Items

Advanced search

Nitric acid in the stratosphere based on Odin observations from 2001 to 2009 – Part 1: A global climatology

The Sub-Millimetre Radiometer (SMR) on board the Odin satellite, launched in February 2001, observes thermal emissions of stratospheric nitric acid (HNO3) originating from the Earth limb in a band centred at 544.6 GHz. Height-resolved measurements of the global distribution of nitric acid in the stratosphere were performed approximately on two observation days per week. An HNO3 climatology based on more than 7 years of observations from August 2001 to April 2009 covering the vertical range between typically ~19 and 45 km (~1.5–60 hPa or ~500–1800 K in terms of potential temperature) was created. The study highlights the spatial and seasonal variation of nitric acid in the stratosphere, characterised by a pronounced seasonal cycle at middle and high latitudes with maxima during late fall and minima during spring, strong denitrification in the lower stratosphere of the Antarctic polar vortex during winter (the irreversible removal of NOy by the sedimentation of cloud particles containing HNO3), as well as large quantities of HNO3 formed every winter at high-latitudes in the middle and upper stratosphere. A strong inter-annual variability is observed in particular at high latitudes. A comparison with a stratospheric HNO3 climatology, based on over 7 years of UARS/MLS (Upper Atmosphere Research Satellite/Microwave Limb Sounder) measurements from the 1990s, shows good consistency and agreement of the main morphological features in the potential temperature range ~465 to ~960 K, if the different characteristics of the data sets such as the better altitude resolution of Odin/SMR as well as the slightly different altitude ranges are considered. Odin/SMR reaches higher up and UARS/MLS lower down in the stratosphere. An overview from 1991 to 2009 of stratospheric nitric acid is provided (with a short gap between 1998 and 2001), if the global measurements of both experiments are taken together.
Nitric acid in the stratosphere based on Odin observations from 2001 to 2009 – Part 2: High-altitude polar enhancements

The wintertime abundance of nitric acid (HNO3) in the polar upper stratosphere displays a strong inter-annual variability, and is known to be strongly influenced by energetic particle precipitation (EPP), primarily by protons during solar proton events (SPEs), but also by precipitating auroral or relativistic electrons. We analyse a multi-year record (August 2001 to April 2009) of middle atmospheric HNO3 measurements by the Sub-Millimeter Radiometer instrument aboard the Odin satellite, with a focus on the polar upper stratosphere. SMR observations show clear evidence of two different types of polar high-altitude HNO3 enhancements linked to EPP. In the first type, referred to as direct enhancements by analogy with the EPP/NOx direct effect, enhanced HNO3 mixing ratios are observed for a short period (1 week) after a SPE, upwards of a level typically in the mid-stratosphere. In a second type, referred to as indirect enhancements by analogy with the EPP/NOx indirect effect, the descent of mesospheric air triggers a stronger and longer-lasting enhancement. Each of the three major SPEs that occurred during the Northern Hemisphere autumn or winter, in November 2001, October–November 2003 and January 2005, are observed to lead to both direct and indirect HNO3 enhancements. On the other hand, indirect enhancements occur recurrently in winter, are stronger in the Southern Hemisphere, and are influenced by EPP at higher altitudes.
Cloud condensation nuclei measurements in the marine boundary layer of the Eastern Mediterranean: CCN closure and droplet growth kinetics

Measurements of cloud condensation nuclei (CCN) concentrations (cm−3) between 0.2 and 1.0% supersaturation, aerosol size distribution and chemical composition were performed at a remote marine site in the eastern Mediterranean, from September to October 2007 during the FAME07 campaign. Most of the particles activate at ~0.6% supersaturation, characteristic of the aged nature of the aerosol sampled. Application of Köhler theory, using measurements of bulk composition, size distribution, and assuming that organics are insoluble resulted in agreement between predicted and measured CCN concentrations within 7±11% for all supersaturations, with a tendency for CCN underprediction (16±6%; r2=0.88) at the lowest supersaturations (0.21%). Including the effects of the water-soluble organic fraction (which represent around 70% of the total organic content) reduces the average underprediction bias at the low supersaturations, resulting in a total closure error of 0.6±6%. Using threshold droplet growth analysis, the growth kinetics of ambient CCN is consistent with NaCl calibration experiments; hence the presence of aged organics does not suppress the rate of water uptake in this environment. The knowledge of the soluble salt fraction is sufficient for the description of the CCN activity in this area.
Regional modelling of tracer transport by tropical convection – Part 1: Sensitivity to convection parameterization

