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.     

Prymnesium parvum: The Texas Experience1

Southard, Gregory M., Loraine T. Fries, and Aaron Barkoh, 2010. Prymnesium parvum: The Texas Experience. Journal of the American Water Resources Association (JAWRA) 46(1):14-23. DOI: 10.1111/j.1752-1688.2009.00387.x Abstract: Golden alga Prymnesium parvum was first identified in Texas during a fish kill investigation on the Pecos River in 1985. Since then golden alga kills occurred sporadically in a variety of waters in the western part of the state until 2001 when the alga became endemic in the Brazos, Canadian, Colorado, Red, and Rio Grande river systems, including the water supplies of two public fish hatcheries, the Possum Kingdom and Dundee state fish hatcheries. The increasing area adversely affected by the alga and frequent massive fish kills heightened public and political awareness and concerns regarding the ecological and economic impacts of P. parvum blooms. The Texas Parks and Wildlife Department (TPWD), the wildlife conservation agency of the state, responded to these concerns with a program to assess the ecological and economic impacts and to develop management options. To date 33 water bodies have been affected and losses are conservatively estimated at 34 million fish valued at US$13 million. Several sport fisheries, including smallmouth bass Micropterus dolomieu, striped bass Morone saxatilis, channel catfish Ictalurus punctatus, and blue catfish Ictalurus furcatus, have been severely affected. Additionally, 26 imperiled fish species occur in the affected water basins and some have been adversely affected. Economic losses associated with reduced fishing and other water-based recreational activities appear considerable. The combined economic losses to three counties (Palo Pinto, Stephens, and Young) surrounding Possum Kingdom reservoir for 2001 and 2003 were estimated at US$2.8 million and US$1.1 million, respectively. This paper describes how the TPWD responded to public and political concerns relative to the emergence of golden alga, its harmful effects to fisheries, and its historic and current statewide distribution.     

Reclaimed Mineland Curve Number Response to Temporal Distribution of Rainfall1

Warner, Richard C., Carmen T. Agouridis, Page T. Vingralek, and Alex W. Fogle, 2010. Reclaimed Mineland Curve Number Response to Temporal Distribution of Rainfall. Journal of the American Water Resources Association (JAWRA) 46(4): 724-732. DOI: 10.1111/j.1752-1688.2010.00444.x Abstract: The curve number (CN) method is a common technique to estimate runoff volume, and it is widely used in coal mining operations such as those in the Appalachian region of Kentucky. However, very little CN data are available for watersheds disturbed by surface mining and then reclaimed using traditional techniques. Furthermore, as the CN method does not readily account for variations in infiltration rates due to varying rainfall distributions, the selection of a single CN value to encompass all temporal rainfall distributions could lead engineers to substantially under- or over-size water detention structures used in mining operations or other land uses such as development. Using rainfall and runoff data from a surface coal mine located in the Cumberland Plateau of eastern Kentucky, CNs were computed for conventionally reclaimed lands. The effects of temporal rainfall distributions on CNs was also examined by classifying storms as intense, steady, multi-interval intense, or multi-interval steady. Results indicate that CNs for such reclaimed lands ranged from 62 to 94 with a mean value of 85. Temporal rainfall distributions were also shown to significantly affect CN values with intense storms having significantly higher CNs than multi-interval storms. These results indicate that a period of recovery is present between rainfall bursts of a multi-interval storm that allows depressional storage and infiltration rates to rebound.     

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.     

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.     

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.     

Influence of roads and inhabited areas on metal concentrations in terrestrial mosses

The guidelines regarding sampling terrestrial mosses for biomonitoring the atmospheric contamination in a region specifically recommend that sampling close to focal points of contamination (i.e. roads, populated areas, etc.) should be avoided for satisfactory characterization of general patterns of contamination. However, these recommendations cannot always be followed in many parts of the world with dense, highly dispersed populations. The aim of the present study was to determine how the distances between sampling sites (SS) and contamination foci such as roads, isolated houses and urban nuclei affect regular, large-scale sampling networks. Metal concentrations obtained in biennial sampling surveys carried out between 2000 and 2006 in Galicia (NW Spain) were used, and the relative proportions of the concentrations corresponding to small-scale and large-scale processes were calculated. The possible relationship between the mean concentrations corresponding to small-scale processes in the different sampling surveys and the distances from SS to roads, buildings and urban nuclei was established by a GIS. Outliers in the data were identified at many of the SS and frequency statistics revealed the absence of any relationship between the distance to these foci and the concentrations of metals in the moss. The method also revealed many instances of the influence of one or more small-scale contamination foci such as airports and railways (often not considered in the sampling recommendations) on SS. Relocation of such SS would improve the representativeness of the sampling grid.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.     

Polycyclic aromatic hydrocarbons in air on small spatial and temporal scales – II. Mass size distributions and gas-particle partitioning

Polycyclic aromatic hydrocarbons (PAHs) were measured together with inorganic air pollutants at two urban sites and one rural background site in the Banja Luka area, Bosnia and Hercegovina, during 72 h in July 2008 using a high time resolution (5 samples per day) with the aim to study gas-particle partitioning, aerosol mass size distributions and to explore the potential of a higher time resolution (4 h-sampling).In the particulate phase the mass median diameters of the PAHs were found almost exclusively in the accumulation mode (0.1–1.0 μm of size). These were larger for semivolatile PAHs than for non-volatile PAHs. Gas-particle partitioning of semivolatile PAHs was strongly influenced by temperature. The results suggest that the Junge–Pankow model is inadequate to explain the inter-species variation and another process must be significant for phase partitioning which is less temperature sensitive than adsorption. Care should be taken when interpreting slopes m of plots of the type log K_p = m log p_L⁰ + b based on 24 h means, as these are found sensitive to the time averaging, i.e. tend to be higher than when based on 12 h-mean samples.     

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.