates the climate response to the episodicity of the fires, based on the standard approach which releases emissions every day, and contrasts that to the response when fires are represented as intense pulses of emissions that occur only over 1–2 days on a monthly, yearly, or five-yearly basis. Overall we find that in the modified cases with increased levels of episodicity, the all sky direct effect radiative forcing increases, the clear sky direct effect radiative forcing remains relatively constant, and the magnitude of the indirect effect radiative forcing decreases by about 1 W m−2 (from −1.6 to −0.6 W m−2). In the long term, we find that an increase in aerosol emission episodicity leads to an asymmetric change in indirect radiative forcing in the Northern Hemisphere compared to the Southern Hemisphere contributes to a slight shift in the annual average position of the intertropical convergence zone (ITCZ). This shift is found to have a mixed effect on the overall performance of the model at predicting precipitation rates in the tropics. Given these results we conclude that future studies that look to assess the present day global climate impacts of fire aerosols should consider the need to accurately represent fire episodicity.
Tethered balloon-borne aerosol measurements: seasonal and vertical variations of aerosol constituents over Syowa Station, Antarctica

Tethered balloon-borne aerosol measurements were conducted at Syowa Station, Antarctica, during the 46th Japanese Antarctic expedition (2005–2006). Direct aerosol sampling was operated from near the surface to the lower free troposphere (approximately 2500 m) using a balloon-borne aerosol impactor. Individual aerosol particles were analyzed using a scanning electron microscope equipped with an energy dispersive X-ray spectrometer. Seasonal and vertical features of aerosol constituents and their mixing states were investigated. Results show that sulfate particles were predominant in the boundary layer and lower free troposphere in summer, whereas sea-salt particles were predominant during winter through spring. Minerals, MgSO4, and sulfate containing K were identified as minor aerosol constituents in both boundary layer and free troposphere over Syowa Station. Although sea-salt particles were predominant during winter through spring, the relative abundance of sulfate particles increased in the boundary layer when air masses fell from the free troposphere over the Antarctic coast and continent. Sea-salt particles were modified considerably through heterogeneous reactions with SO42− CH3SO3− and their precursors during summer, and were modified slightly through heterogeneous reactions with NO3− and its precursors. During winter through spring, sea-salt modification was insignificant, particularly in the cases of high relative abundance of sea-salt particles and higher number concentrations. In August, NO3− and its precursors contributed greatly to sea-salt modification over Syowa Station. Because of the occurrence of sea-salt fractionation on sea ice, Mg-rich sea-salt particles were identified during the months of April through November. In contrast, Mg-free sea-salt particles and slightly Mg-rich sea-salt particles coexisted in the lower troposphere during summer. Thereby, Mg separation can proceed by sea-salt fractionation during summer in Antarctic regions.
Regional inversion of CO2 ecosystem fluxes from atmospheric measurements: reliability of the uncertainty estimates

The Bayesian framework of CO2 flux inversions permits estimates of the retrieved flux uncertainties. Here, the reliability of these theoretical estimates is studied through a comparison against the misfits between the inverted fluxes and independent measurements of the CO2 Net Ecosystem Exchange (NEE) made by the eddy covariance technique at local (few hectares) scale. Regional inversions at 0.5° resolution are applied for the western European domain where ~ 50 eddy covariance sites are operated. These inversions are conducted for the period 2002–2007. They use a mesoscale atmospheric transport model, a prior estimate of the NEE from a terrestrial ecosystem model and rely on the variational assimilation of in situ continuous measurements of CO2 atmospheric mole fractions. Averaged over monthly periods and over the whole domain, the misfits are in good agreement with the theoretical uncertainties for prior and inverted NEE, and pass the chi-square test for the variance at the 30% and 5% significance levels respectively, despite the scale mismatch and the independence between the prior (respectively inverted) NEE and the flux measurements. The theoretical uncertainty reduction for the monthly NEE at the measurement sites is 53% while the inversion decreases the standard deviation of the misfits by 38%. These results build confidence in the NEE estimates at the European/monthly scales and in their theoretical uncertainty from the regional inverse modelling system. However, the uncertainties at the monthly (respectively annual) scale remain larger than the amplitude of the inter-annual variability of monthly (respectively annual) fluxes, so that this study does not engender confidence in the inter-annual variations. The uncertainties at the monthly scale are significantly smaller than the seasonal variations. The seasonal cycle of the inverted fluxes is thus reliable. In particular, the CO2 sink period over the European continent likely ends later than represented by the prior ecosystem model.