Air pollutant concentrations near three Texas roadways, part II: Chemical characterization and transformation of pollutants

Spatial gradients of vehicular emitted air pollutants were measured in the vicinity of three roadways in the Austin, Texas area: (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 with significant truck traffic. A mobile monitoring platform was used to characterize the gradients of CO and NO_x concentrations with increased distance from each roadway, while concentrations of carbonyls in the gas-phase and fine particulate matter mass and composition were measured at stationary sites upwind and at one (I-35 and FM-973) or two (SH-71) downwind sites. Regardless of roadway type or wind direction, concentrations of carbon monoxide (CO), nitric oxide (NO), and oxides of nitrogen (NO_x) returned to background levels within a few hundred meters of the roadway. Under perpendicular wind conditions, CO, NO and NO_x concentrations decreased exponentially with increasing distance perpendicular to the roadways. The decay rate for NO was more than a factor of two greater than for CO, and it comprised a larger fraction of NO_x closer to the roadways than further downwind suggesting the potential significance of near roadway chemical processing as well as atmospheric dilution. Concentrations of most carbonyl species decreased with distance downwind of SH-71. However, concentrations of acetaldehyde and acrolein increased farther downwind of SH-71, suggesting chemical generation from the oxidation of primary vehicular emissions. The behavior of particle-bound organic species was complex and further investigation of the size-segregated chemical composition of particulate matter (PM) at increasing downwind distances from roadways is warranted. Fine particulate matter (PM_2.5) mass concentrations, polycyclic aromatic hydrocarbons (PAHs), hopanes, and elemental carbon (EC) concentrations generally exhibited concentrations that decreased with distance downwind of SH-71. Concentrations of organic carbon (OC) increased from upwind concentrations immediately downwind of SH-71 and continued to increase further downwind from the roadway. This behavior may have primarily resulted from condensation of semi-volatile organic species emitted from vehicle sources with transport downwind of the roadway.     

Air pollutant emissions associated with forest,grassland, and agricultural burning in Texas

Outdoor fires, such as wildfires and prescribed burns, can emit substantial amounts of particulate matter and other pollutants into the atmosphere. In Texas, an inventory of forest, grassland and agricultural burning activities revealed that fires consumed vegetation on 1.6 and 1.7 million acres of land, in 1996 and 1997, respectively. Emissions from the fires were estimated based on survey and field data on acres burned and land cover and literature data on fuel consumption and emission factors. Fire data were allocated spatially by county and temporally by month. While fire events can cause high transient air pollutant concentrations, for most criteria pollutants, the fire emissions were a relatively small fraction of the annual emission inventory for the State. For fine particulate matter, however, the annual emission estimates were 40,000 tons/yr, which is likely to represent a significant fraction of the State's emission inventory, especially in the counties where the emissions are concentrated.     

Modeling the impacts of traffic emissions on air toxics concentrations near roadways

The dispersion formulation incorporated in the U.S. Environmental Protection Agency's AERMOD regulatory dispersion model is used to estimate the contribution of traffic-generated emissions of select VOCs – benzene, 1,3-butadiene, toluene – to ambient air concentrations at downwind receptors ranging from 10-m to 100-m from the edge of a major highway in Raleigh, North Carolina. The contributions are computed using the following steps: 1) Evaluate dispersion model estimates with 10-min averaged NO data measured at 7 m and 17 m from the edge of the road during a field study conducted in August, 2006; this step determines the uncertainty in model estimates. 2) Use dispersion model estimates and their uncertainties, determined in step 1, to construct pseudo-observations. 3) Fit pseudo-observations to actual observations of VOC concentrations measured during five periods of the field study. This provides estimates of the contributions of traffic emissions to the VOC concentrations at the receptors located from 10 m to 100 m from the road. In addition, it provides estimates of emission factors and background concentrations of the VOCs, which are supported by independent estimates from motor vehicle emissions models and regional air quality measurements. The results presented in the paper demonstrate the suitability of the formulation in AERMOD for estimating concentrations associated with mobile source emissions near roadways. This paper also presents an evaluation of the key emissions and dispersion modeling inputs necessary for conducting assessments of local-scale impacts from traffic emissions.     