The general objective of this series of papers is to evaluate long duration limited area simulations with idealised tracers as a tool to assess tracer transport in chemistry-transport models (CTMs). In this first paper, we analyse the results of six simulations using different convection closures and parameterizations. The simulations are using the Grell and Dévényi (2002) mass-flux framework for the convection parameterization with different closures (Grell = GR, Arakawa-Shubert = AS, Kain-Fritch = KF, Low omega = LO, Moisture convergence = MC) and an ensemble parameterization (EN) based on the other five closures. The simulations are run for one month during the SCOUT-O3 field campaign lead from Darwin (Australia). They have a 60 km horizontal resolution and a fine vertical resolution in the upper troposphere/lower stratosphere. Meteorological results are compared with satellite products, radiosoundings and SCOUT-O3 aircraft campaign data. They show that the model is generally in good agreement with the measurements with less variability in the model. Except for the precipitation field, the differences between the six simulations are small on average with respect to the differences with the meteorological observations. The comparison with TRMM rainrates shows that the six parameterizations or closures have similar behaviour concerning convection triggering times and locations. However, the 6 simulations provide two different behaviours for rainfall values, with the EN, AS and KF parameterizations (Group 1) modelling better rain fields than LO, MC and GR (Group 2). The vertical distribution of tropospheric tracers is very different for the two groups showing significantly more transport into the TTL for Group 1 related to the larger average values of the upward velocities. Nevertheless the low values for the Group 1 fluxes at and above the cold point level indicate that the model does not simulate significant overshooting. For stratospheric tracers, the differences between the two groups are small indicating that the downward transport from the stratosphere is more related to the turbulent mixing parameterization than to the convection parameterization.
Aerosol- and updraft-limited regimes of cloud droplet formation: influence of particle number, size and hygroscopicity on the activation of cloud condensation nuclei (CCN)

We have investigated the formation of cloud droplets under pyro-convective conditions using a cloud parcel model with detailed spectral microphysics and with the κ-Köhler model approach for efficient and realistic description of the cloud condensation nucleus (CCN) activity of aerosol particles. Assuming a typical biomass burning aerosol size distribution (accumulation mode centred at 120 nm), we have calculated initial cloud droplet number concentrations (NCD) for a wide range of updraft velocities (w=0.25–20 m s−1) and aerosol particle number concentrations (NCN=200–105 cm−3) at the cloud base. Depending on the ratio between updraft velocity and particle number concentration (w/NCN), we found three distinctly different regimes of CCN activation and cloud droplet formation: (1) An aerosol-limited regime that is characterized by high w/NCN ratios (>≈10−3 m s−1 cm3), high maximum values of water vapour supersaturation (Smax>≈0.5%), and high activated fractions of aerosol particles (NCN/NCN>≈90%). In this regime NCD is directly proportional to NCN and practically independent of w. (2) An updraft-limited regime that is characterized by low w/NCN ratios (<≈10−4 m s−1 cm3), low maximum values of water vapour supersaturation (Smax<≈0.2%), and low activated fractions of aerosol particles (NCD/NCN<≈20%). In this regime NCD is directly proportional to w and practically independent of NCN. (3) An aerosol- and updraft-sensitive regime (transitional regime), which is characterized by parameter values in between the two other regimes and covers most of the conditions relevant for pyro-convection. In this regime NCD depends non-linearly on both NCN and w. In sensitivity studies we have tested the influence of aerosol particle size distribution and hygroscopicity on NCD. Within the range of effective hygroscopicity parameters that is characteristic for continental atmospheric aerosols (κ≈0.05–0.6), we found that NCD depends rather weakly on the actual value of κ. A compensation of changes in κ and Smax leads to an effective buffering of NCD. Only for aerosols with very low hygroscopicity (κ<0.05) and also in the updraft-limited regime for aerosols with higher than average hygroscopicity (κ>0.3) did the relative sensitivities ∂lnNCD/∂lnκ≈ (ΔNCD/NCD)/(Δκ/κ) exceed values of ~0.2, indicating that a 50% difference in κ would change NCD by more than 10%. The influence of changing size distribution parameters was stronger than that of particle hygroscopicity. Nevertheless, similar regimes of CCN activation were observed in simulations with varying types of size distributions (polluted and pristine continental and marine aerosols with different proportions of nucleation, Aitken, accumulation, and coarse mode particles). In general, the different regimes can be discriminated with regard to the relative sensitivities of NCD against w and NCN (∂lnNCD/∂lnw and ∂lnNCD/∂lnNCN). We propose to separate the different regimes by relative sensitivity ratios, (∂lnNCD/∂lnw)/(∂lnNCD/∂lnNCN) of 4:1 and 1:4, respectively. The results of this and related studies suggest that the variability of initial cloud droplet number concentration in convective clouds is mostly dominated by the variability of updraft velocity and aerosol particle number concentration in the accumulation and Aitken mode. Coarse mode particles and the variability of particle composition and hygroscopicity appear to play major roles only at low supersaturation in the updraft-limited regime of CCN activation (Smax<0.2%).
Regional modelling of tracer transport by tropical convection – Part 2: Sensitivity to model resolutions

