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Real refractive indices and volatility of secondary organic aerosol generated from photooxidation and ozonolysis of limonene, α-pinene and toluene

Thermodenuding particles can provide insights into aerosol composition and may be a way to create particles in laboratory chambers that better mimic the atmosphere. The relative volatility of secondary organic aerosol (SOA) was investigated by evaporating organics from the particles using a thermodenuder (TD) at temperatures between &sim;60 and 100 °C. Volatility was influenced by the parent hydrocarbon, oxidation chemistry and relative humidity (RH). For SOA generated from ozonolysis, limonene had lower volatility than α-pinene, and OH scavengers had no influence on volatility. For photooxidation, α-pinene SOA was slightly more volatile than limonene SOA. Increasing RH also modestly increased volatility, while toluene SOA was unaffected by heating to 98 °C. For both α-pinene and limonene, the concentration of NOx and the HC / NOx ratio had no discernible effect on SOA volatility. Refractive indices for the original and denuded particles were retrieved from polar nephelometer measurements using parallel and perpendicular polarized 532 nm light. Retrievals were performed with a genetic algorithm method using Mie–Lorenz scattering theory and measured particle size distributions. Retrieved refractive indices for the SOA before thermodenuding varied between 1.35 and 1.61 depending on several factors, including parent hydrocarbon, oxidation chemistry, and SOA generation temperature. For high NOx SOA, as particles shrink, their refractive index returns to the value of the corresponding size particles before heating (limonene) or slightly higher (α-pinene). For low NOx however, the resulting refractive index is 0.05 ± 0.02 lower than the corresponding size undenuded particles. Additionally, for α-pinene SOA from ozonolysis with OH radical scavenger, resulting refractive indices were higher by about 0.03 after heating. Consistent with no change in size, refractive indices of toluene SOA were unaffected by heating. Finally, refractive index data available to date are reviewed, leading to the suggestion that the most representative values for mr at λ =532 nm for biogenic and anthropogenic SOA are 1.44 and 1.55, respectively.
Contribution from the ten major emission sectors in Europe and Denmark to the health-cost externalities of air pollution using the EVA model system – an integrated modelling approach

We have developed an integrated model system, EVA (Economic Valuation of Air pollution), based on the impact-pathway chain, to assess the health-related economic externalities of air pollution resulting from specific emission sources or sectors, which can be used to support policy-making with respect to emission control. Central for the system is a newly developed tagging method capable of calculating the contribution from a specific emission source or sector to the overall air pollution levels, taking into account the non-linear atmospheric chemistry. The main objective of this work is to identify the anthropogenic emission sources in Europe and Denmark that contribute the most to human health impacts. In this study, we applied the EVA system to Europe and Denmark, with a detailed analysis of health-related external costs from the ten major emission sectors and their relative contributions. The paper contains a thorough description of the EVA system, the main results from the assessment of the main contributors and a discussion of the most important atmospheric chemical reactions relevant for interpreting the results. The main conclusion from the analysis is that the major contributors to health-related external costs are major power production, agriculture, road traffic, and non-industrial domestic combustion, including wood combustion. We conclude that when regulating the emissions of ammonia from the agricultural sector, both the impacts on nature and on human health should be taken into account. This study confirms that air pollution constitutes a serious problem for human health and that the related external costs are considerable. The results in this work emphasize the importance of defining the right questions in the decision-making process. The results from assessing the impacts from each emission sector depend clearly on the assumption that the other emission sectors are not changed, especially emissions changing concentrations of atmospheric OH and therefore lifetimes of other chemical species.
Assessment of past, present and future health-cost externalities of air pollution in Europe and the contribution from international ship traffic using the EVA model system

