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.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

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.     

Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry

The high-molecular weight water-soluble organic compounds present in atmospheric aerosols underwent functional-group characterization using liquid chromatography tandem mass spectrometry (LC-MS/MS), with a focus on understanding the chemical structure and origins of humic-like substances (HULIS) in the atmosphere. Aerosol samples were obtained from several locations in North America at times when primary sources contributing to organic aerosol were well-characterized: Riverside, CA, Fresno, CA, urban and peripheral Mexico City, Atlanta, GA, and Bondville, IL. Chemical analysis targeted identification and quantification of functional groups, such as aliphatic, aromatic, and bulk carboxylic acids, organosulfates, and carbohydrate-like substances that comprise species with molecular weights (MW) 200–600 amu. Measured high-MW functional groups were compared to modeled primary sources with the purpose of identifying associations between aerosol sources, high-MW aerosol species, and HULIS. Mobile source emissions were linked to high-molecular weight carboxylic acids, especially aromatic acids, biomass burning was associated with carboxylic acids and carbohydrate-like substances, and secondary organic aerosol (SOA) correlated well with the total amount of HULIS measured, whereas organosulfates showed no correlation with aerosol sources and exhibited unique spatial trends. These results suggested the importance of motor vehicles, biomass burning, and SOA as important sources of precursors to HULIS. Structural characteristics of atmospheric HULIS were compared to terrestrial humic and fulvic acids and revealed striking similarities in chemical structure, with the exception of organosulfates which were unique to atmospheric HULIS.     

Predictive models of turbidity and water depth in the Doñana marshes using Landsat TM and ETM+ images

We have used Landsat-5 TM and Landsat-7 ETM+ images together with simultaneous ground-truth data at sample points in the Doñana marshes to predict water turbidity and depth from band reflectance using Generalized Additive Models. We have point samples for 12 different dates simultaneous with 7 Landsat-5 and 5 Landsat-7 overpasses. The best model for water turbidity in the marsh explained 38% of variance in ground-truth data and included as predictors band 3 (630–690 nm), band 5 (1550–1750 nm) and the ratio between bands 1 (450–520 nm) and 4 (760–900 nm). Water turbidity is easier to predict for water bodies like the Guadalquivir River and artificial ponds that are deep and not affected by bottom soil reflectance and aquatic vegetation. For the latter, a simple model using band 3 reflectance explains 78.6% of the variance. Water depth is easier to predict than turbidity. The best model for water depth in the marsh explains 78% of the variance and includes as predictors band 1, band 5, the ratio between band 2 (520–600 nm) and band 4, and bottom soil reflectance in band 4 in September, when the marsh is dry. The water turbidity and water depth models have been developed in order to reconstruct historical changes in Doñana wetlands during the last 30 years using the Landsat satellite images time series.     

Perceived Effects of Setting Attributes on Visitor Experiences in Wilderness: Variation with Situational Context and Visitor Characteristics

Understanding how setting attributes influence the nature of the visitor experience is crucial to effective recreation management. Highly influential attributes are useful indicators to monitor within a planning framework, such as Limits of Acceptable Change. This study sought to identify the setting attributes perceived to have the most profound effect on the ability to have “a real wilderness experience” and to assess the degree to which attribute importance varied with situational context and visitor characteristics. To this end, exiting hikers were surveyed at moderate and very high use trailheads in Alpine Lakes Wilderness, WA (USA), and Three Sisters Wilderness, OR (USA). They were asked about the degree to which encountering varying levels of different setting attributes would add to or detract from their experience. Attributes with the largest range of effect on experience, based on evaluations of different levels, were considered most important. The most influential attributes were litter and several types of campsite interaction—people walking through camp and number of other groups camping close by. The perceived importance of setting attributes did not vary much between wilderness locations with substantially different use levels, suggesting that conclusions are robust and generalizable across wilderness areas. There also was little difference in the perceptions of day and overnight visitors. In contrast, we found substantial variation in the perceived importance of setting attributes with variation in wilderness experience, knowledge, attachment, and motivation. Our results validate the emphasis of many wilderness management plans on indicators of social interaction, such as number of encounters.     

Vulnerability of Rehabilitated Agricultural Production Systems to Invasion by Nontarget Plant Species

Vast areas of arable land have been retired from crop production and “rehabilitated” to improved system states through landowner incentive programs in the United States (e.g., Conservation and Wetland Reserve Programs), as well as Europe (i.e., Agri-Environment Schemes). Our review of studies conducted on invasion of rehabilitated agricultural production systems by nontarget species elucidates several factors that may increase the vulnerability of these systems to invasion. These systems often exist in highly fragmented and agriculturally dominated landscapes, where propagule sources of target species for colonization may be limited, and are established under conditions where legacies of past disturbance persist and prevent target species from persisting. Furthermore, rehabilitation approaches often do not include or successfully attain all target species or historical ecological processes (e.g., hydrology, grazing, and/or fire cycles) key to resisting invasion. Uncertainty surrounds ways in which nontarget species may compromise long term goals of improving biodiversity and ecosystem services through rehabilitation efforts on former agricultural production lands. This review demonstrates that more studies are needed on the extent and ecological impacts of nontarget species as related to the goals of rehabilitation efforts to secure current and future environmental benefits arising from this widespread conservation practice.     

A global assessment of chromium pollution using sperm whales (Physeter macrocephalus) as an indicator species

Chromium (Cr) is a well-known human carcinogen and a potential reproductive toxicant, but its contribution to ocean pollution is poorly understood. The aim of this study was to provide a global baseline for Cr as a marine pollutant using the sperm whale (Physeter macrocephalus) as an indicator species. Biopsies were collected from free-ranging whales around the globe during the voyage of the research vessel The Odyssey. Total Cr levels were measured in 361 sperm whales collected from 16 regions around the globe detectable levels ranged from 0.9 to 122.6 μg Cr g tissue⁻¹ with a global mean of 8.8 ± 0.9 μg g⁻¹. Two whales had undetectable levels. The highest levels were found in sperm whales sampled in the waters near the Islands of Kiribati in the Pacific (mean = 44.3 ± 14.4) and the Seychelles in the Indian Ocean (mean = 19.5 ± 5.4 μg g⁻¹). The lowest mean levels were found in whales near the Canary Islands (mean = 3.7 ± 0.8 μg g⁻¹) and off of the coast of Sri Lanka (mean = 3.3 ± 0.4 μg g⁻¹). The global mean Cr level in whale skin was 28-times higher than mean Cr skin levels in humans without occupational exposure. The whale levels were more similar to levels only observed previously in human lung tissue from workers who died of Cr-induced lung cancer. We conclude that Cr pollution in the marine environment is significant and that further study is urgently needed.