Surface ozone background in the United States: Canadian and Mexican pollution influences

We use a global chemical transport model (GEOS-Chem) with 1° × 1° horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 ± 8 ppb and 30 ± 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 ± 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.     

Ultrafine particles near a major roadway in Raleigh,North Carolina: Downwind attenuation and correlation with traffic-related pollutants

Ultrafine particles (UFPs, diameter < 100 nm) and co-emitted pollutants from traffic are a potential health threat to nearby populations. During summertime in Raleigh, North Carolina, UFPs were simultaneously measured upwind and downwind of a major roadway using a spatial matrix of five portable industrial hygiene samplers (measuring total counts of 20–1000 nm particles). While the upper sampling range of the portable samplers extends past the defined “ultrafine” upper limit (100 nm), the 20–1000 nm number counts had high correlation (Pearson R = 0.7–0.9) with UFPs (10–70 nm) measured by a co-located research-grade analyzer and thus appear to be driven by the ultrafine range. Highest UFP concentrations were observed during weekday morning work commutes, with levels at 20 m downwind from the road nearly fivefold higher than at an upwind station. A strong downwind spatial gradient was observed, linearly approximated over the first 100 m as an 8% drop in UFP counts per 10 m distance. This result agreed well with UFP spatial gradients estimated from past studies (ranging 5–12% drop per 10 m). Linear regression of other vehicle-related air pollutants measured in near real-time (10-min averages) against UFPs yielded moderate to high correlation with benzene (R² = 0.76), toluene (R² = 0.49), carbon monoxide (R² = 0.74), nitric oxide (R² = 0.80), and black carbon (R² = 0.65). Overall, these results support the notion that near-road levels of UFPs are heavily influenced by traffic emissions and correlate with other vehicle-produced pollutants, including certain air toxics.     

Tethered balloon-based soundings of ozone,aerosols, and solar radiation near Mexico City during MIRAGE-MEX

A tethered balloon sampling system was used to measure vertical profiles of ozone, particles, and solar radiation in the atmospheric boundary layer on the northern edge of Mexico City, in March 2006 as part of the Megacity Impact on Regional and Global Environment-Mexico experiment. Several commercial sensors, designed for surface applications, were deployed on a tethered balloon platform.Profiles indicate that for these 3 scalars the boundary layer (surface up to 700 m) was well mixed in the period 10:00–16:00 LST. Good agreement was observed for median surface and balloon ozone and particle number concentrations. For most profiles, the surface deposition of ozone was not significant compared to median profile concentrations. Particle number concentration (0.3, 0.5, 1.0 and 5.0 μm) also showed little variation with attitude. Radiatprofiles showed a monotonic increase in diffuse radiation from the maximum altitude of profiles to the surface. Consequently, it was inferred that surface measurements of these likely were representative of lower boundary layer values during this time period.     

Evaluation and application of biomagnetic monitoring of traffic-derived particulate pollution

Inhalation of particulate pollutants below 10 μm in size (PM₁₀) is associated with adverse health effects. Here we use magnetic remanence measurements of roadside tree leaves to examine levels of vehicle-derived PM around Lancaster, UK. Leaf saturation remanence (SIRM) values exhibit strong correlation with both the SIRM and particulate mass of co-located, pumped-air samples, indicating that these leaf magnetic values are an effective proxy for ambient PM₁₀ concentrations. Biomagnetic monitoring using tree leaves can thus provide high spatial resolution data sets for assessment of particulate pollution levels at pedestrian-relevant heights. Leaf SIRM values not only increase with proximity to roads with higher traffic volumes, but are also ～100% higher at 0.3 m than at ～1.5–2 m height. Magnetic and SEM data indicate that the particle populations are dominated by spherical, iron-rich particles ～0.1–1 μm in diameter, with fewer larger, more angular, silica-rich particles. Comparison of the roadside leaf-calculated PM₁₀ concentrations with PM₁₀ concentrations predicted by a widely-used atmospheric dispersion model indicates some agreement between them. However, the model under-predicts PM₁₀ concentrations at ‘urban hotspots’ such as major–minor road junctions and traffic lights. Conversely, the model over-predicts PM₁₀ concentrations with distance from the road wherever one tree is screened by another, indicating the filtering/protective effect of roadside trees in leaf.     

Temperature dependence of secondary organic aerosol

Temperature was found to have a dramatic effect on secondary organic aerosol formation from two ozonolysis systems, cyclohexene and α-pinene. Isothermal experiments were conducted for both systems where the lowest temperature, 278 K, formed approximately 2.5–3 times and 5–6 times the SOA formed at 300 K and 318 K, respectively. Changing the cyclohexene system temperature to a different isothermal experimental set point after completion of SOA formation did not lead to sufficient condensation/evaporation to reproduce the SOA formation at other temperature set points. When the system temperature was cycled between two set points at the end of an experiment, the α-pinene system showed reversibility between the initial temperature 318 K and 300 K. For temperature cycles between the initial temperature of 300 K–318 K, an irreversible loss of mass is observed after the first heating cycle with reversibility observed between subsequent temperature cycles. The SOA formed at 278 K was reversible over a 22 K range but was unable to evaporate sufficiently to match the SOA mass formed at 300 K. Hygroscopicity measurements, taken after the completion of SOA formation, indicate that hygroscopicity of the aerosol is also a function of temperature and that the aerosol does not continue to be oxidized after initial growth is complete. The differing hygroscopicity of the semi-volatile component of the aerosol is evident during system temperature changes after completion of the experiment.     

