In situ experimental study of carbon monoxide generation by gasoline-powered electric generator in an enclosed space

On the basis of currently available data, approximately 97% of generator-related carbon monoxide (CO) fatalities are caused by operating currently marketed, carbureted spark-ignited gasoline-powered generators (not equipped with emission controls) in enclosed spaces. To better understand and to reduce the occurrence of these fatalities, research is needed to quantify CO generation rates, develop and test CO emission control devices, and evaluate CO transport and exposure when operating a generator in an enclosed space. As a first step in these efforts, this paper presents measured CO generation rates from a generator without any emission control devices operating in an enclosed space under real weather conditions. This study expands on previously published information from the U.S. Consumer Product Safety Commission. Thirteen separate tests were conducted under different weather conditions at half and full generator load settings. It was found that the CO level in the shed reached a maximum value of 29,300 +/- 580 mg/m3, whereas the oxygen (O2) was depleted to a minimum level of 16.2 +/- 0.02% by volume. For the test conditions of real weather and generator operation, the CO generation and the O2 consumption could be expressed as time-averaged generation/consumption rates. It was also found that the CO generation and O2 consumption rates can be correlated to the O2 levels in the space and the actual load output from the generator. These correlations are shown to agree well with the measurements.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Modeling the surface–atmosphere exchange of ammonia

New parameterizations for surface–atmosphere exchange of ammonia are presented for application in atmospheric transport models and compared with parameterizations of the literature. The new parameterizations are based on a combination of the results of three years of ammonia flux measurements over a grassland canopy (dominated by Lolium perenne and Poa trivialis) near Wageningen, the Netherlands and existing parameterizations from literature. First, a model for the surface–atmosphere exchange of ammonia that includes the concentration at the external leaf surface is derived and validated. Second, a parameterization for the stomatal compensation point (expressed as Γ_s, the ratio of [NH₄⁺]/[H⁺] in the leaf apoplast) that accounts for the observed seasonal variation is derived from the measurements. The new, temperature-dependent Γ_s describes the observed seasonal behavior very well. It is noted, however, that senescence of plants and field management practices will also influence the seasonal variation of Γ_s on a shorter timescale. Finally, a relation that links Γ_s to the atmospheric pollution level of the location through the ‘long-term’ NH₃ concentration in the air is proposed.     

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.     

Spatial variability of carbonaceous aerosols and associated source tracers in two cites in the Midwestern United States

Semi-continuous and 24-h averaged measurements of fine carbonaceous aerosols were made concurrently at three sites within each of two U.S. Midwestern Cities; Detroit, Michigan and Cleveland, Ohio; during two, one-month intensive campaigns conducted in July of 2007 and January & February of 2008. A comparison of 24-h measurements revealed substantial intra-urban variability in carbonaceous aerosols consistent with the influence of local sources, and excesses in both PM_2.5 organic carbon (OC) and elemental carbon (EC) were identified at individual sites within each city. High time-resolved black carbon (BC) measurements indicated that elemental carbon concentrations were higher at sites adjacent to freeways and busy surface streets, and temporal patterns suggested that excess EC at sites adjacent to freeways was dominated by mobile source emissions while excesses in EC away from traffic corridors was dominated by point/area source emissions. The site-to-site variability in OC concentrations was approximately 7% within the neighborhood scale (0.5–4 km) and between 4 and 27% at the urban scale (4–100 km). In contrast, measurements of organic source tracers, in conjunction with a Chemical Mass Balance (CMB) source-apportionment model, indicated that the spatial variation in the contribution of both mobile and stationary sources to PM_2.5 OC often exceeded the variation in OC mass concentration by a factor of 3 or more. Markers for mobile sources, biomass smoke, natural gas, and coal combustion differed by as much as 60% within the neighborhood scale and by greater than 200% within the urban scale. The observations made during this study suggest that the urban excess of carbonaceous aerosols is much more complex than has been previously reported and that a more rigorous, source-oriented approach should be taken in order to assess the risk associated with exposure to carbonaceous aerosols within the industrialized environments of the Midwestern United States.     

A contribution of brown carbon aerosol to the aerosol light absorption and its radiative forcing in East Asia

Brown carbon aerosols were recently found to be ubiquitous and effectively absorb solar radiation. We use a 3-D global chemical transport model (GEOS-Chem) together with aircraft and ground based observations from the TRACE-P and the ACE-Asia campaigns to examine the contribution of brown carbon aerosol to the aerosol light absorption and its climatic implication over East Asia in spring 2001. We estimated brown carbon aerosol concentrations in the model using the mass ratio of brown carbon to black carbon (BC) aerosols based on measurements in China and Europe. The comparison of simulated versus observed aerosol light absorption showed that the model accounting for brown carbon aerosol resulted in a better agreement with the observations in East Asian-Pacific outflow. We then used the model results to compute the radiative forcing of brown carbon, which amounts up to ?2.4 W m^?2 and 0.24 W m^?2 at the surface and at the top of the atmosphere (TOA), respectively, over East Asia. Mean radiative forcing of brown carbon aerosol is ?0.43 W m^?2 and 0.05 W m^?2 at the surface and at the TOA, accounting for about 15% of total radiative forcing (?2.2 W m^?2 and 0.33 W m^?2) by absorbing aerosols (BC + brown carbon aerosol), having a significant climatic implication in East Asia.     

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.     

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.     

Do EU pesticide standards promote environmentally-friendly production of fresh export vegetables in developing countries? The evidence from Kenyan green bean industry

Developed countries are major markets for developing country fresh produce. Demand by developed country consumers for spotless produce has encouraged developing country consumers to rely increasingly on pesticides in producing fresh export vegetables. However developed country pesticide standards enacted in response to reports of increased farmer and farm worker pesticide poisoning and the food safety scandals of the 1980s and 1990s require changes in the way growers use pesticides. The EU has especially developed stringent food safety standards relating to, among other things, pesticide usage. Under EU pesticide standards (EU-PS) farmers are trained by their buyers on safe use of pesticides and then closely monitored under contract. This paper looks at the impact of these standards on developing country farmers’ use of alternative pest management practices, pesticide protective clothing and the actual usage of pesticides. It finds that compliance with EU-PS increases the use of alternative pest management practices and protective clothing. However, EU-PS has mixed effect on the quantity of pesticides used. The paper also finds that farmer’s education and access to information play an important role in the use of alternative pest management practices. The paper concludes that EU-PS encourage the use of alternative pest management practices and pesticide protective gear in production of fresh export vegetables. The findings imply that EU-PS promote environmentally-friendly methods of production of fresh export vegetables in developing countries.     

Sustainable nations: what do aggregate indexes tell us?

What is a ‘sustainable nation’ and how can we identify and rank ‘sustainable nations?’ Are nations producing and consuming in a sustainable way? Although several aggregate indexes have been proposed to answer such questions, comprehensive and internationally comparable data are not available for most of these. This paper quantitatively compares three aggregate indexes of sustainability: the World Bank’s ‘Genuine Savings’ measure, the ‘Ecological Footprint,’ and the ‘Environmental Sustainability Index.’ These three indexes are available for a large number of countries and also seem to be the most influential among the aggregate indexes. This paper first discusses the main limitations and weaknesses of each of these indexes. Subsequently, it shows that rankings of sustainable nations and aggregate assessments of unsustainable world population and world GDP shares vary considerably among these indexes. This disagreement leads to suggestions for analysis and policy. One important insight is that climate change, arguable the most serious threat currently faced by humanity, is not or arbitrarily captured by the indexes.