Equilibration time scales of organic aerosol inside thermodenuders: Evaporation kinetics versus thermodynamics

The interpretation of thermodenuder (TD) data often relies on the assumption that thermodynamic equilibrium is reached inside the instrument. We modeled the evaporation of three organic aerosol types (adipic acid, α-pinene SOA and aged OA) inside a thermodenuder with a mass transfer model, and calculated equilibration time scales for these systems at realistic conditions. The equilibrium times varied from less than a second to several hours, decreasing with increasing aerosol concentrations, decreasing particle sizes, decreasing volatilities and increasing mass accommodation coefficients. The results indicate that generally TDs measure particle evaporation rates rather than equilibria, and time-dependent modeling of the evaporation is usually needed to interpret the data. Measurements at varying residence times and temperatures, on the other hand, are desirable to investigate the equilibration of the studied aerosol and decouple the kinetic effects from the effects caused by the thermodynamic properties of the aerosol. Organic aerosol is likely to be further from equilibrium under typical field conditions compared with laboratory data. When determining the aerosol properties from TD data, assuming incorrectly equilibrium results in under-prediction of the vaporization enthalpy of the evaporating species. Similar under-estimation is predicted if multicomponent aerosols are approximated with single-component properties.     

Ambient TSP concentration and dustfall in major cities of China: Spatial distribution and temporal variability

Based on environmental monitoring data in 93 major cities and meteorological records at 398 weather stations in China from 1981 to 2007, total suspended particle (TSP) concentration, the intensity of dustfall, and sand and dust storm frequency (F_d) were analysed. During the past 27 years, the annual average TSP concentration (C_TSP) in 93 cities was 402 μg m^?3. Annual average C_TSP decreased from the north to the south and from inland to the coast areas with a peak value of 628.8 μg m^?3 in Lanzhou. In the 1980s, 1990s and 2000s, annual average C_TSP was 628.7, 319.2, and 250.1 μg m^?3, respectively. Annual average intensity of dustfall (I_d) was 240.5 t km^?2 a^?1, decreased from northern to southern China and from inland to the coast areas with the maximum value of 717.2 t km^?2 a^?1 in Baotou. In the 1980s, 1990s and 2000s, annual average I_d was 334.8, 220.9, 146 t km^?2 a^?1 respectively. Annual average I_d in the Loess Plateau region was commonly higher than 200 t km^?2 a^?1. The annual average F_d decreased from arid regions in northwestern China to humid areas in southeastern China with two sand and sand storm centers existing in Xinjiang Taklamakan Desert and western Inner Mongolia. The annual average F_d in the 1980s, 1990s, 2000s was 16, 8, 6 days respectively, decreased steadily from 18 days in 1981–5 days in 2007. Annual average I_d had a positive linear relation to annual average C_TSP (R² = 0.96). Annual average F_d had a positive relation with annual average C_TSP (R² = 0.97) as well as annual average I_d (R² = 0.94). TSP was the chief pollutant influencing Air Pollution Index (API) in northern China in spring and winter seasons. Sand and dust storm might be a major factor affecting the temporal variability and spatial distribution of TSP and dustfall in China.     

Using a reduced Common Representative Intermediates (CRIv2-R5) mechanism to simulate tropospheric ozone in a 3-D Lagrangian chemistry transport model

A reduced chemical scheme (CRIv2-R5) which describes ozone formation from the tropospheric degradation of methane and 22 emitted non-methane hydrocarbons and oxygenated volatile organic compounds has been applied in a global-3D chemistry transport model (STOCHEM). The scheme, which contains 220 species in 609 reactions, has been used to simulate ozone and its precursors for the meteorological year of 1998 and the results have been compared with those from STOCHEM runs with its original chemistry. Compared with the original chemistry scheme, the degradation of a larger number of more reactive VOCs in the CRI scheme results in the formation (and their consequent transportation) of more NO_x active reservoirs thus leading to formation of more ozone away from land-based sources. Conversely, the more reactive VOCs also lead to greater removal of OH in continental areas and greater formation of OH in marine environments. STOCHEM run with the CRI scheme simulates more ozone (by up to 10 ppb), which results in better agreement with observed vertical ozone profiles. The CRI scheme transforms the globally and annually integrated ozone budget for the considered year in STOCHEM from a net loss of ?55 Tg yr^?1 to a net gain of +50 Tg yr^?1.     

