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Estimates of turbulent diffusivities and energy dissipation rates from satellite measurements of spectra of stratospheric refractivity perturbations

Approaches for estimations of effective turbulent diffusion and energetic parameters from characteristics of anisotropic and isotropic spectra of perturbations of atmospheric refractivity, density and temperature are developed. The approaches are applied to the data obtained with the GOMOS instrument for measurements of stellar scintillations on-board the Envisat satellite to estimate turbulent Thorpe scales, LT, diffusivities, K, and energy dissipation rates, ϵ, in the stratosphere. At low latitudes, effective values are LT ~ 1–1.1 m, ϵ ~ (1.8–2.4) × 10−5 W kg−1, and K ~ (1.2–1.6) × 10−2 m2 s−1 at altitudes of 30–45 km in September–November 2004, depending on different assumed values of parameters of anisotropic and isotropic spectra. Respective standard deviations of individual values, including all kinds of variability, are δLT ~ 0.6–0.7 m, δϵ ~ (2.3–3.5) × 10−2 W kg−1, and δK ~ (1.7–2.6) × 10−2 m2 s−1. These values correspond to high-resolution balloon measurements of turbulent characteristics in the stratosphere, and to previous satellite stellar scintillation measurements. Distributions of turbulent characteristics at altitudes of 30–45 km in low latitudes have maxima at longitudes corresponding to regions of increased gravity wave dissipation over locations of stronger convection. Correlations between parameters of anisotropic and isotropic spectra are evaluated.
Physical–chemical characterisation of the particulate matter inside two road tunnels in the São Paulo Metropolitan Area

The notable increase in biofuel usage by the road transportation sector in Brazil during recent years has significantly altered the vehicular fuel composition. Consequently, many uncertainties are currently found in particulate matter vehicular emission profiles. In an effort to better characterise the emitted particulate matter, measurements of aerosol physical and chemical properties were undertaken inside two tunnels located in the São Paulo Metropolitan Area (SPMA). The tunnels show very distinct fleet profiles: in the Jânio Quadros (JQ) tunnel, the vast majority of the circulating fleet are light duty vehicles (LDVs), fuelled on average with the same amount of ethanol as gasoline. In the Rodoanel (RA) tunnel, the particulate emission is dominated by heavy duty vehicles (HDVs) fuelled with diesel (5% biodiesel). In the JQ tunnel, PM2.5 concentration was on average 52 μg m−3, with the largest contribution of organic mass (OM, 42%), followed by elemental carbon (EC, 17%) and crustal elements (13%). Sulphate accounted for 7% of PM2.5 and the sum of other trace elements was 10%. In the RA tunnel, PM2.5 was on average 233 μg m−3, mostly composed of EC (52%) and OM (39%). Sulphate, crustal and the trace elements showed a minor contribution with 5%, 1%, and 1%, respectively. The average OC : EC ratio in the JQ tunnel was 1.59 ± 0.09, indicating an important contribution of EC despite the high ethanol fraction in the fuel composition. In the RA tunnel, the OC : EC ratio was 0.49 ± 0.12, consistent with previous measurements of diesel-fuelled HDVs. Besides bulk carbonaceous aerosol measurement, polycyclic aromatic hydrocarbons (PAHs) were quantified. The sum of the PAHs concentration was 56 ± 5 ng m−3 and 45 ± 9 ng m−3 in the RA and JQ tunnel, respectively. In the JQ tunnel, benzo(a)pyrene (BaP) ranged from 0.9 to 6.7 ng m−3 (0.02–0.1&permil; of PM2.5) whereas in the RA tunnel BaP ranged from 0.9 to 4.9 ng m−3 (0.004–0. 02&permil; of PM2.5), indicating an important relative contribution of LDVs emission to atmospheric BaP. Real-time measurements performed in both tunnels provided aerosol size distributions and optical properties. The average particle count yielded 73 000 cm−3 in the JQ tunnel and 366 000 cm−3 in the RA tunnel, with an average diameter of 48 nm in the former and 39 nm in the latter. Aerosol single scattering albedo, calculated from scattering and absorption observations in the JQ tunnel, indicates a value of 0.5 associated with LDVs. Such single scattering albedo is 20–50% higher than observed in previous tunnel studies, possibly as a result of the large biofuel usage. Given the exceedingly high equivalent black carbon loadings in the RA tunnel, real time light absorption measurements were possible only in the JQ tunnel. Nevertheless, using EC measured from the filters, a single scattering albedo of 0.31 for the RA tunnel has been estimated. The results presented here characterise particulate matter emitted from nearly 1 million vehicles fuelled with a considerable amount of biofuel, providing a unique experimental site worldwide.
Black carbon over the South China Sea and in various continental locations in South China