Ultrafine particles at three different sampling locations in Taiwan

Atmospheric ultrafine particles (UPs or PM_0.1) were investigated at the roadside of Syuefu road in Hsinchu city, in the Syueshan highway tunnel in Taipei and in the NTU Experimental Forest in Nantou, Taiwan. A SMPS (TSI 3936) and three MOUDIs (MSP 110) were collocated to determine the number and mass concentrations of the PM_0.1 simultaneously. The filter samples were further analyzed for organic carbon (OC), element carbon (EC), water-soluble ions and trace elements. Taking into account the OC artifact of PM_0.1, good chemical mass closure (ratio of the reconstructed chemical mass to the gravimetrical mass of PMs) was obtained with an unknown percentage of 10.6, 26.2 and 37.2% at the roadside, tunnel and forest, respectively. The unexplained mass was attributed to aerosol water in this study. The artifact at the roadside, tunnel and the forest PM_0.1 mass was found to be as high as 51.6 ± 10.7%, 20.0 ± 5.4% and 85.6 ± 18.4%, respectively. Finally, the effective density of the roadside, tunnel and forest PM_0.1 was calculated based on the results of chemical speciation and found to be 1.45, 1.29 and 1.22 g cm^?3, respectively, which was in good agreement with that obtained by using the method of Spencer et al. (2007). Based on these results, it is foreseeable that the number concentration of the SMPS can be converted using the effective density determined by Spencer et al. (2007) for the real time measurement of the PM_0.1 concentration.     

Atmospheric trace element concentrations in total suspended particles near Paris,France

To evaluate today’s trace element atmospheric concentrations in large urban areas, an atmospheric survey was carried out for 18 months, from March 2002 to September 2003, in Saclay, nearby Paris. The total suspended particulate matter (TSP) was collected continuously on quartz fibre filters. The TSP contents were determined for 36 elements (including Ag, Bi, Mo and Sb) using two analytical methods: Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The measured concentrations were in agreement within the uncertainties with the certified values for the polycarbonate reference material filter SRM-2783 (National Institute for Standard Technology NIST, USA). The measured concentrations were significantly lower than the recommended atmospheric concentrations. In 2003, the Pb atmospheric level at Saclay was 15 ng/m³, compared to the 500 ng/m³ guideline level and to the 200 ng/m³ observed value in 1994. The typical urban background TSP values of 1–2, 0.2–1, 4–6, 10–30 and 3–5 ng/m³ for As, Co, Cr, Cu and Sb, respectively, were inferred from this study and were compared with the literature data. The typical urban background TSP concentrations could not be realised for Cd, Pb and Zn, since these air concentrations are highly influenced by local features. The Zn concentrations and Zn/Pb ratio observed in Saclay represented a characteristic fingerprint of the exceptionally large extent of zinc-made roofs in Paris and its suburbs. The traffic-related origin of Ba, Cr, Cu, Pb and Sb was demonstrated, while the atmospheric source(s) of Ag was not identified.     

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.     

Ambient air concentrations of polycyclic aromatic hydrocarbons,fluoride, suspended particles and particulate carbon in areas near aluminum production plants

