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Impact of mineral dust on nitrate, sulfate, and ozone in transpacific Asian pollution plumes

We use a 3-D global chemical transport model (GEOS-Chem) to interpret aircraft observations of nitrate and sulfate partitioning in transpacific dust plumes during the INTEX-B campaign of April–May 2006. The model includes explicit transport of size-resolved mineral dust and its alkalinity, nitrate, and sulfate content. The observations show that particulate nitrate is primarily associated with dust, sulfate is primarily associated with ammonium, and Asian dust remains alkaline across the Pacific. This can be reproduced in the model by using a reactive uptake coefficient for HNO3 on dust (γ(HNO3) ~10−3) much lower than commonly assumed in models and possibly reflecting limitation of uptake by dust dissolution. The model overestimates gas-phase HNO3 by a factor of 2–3, typical of previous model studies; we show that this cannot be corrected by uptake on dust. We find that the fraction of aerosol nitrate on dust in the model increases from ~30% in fresh Asian outflow to 80–90% over the Northeast Pacific, reflecting in part the volatilization of ammonium nitrate and the resulting transfer of nitrate to the dust. Consumption of dust alkalinity by uptake of acid gases in the model is slow relative to the lifetime of dust against deposition, so that dust does not acidify (at least not in the bulk). This limits the potential for dust iron released by acidification to become bio-available upon dust deposition. Observations in INTEX-B show no detectable ozone depletion in Asian dust plumes, consistent with the model. Uptake of HNO3 by dust, suppressing its recycling to NOx, reduces Asian pollution influence on US surface ozone in the model by 10–15% or up to 1 ppb.
Elemental analysis of chamber organic aerosol using an aerodyne high-resolution aerosol mass spectrometer

The elemental composition of laboratory chamber secondary organic aerosol (SOA) from glyoxal uptake, α-pinene ozonolysis, isoprene photooxidation, single-ring aromatic photooxidation, and naphthalene photooxidation is evaluated using Aerodyne high-resolution time-of-flight mass spectrometer data. SOA O/C ratios range from 1.13 for glyoxal uptake experiments to 0.30–0.43 for α-pinene ozonolysis. The elemental composition of α-pinene and naphthalene SOA is also confirmed by offline mass spectrometry. The fraction of organic signal at m/z 44 is generally a good measure of SOA oxygenation for α-pinene/O3, isoprene/high-NOx, and naphthalene SOA systems. The agreement between measured and estimated O/C ratios tends to get closer as the fraction of organic signal at m/z 44 increases. This is in contrast to the glyoxal uptake system, in which m/z 44 substantially underpredicts O/C. Although chamber SOA has generally been considered less oxygenated than ambient SOA, single-ring aromatic- and naphthalene-derived SOA can reach O/C ratios upward of 0.7, well within the range of ambient PMF component OOA, though still not as high as some ambient measurements. The spectra of aromatic and isoprene-high-NOx SOA resemble that of OOA, but the spectrum of glyoxal uptake does not resemble that of any ambient organic aerosol PMF component.
Enhancement of marine cloud albedo via controlled sea spray injections: a global model study of the influence of emission rates, microphysics and transport

Modification of cloud albedo by controlled emission of sea spray particles into the atmosphere has been suggested as a possible geoengineering option to slow global warming. Previous global studies have imposed changes in cloud drop concentration in low level clouds to explore the radiative and climatic effects. Here, we use a global aerosol transport model to quantify how an imposed flux of sea spray particles affects the natural aerosol processes, the particle size distribution, and concentrations of cloud drops. We assume that the proposed fleet of vessels emits sea spray particles with a wind speed-dependent flux into four regions of persistent stratocumulus cloud off the western coasts of continents. The model results show that fractional changes in cloud drop number concentration (CDNC) vary substantially between the four regions because of differences in wind speed (which affects the spray efficiency of the vessels), transport and particle deposition rates, and because of variations in aerosols from natural and anthropogenic sources. Using spray emission rates comparable to those implied by previous studies we find that the predicted CDNC changes are very small (maximum 20%) and in one of the four regions even negative. The weak or negative effect is because the added particles suppress the in-cloud supersaturation and prevent existing aerosol particles from forming cloud drops. A scenario with five times higher emissions (considerably higher than previously assumed) increases CDNC on average by 45–163%, but median concentrations are still below the 375 cm−3 assumed in previous studies. An inadvertent effect of the spray emissions is that sulphur dioxide concentrations are suppressed by 1–2% in the seeded regions and sulphuric acid vapour by 64–68% due to chemical reactions on the additional salt particles. The impact of this suppression on existing aerosol is negligible in the model, but should be investigated further in the real environment so that inadvertent impacts can be excluded.
The sensitivity of stratocumulus-capped mixed layers to cloud droplet concentration: do LES and mixed-layer models agree?