Black carbon (BC) is an important atmospheric constituent as an air pollutant and as a climate forcer. To our knowledge, field measurements of BC have not been reported over the South China Sea. Observations of light-absorption coefficients (σabs) and BC concentrations by Aethalometer were conducted on Yongxing Island in the South China Sea and at five continental sites in the Pearl River delta (PRD) region, South China, in two periods: 16 May–20 June 2008 in the rainy season and 12 December 2008–8 January 2009 in the dry season. At the oceanic site, the daily average BC concentrations varied from 0.28 to 2.14 μg m−3 and variations of BC were small between the two periods (0.67 in the dry season sampling period and 0.54 μg m−3 in the rainy season sampling period). Similarly, little difference in BC level was found at a rural site in PRD between the two sampling periods (2.88 and 2.62 μg m–3). At the PRD urban sites, the daily average concentration of BC ranged from 1.56 to 37.9 μg m−3, higher in the dry season sampling period (12.31 μg m–3) and lower in the rainy season sampling period (6.17 μg m–3). The observed average σabs values in rainy vs. dry season sampling periods are 119 vs. 62 Mm−1 at the PRD urban sites, 29 vs. 26 Mm−1 at the PRD background site, and 8.4 vs. 7.2 Mm−1 at the marine site. At urban/suburban PRD sites, BC was observed to have a diurnal pattern of higher concentrations at night and at the urban sites a small peak in the early morning rush hour.
Net influence of an internally generated quasi-biennial oscillation on modelled stratospheric climate and chemistry

A Goddard Earth Observing System Chemistry-Climate Model (GEOSCCM) simulation with strong tropical non-orographic gravity wave drag (GWD) is compared to an otherwise identical simulation with near-zero tropical non-orographic GWD. The GEOSCCM generates a quasi-biennial oscillation (QBO) zonal wind signal in response to a tropical peak in GWD that resembles the zonal and climatological mean precipitation field. The modelled QBO has a frequency and amplitude that closely resembles observations. As expected, the modelled QBO improves the simulation of tropical zonal winds and enhances tropical and subtropical stratospheric variability. Also, inclusion of the QBO slows the meridional overturning circulation, resulting in a generally older stratospheric mean age of air. Slowing of the overturning circulation, changes in stratospheric temperature and enhanced subtropical mixing all affect the annual mean distributions of ozone, methane and nitrous oxide. Furthermore, the modelled QBO enhances polar stratospheric variability in winter. Because tropical zonal winds are easterly in the simulation without a QBO, there is a relative increase in tropical zonal winds in the simulation with a QBO. Extratropical differences between the simulations with and without a QBO thus reflect the westerly shift in tropical zonal winds: a relative strengthening of the polar stratospheric jet, polar stratospheric cooling and a weak reduction in Arctic lower stratospheric ozone.
Modelling the impact of megacities on local, regional and global tropospheric ozone and the deposition of nitrogen species

We examine the effects of ozone precursor emissions from megacities on present-day air quality using the global chemistry–climate model UM-UKCA (UK Met Office Unified Model coupled to the UK Chemistry and Aerosols model). The sensitivity of megacity and regional ozone to local emissions, both from within the megacity and from surrounding regions, is important for determining air quality across many scales, which in turn is key for reducing human exposure to high levels of pollutants. We use two methods, perturbation and tagging, to quantify the impact of megacity emissions on global ozone. We also completely redistribute the anthropogenic emissions from megacities, to compare changes in local air quality going from centralised, densely populated megacities to decentralised, lower density urban areas. Focus is placed not only on how changes to megacity emissions affect regional and global NOx and O3, but also on changes to NOy deposition and to local chemical environments which are perturbed by the emission changes. The perturbation and tagging methods show broadly similar megacity impacts on total ozone, with the perturbation method underestimating the contribution partially because it perturbs the background chemical environment. The total redistribution of megacity emissions locally shifts the chemical environment towards more NOx-limited conditions in the megacities, which is more conducive to ozone production, and monthly mean surface ozone is found to increase up to 30% in megacities, depending on latitude and season. However, the displacement of emissions has little effect on the global annual ozone burden (0.12% change). Globally, megacity emissions are shown to contribute ~3% of total NOy deposition. The changes in O3, NOx and NOy deposition described here are useful for quantifying megacity impacts and for understanding the sensitivity of megacity regions to local emissions. The small global effects of the 100% redistribution carried out in this study suggest that the distribution of emissions on the local scale is unlikely to have large implications for chemistry–climate processes on the global scale.
Biogenic and biomass burning organic aerosol in a boreal forest at Hyytiälä, Finland, during HUMPPA-COPEC 2010