Concentrations of airborne polycyclic aromatic hydrocarbons (PAH), fluoride, suspended particles and particulate carbon were determined in four different residential areas near aluminum industries. Two of the areas were exposed to pollutants from primary aluminum production, the third area was close to a plant manufacturing electrodes for the aluminum industry while the fourth area received pollutants from the production of aluminum as well as electrodes. The sampling time was 24 h and the samples were collected every eighth day for about 16 months. The concentrations of PAH were high compared to levels in other polluted areas with industry and dense traffic. The average concentrations for benzo(a)pyrene (BaP) were above 10 ngm⁻³, which has been proposed as a guideline in some countries, at all sites. The highest air concentration of BaP measured in the present study was 160 ng m⁻³. At two of the stations the fluoride concentrations exceeded the 24-h national guideline of 25 μgm⁻³, which has been set to protect human health. In a few cases the concentrations of suspended particles were high while the levels of carbon agreed with concentrations reported in urban and residential areas in U.S.A. The concentrations varied with time and the variation was caused mainly by the changes of the meteorological conditions. The frequency distributions were skew for all components and close to logarithmic normal. PAH were well correlated with fluoride, which is an aluminum production tracer, indicating that they are of the same origin. The aluminum industry did not seem to be the main source of particulate matter and carbon in air. Apportionment studies of the organic pollutants were carried out by cluster analysis, and the results showed that the aluminum production is the main source to the PAH in ambient air in these areas.     

Small mammal populations at hazardous waste disposal sites near Houston, Texas, USA

Small mammals were trapped, tagged and recaptured in 0.45 ha plots at six hazardous industrial waste disposal sites to determine if populations, body mass and age structures were different from paired control site plots. Low numbers of six species of small mammals were captured on industrial waste sites or control sites. Only populations of hispid cotton rats at industrial waste sites and control sites were large enough for comparisons. Overall population numbers, age structure, and body mass of adult male and female cotton rats were similar at industrial waste sites and control sites. Populations of small mammals (particularly hispid cotton rats) may not suffice as indicators of environments with hazardous industrial waste contamination.     

Morphological, biochemical, and histopathological indices and contaminant burdens of cotton rats (Sigmodon hispidus) at three hazardous waste sites near Houston, Texas, USA

Male cotton rats (Sigmodon hispidus) were studied at three industrial waste sites near Houston, Texas, to determine whether various morphological, biochemical, and histopathological indices provided evidence of contaminant exposure and toxic insult. Only modest changes were detected in cotton rats residing at waste sites compared with reference sites. No single parameter was consistently altered, except hepatic cytochrome P-450 concentration which was lower ( [Formula: see text] ) at two waste sites, and tended to be lower ( [Formula: see text] ) at a third waste site. Elevated petroleum hydrocarbon concentrations were detected in rats at one waste site, but contaminant burdens of rats from the other sites were unremarkable. Unlike rats captured in summer, those trapped in winter exhibited hepatocellular hypertrophy and up to a 65% increase in liver: body weight ratio, cytochrome P-450 concentration, and activities of aniline hydroxylase, aryl hydrocarbon hydroxylase, and glutathione S-transferase. Although genotoxicity has been previously documented in cotton rats residing at two of the waste sites, biomarkers in the present study provided little evidence of exposure and damage.     

Industrial odor sources and air pollutant concentrations in Globeville,a Denver,Colorado neighborhood

An odor of unknown origin described as a “tar” or “asphalt” smell has become unbearable for many of Globeville, CO, residents over the past few years. Residents report during odor events burning eyes and throat, headaches, skin irritation, and problems sleeping. This study was undertaken to identify the potential sources of the odor and the concentrations of air pollutants making up the odor by conducting meteorological correlations and sampling for a panel of volatile organic compounds (VOCs), sulfur gases, and polycyclic aromatic hydrocarbons (PAHs) in the neighborhood and near suspected sources. Wind speed and direction data collected every 1 min in the neighborhood indicate that when the odor is noticed, the community is directly downwind of a wood preservation facility and an asphalt roofing facility. Air samples collected during high-intensity odor events have shown concentrations of methylene chloride, hexane, toluene, naphthalene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene, each at least two times higher than background concentrations. Naphthalene and the other PAHs are known pollutants emitted from wood treatment processes, and are known to have a coal tar odor. Naphthalene was present in a sample collected directly adjacent to the Koppers facility and was not present in any background samples. Single-compound odor and health thresholds, however, were never surpassed. Given the technical and regulatory challenges of sampling odors and controlling emissions, it is recommended that Globeville residents and neighboring industry pursue a “good neighbor policy” to solve the odor issue. Specific offending industrial processes could be identified for which there exist cost-effective control technologies that would reduce exposure to odors and air toxics in Globeville.