The sensitivity of a stratocumulus-capped mixed layer to a change in cloud droplet concentration is evaluated with a large-eddy simulation (LES) and a mixed layer model (MLM). The strength of the second aerosol indirect effect simulated by the two model types agrees within 50% for cases in which the LES-simulated boundary layer remains well mixed, if the MLM entrainment closure includes the effects of cloud droplet sedimentation. To achieve this agreement, parameters in the MLM entrainment closure and the drizzle parameterization must be retuned to match the LES. This is because the LES advection scheme and microphysical parameterization significantly bias the entrainment rate and precipitation profile compared to observational best guesses. Before this modification, the MLM simulates more liquid water path and much more drizzle at a given droplet concentration than the LES and is more sensitive to droplet concentration, even undergoing a drizzle-induced boundary layer collapse at low droplet concentrations. After this modification, both models predict a comparable decrease of cloud liquid water path as droplet concentration increases, cancelling 30–50% of the Twomey effect for our case. The agreement breaks down at the lowest simulated droplet concentrations, for which the boundary layer in the LES is not well mixed. Our results highlight issues with both types of model. Potential LES biases due to inadequate resolution, subgrid mixing and parameterized microphysics must be carefully considered when trying to make a quantitative inference of the second indirect effect from an LES of a stratocumulus-topped boundary layer. On the other hand, even slight internal decoupling of the boundary layer invalidates the central assumption of an MLM, substantially limiting the range of conditions that MLM-predicted sensitivities to droplet concentration are meaningful.
Seasonal variations of concentrations and optical properties of water soluble HULIS collected in urban environments

Major contributors to the organic aerosol include water-soluble macromolecular compounds (e.g. HULISWS: Water Soluble Humic LIke Substances). The nature and sources of HULISWS are still largely unknown. This work is based on a monitoring in six different French cities performed during summer and winter seasons. HULISWS analysis was performed with a selective method of extraction complemented by carbon quantification. UV spectroscopy was also applied for their chemical characterisation. HULISWS carbon represent an important contribution to the organic aerosol mass in summer and winter, as it accounts for 12–22% of Organic Carbon and 34–40% of Water Soluble Organic Carbon. We found strong differences in the optical properties (specific absorbance at 250, 272, 280 nm and E2/E3 ratio) and therefore in the chemical structure between HULISWS from samples of summer- and wintertime. These differences highlight different processes responsible for emissions and formation of HULISWS according to the season, namely biomass burning in winter, and secondary processes in summer. Specific absorbance can also be considered as a rapid and useful indicator of the origin of HULISWS in urban environment.
NO3 radical measurements in a polluted marine environment: links to ozone formation