A new condensed toluene mechanism for Carbon Bond: CB05-TU

Toluene is ubiquitous in urban atmospheres and is a precursor to tropospheric ozone and aerosol (smog). An important characteristic of toluene chemistry is the tendency of some degradation products (e.g., cresols and methyl-catechols) to form organic nitro and nitrate compounds that sequester NOx (NO and NO₂) from active participation in smog formation. Explaining the NOx sinks in toluene degradation has made mechanism development more difficult for toluene than for many other organic compounds. Another challenge for toluene is explaining sources of radicals early in the degradation process. This paper describes the development of a new condensed toluene mechanism consisting of 26 reactions, and evaluates the performance of CB05 with this new toluene scheme (Toluene Update, TU) against 38 chamber experiments at 7 different environmental chambers, and provides recommendations for future developments. CB05 with the current toluene mechanism (CB05-Base) under-predicted the maximum O₃ and O₃ production rate for many of these toluene–NOx chamber experiments, especially under low-NOx conditions ([NOx]_t=0 < 100 ppb). CB05 with the new toluene mechanism (CB05-TU) includes changes to the yields and reactions of cresols and ring-opening products, and showed better performance than CB05-Base in predicting the maximum O₃, O₃ formation rate, NOx removal rate and cresol concentration. Additional environmental chamber simulations with xylene–NOx experiments showed that the TU mechanism updates tended to improve mechanism performance for xylene.     

Why ozonolysis may not increase the hydrophilicity of particles

It is commonly assumed that atmospheric oxidation of hydrocarbon particles or hydrocarbon coatings on particles leads to polar products and increased water uptake, altering atmospheric visibility and increasing the likelihood they will act as cloud condensation nuclei (CCN). We show here through laboratory experiments that increased water uptake depends on the 3-dimensional structure of the particles. Laboratory studies of particles formed during ozonolysis of surface-bound alkenes, present as terminally unsaturated self-assembled monolayers (C8= SAM) on a silica substrate, were carried out at room temperature and 1 atm pressure. SAMs were exposed to ～10¹³ O₃ molecules cm^?3 for 40 min and resultant particles were analyzed using single particle Fourier transform infrared micro-spectroscopy (micro-FTIR) and secondary ion mass spectroscopy (SIMS). Spectroscopy results show that –COOH and other polar groups are formed but are buried inside a hydrophobic shell, consistent with earlier observations (McIntire et al., 2005, Moussa et al., 2009) that water uptake does not increase after reaction of the terminal alkene with O₃. These insights into the 3-D structure of particles formed on oxidation have important implications for the ability of secondary organic aerosols to act as CCN. In addition, the nature of the surface of the particles is expected to determine their uptake into biological systems such as the surface of the lungs.     

Uncertainty in health risks due to anthropogenic primary fine particulate matter from different source types in Finland

The emission-exposure and exposure-response (toxicity) relationships are different for different emission source categories of anthropogenic primary fine particulate matter (PM_2.5). These variations have a potentially crucial importance in the integrated assessment, when determining cost-effective abatement strategies. We studied the importance of these variations by conducting a sensitivity analysis for an integrated assessment model. The model was developed to estimate the adverse health effects to the Finnish population attributable to primary PM_2.5 emissions from the whole of Europe. The primary PM_2.5 emissions in the whole of Europe and in more detail in Finland were evaluated using the inventory of the European Monitoring and Evaluation Programme (EMEP) and the Finnish Regional Emission Scenario model (FRES), respectively. The emission-exposure relationships for different primary PM_2.5 emission source categories in Finland have been previously evaluated and these values incorporated as intake fractions into the integrated assessment model. The primary PM_2.5 exposure-response functions and toxicity differences for the pollution originating from different source categories were estimated in an expert elicitation study performed by six European experts on air pollution health effects. The primary PM_2.5 emissions from Finnish and other European sources were estimated for the population of Finland in 2000 to be responsible for 209 (mean, 95% confidence interval 6–739) and 357 (mean, 95% CI 8–1482) premature deaths, respectively. The inclusion of emission-exposure and toxicity variation into the model increased the predicted relative importance of traffic related primary PM_2.5 emissions and correspondingly, decreased the predicted relative importance of other emission source categories. We conclude that the variations of emission-exposure relationship and toxicity between various source categories had significant impacts for the assessment on premature deaths caused by primary PM_2.5.     

