The influence of sampling protocol on nonmethane hydrocarbon mixing ratios

The effect of sampling protocol on ambient air hydrocarbon mixing ratios was examined on eight sampling days in Los Angeles during 2007 and 2008. Four protocols, which were based on previously published multi-city urban hydrocarbon studies in the United States, were compared and differences were quantified. Whole air canister samples were collected and analyzed for nonmethane hydrocarbons (NMHCs). Differing sampling protocols resulted in large differences in mixing ratios, up to an order of magnitude, for certain NMHCs on the same sampling day. However, the magnitude of the variability between NMHC levels obtained by the four protocols was not consistent throughout the eight sampling days. It was found that sampling time, followed by sampling location, had the greatest influence on the magnitude of the mixing ratio. Ratios between hydrocarbons, often used in urban studies to gain information on emission sources, also varied depending on the protocol used. Comparison of absolute NMHC mixing ratios collected in urban environments using differing sampling protocols should be made with care.     

On-road traffic emissions in a megacity

A new annual bottom–up emission inventory of criteria pollutants and greenhouse gases from on-road mobile sources was developed for 2006 for the metropolitan area of Buenos Aires, Argentina, within a four-year regional project aimed at providing tools for chemical weather forecast in South America. Under the scarcity of local emission factors, we collected data from measuring campaigns performed in Argentina, Brazil, Chile and Colombia and compiled a data set of regional emission factors representative of Latin American fleets and driving conditions. The estimated emissions were validated with respect to downscaled national estimates and the EDGAR global emission database. Our results highlight the role of older technologies accounting in average for almost 80% of the emissions of all species. The area exhibits higher specific emissions than developed countries, with figures two times higher for criteria pollutants. We analyzed the effect on emissions of replacing gasoline by compressed natural gas, occurring in Argentina since 1995. We identified (i) a relationship between number of vehicles and a compound socioeconomic indicator, and (ii) time-lags in vehicle technologies between developed and developing countries, which can be respectively applied for spatial disaggregation and the development of projections for other Latin American cities. The results may also be employed to complement global emission inventories and by local policy makers as an environmental management tool.     

Influence of regional development policies and clean technology adoption on future air pollution exposure

Future air pollution emissions in the year 2030 were estimated for the San Joaquin Valley (SJV) in central California using a combined system of land use, mobile, off-road, stationary, area, and biogenic emissions models. Four scenarios were developed that use different assumptions about the density of development and level of investment in transportation infrastructure to accommodate the expected doubling of the SJV population in the next 20 years. Scenario 1 reflects current land-use patterns and infrastructure while scenario 2 encouraged compact urban footprints including redevelopment of existing urban centers and investments in transit. Scenario 3 allowed sprawling development in the SJV with reduced population density in existing urban centers and construction of all planned freeways. Scenario 4 followed currently adopted land use and transportation plans for the SJV. The air quality resulting from these urban development scenarios was evaluated using meteorology from a winter stagnation event that occurred on December 15th, 2000 to January 7th 2001. Predicted base-case PM2.5 mass concentrations within the region exceeded 35 μg m^?3 over the 22-day episode. Compact growth reduced the PM2.5 concentrations by ～1 μg m^?3 relative to the base-case over most of the SJV with the exception of increases (～1 μg m^?3) in urban centers driven by increased concentrations of elemental carbon (EC) and organic carbon (OC). Low-density development increased the PM2.5 concentrations by 1–4 μg m^?3 over most of the region, with decreases (0.5–2 μg m^?3) around urban areas. Population-weighted average PM2.5 concentrations were very similar for all development scenarios ranging between 16 and 17.4 μg m^?3. Exposure to primary PM components such as EC and OC increased 10–15% for high density development scenarios and decreased by 11–19% for low-density scenarios. Patterns for secondary PM components such as nitrate and ammonium ion were almost exactly reversed, with a 10% increase under low-density development and a 5% decrease under high density development. The increased human exposure to primary pollutants such as EC and OC could be predicted using a simplified analysis of population-weighted primary emissions. Regional planning agencies should develop thresholds of population-weighted primary emissions exposure to guide the development of growth plans. This metric will allow them to actively reduce the potential negative impacts of compact growth while preserving the benefits.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

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.     

Hydrocarbon emission fingerprints from contemporary vehicle/engine technologies with conventional and new fuels

The present paper presents results from the analysis of 29 individual C₂–C₉ hydrocarbons (HCs) specified in the European Commission Ozone Directive. The 29 HCs are measured in exhaust from common, contemporary vehicle/engine/fuel technologies for which very little or no data is available in the literature. The obtained HC emission fingerprints are compared with fingerprints deriving from technologies that are being phased out in Europe. Based on the total of 138 emission tests, thirteen type-specific fingerprints are extracted (Mean ± SD percentage contributions from individual HCs to the total mass of the 29 HCs), essential for receptor modelling source apportionment. The different types represent exhaust from Euro3 and Euro4 light-duty (LD) diesel and petrol-vehicles, Euro3 heavy-duty (HD) diesel exhaust, and exhaust from 2-stroke preEuro, Euro1 and Euro2 mopeds. The fuels comprise liquefied petroleum gas, petrol/ethanol blends (0–85% ethanol), and mineral diesel in various blends (0–100%) with fatty acid methyl esters, rapeseed methyl esters palm oil methyl esters, soybean oil methyl or sunflower oil methyl esters. Type-specific tracer compounds (markers) are identified for the various vehicle/engine/fuel technologies.An important finding is an insignificant effect on the HC fingerprints of varying the test driving cycle, indicating that combining HC fingerprints from different emission studies for receptor modelling purposes would be a robust approach.The obtained results are discussed in the context of atmospheric ozone formation and health implications from emissions (mg km^?1 for LD and mopeds and mg kW h^?1 for HD, all normalised to fuel consumption: mg dm^?3 fuel) of the harmful HCs, benzene and 1,3-butadiene.Another important finding is a strong linear correlation of the regulated “total” hydrocarbon emissions (tot-HC) with the ozone formation potential of the 29 HCs (ΣPO₃ = (1.66 ± 0.04) × tot-RH; r² = 0.93). Tot-HC is routinely monitored in emission control laboratories, whereas C₂–C₉ are not. The revealed strong correlations broadens the usability of data from vehicle emission control laboratories and facilitates the comparison of the ozone formation potential of HCs in exhaust from of old and new vehicle/engine/fuel technologies.     

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.     

High and low value fish chains in the Mekong Delta: challenges for livelihoods and governance

This paper investigates the structure, function and wealth distribution within the Pangasius hypophthalmus and Henicorhynchus spp./Labiobarbus spp. value chains in the Mekong Delta of Vietnam. The analysis is driven by key questions relating to the form and function of value chains, their contribution to the livelihoods of farmers and fishers, the effectiveness of government policy and the potential for value chain governance mechanisms, such as contracts and certification, to steer towards sustainable production. The results indicate that actors in the high value Pangasius hypopthalmus export chain have a higher potential income, but face considerably higher economic vulnerability from global markets. Alternatively, Henichorhychus/Labiobarbus spp. fishers are severely constrained in their ability to negotiate higher prices for their fish but appear to be less vulnerable to economic and environmental change. The paper concludes that for value chain governance to improve the livelihoods of fishers and farmers in both high and low value chains, new arrangements are needed that better accommodate customary institutions and informal market relations.     

Universal criteria for assessing the ecological state of soil algocenoses

A set of criteria allowing demarcation between algocenoses is proposed. These criteria characterize the species composition, group of dominants, and taxonomic and ecological structure of algocenoses.