Multispecies remote sensing measurements of vehicle emissions on Sherman Way in Van Nuys,California

As part of the 2010 Van Nuys tunnel study, researchers from the University of Denver measured on-road fuel-specific light-duty vehicle emissions from nearly 13,000 vehicles on Sherman Way (0.4 miles west of the tunnel) in Van Nuys, California, with its multispecies Fuel Efficiency Automobile Test (FEAT) remote sensor a week ahead of the tunnel measurements. The remote sensing mean gram per kilogram carbon monoxide (CO), hydrocarbon (HC), and oxide of nitrogen (NO_x) measurements are 8.9% lower, 41% higher, and 24% higher than the tunnel measurements, respectively. The remote sensing CO/NO_x and HC/NO_x mass ratios are 28% lower and 20% higher than the comparable tunnel ratios. Comparisons with the historical tunnel measurements show large reductions in CO, HC, and NO_x over the past 23 yr, but little change in the HC/NO_x mass ratio since 1995. The fleet CO and HC emissions are increasingly dominated by a few gross emitters, with more than a third of the total emissions being contributed by less than 1% of the fleet. An example of this is a 1995 vehicle measured three times with an average HC emission of 419 g/kg fuel (two-stroke snowmobiles average 475 g/kg fuel), responsible for 4% of the total HC emissions. The 2008 economic downturn dramatically reduced the number of new vehicles entering the fleet, leading to an age increase (>1 model year) of the Sherman Way fleet that has increased the fleet's ammonia (NH₃) emissions. The mean NH₃ levels appear little changed from previous measurements collected in the Van Nuys tunnel in 1993. Comparisons between weekday and weekend data show few fleet differences, although the fraction of light-duty diesel vehicles decreased from the weekday (1.7%) to Saturday (1.2%) and Sunday (0.6%).

Implications: On-road remote sensing emission measurements of light-duty vehicles on Sherman Way in Van Nuys, California, show large historical emission reductions for CO and HC emissions despite an older fleet arising from the 2008 economic downturn. Fleet CO and HC emissions are increasingly dominated by a few gross emitters, with a single 1995 vehicle measured being responsible for 4% of the entire fleet's HC emissions. Finding and repairing and/or scrapping as little as 2% of the fleet would reduce on-road tailpipe emissions by as much as 50%. Ammonia emissions have locally increased with the increasing fleet age.     

Capacity of biochar application to maintain energy crop productivity: soil chemistry, sorghum growth, and runoff water quality effects

Pyrolysis of crop biomass generates a by-product, biochar, which can be recycled to sustain nutrient and organic C concentrations in biomass production fields. We evaluated effects of biochar rate and application method on soil properties, nutrient balance, biomass production, and water quality. Three replications of eight sorghum [ (L.) Moench] treatments were installed in box lysimeters under greenhouse conditions. Treatments comprised increasing rates (0, 1.5, and 3.0 Mg ha) of topdressed or incorporated biochar supplemented with N fertilizer or N, P, and K fertilizer. Simulated rain was applied at 21 and 34 d after planting, and mass runoff loss of N, P, and K was measured. A mass balance of total N, P, and K was performed after 45 d. Returning 3.0 Mg ha of biochar did not affect sorghum biomass, soil total, or Mehlich-3-extractable nutrients compared to control soil. Yet, biochar contributed to increased concentration of dissolved reactive phosphorus (DRP) and mass loss of total phosphorus (TP) in simulated runoff, especially if topdressed. It was estimated that up to 20% of TP in topdressed biochar was lost in surface runoff after two rain events. Poor recovery of nutrients during pyrolysis and excessive runoff loss of nutrients for topdressed biochar, especially K, resulted in negative nutrient balances. Efforts to conserve nutrients during pyrolysis and incorporation of biochar at rates derived from annual biomass yields will be necessary for biochar use in sustainable energy crop production.     

Long-Term Community Dynamics of Small Landbirds with and Without Exposure to Extensive Disturbance from Military Training Activities

Military training activities are known to impact individual species, yet our understanding of how such activities influence animal communities is limited. In this study, we used long-term data in a case study approach to examine the extent to which the local small landbird community differed between a site in northeast Kansas that experienced intensive disturbance from military training activities (Ft. Riley Military Installation) and a similar, nearby site that experienced minimal human disturbance (Konza Prairie Biological Station). In addition, we characterized how the regional pool of potential colonizers influenced local community dynamics using Breeding Bird Survey data. From 1991 to 2001, most species of small terrestrial landbirds (73%) recorded during breeding surveys were found at both sites and the mean annual richness at Ft. Riley (39.0 ± 2.86 [SD]) was very similar to that of Konza Prairie (39.4 ± 2.01). Richness was maintained at relatively constant levels despite compositional changes because colonizations compensated local extinctions at both sites. These dynamics were driven primarily by woodland species that exhibited stochastic losses and gains and were present at a low local and regional abundance. Our results suggest that military training activities may mimic natural disturbances for some species in this area because the small landbird community did not differ markedly between sites with and sites without extensive human disturbance. Although our results suggest that military training is not associated with large changes in the avian community, additional studies are needed to determine if this pattern is found in other ecological communities.     