Sea salt concentrations across the European continent

The oceans are a major source for particles that play an important role in many atmospheric processes. In Europe sea salt may contribute significantly to particulate matter concentrations. We have compiled sodium concentration data as a tracer for sea salt for 89 sites in Europe to provide more insight in the distribution of sea salt across Europe. The annual average sea salt concentrations above land were estimated to range between 0.3 and almost 13 μg m^?3. Maximum concentrations are found at the Irish coast. At coastal sites along the Atlantic and North Sea coast concentrations tend to be around 5 μg m^?3. More inland locations up to about 300 km away from the coast tend to show concentrations between 2 and 5 μg m^?3, whereas sites further away from the coast are characterized by lower concentrations. An analysis of the representativity of the data with respect to a long term average showed that the long average is associated with a standard deviation of around 15%. The compilation of observations provides an improved overview of sea salt concentrations in Europe as well as an improved basis for model validation. Verification of the results of the LOTOS-EUROS model learned that the model represents well the spatial variability of the observed sea salt concentrations very well. However, the absolute concentrations are significantly overestimated due to large uncertainties in the emission and dry deposition parameterizations. Using the high explained variability in the gradients across Europe, the bias-corrected modelled distribution serves as a best estimate of the sea salt distribution across Europe for 2005.     

Sustainable development in a natural resource rich economy: the case of Chile in 1985–2004

Searching for practical means to assessing economic growth’s sustainability, we extend a standard theoretical model to calculate “true” income measures for Chile, during the 1985–2004 period, and use estimates of natural capital depreciation to obtain genuine national saving measures. We found that, for the period, Chile’s economic growth was sustainable, even when approximately 2.5% of the income recorded by national accounts corresponded to depreciation of natural resources plus costs of atmospheric pollution. This performance can be partially explained by policies implemented to force fiscal responsibility and to assure wise public investment and expending during a natural resource driven growth. This evidence reinforces recent findings contradicting the natural resource curse, and the indirect negative effect of resource abundance over growth that would operate through the quality of institutions.     

Sea-level rise vulnerability in the countries of the Coral Triangle

Sea-level rise is a major threat facing the Coral Triangle countries in the twenty-first century. Assessments of vulnerability and adaptation that consider the interactions among natural and social systems are critical to identifying habitats and communities vulnerable to sea-level rise and for supporting the development of adaptation strategies. This paper presents such an assessment using the DIVA model and identifies vulnerable coastal regions and habitats in Coral Triangle countries at national and sub-national levels (administrative provinces). The following four main sea-level rise impacts are assessed in ecological, social and economic terms over the twenty-first century: (1) coastal wetland change, (2) increased coastal flooding, (3) increased coastal erosion, and (4) saltwater intrusion into estuaries and deltas. The results suggest that sea-level rise will significantly affect coastal regions and habitats in the Coral Triangle countries, but the impacts will differ across the region in terms of people flooded annually, coastal wetland change and loss, and damage and adaptation costs. Indonesia is projected to be most affected by coastal flooding, with nearly 5.9 million people expected to experience flooding annually in 2100 assuming no adaptation. However, if adaptation is considered, this number is significantly reduced. By the end of the century, coastal wetland loss is most significant for Indonesia in terms of total area lost, but the Solomon Islands are projected to experience the greatest relative loss of coastal wetlands. Damage costs associated with sea-level rise are highest in the Philippines (US $6.5 billion/year) and lowest in the Solomon Islands (US $70,000/year). Adaptation is estimated to reduce damage costs significantly, in particular for the Philippines, Indonesia, and Malaysia (between 68 and 99%). These results suggest that the impacts of sea-level rise are likely to be widespread in the region and adaptation measures must be broadly applied.