Simulation of global warming potential (GWP) from rice fields in the Tai-Lake region,China by coupling 1:50,000 soil database with DNDC model

Quantifying greenhouse gas (GHG) emissions from wetland ecosystems is a relatively new issue in global climate change studies. China has approximately 22% of the world's rice paddies and 38% of the world's rice production, which are crucial to accurately estimate the global warming potential (GWP) at regional scale. This paper reports an application of a biogeochemical model (DeNitrification and DeComposition or DNDC) for quantifying GWP from rice fields in the Tai-Lake region of China. For this application, DNDC is linked to a 1:50,000 soil database, which was derived from 1107 paddy soil profiles compiled during the Second National Soil Survey of China in the 1980–1990s. The simulated results show that the 2.34 Mha of paddy soil cultivated in rice–wheat rotation in the Tai-Lake region emitted about ?1.48 Tg C, 0.84 Tg N and 5.67 Tg C as CO₂, N₂O, and CH₄ respectively, with a cumulative GWP of 565 Tg CO₂ equivalent from 1982 to 2000. As for soil subgroups, the highest GWP (26,900 kg CO₂ equivalent ha^?1 yr^?1) was linked to gleyed paddy soils accounting for about 4.4% of the total area of paddy soils. The lowest GWP (5370 kg CO₂ equivalent ha^?1 yr^?1) was associated with submergenic paddy soils accounting for about 0.32% of the total area of paddy soils. The most common soil in the area was hydromorphic paddy soils, which accounted for about 53% of the total area of paddy soils with a GWP of 12,300 kg CO₂ equivalent ha^?1 yr^?1. On a regional basis, the annual averaged GWP in the polder, Tai-Lake plain, and alluvial plain soil regions was distinctly higher than that in the low mountainous and Hilly soil regions. As for administrative areas, the average annual GWP of counties in Shanghai city was high. Conversely, the average annual GWP of counties in Jiangsu province was low. The high variability in soil properties throughout the Tai-Lake region is important and affects the net greenhouse gas emissions. Therefore, the use of detailed soil data sets with high-resolution digital soil maps is essential to improve the accuracy of GWP estimates with process-based models at regional and national scales.     

Analysis of air pollution data at a mixed source location using boosted regression trees

This paper explores the use of boosted regression trees to draw inferences concerning the source characteristics at a location of high source complexity. Models are developed for hourly concentrations of nitrogen oxides (NO_X) close to a large international airport. Model development is discussed and methods to quantify model uncertainties developed. It is shown that good explanatory models can be developed and further, allowing for interactions between model variables significantly improves the model fits compared with non-interacting models. Methods are used to determine which variables exert most influence over predicted concentrations and to explore the NO_X dependency for each. Model predictions are used to estimate aircraft take-off contributions to total concentrations of NO_X and determine how these predictions are affected by annual variations in meteorological conditions and runway use patterns. Furthermore, the results relating to the aircraft contributions to total NO_X concentration are compared with those from a more detailed independent field campaign. Finally, we find empirical evidence that plumes from larger aircraft disperse more rapidly from the point of release compared with smaller aircraft. The reasons for this behaviour and the implications are discussed.     

Near roadway concentrations of organic source markers

Concentrations of elemental carbon (EC), organic carbon (OC), and 33 organic source markers (12 alkanes, 18 polycyclic aromatic hydrocarbons and ketones, and 3 hopanes) are reported near a highway in Raleigh, NC with an annual average daily traffic count of approximately 125,000 vehicles. Daily samples (24-h) were collected at two locations, one approximately 10 m and the other 275 m perpendicular from the road. Concentrations of OC were similar between near (mean = 7.6 μg m^?3) and far (8.0 μg m^?3) locations, but concentrations of most organic species at the near site were between 1.5 and 2 times higher than those at the far site.     

Air pollutant concentrations near three Texas roadways,Part I: Ultrafine particles

Vehicular emitted air pollutant concentrations were studied near three types of roadways in Austin, Texas: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway dominated by truck traffic. Air pollutants examined include carbon monoxide (CO), oxides of nitrogen (NO_x), and carbonyl species in the gas-phase. In the particle phase, ultrafine particle (UFP) concentrations (diameter < 100 nm), fine particulate matter (PM_2.5, diameter < 2.5 μm) mass and carbon content and several particle-bound organics were examined. All roadways had an upwind stationary sampling location, one or two fixed downwind sample locations and a mobile monitoring platform that characterized pollutant concentrations fall-off with increased distance from the roadways. Data reported in this paper focus on UFP while other pollutants and near-roadway chemical processes are examined in a companion paper. Traffic volume, especially heavy-duty traffic, wind speed, and proximity to the road were found to be the most important factors determining UFP concentrations near the roadways. Since wind directions were not consistent during the sampling periods, distances along wind trajectories from the roadway to the sampling points were used to study the decay characteristics of UFPs. Under perpendicular wind conditions, for all studied roadway types, particle number concentrations increased dramatically moving from the upwind side to the downwind side. The elevated particle number concentrations decay exponentially with increasing distances from the roadway with sharp concentration gradients observed within 100–150 m, similar to previously reported studies. A single exponential decay curve was found to fit the data collected from all three roadways very well under perpendicular wind conditions. No consistent pattern was observed for UFPs under parallel wind conditions. However, regardless of wind conditions, particle concentrations returned to background levels within a few hundred meters of the roadway. Within measured UFP size ranges, smaller particles (6–25 nm) decayed faster than larger ones (100–300 nm). Similar decay rates were observed among UFP number, surface, and volume.