Submicron aerosol particles were collected during July and August 2010 in Hyytiälä, Finland, to determine the composition and sources of aerosol at that boreal forest site. Submicron particles were collected on Teflon filters and analyzed by Fourier transform infrared (FTIR) spectroscopy for organic functional groups (OFGs). Positive matrix factorization (PMF) was applied to aerosol mass spectrometry (AMS) measurements and FTIR spectra to identify summertime sources of submicron aerosol mass at the sampling site. The two largest sources of organic mass (OM) in particles identified at Hyytiälä were (1) biogenic aerosol from surrounding local forest and (2) biomass burning aerosol, transported 4–5 days from large wildfires burning near Moscow, Russia, and northern Ukraine. The robustness of this apportionment is supported by the agreement of two independent analytical methods for organic measurements with three statistical techniques. FTIR factor analysis was more sensitive to the chemical differences between biogenic and biomass burning organic components, while AMS factor analysis had a higher time resolution that more clearly linked the temporal behavior of separate OM factors to that of different source tracers even though their fragment mass spectrum were similar. The greater chemical sensitivity of the FTIR is attributed to the nondestructive preparation and the functional group specificity of spectroscopy. The FTIR spectra show strong similarities among biogenic and biomass burning factors from different regions as well as with reference OM (namely olive tree burning organic aerosol and α-pinene chamber secondary organic aerosol (SOA)). The biogenic factor correlated strongly with temperature and oxidation products of biogenic volatile organic compounds (BVOCs), included more than half of the oxygenated OFGs (carbonyl groups at 29% and carboxylic acid groups at 22%), and represented 35% of the submicron OM. Compared to previous studies at Hyytiälä, the summertime biogenic OM is 1.5 to 3 times larger than springtime biogenic OM (0.64 μg m−3 and 0.4 μg m−3, measured in 2005 and 2007, respectively), even though it contributed only 35% of OM. The biomass burning factor contributed 25% of OM on average and up to 62% of OM during three periods of transported biomass burning emissions: 26–28 July, 29–30 July, and 8–9 August, with OFG consisting mostly of carbonyl (41%) and alcohol (25%) groups. The high summertime terrestrial biogenic OM (1.7 μg m−3) and the high biomass burning contributions (1.2 μg m−3) were likely due to the abnormally high temperatures that resulted in both stressed boreal forest conditions with high regional BVOC emissions and numerous wildfires in upwind regions.
CCN activity of organic aerosols observed downwind of urban emissions during CARES

During the Carbonaceous Aerosols and Radiative Effects Study (CARES), activation fraction of size-resolved aerosol particles and aerosol chemical composition were characterized at the T1 site (~60 km downwind of Sacramento, California) from 10 June to 28 June 2010. The hygroscopicity of cloud condensation nuclei (CCN)-active particles (κCCN) with diameter from 100 to 170 nm, derived from the size-resolved activated fraction, varied from 0.10 to 0.21, with an average of 0.15, which was substantially lower than that proposed for continental sites. The low κCCN value was due to the high organic volume fraction, averaged over 80% at the T1 site. The derived κCCN exhibited little diurnal variation, consistent with the relatively constant organic volume fraction observed. At any time, over 90% of the size-selected particles with diameter between 100 and 171 nm were CCN active, suggesting most particles within this size range were aged background particles. Due to the large organic volume fraction, organic hygroscopicity (κorg) strongly impacted particle hygroscopicity and therefore calculated CCN concentration. For the vast majority of the cases, an increase of κorg from 0.03 to 0.18, which are within the typical range, doubled the calculated CCN concentration. Organic hygroscopicity was derived from κCCN and aerosol chemical composition, and its variations with the fraction of total organic mass spectral signal at m / z 44 (f44) and O : C were compared to results from previous studies. Overall, the relationships between κorg and f44 are quite consistent for organic aerosol (OA) observed during field studies and those formed in a smog chamber. Compared to the relationship between κorg and f44, the relationship between κorg and O : C exhibits more significant differences among different studies, suggesting κorg may be better parameterized using f44. A least squares fit yielded κorg = 2.10(±0.07) × f44 − 0.11(±0.01) with a Pearson R2 value of 0.71. One possible explanation for the stronger correlation between κorg and f44 is that the m / z 44 signal (mostly contributed by the CO2+ ion) is more closely related to organic acids, which may dominate the overall κorg due to their relatively high water solubility and hygroscopicity.
Physics of Stratocumulus Top (POST): turbulent mixing across capping inversion

