South Pole Antarctica observations and modeling results: New insights on HOx radical and sulfur chemistry

Measurements of OH, H₂SO₄, and MSA at South Pole (SP) Antarctica were recorded as a part of the 2003 Antarctic Chemistry Investigation (ANTCI 2003). The time period 22 November, 2003–2 January, 2004 provided a unique opportunity to observe atmospheric chemistry at SP under both natural conditions as well as those uniquely defined by a solar eclipse event. Results under natural solar conditions generally confirmed those reported previously in the year 2000. In both years the major chemical driver leading to large scale fluctuations in OH was shifts in the concentration levels of NO. Like in 2000, however, the 2003 observational data were systematically lower than model predictions. This can be interpreted as indicating that the model mechanism is still missing a significant HO_x sink reaction(s); or, alternatively, that the OH calibration source may have problems. Still a final possibility could involve the integrity of the OH sampling scheme which involved a fixed building site. As expected, during the peak in the solar eclipse both NO and OH showed large decreases in their respective concentrations. Interestingly, the observational OH profile could only be approximated by the model mechanism upon adding an additional HO_x radical source in the form of snow emissions of CH₂O and/or H₂O₂. This would lead one to think that either CH₂O and/or H₂O₂ snow emissions represent a significant HO_x radical source under summertime conditions at SP. Observations of H₂SO₄ and MSA revealed both species to be present at very low concentrations (e.g., 5 × 10⁵ and 1 × 10⁵ molec cm^?3, respectively), but similar to those reported in 2000. The first measurements of SO₂ at SP demonstrated a close coupling with the oxidation product H₂SO₄. The observed low concentrations of MSA appear to be counter to the most recent thinking by glacio-chemists who have suggested that the plateau's lower atmosphere should have elevated levels of MSA. We speculate here that the absence of MSA may reflect efficient atmospheric removal mechanisms for this species involving either dynamical and/or chemical processes.     

Use of CALPUFF for exposure assessment in a near-field,complex terrain setting

CALPUFF is an atmospheric source-receptor model recommended by the U.S. Environmental Protection Agency for use on a case-by-case basis in complex terrain and wind conditions. The ability of the model to provide useful information for exposure assessments in areas with those topographical and meteorological conditions has received little attention. This is an important knowledge gap for use of CALPUFF outside of regulatory applications, such as exposure analyses conducted in support of risk assessments and health studies. We compared deposition of cadmium (Cd), lead (Pb), and zinc (Zn) calculated with CALPUFF as a result of emissions from a zinc smelter with corresponding concentrations of the metals measured in attic dust and soil samples obtained from the surrounding area. On a point-by-point analysis, predictions from CALPUFF explained 11% (lead) to 53% (zinc) of the variability in concentrations measured in attic dust. Levels of heavy metals in soil interpolated to 100 residential addresses from the distribution of concentrations measured in soil samples also agreed well with deposition predicted with CALPUFF: R² of 0.46, 0.76, and 079 for Pb, Cd, and Zn, respectively. Community-average concentrations of Cd, Pb, and Zn measured in soil were significantly (p < 0.0001) and strongly correlated (R² ranged from 0.77 to 0.98) with predicted deposition rates. These findings demonstrate that CALPUFF can provide reasonably accurate predictions of the patterns of long-term air pollutant deposition in the near-field associated with emissions from a discrete source in complex terrain. Because deposition estimates are calculated as a linear function of air concentrations, CALPUFF is expected to be reliable model for prediction of long-term average, near-field ambient air concentrations in complex terrain as well.     

Characterisation of particulate exposure during fireworks displays

Little is known about the level and content of exposure to fine particles (PM_2.5) among persons who attend fireworks displays and those who live nearby. An evaluation of the levels of PM_2.5 and their elemental content was carried out during the nine launches of the 2007 Montréal International Fireworks Competition. For each event, a prediction of the location of the firework plume was obtained from the Canadian Meteorological Centre (CMC) of the Meteorological Service of Canada. PM_2.5 was measured continuously with a photometer (Sidepak?, TSI) within the predicted plume location (“predicted sites”), and integrated samples were collected using portable personal samplers. An additional sampler was located on a nearby roof (“fixed site”). The elemental composition of the collected PM_2.5 samples from the “predicted sites” was determined using both a non-destructive energy dispersive ED-XRF method and an ICP-MS method with a near-total microwave-assisted acid digestion. The elemental composition of the “fixed site” samples was determined by the ICP-MS with the near-total digestion method. The highest PM_2.5 levels reached nearly 10 000 μg m^?3, roughly 1000 times background levels. Elements such as K, Cl, Al, Mg and Ti were markedly higher in plume-exposed filters. This study shows that 1) persons in the plume and in close proximity to the launch site may be exposed to extremely high levels of PM_2.5 for the duration of the display and, 2) that the plume contains specific elements for which little is known of their acute cardio-respiratory toxicity.     