Implications: Meteorological correlations and samples of volatile organic compounds (VOCs), sulfur gases, and polycyclic aromatic hydrocarbons (PAHs) in the Globeville, CO, neighborhood and near suspected sources during odor events indicate potential industrial sources of a transient and noxious odor. Legislative approaches have proven unfruitful and no health or odor thresholds were typically violated. New approaches are warranted to address odor mixture effects in neighborhoods near industrial facilities.     

Seasonal change of persistent organic pollutant concentrations in air at Niigata area,Japan

The concentrations of persistent organic pollutants (POPs), such as HCB, alpha-, beta-, gamma- and delta-HCH, trans- and cis-chlordane (t-CHL, c-CHL), DDE, DDD and DDT, in ambient air have been measured at five sampling points in Niigata area, Japan (Niigata, Maki, Tsubame, Jouzo and Yahiko) during the period from September 1999 to November 2001. HCB, alpha-HCH, t-CHL and c-CHL showed higher concentrations than the other chemicals in all locations. All the POPs except t-CHL and c-CHL collected at urban sites of the Niigata Plain was almost the same in their concentration levels. Higher concentrations of t-CHL and c-CHL in residential areas should be attributed to the past usage of the chemical as a termiticide. At Yahiko (remote site), most of the POPs showed lower concentrations than those measured at the other sampling sites, although alpha-HCH and gamma-HCH were comparable with the concentrations found at the other sampling sites. All POPs except alpha-HCH and gamma-HCH tend to decrease 41-80% in their concentrations from 2000 to 2001. The lower POPs concentrations in winter and the higher POPs concentrations in summer at every sampling point can be partly explained by temperature differences. Applying the equation of the logarithm of the POP partial pressure in air versus reciprocal temperature (lnPa=m/T+b) to our data, linear relations were observed. HCB gave a poor linearity and the smallest slope, while beta-HCH, t-CHL and c-CHL gave good linearities and large slopes in the equation. The results suggest that HCB level is influenced by not only the emission from terrestrial sources but the global-scale background pollution. A peculiar observation is that beta-HCH concentration measured in our study showed large temperature dependence, indicating there could be a source of contamination in the surrounding areas.     

Spatial inhomogeneity in pollutant concentrations, and their implications for air quality model evaluation

The Southern California Air Quality Study database provides a valuable resource with which to test urban-scale photochemical models and to achieve a better understanding of the atmospheric dynamics of pollutant formation. The CIT model was evaluated using the SCAQS database according to traditional model performance guidelines. A first application, reported previously, focused on model enhancement and application of the model to the 27–29 August 1987 episode. This study evaluates the CIT model using the 24–25 June SCAQS episode, providing further evaluation of the model. Results show that the CIT airshed model can follow the diurnal variations of reactive species and the transport for relatively unreactive species. The normalized gross error for ozone was 31 % in June compared to 38% in August. However, to fully judge model performance in proper perspective, a question arises: “How well do the measurements reflect the air quality surrounding the monitoring station, not just in that location?” This is an important but seldom quantitatively considered factor, not only in model evaluation but in the study of health effects as well. Analyses indicate that individual concentration measurements only approximately represent the true volume-averaged concentrations within a computational grid cell and that significant spatial variations exist. Thus any evaluation of models using these data sets should take these local variations into consideration. A series of tests found that the local inhomogeneities had a normalized gross error in the range of 25–45% depending on the pollutant. In this context, the performance of the CIT model is consistent with known modeling limitations such as emissions inventories and sub-grid scale variation of observations.     