An integrated model system, EVA (Economic Valuation of Air pollution), based on the impact-pathway chain has been developed to assess the health-related economic externalities of air pollution resulting from specific emission sources or sectors. The model system can be used to support policy-making with respect to emission control. In this study, we apply the EVA system to Europe, and perform a more detailed assessment of past, present, and future health-cost externalities of the total air pollution levels in Europe (including both natural and anthropogenic sources), represented by the years 2000, 2007, 2011, and 2020. We also assess the contribution to the health-related external costs from international ship traffic with special attention to the international ship traffic in the Baltic and North seas, since special regulatory actions on sulfur emissions, called SECA (sulfur emission control area), have been introduced in these areas. We conclude that, despite efficient regulatory actions in Europe in recent decades, air pollution still constitutes a serious problem for human health. Hence the related external costs are considerable. The total health-related external costs for the whole of Europe are estimated at 803 bn euros yr−1 for the year 2000, decreasing to 537 bn euros yr−1 in the year 2020. We estimate the total number of premature deaths in Europe in the year 2000 due to air pollution to be around 680 000 yr−1, decreasing to approximately 450 000 in the year 2020. The contribution from international ship traffic in the Northern Hemisphere was estimated to 7% of the total health-related external costs in Europe in the year 2000, increasing to 12% in the year 2020. In contrast, the contribution from international ship traffic in the Baltic Sea and the North Sea decreases 36% due to the regulatory efforts of reducing sulfur emissions from ship traffic in SECA. Introducing this regulatory instrument for all international ship traffic in the Northern Hemisphere, or at least in areas close to Europe, would have a significant positive impact on human health in Europe.
Biomass burning contribution to Beijing aerosol

Biomass burning, the largest global source of elemental carbon (EC) and primary organic carbon (OC), is strongly associated with many subjects of great scientific concern, such as secondary organic aerosol and brown carbon which exert important effects on the environment and on climate in particular. This study investigated the relationships between levoglucosan and other biomass burning tracers (i.e., water soluble potassium and mannosan) based on both ambient samples collected in Beijing and source samples. Compared with North America and Europe, Beijing was characterized by high ambient levoglucosan concentrations and low winter to summer ratios of levoglucosan, indicating significant impact of biomass burning activities throughout the year in Beijing. Comparison of levoglucosan and water soluble potassium (K+) levels suggested that it was acceptable to use K+ as a biomass burning tracer during summer in Beijing, while the contribution of fireworks to K+ could be significant during winter. Moreover, the levoglucosan to K+ ratio was found to be lower during the typical summer period (0.21 ± 0.16) compared with the typical winter period (0.51 ± 0.15). Levoglucosan correlated strongly with mannosan (R2 = 0.97) throughout the winter and the levoglucosan to mannosan ratio averaged 9.49 ± 1.63, whereas levoglucosan and mannosan exhibited relatively weak correlation (R2 = 0.73) during the typical summer period when the levoglucosan to mannosan ratio averaged 12.65 ± 3.38. Results from positive matrix factorization (PMF) model analysis showed that about 50% of the OC and EC in Beijing were associated with biomass burning processes. In addition, a new source identification method was developed based on the comparison of the levoglucosan to K+ ratio and the levoglucosan to mannosan ratio among different types of biomass. Using this method, the major source of biomass burning aerosol in Beijing was suggested to be the combustion of crop residuals, while the contribution from softwood burning was also non-negligible, especially in winter.
Direct entrainment and detrainment rate distributions of individual shallow cumulus clouds in an LES

Probability distribution functions of shallow cumulus cloud core entrainment and detrainment rates are calculated using 4362 individual cumulus clouds isolated from LES (large eddy simulation) using a cloud tracking algorithm. Calculation of the mutual information between fractional entrainment/detrainment and a variety of mean cloud core properties suggests that fractional entrainment rate is best predicted by the mean cloud buoyancy B and the environmental buoyancy lapse rate dθρ/dz at that level, while fractional detrainment is best predicted by the mean vertical velocity w and the critical mixing fraction χc. Fractional entrainment and detrainment rates are relatively insensitive to cloud core horizontal area, and the perimeter of horizontal cloud core sections display an a0.73 dependence. This implies that cloud core mass entrainment flux E is proportional to cloud core cross-sectional area instead of cloud core surface area, as is generally assumed. Empirical best-fit relations for ε(B, dθρ/dz and δ(w, χc) are found for both individual shallow cumulus clouds and cloud ensembles. It is found that clouds with high buoyancy in strong stratification experience low entrainment rates, while clouds with high vertical velocities and critical mixing fractions experience low detrainment rates.
Modeling upper tropospheric and lower stratospheric water vapor anomalies

