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.     

Denitrification in anaerobic lagoons used to treat swine wastewater

Anaerobic lagoons are commonly used for the treatment of swine wastewater. Although these lagoons were once thought to be relatively simple, their physical, chemical, and biological processes are very complex. This study of anaerobic lagoons had two objectives: (i) to quantify denitrification enzyme activity (DEA) and (ii) to evaluate the influence of lagoon characteristics on the DEA. The DEA was measured by the acetylene inhibition method. Wastewater samples and physical and chemical measurements were taken from the wastewater column of nine anaerobic swine lagoons from May 2006 to May 2009. These lagoons were typical for anaerobic swine lagoons in the Carolinas relative to their size, operation, and chemical and physical characteristics. Their mean value for DEA was 87 mg N2O-N m(-3) d(-1). In a lagoon with 2-m depth, this rate of DEA would be compatible with 1.74 kg N ha(-1) d(-1) When nonlimiting nitrate was added, the highest DEA was compatible with 4.38 kg N ha(-1) d(-1) loss. Using stepwise regression for this treatment, the lagoon characteristics (i.e., soluble organic carbon, total nitrogen, temperature, and NO3-N) provided a final step model R2 of 0.69. Nitrous oxide from incomplete denitrification was not a significant part of the system nitrogen balance. Although alternate pathways of denitrification may exist within or beneath the wastewater column, this paper documents the lack of sufficient denitrification enzyme activity within the wastewater column of these anaerobic lagoons to support large N2 gas losses via classical nitrification and denitrification.     

Oxidative enzymes in tissues of the catfish (<Emphasis Type="Italic">Clarias gariepinus</Emphasis>) exposed to varying levels of cadmium

The activities of some oxidative enzymes (aldehyde oxidase, AO, EC 1.2.3.1; xanthine oxidase, XO, EC 1.17.3.2; sulphite oxidase, SO, EC 1.8.3.1; and monoamine oxidase, MO, EC 1.4.3.4) were investigated in the liver, gill, kidney, brain and muscle of a variety of African catfish (Clarias gariepinus) after 7 and 21 days of exposure to 0.1, 0.2 and 0.4 ppm cadmium (Cd) in ambient water. MO, SO and AO activities were significantly (p < 0.05) decreased in a dose-dependent manner in the liver, kidney and gill in the 7-day Cd-exposed fish when compared to control. Conversely, brain MO, AO and SO activities were significantly (p < 0.05) elevated in a dose-dependent manner in the same fishes relative to control. As in the 7-day Cd-exposed fish, the activities of MO, AO and SO were significantly (p < 0.05) decreased in a dose-dependent manner in the gill, kidney and liver of catfish exposed for 21 days. Same is true for XO in these organs after both duration of exposure, except in the liver where no significant change was observed relative to control. The inhibition of these oxidative enzymes in the liver, gill and kidney of catfish may interfere with their biotransformation function, and ultimately the survival of the fish may be compromised.