High spatial resolution measurements of temperature and liquid water content, accompanied by moderate-resolution measurements of humidity and turbulence, collected during the Physics of Stratocumulus Top experiment are analyzed. Two thermodynamically, meteorologically and even optically different cases are investigated. An algorithmic division of the cloud-top region into layers is proposed. Analysis of dynamic stability across these layers leads to the conclusion that the inversion capping the cloud and the cloud-top region is turbulent due to the wind shear, which is strong enough to overcome the high static stability of the inversion. The thickness of this mixing layer adapts to wind and temperature jumps such that the gradient Richardson number stays close to its critical value. Turbulent mixing governs transport across the inversion, but the consequences of this mixing depend on the thermodynamic properties of cloud top and free troposphere. The effects of buoyancy sorting of the mixed parcels in the cloud-top region are different in conditions that permit or prevent cloud-top entrainment instability. Removal of negatively buoyant air from the cloud top is observed in the first case, while buildup of the diluted cloud-top layer is observed in the second one.
Long-term measurements of aerosol and carbon monoxide at the ZOTTO tall tower to characterize polluted and pristine air in the Siberian taiga

Siberia is one of few continental regions in the Northern Hemisphere where the atmosphere may sometimes approach pristine background conditions. We present the time series of aerosol and carbon monoxide (CO) measurements between September 2006 and December 2011 at the Zotino Tall Tower Observatory (ZOTTO) in Central Siberia (61° N; 89° E). We investigate the seasonal, weekly and diurnal variations of aerosol properties (including absorption and scattering coefficients and derived parameters, such as equivalent black carbon (BCe), Ångström exponent, single scattering albedo, and backscattering ratio) and the CO mixing ratios. Criteria were established to distinguish polluted from near-pristine air masses, providing quantitative characteristics for each type. Depending on the season, 23–36% of the sampling time at ZOTTO was found to be representative of a clean atmosphere. The summer pristine data indicate that primary biogenic and secondary organic aerosol formation are quite strong particle sources in the Siberian taiga. The summer seasons 2007–2008 were dominated by an Aitken mode around 80 nm size, whereas the summer 2009 with prevailing easterly winds produced particles in the accumulation mode around 200 nm size. We found these differences to be mainly related to air temperature, through its effect on the production rates of biogenic volatile organic compounds (VOC) precursor gases. In winter, the particle size distribution peaked at 160 nm, and the footprint of clean background air was characteristic for aged particles from anthropogenic sources at great distances from ZOTTO and diluted biofuel burning emissions from domestic heating. The wintertime polluted air originates mainly from large cities south and southwest of the site; these particles have a dominant mode around 100 nm, and the ΔBCe / ΔCO ratio of 7–11 ng m−3 ppb−1 suggests dominant contributions from coal and biofuel burning for heating. During summer, anthropogenic emissions are the dominant contributor to the pollution particles at ZOTTO, while only 12% of the polluted events are classified as biomass-burning-dominated, but then often associated with extremely high CO concentrations and aerosol absorption coefficients. Two biomass-burning case studies revealed different ΔBCe / ΔCO ratios from different fire types, with the agricultural fires in April~2008 yielding a very high ratio of 21 ng m−3 ppb−1. Overall, we find that anthropogenic sources dominate the aerosol population at ZOTTO most of the time, even during nominally clean episodes in winter, and that near-pristine conditions are encountered only in the growing season and then only episodically.
Atmospheric organic matter in clouds: exact masses and molecular formula identification using ultrahigh-resolution FT-ICR mass spectrometry

Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gas- and particulate-phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at the Storm Peak Laboratory near Steamboat Springs, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh-resolution mass spectra of the samples after using a reversed-phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS and CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of &sim;0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOx oxidation. Multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite were observed, indicating the significance of nitrate radical reactions on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur-containing compounds) were also observed; however further investigation is needed to determine the origin of the reduced sulfur-containing compounds. Overall, the molecular composition determined using ultrahigh-resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic anion composition in the Rocky Mountain area that could help to improve the understanding of aqueous-phase processes.