The domain-filling, forward trajectory calculation model developed by Schoeberl and Dessler (2011) is used to further investigate processes that produce upper tropospheric and lower stratospheric water vapor anomalies. We examine the pathways parcels take from the base of the tropical tropopause layer (TTL) to the lower stratosphere. Most parcels found in the lower stratosphere arise from East Asia, the Tropical West Pacific (TWP) and Central/South America. The belt of TTL parcel origins is very wide compared to the final dehydration zones near the top of the TTL. This is due to the convergence of rising air due to the stronger diabatic heating near the tropopause relative to levels above and below. The observed water vapor anomalies – both wet and dry – correspond to regions where parcels have minimal displacement from their initialization. These minimum displacement regions include the winter TWP and the Asian and American monsoons. To better understand the stratospheric water vapor concentration we introduce the water vapor spectrum and investigate the source of the wettest and driest components of the spectrum. We find that the driest air parcels originate below the TWP, moving upward to dehydrate in the TWP cold upper troposphere. The wettest air parcels originate at the edges of the TWP as well as in the summer American and Asian monsoons. The wet air parcels are important since they skew the mean stratospheric water vapor distribution toward higher values. Both TWP cold temperatures that produce dry parcels as well as extra-TWP processes that control the wet parcels determine stratospheric water vapor.
The roles of vertical advection and eddy diffusion in the equatorial mesospheric semi-annual oscillation (MSAO)

Observations of the mesospheric semi-annual oscillation (MSAO) in the equatorial region have been reported dating back several decades. Seasonal variations in both species densities and airglow emissions are well documented. The extensive observations available offer an excellent case study for comparison with model simulations. A broad range of MSAO measurements is summarised with emphasis on the 80–100 km region. The objective here is not to address directly the complicated driving forces of the MSAO, but rather to employ a combination of observations and model simulations to estimate the limits of some of the underlying dynamical processes. Photochemical model simulations are included for near-equinox and near-solstice conditions, the two times with notable differences in the observed MSAO parameters. Diurnal tides are incorporated in the model to facilitate comparisons of observations made at different local times. The roles of water vapour as the "driver" species and ozone as the "response" species are examined to test for consistency between the model results and observations. The simulations suggest the interactions between vertical eddy diffusion and background vertical advection play a significant role in the MSAO phenomenon. Further, the simulations imply there are rigid limits on vertical advection rates and eddy diffusion rates. For August at the Equator, 90 km altitude, the derived eddy diffusion rate is approximately 1 × 106 cm2 s−1 and the vertical advection is upwards at 0.8 cm s−1. For April the corresponding values are 4 × 105 cm2 s−1 and 0.1 cm s−1. These results from the current 1-D model simulations will need to be verified by a full 3-D simulation. Exactly how vertical advection and eddy diffusion are related to gravity wave momentum as discussed by Dunkerton (1982) three decades ago remains to be addressed.
Online measurements of the emissions of intermediate-volatility and semi-volatile organic compounds from aircraft

A detailed understanding of the climate and air quality impacts of aviation requires measurements of the emissions of intermediate-volatility and semi-volatile organic compounds (I/SVOCs) from aircraft. Currently both the amount and chemical composition of aircraft I/SVOC emissions remain poorly characterized. Here we characterize I/SVOC emissions from aircraft, using a novel instrument for the online, quantitative measurement of the mass loading and composition of low-volatility organic vapors. Emissions from the NASA DC8 aircraft were sampled on the ground 143 m downwind of the engines and characterized as a function of engine power from idle (4% maximum rated thrust) through 85% power. Results show that I/SVOC emissions are highest during engine idle operating conditions, with decreasing but non-zero I/SVOC emissions at higher engine powers. Comparison of I/SVOC emissions with total hydrocarbon (THC) measurements, VOC measurements, and an established emissions profile indicates that I/SVOCs comprise 10–20% of the total organic gas-phase emissions at idle, and an increasing fraction of the total gas-phase organic emissions at higher powers. Positive matrix factorization of online mass spectra is used to identify three distinct types of I/SVOC emissions: aliphatic, aromatic and oxygenated. The volatility and chemical composition of the emissions suggest that unburned fuel is the dominant source of I/SVOCs at idle, while pyrolysis products make up an increasing fraction of the I/SVOCs at higher powers. Oxygenated I/SVOC emissions were detected at lower engine powers (≤30%) and may be linked to cracked, partially oxidized or unburned fuel components.
A one-year comprehensive chemical characterisation of fine aerosol (PM2.5) at urban, suburban and rural background sites in the region of Paris (France)