Black carbon concentrations in precipitation and near surface air in and near Halifax,Nova Scotia

Black carbon (soot) concentrations have been measured in rain water, snow samples and near surface air at several locations in Nova Scotia, Canada. The average black carbon concentration in near surface air in summer was found to be 0.54 μg m^-3 compared to 1.74 μg m^-3 in the winter season. These values are comparable to black carbon concentrations found in other mid-size urban areas. The black carbon concentration in rain water and snow samples varied between an undetectable amount to about 20 μg kg^-1 of rain (or melt) water. The relatively low concentrations of black carbon in precipitation are attributed to extratropical cyclones that often develop off-shore to the east and south of Nova Scotia in relatively clean conditions of the marine boundary layer.     

Air pollutant emissions from the development,production, and processing of Marcellus Shale natural gas

The Marcellus Shale is one of the largest natural gas reserves in the United States; it has recently been the focus of intense drilling and leasing activity. This paper describes an air emissions inventory for the development, production, and processing of natural gas in the Marcellus Shale region for 2009 and 2020. It includes estimates of the emissions of oxides of nitrogen (NO_x), volatile organic compounds (VOCs), and primary fine particulate matter (≤2.5 µm aerodynamic diameter; PM_2.5) from major activities such as drilling, hydraulic fracturing, compressor stations, and completion venting. The inventory is constructed using a process-level approach; a Monte Carlo analysis is used to explicitly account for the uncertainty. Emissions were estimated for 2009 and projected to 2020, accounting for the effects of existing and potential additional regulations. In 2020, Marcellus activities are predicted to contribute 6–18% (95% confidence interval) of the NO_x emissions in the Marcellus region, with an average contribution of 12% (129 tons/day). In 2020, the predicted contribution of Marcellus activities to the regional anthropogenic VOC emissions ranged between 7% and 28% (95% confidence interval), with an average contribution of 12% (100 tons/day). These estimates account for the implementation of recently promulgated regulations such as the Tier 4 off-road diesel engine regulation and the U.S. Environmental Protection Agency's (EPA) Oil and Gas Rule. These regulations significantly reduce the Marcellus VOC and NO_x emissions, but there are significant opportunities for further reduction in these emissions using existing technologies.

Implications: The Marcellus Shale is one of the largest natural gas reserves in United States. The development and production of this gas may emit substantial amounts of oxides of nitrogen and volatile organic compounds. These emissions may have special significance because Marcellus development is occurring close to areas that have been designated nonattainment for the ozone standard. Control technologies exist to substantially reduce these impacts. PM_2.5 emissions are predicted to be negligible in a regional context, but elemental carbon emissions from diesel powered equipment may be important.     

Reproductive success of barn swallows nesting near a selenium-contaminated lake in east Texas, USA

Reproductive success and contaminant levels in 1986 and 1987 were compared between Barn Swallows nesting at selenium-contaminated Martin Lake, Texas, USA, and swallows nesting at a reference site. Nests were initiated about the same time or earlier at Martin Lake than at the reference site and clutch size was similar between the two locations. Nest success was significantly higher at Martin Lake than at the reference site and no embryo or chick deformities were documented. Selenium concentrations in 14 of 20 eggs from Martin Lake were above background (> 3 ppm, dry weight); two of 20 eggs contained > 5 ppm, a concentration associated with a 20% embryo mortality/deformity rate in some bird species. Selenium concentrations in the kidneys of adult swallows were higher at Martin Lake (mean = 14 ppm dry weight) than at the reference site (5.8 ppm). DDE, the only detected organochlorine compound, was in two of 10 eggs from Martin Lake; these concentrations were below those associated with chronic poisoning and reproductive problems. The maximum mercury concentration in livers of adult Barn Swallows (0.83 ppm, dry weight) was within the range for background levels (< 5 ppm).     