The general objective of this series of two papers is to evaluate long duration limited-area simulations with idealised tracers as a possible tool to assess the tracer transport in chemistry-transport models (CTMs). In this second paper we analyse the results of three simulations using different horizontal and vertical resolutions. The goal is to study the impact of the model spatial resolution on convective transport of idealized tracer in the tropics. The reference simulation (REF) uses a 60 km horizontal resolution and 300 m vertically in the upper troposphere/lower stratosphere (UTLS). A 20 km horizontal resolution simulation (HR) is run as well as a simulation with 850 m vertical resolution in the UTLS (CVR). The simulations are run for one month during the SCOUT-O3 field campaign. Aircraft data, TRMM rainrate estimates and radiosoundings have been used to evaluate the simulations. They show that the HR configuration gives generally a better agreement with the measurements than the REF simulation. The CVR simulation gives generally the worst results. The vertical distribution of the tropospheric tracers for the simulations has a similar shape with a ~15 km altitude maximum for the 6h-lifetime tracer of 0.4 ppbv for REF, 1.2 for HR and 0.04 for CVR. These differences are related to the dynamics produced by the three simulations that leads to larger values of the upward velocities on average for HR and lower for CVR compared to REF. HR simulates more frequent and stronger convection leading to enhanced fluxes compared to REF and higher detrainment levels compared to CVR. HR provides also occasional overshoots over the cold point dynamical barrier. For the stratospheric tracers the differences between the three simulations are small. The diurnal cycle of the fluxes of all tracers in the Tropical Tropopause Layer exhibits a maximum linked to the maximum of convective activity.
Long-term tropospheric formaldehyde concentrations deduced from ground-based fourier transform solar infrared measurements

We report a 13-year (1992–2005) dataset of total column measurements of formaldehyde (HCHO) over Lauder, New Zealand, inferred from solar infrared spectra measured using a high-resolution Fourier Transform Spectrometer (FTS). Ambient HCHO concentrations at this rural location are often close to levels typical of remote marine environments (<250 ppt), which are close to the detection limit using standard techniques. Consequently we develop a new method that successfully produces HCHO columns with sufficient sensitivity throughout the whole season. HCHO columns over Lauder have a strong seasonal cycle (±50%), with a mean column of 4.9×1015 molecules cm−2, peaking during summer months. A simple box model of CH4 oxidation reproduces the observed broad-scale seasonal cycle, but significantly underestimates the seasonal peak HCHO ground concentrations during summer. This suggests the existence of an additional significant source of HCHO, possibly isoprene that cannot be explained by oxidation of CH4 alone. The ground-based FTS column data compare well with collocated HCHO column measurements from the Global Ozone Monitoring Experiment (GOME) satellite instrument during the operational period of GOME (1996–2001, r2=0.65, mean bias=10%, n=48).
Impact of dust aerosols on the radiative budget, surface heat fluxes, heating rate profiles and convective activity over West Africa during March 2006

The present work analyses the effect of dust aerosols on the surface and top of atmosphere radiative budget, surface temperature, sensible heat fluxes, atmospheric heating rate and convective activity over West Africa. The study is focused on the regional impact of a major dust event over the period of 7–14 March 2006 through numerical simulations performed with the mesoscale, nonhydrostatic atmospheric model MesoNH. Due to its importance on radiative budgets, a specific attention has been paid to the representation of dust single scattering albedo (SSA) in MesoNH by using inversions of the AErosol RObotic NETwork (AERONET). The radiative impacts are estimated using two parallel simulations, one including radiative effects of dust and the other without them. The simulations of dust aerosol impacts on the radiative budget indicate remarkable instantaneous (at midday) decrease of surface shortwave (SW) radiations over land, with regional (9°–17° N, 10° W–20° E) mean of −137 W/m2 during the 9 to 12 March period. The surface dimming resulting from the presence of dust is shown to cause important reduction of both surface temperature (up to 4°C) and sensible heat fluxes (up to 100 W/m2), which is consistent with experimental observations. At the top of the atmosphere, the SW cooling (regional mean of −12.0 W/m2) induced by mineral dust is shown to dominate the total net (shortwave + longwave) effect. The maximum SW heating occurs within the dusty layer with values comprised between 4 and 7° K by day and LW effect results in a cooling of −0.10/−0.20° K by day. Finally, the simulations suggest the decrease of the convective available potential energy (CAPE) over the region in the presence of mineral dust.
Chemically-resolved aerosol volatility measurements from two megacity field studies