Studies describing the chemical composition of fine aerosol (PM2.5) in urban areas are often conducted for a few weeks only and at one sole site, giving thus a narrow view of their temporal and spatial characteristics. This paper presents a one-year (11 September 2009–10 September 2010) survey of the daily chemical composition of PM2.5 in the region of Paris, which is the second most populated "Larger Urban Zone" in Europe. Five sampling sites representative of suburban (SUB), urban (URB), northeast (NER), northwest (NWR) and south (SOR) rural backgrounds were implemented. The major chemical components of PM2.5 were determined including elemental carbon (EC), organic carbon (OC), and the major ions. OC was converted to organic matter (OM) using the chemical mass closure methodology, which leads to conversion factors of 1.95 for the SUB and URB sites, and 2.05 for the three rural ones. On average, gravimetrically determined PM2.5 annual mass concentrations are 15.2, 14.8, 12.6, 11.7 and 10.8 μg m−3 for SUB, URB, NER, NWR and SOR sites, respectively. The chemical composition of fine aerosol is very homogeneous at the five sites and is composed of OM (38–47%), nitrate (17–22%), non-sea-salt sulfate (13–16%), ammonium (10–12%), EC (4–10%), mineral dust (2–5%) and sea salt (3–4%). This chemical composition is in agreement with those reported in the literature for most European environments. On an annual scale, Paris (URB and SUB sites) exhibits its highest PM2.5 concentrations during late autumn, winter and early spring (higher than 15 μg m−3 on average, from December to April), intermediates during late spring and early autumn (between 10 and 15 μg m−3 during May, June, September, October, and November) and the lowest during summer (below 10 μg m−3 during July and August). PM levels are mostly homogeneous on a regional scale, during the whole project (e.g. for URB plotted against NER sites: slope = 1.06, r2=0.84, n=330), suggesting the importance of mid- or long-range transport, and regional instead of local scale phenomena. During this one-year project, two thirds of the days exceeding the PM2.5 2015 EU annual limit value of 25 μg m−3 were due to continental import from countries located northeast, east of France. This result questions the efficiency of local, regional and even national abatement strategies during pollution episodes, pointing to the need for a wider collaborative work with the neighbouring countries on these topics. Nevertheless, emissions of local anthropogenic sources lead to higher levels at the URB and SUB sites compared to the others (e.g. 26% higher on average at the URB than at the NWR site for PM2.5, during the whole campaign), which can even be emphasised by specific meteorological conditions such as low boundary layer heights. OM and secondary inorganic species (nitrate, non-sea-salt sulfate and ammonium, noted SIA) are mainly imported by mid- or long-range transport (e.g. for NWR plotted against URB sites: slope = 0.79, r2=0.72, n=335 for OM, and slope = 0.91, r2=0.89, n=335 for SIA) whereas EC is primarily locally emitted (e.g. for SOR plotted against URB sites: slope = 0.27; r2=0.03; n=335). This database will serve as a basis for investigating carbonaceous aerosols, metals as well as the main sources and geographical origins of PM in the region of Paris.
Influence of observed diurnal cycles of aerosol optical depth on aerosol direct radiative effect

The diurnal variability of aerosol optical depth (AOD) can be significant, depending on location and dominant aerosol type. However, these diurnal cycles have rarely been taken into account in measurement-based estimates of aerosol direct radiative forcing (ADRF) or aerosol direct radiative effect (ADRE). The objective of our study was to estimate the influence of diurnal aerosol variability at the top of the atmosphere ADRE estimates. By including all the possible AERONET sites, we wanted to assess the influence on global ADRE estimates. While focusing also in more detail on some selected sites of strongest impact, our goal was to also see the possible impact regionally. We calculated ADRE with different assumptions about the daily AOD variability: taking the observed daily AOD cycle into account and assuming diurnally constant AOD. Moreover, we estimated the corresponding differences in ADREs, if the single AOD value for the daily mean was taken from the the Moderate Resolution Imaging Spectroradiometer (MODIS) Terra or Aqua overpass times, instead of accounting for the true observed daily variability. The mean impact of diurnal AOD variability on 24 h ADRE estimates, averaged over all AERONET sites, was rather small and it was relatively small even for the cases when AOD was chosen to correspond to the Terra or Aqua overpass time. This was true on average over all AERONET sites, while clearly there can be much stronger impact in individual sites. Examples of some selected sites demonstrated that the strongest observed AOD variability (the strongest morning afternoon contrast) does not typically result in a significant impact on 24 h ADRE. In those cases, the morning and afternoon AOD patterns are opposite and thus the impact on 24 h ADRE, when integrated over all solar zenith angles, is reduced. The most significant effect on daily ADRE was induced by AOD cycles with either maximum or minimum AOD close to local noon. In these cases, the impact on 24 h ADRE was typically around 0.1–0.2 W m−2 (both positive and negative) in absolute values, 5–10% in relative ones.