Spatial variability of unpaved road dust PM10 emission factors near El Paso, Texas

The testing re-entrained aerosol kinetic emissions from roads technique is compared with distance-based emission factors (EFs; g/VKT) measured downwind of a dirt road by using towers instrumented with real-time meteorological and particle sensors at multiple heights. The emission potential (EP), defined as the EF divided by the vehicle speed (m/sec), and weight index permits the intercomparison of emissions from multiple roadways surveyed by the TRAKER vehicle. A survey of 72 km of unpaved roads on the Ft. Bliss Military Base near El Paso, Texas, indicated that 60% of all measured EPs fell between 6.7 (g/VKT)/(m/sec) and 9.6 (g/VKT)/(m/sec). The EP measured across the base was approximately 50% lower than those collected in the vicinity of the instrumented towers. This implies that EFs measured for other vehicles on the same test section should be reduced by 50% to more accurately represent EFs for the entire military base. Using geographic information system-based soil maps, the inferred EFs are related to differences in soil types over the survey area. Variations among five different soil types accounted for <10% of variation in EP. Individual measurements using the testing re-entrained aerosol kinetic emissions from roads technique did show larger spatial variations in EP; however, these were not effectively captured by the soil classifications, partly because of the comparatively coarse spatial classification used in the soil survey data.     

Air pollutant emissions from rice straw open field burning in India, Thailand and the Philippines

Rice is a widely grown crop in Asia. China (30%) and India (21%) contribute to about half of the world's total rice production. In this study, three major rice-producing countries in Asia are considered, India, Thailand and the Philippines (the later two contributing 4% and 2% of the world's rice production). Rice straw is one of the main field based residues produced along with this commodity and its applications vary widely in the region. Although rice production practises vary from one country to another, open burning of straw is a common practice in these countries.In this study, an approach was followed aiming at (a) determining the quantity of rice straw being subject to open field burning in those countries, (b) congregating pollutant specific emissions factors for rice straw burning, and (c) quantifying the resulting air pollutant emissions. Uncertainties in the results obtained as compared to a global approach are also discussed.     

Prediction of sulfur dioxide concentrations at a site near downtown Santiago,Chile

We have analyzed the possibility to predict hourly averages of sulfur dioxide concentrations in the atmosphere at a site not far from the downtown area in the city of Santiago, Chile. We have compared the forecasts produced assuming persistence, linear regressions and feed forward neural networks. The effect of meteorological conditions is included by using forecasted values of temperature, relative humidity and wind speed at the time of the intended prediction as inputs to the different models. The best predictions for hourly averages are obtained with a three-layer neural network that has hourly averages of sulfur dioxide concentrations every 6 h on the previous day plus the actual values of the meteorological variables as input. Training the network with 1995 data, error in 8 h in advance prediction for 1996 data is of the order of 30%.     

Description and evaluation of a model of deposition velocities for routine estimates of air pollutant dry deposition over North America.: Part I: model development

This paper describes the development of a detailed dry deposition model for routine computation of dry deposition velocities of SO₂, O₃, HNO₃ and fine particle SO₄²⁻ across much of North America. Four different dry deposition/surface exchange sub-models have been combined with the current Canadian weather forecast model (Global Environmental Multiscale model) with a 3 h time resolution and a horizontal spatial resolution of 35 km. The present model uses the US Geological Survey North American Land Cover Characteristics data to obtain fourteen different land use and five seasonal categories. The four sub-models used are a multi-layer model for gaseous species over taller canopy land-use types, a big-leaf model for gaseous species over lower canopies (including bare soil and water) and for HNO₃ under all surface types and, two different models for SO₄²⁻, one for tall canopies and the other for short canopies. All necessary parameters for each sub-model, chemical species, land-use and seasonal categories have been selected from available data libraries or from the values reported in the literature. The purpose for developing this model (referred to as the Routine Deposition Model (RDM)), when coupled with air concentration data, is to provide estimates of seasonal dry deposition, which can be combined with wet deposition to produce total deposition estimates. Model theory is discussed in this paper and model sensitivity tests and results will be presented in a companion paper.