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 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.     

Airborne molds and mycotoxins associated with handling of corn silage and oilseed cakes in agricultural environment

In agricultural areas, the contamination of feedstuffs with molds and mycotoxins presents major environmental and health concerns. During cattle feeding, fungi and mycotoxins were monitored in corn silage, oilseed cakes and bioaerosols collected in Normandy. Most of the corn silages were found to be contaminated by deoxynivalenol (mean concentration: 1883 μg kg^?1) while a few of oilseed cakes were contaminated by alternariol, fumonisin B₁ or gliotoxin. In ambient bioaerosols, the values for fungi per cubic meter of air varied from 4.3 × 10² to 6.2 × 10⁵ cfu m^?3. Seasonal variations were observed with some species like Aspergillus fumigatus which significantly decreased between the 2 seasons (P = 0.0186) while the Penicillium roqueforti group significantly increased during the second season (P = 0.0156). In the personal bioaerosols, the values for fungi per cubic meter of air varied from 3.3 10³ to 1.7 10⁶ cfu m^?3 and the number of A. fumigatus spores significantly decreased between the 2 seasons (P = 0.0488). Gliotoxin, an immunosuppressive mycotoxin, was quantified in 3 personal filters at 3.73 μg m^?3, 1.09 μg m^?3 and 2.97 μg m^?3.     

Overcoming latecomer disadvantage through learning processes: Taiwan’s venture into wind power development

Research into national innovation systems (NISs) has received extensive academic and policy attention, and is especially relevant with latecomer countries seeking to innovate in challenging industrial environments. In playing catch up with their early industrializing counterparts, methods of learning take on increased importance in determining industrial success for latecomers. The wind turbine technology innovation system is one that is highly dependent on both the extent of the national learning processes and the strength of the national social-institutional setting. This research investigates the case of Taiwan, a country which has embarked on a program to build its national innovative capacity in wind turbine technologies with specific emphasis on Taiwan’s social sector. Within this system, the spotlight will be on four types of learning processes that interplay during wind turbine development: learning by searching, learning by doing, learning by using, and learning by interacting. Through a case study of the emergence of Taiwan’s burgeoning large-scale wind power technology initiatives, the paper aims to add to the understanding on how methods of learning impact upon the success of innovation systems. The findings show that the industry’s future prospects are constrained because of the limited learning by interacting processes between turbine component producers, turbine owners, and researchers and because of weaknesses in the institutional framework. This research also recognizes the importance that culture has on dominant forms of learning.     

Sex-specific predation on two lizard species by kestrels

Sex-biased predation is thought to have important implications for sexual selection, sex allocation, and population dynamics (Magnhagen, 1991; Le-Galliard et al., 2005 for an example in lizards). Most studies found that males are subjected to higher predation pressure than females during the reproductive season (Korpimäki, 1985; Lodé et al., 2004; Christe et al., 2006; Costantini et al., 2007). In that period, males are very mobile, emit acoustic signals and exhibit brilliant colourations, which are needed to attract females but may make them more visible to predators. With regard to lizards, a recent study provided the first evidence that males of a lizard species may be preyed on more than females (Costantini et al., 2007). In the present study, we investigated whether there is sex-biased predation on two small lacertid species, the common wall lizard Podarcis muralis (Laurenti, 1768) and the Italian wall lizard Podarcis sicula (Rafinesque-Schmaltz, 1810), by Eurasian kestrels (Falco tinnunculus) during the reproductive season. We also examined whether (1) the rate of predation differed between species and (2) the rate of predation differed across years or among hunting habitats for each species.     

Evaluating The National Land Cover Database Tree Canopy and Impervious Cover Estimates Across the Conterminous United States: A Comparison with Photo-Interpreted Estimates

The 2001 National Land Cover Database (NLCD) provides 30-m resolution estimates of percentage tree canopy and percentage impervious cover for the conterminous United States. Previous estimates that compared NLCD tree canopy and impervious cover estimates with photo-interpreted cover estimates within selected counties and places revealed that NLCD underestimates tree and impervious cover. Based on these previous results, a wall-to-wall comprehensive national analysis was conducted to determine if and how NLCD derived estimates of tree and impervious cover varies from photo-interpreted values across the conterminous United States. Results of this analysis reveal that NLCD significantly underestimates tree cover in 64 of the 65 zones used to create the NCLD cover maps, with a national average underestimation of 9.7% (standard error (SE) = 1.0%) and a maximum underestimation of 28.4% in mapping zone 3. Impervious cover was also underestimated in 44 zones with an average underestimation of 1.4% (SE = 0.4%) and a maximum underestimation of 5.7% in mapping zone 56. Understanding the degree of underestimation by mapping zone can lead to better estimates of tree and impervious cover and a better understanding of the potential limitations associated with NLCD cover estimates.