The volatilities of different chemical species in ambient aerosols are important but remain poorly characterized. The coupling of a recently developed rapid temperature-stepping thermodenuder (TD, operated in the range 54–230°C) with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during field studies in two polluted megacities has enabled the first direct characterization of chemically-resolved urban particle volatility. Measurements in Riverside, CA and Mexico City are generally consistent and show ambient nitrate as having the highest volatility of any AMS standard aerosol species while sulfate showed the lowest volatility. Total organic aerosol (OA) showed volatility intermediate between nitrate and sulfate, with an evaporation rate of 0.6%·K−1 near ambient temperature, although OA dominates the residual species at the highest temperatures. Different types of OA were characterized with marker ions, diurnal cycles, and positive matrix factorization (PMF) and show significant differences in volatility. Reduced hydrocarbon-like OA (HOA, a surrogate for primary OA, POA), oxygenated OA (OOA, a surrogate for secondary OA, SOA), and biomass-burning OA (BBOA) separated with PMF were all determined to be semi-volatile. The most aged OOA-1 and its dominant ion, CO2+, consistently exhibited the lowest volatility, with HOA, BBOA, and associated ions for each among the highest. The similar or higher volatility of HOA/POA compared to OOA/SOA contradicts the current representations of OA volatility in most atmospheric models and has important implications for aerosol growth and lifetime. A new technique using the AMS background signal was demonstrated to quantify the fraction of species up to four orders-of-magnitude less volatile than those detectable in the MS mode, which for OA represent ~5% of the non-refractory (NR) OA signal. Our results strongly imply that all OA types should be considered semivolatile in models. The study in Riverside identified organosulfur species (e.g. CH3HSO3+ ion, likely from methanesulfonic acid), while both studies identified ions indicative of amines (e.g. C5H12N+) with very different volatility behaviors than inorganic-dominated ions. The oxygen-to-carbon ratio of OA in each ambient study was shown to increase both with TD temperature and from morning to afternoon, while the hydrogen-to-carbon ratio showed the opposite trend.
Modelling the impacts of ammonia emissions reductions on North American air quality

A unified regional air-quality modelling system (AURAMS) was used to investigate the effects of reductions in ammonia emissions on regional air quality, with a focus on particulate-matter formation. Three simulations of one-year duration were performed for a North American domain: (1) a base-case simulation using 2002 Canadian and US national emissions inventories augmented by a more detailed Canadian emissions inventory for agricultural ammonia; (2) a 30% North-American-wide reduction in agricultural ammonia emissions; and (3) a 50% reduction in Canadian beef-cattle ammonia emissions. The simulations show that a 30% continent-wide reduction in agricultural ammonia emissions lead to reductions in median hourly PM2.5 mass of <1 μg m−3 on an annual basis. The atmospheric response to these emission reductions displays marked seasonal variations, and on even shorter time scales, the impacts of the emissions reductions are highly episodic: 95th-percentile hourly PM2.5 mass decreases can be up to a factor of six larger than the median values. A key finding of the modelling work is the linkage between gas and aqueous chemistry and transport; reductions in ammonia emissions affect gaseous ammonia concentrations close to the emissions site, but substantial impacts on particulate matter and atmospheric deposition often occur at considerable distances downwind, with particle nitrate being the main vector of ammonia/um transport. Ammonia emissions reductions therefore have trans-boundary consequences downwind. Calculations of critical-load exceedances for sensitive ecosystems in Canada suggest that ammonia emission reductions will have a minimal impact on current ecosystem acidification within Canada, but may have a substantial impact on future ecosystem acidification. The 50% Canadian beef-cattle ammonia emissions reduction scenario was used to examine model sensitivity to uncertainties in the new Canadian agricultural ammonia emissions inventory, and the simulation results suggest that further work is needed to improve the emissions inventory for this particular sector. It should be noted that the model in its current form neglects coarse mode base cation chemistry, so the predicted effects of ammonia emissions reductions shown here should be considered upper limits.