Nighttime chemistry in polluted regions is dominated by the nitrate radical (NO3) including its direct reaction with natural and anthropogenic hydrocarbons, its reaction with NO2 to form N2O5, and subsequent reactions of N2O5 to form HNO3 and chlorine containing photolabile species. We report nighttime measurements of NO3, NO2, and O3, in the polluted marine boundary layer southwest of Vancouver, BC during a three week study in the summer of 2005. The concentration of N2O5 was calculated using the well known equilibrium, NO3+NO2↔N2O5. Median overnight mixing ratios of NO3, N2O5 and NO2 were 10.3 ppt, 122 ppt and 8.3 ppb with median N2O5/NO3 molar ratios of 13.1 and median nocturnal partitioning of 4.9%. Due to the high levels of NO2 that can inhibit approach to steady-state, we use a method for calculating NO3 lifetimes that does not assume the steady-state approximation. Median and average lifetimes of NO3 in the NO3-N2O5 nighttime reservoir were 1.1–2.3 min. We have determined nocturnal profiles of the pseudo first order loss coefficient of NO3 and the first order loss coefficients of N2O5 by regression of the NO3 inverse lifetimes with the [N2O5]/[NO3] ratio. Direct losses of NO3 are highest early in the night, tapering off as the night proceeds. The magnitude of the first order loss coefficient of N2O5 is consistent with, but not verification of, recommended homogeneous rate coefficients for reaction of N2O5 with water vapor early in the night, but increases significantly in the latter part of the night when relative humidity increases beyond 75%, consistent with heterogeneous reactions of N2O5 with aerosols with a rate constant khet=(1.2±0.4)×10−3 s−1−(1.6±0.4)×10−3 s−1. Analysis indicates that a correlation exists between overnight integrated N2O5 concentrations in the marine boundary layer, a surrogate for the accumulation of chlorine containing photolabile species, and maximum 1-h average O3 at stations in the Lower Fraser Valley the next day when there is clear evidence of a sea breeze transporting marine air into the valley. The range of maximum 1-h average O3 increase attributable to the correlation is ΔO3=+1.1 to +8.3 ppb throughout the study for the average of 20 stations, although higher increases are seen for stations far downwind of the coastal urban area. The correlation is still statistically significant on the second day after a nighttime accumulation, but with a different spatial pattern favouring increased O3 at the coastal urban stations, consistent with transport of polluted air back to the coast.
Aged organic aerosol in the Eastern Mediterranean: the Finokalia Aerosol Measurement Experiment – 2008

Aged organic aerosol (OA) was measured at a remote coastal site on the island of Crete, Greece during the Finokalia Aerosol Measurement Experiment-2008 (FAME-2008), which was part of the EUCAARI intensive campaign of May 2008. The site at Finokalia is influenced by air masses from different source regions, including long-range transport of pollution from continental Europe. A quadrupole aerosol mass spectrometer (Q-AMS) was employed to measure the size-resolved chemical composition of non-refractory submicron aerosol (NR-PM1), and to estimate the extent of oxidation of the organic aerosol. Factor analysis was used to gain insights into the processes and sources affecting the OA composition. The particles were internally mixed and liquid. The largest fraction of the dry NR-PM1 sampled was ammonium sulfate and ammonium bisulfate, followed by organics and a small amount of nitrate. The variability in OA composition could be explained with two factors of oxygenated organic aerosol (OOA) with differing extents of oxidation but similar volatility. Hydrocarbon-like organic aerosol (HOA) was not detected. There was no statistically significant diurnal variation in the bulk composition of NR-PM1 such as total sulfate or total organic aerosol concentrations. However, the OA composition exhibited statistically significant diurnal variation with more oxidized OA in the afternoon. The organic aerosol was highly oxidized, regardless of the source region. Total OA concentrations also varied little with source region, suggesting that local sources had only a small effect on OA concentrations measured at Finokalia. The aerosol was transported for about one day before arriving at the site, corresponding to an OH exposure of approximately 4×1011 molecules cm−3 s. The constant extent of oxidation suggests that atmospheric aging results in a highly oxidized OA at these OH exposures, regardless of the aerosol source.
Impact of brown and clear carbon on light absorption enhancement, single scatter albedo and absorption wavelength dependence of black carbon