Aerosol speciation and mass prediction from toluene oxidation under high NOx conditions

A kinetically based gas-particle partitioning box model is used to highlight the importance of parameter representation in the prediction of secondary organic aerosol (SOA) formation following the photo-oxidation of toluene. The model is initialized using experimental data from York University's indoor smog chamber and provides a prediction of the total aerosol yield and speciation. A series of model sensitivity experiments were performed to study the aerosol speciation and mass prediction under high NO_x conditions (VOC/NO_x = 0.2). Sensitivity experiments indicate vapour pressure estimation to be a large area of weakness in predicting aerosol mass, creating an average total error range of 70 μg m^?3 (range of 5–145 μg m^?3), using two different estimation methods. Aerosol speciation proved relatively insensitive to changes in vapour pressure. One species, 3-methyl-6-nitro-catechol, dominated the aerosol phase regardless of the vapour pressure parameterization used and comprised 73–88% of the aerosol by mass. The dominance is associated with the large concentration of 3-methyl-6-nitro-catechol in the gas-phase. The high NO_x initial conditions of this study suggests that the predominance of 3-methyl-6-nitro-catechol likely results from the cresol-forming branch in the Master Chemical Mechanism taking a significant role in secondary organic aerosol formation under high NO_x conditions. Further research into the yields and speciation leading to this reaction product is recommended.     

Impact of the Knudsen number and mass-transfer expression on multi-phase kinetic modeling

Three different mass-transfer expressions are employed within the Model of Aerosol, Gas, and Interfacial Chemistry (MAGIC) to study gas-phase molecular chlorine and bromine production from NaCl and NaBr aerosols, respectively. Simulations of chamber experiments are performed in which NaCl aerosols react with gas-phase ozone in the presence of UV light, in order to identify the importance of the Knudsen number and mass-transfer expression in systems with varying contributions from gas-phase, aqueous-phase, and interfacial chemistry. In the case of NaBr aerosols, simulations are performed of both dark and photolytic conditions. A range of Knudsen numbers spanning the continuum, transition and free-molecular regimes is studied. Particle size is varied over three orders of magnitude, and particle concentration is changed to keep either (a) total aerosol volume or (b) total aerosol surface area constant. When total aerosol volume is constant, the total amount of surface area available for interfacial reaction increases linearly with Knudsen number. Consequently peak gas-phase Cl₂ and Br₂ concentrations increase by two orders of magnitude from the continuum regime to the free-molecular regime. When total aerosol surface area is constant, total aerosol volume is inversely proportional to Knudsen number, with lesser volume being available at higher Knudsen numbers. Consequently Cl^? depletion in the kinetic regime leads to most gas-phase Cl₂ being produced in the transition regime. Gas-phase Br₂ concentration trends are determined by aqueous-phase reaction mechanisms, leading to a monotonic decrease in production with Knudsen number. At all Knudsen numbers, more gas-phase bromine is produced in the photolytic case than in the dark case, the difference being significant in the transition regime. Results of this study suggest that halogen production is insensitive to the mass-transfer expression used in the simulations.     

Seasonal and diurnal measurements of carbon monoxide and nonmethane hydrocarbons at Mt. Wilson,California: Indirect evidence of atomic Cl in the Los Angeles basin

We present a study of the seasonal and diurnal variability of carbon monoxide and selected volatile organic compounds in the Los Angeles area. Measurements were made during four different nine-day field campaigns in April/May, September, and November, 2007, and February, 2008, at the Mt. Wilson sampling site, which is located at an elevation of approximately 1700 m in the San Gabriel Mountains overlooking Pasadena and the Los Angeles basin. The results were used to characterize the Mt. Wilson site as a representative location for monitoring integrated Los Angeles basin emissions, and, by reference to carbon monoxide emissions, to estimate average annual emissions. The considerable seasonal variability of many hydrocarbons, in both their measured mixing ratios and their relationship to carbon monoxide, was indicative of variable source strengths. Most interestingly, perturbation of C₄ hydrocarbon ratios suggested an enhanced role for chlorine chemistry during the month of September, likely as the result of Los Angeles’ coastal location. Such coastal influence was confirmed by observations of enhanced mixing ratios of marine halocarbons, as well as air mass back trajectories.     

An improved method to study the impact of pesticide sprays on small song birds

Abstract

Four test groups of small songbirds (Zebra Finch, Poephila guttata) were sprayed in a chamber with varying concentrations of fenitrothion. Exposure levels were assessed by monitoring air concentrations, deposits of the active ingredient (AI) on glass plates and droplets/cm² on Kromekote® cards. All indices of exposure were linearly correlated and the mean AI deposit on glass plates for the four groups tested were equivalent to 38, 51, 139 and 255 g/ha or 14%, 18%, 50% and 91% of the highest permissible emitted rate for broadscale forest spraying in Canada. Significant depression in body weights and brain acetylcholinesterase levels were noted only for the highest exposure group. Fenitrothion residues in blood were detectable only at the highest exposure level, and in liver at the two higher levels. Carcass and feather residues were much higher than those in blood and liver, and were detectable at all exposure levels but the residues did not increase linearly with exposure. For one of the spray groups, we were able to compute an equivalent acute oral dose based on matching acetylcholinesterase inhibition.