The presence of clear coatings on atmospheric black carbon (BC) particles is known to enhance the magnitude of light absorption by the BC cores. Based on calculations using core/shell Mie theory, we demonstrate that the enhancement of light absorption (EAbs) by atmospheric black carbon (BC) when it is coated in mildly absorbing material (CBrown) is reduced relative to the enhancement induced by non-absorbing coatings (CClear). This reduction, sensitive to both the CBrown coating thickness and imaginary refractive index (RI), can be up to 50% for 400 nm radiation and 25% averaged across the visible radiation spectrum for reasonable core/shell diameters. The enhanced direct radiative forcing possible due to the enhancement effect of CClear is therefore reduced if the coating is absorbing. Additionally, the need to explicitly treat BC as an internal, as opposed to external, mixture with CBrown is shown to be important to the calculated single scatter albedo only when models treat BC as large spherical cores (>50 nm). For smaller BC cores (or fractal agglomerates) consideration of the BC and CBrown as an external mixture leads to relatively small errors in the particle single scatter albedo of <0.03. It has often been assumed that observation of an absorption Angström exponent (AAE)>1 indicates absorption by a non-BC aerosol. Here, it is shown that BC cores coated in CClear can reasonably have an AAE of up to 1.6, a result that complicates the attribution of observed light absorption to CBrown within ambient particles. However, an AAE<1.6 does not exclude the possibility of CBrown; rather CBrown cannot be confidently assigned unless AAE>1.6. Comparison of these model results to various ambient AAE measurements demonstrates that large-scale attribution of CBrown is a challenging task using current in-situ measurement methods. We suggest that coincident measurements of particle core and shell sizes along with the AAE may be necessary to distinguish absorbing and non-absorbing OC.
Chemical characterisation of iron in dust and biomass burning aerosols during AMMA-SOP0/DABEX: implication for iron solubility

The chemical composition and the soluble fraction were determined in aerosol samples collected during flights of AMMA-SOP0/DABEX campaign, which were conducted in the West African Sahel during dry season (2006). Two aerosol types are encountered in this period: dust particles (DUST) and biomass burning aerosol (BB). Chemical analysis and microscope observations showed that the iron (Fe) found in BB samples mainly originates from dust particles mostly internally mixed in the biomass burning layer. Chemical analyses of samples showed that the Fe solubility is lower in African dust samples than in biomass burning aerosols. Our data provide a first idea of the variability of iron dust solubility in the source region (0.1% and 3.4%). We found a relationship between iron solubility/clay content/source which partly confirms that the variability of iron solubility in this source region is related to the character and origin of the aerosols themselves. In the biomass burning samples, no relationship were found between Fe solubility and either the concentrations of acidic species (SO42−, NO3− or oxalate) or the content of carbon (TC, OC, BC). Therefore, we were unable to determine what processes are involved in this increase of iron solubility. In terms of supply of soluble Fe to oceanic ecosystems on a global scale, the higher solubility observed for Fe in biomass burning could imply an indirect source of Fe to marine ecosystems. But these aerosols are probably not significant because the Sahara is easily the dominant source of Fe to the Atlantic Ocean.
Hygroscopicity and chemical composition of Antarctic sub-micrometre aerosol particles and observations of new particle formation

The Antarctic near-coastal sub-micrometre aerosol particle features in summer were characterised based on measured data on aerosol hygroscopicity, size distributions, volatility and chemical ion and organic carbon mass concentrations. Hysplit model was used to calculate the history of the air masses to predict the particle origin. Additional measurements of meteorological parameters were utilised. The hygroscopic properties of particles mostly resembled those of marine aerosols. The measurements took place at 130 km from the Southern Ocean, which was the most significant factor affecting the particle properties. This is explained by the lack of additional sources on the continent of Antarctica. The Southern Ocean was thus a likely source of the particles and nucleating and condensing vapours. The particles were very hygroscopic (HGF 1.75 at 90 nm) and very volatile. Most of the sub-100 nm particle volume volatilised below 100 °C. Based on chemical data, particle hygroscopic and volatile properties were explained by a large fraction of non-neutralised sulphuric acid together with organic material. The hygroscopic growth factors assessed from chemical data were similar to measured. Hygroscopicity was higher in dry continental air masses compared with the moist marine air masses. This was explained by the aging of the marine organic species and lower methanesulphonic acid volume fraction together with the changes in the inorganic aerosol chemistry as the aerosol had travelled long time over the continental Antarctica. Special focus was directed in detailed examination of the observed new particle formation events. Indications of the preference of negative over positive ions in nucleation could be detected. However, in a detailed case study, the neutral particles dominated the particle formation process. Freshly nucleated particles had the smallest hygroscopic growth factors, which increased subsequent to particle aging.