An appraisal of NOx passive sampling

Associated with chronic and short-term health effects, the public health consequences of ambient air pollution are considerable. Accurate measurement of air pollutants is critical for assessing exposure to pollutants as well as an essential step in reducing public health impacts through implementation of regulations and emission controls. Passive sampling devices are often used for the regional-scale determination of pollutants when knowledge of hourly fluctuations in concentrations is unnecessary. Often advantageously described as cost-effective and simple to use, passive samplers are increasingly utilized as an alternative to conventional active sampling. However, the accuracy of these descriptions is challenged by the findings of the subsequent research. The overall objective of this research was to assess the ability of a well-known passive sampler to accurately measure concentrations of nitrogen oxides (NOx) in the ambient environment. While the passive measurement of numerous pollutants is heavily studied, literature evaluating the use of passive sampling devices for the measurement of NOx is exceedingly limited. NOx is a generic term for a group of highly reactive gases composed of oxygen and nitrogen but most commonly NOx is defined as the sum of nitric oxide (NO) and nitrogen dioxide (NO2). The trapping of NOx using filters coated with 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO) for quantitative analysis was investigated using various methods including ambient sampling, electronic absorption spectroscopy, mass spectrometry, and electron paramagnetic resonance. A first of its kind air sampling campaign in New Zealand measured ambient NOx concentrations at multiple locations using Ogawa passive samplers. High spatial variability in pollutant concentrations was found across the sampling area but accuracy of the concentrations was questioned. At low ambient NOx concentrations PTIO was found to contribute significantly to the analytical absorbance value. The fraction contributed by PTIO became increasingly difficult to quantitate as the contribution was not uniform across exposed filters. Degradation of PTIO during ambient exposure, evident by the loss of the filter color, was heavily dependent on the sampling environment. Intra- and inter-season variations in the magnitude of degradation are reported. Common limitations of various types of passive samplers are presented as well as challenges currently unaddressed in the literature

Indoor air sampling for fine particulate matter and black carbon in industrial communities in Pittsburgh

AbstractImpacts of industrial emissions on outdoor air pollution in nearby communities are well-documented. Fewer studies, however, have explored impacts on indoor air quality in these communities. Because persons in northern climates spend a majority of their time indoors, understanding indoor exposures, and the role of outdoor air pollution in shaping such exposures, is a priority issue. Braddock and Clairton, Pennsylvania, industrial communities near Pittsburgh, are home to an active steel mill and coke works, respectively, and the population experiences elevated rates of childhood asthma. Twenty-one homes were selected for 1-week indoor sampling for fine particulate matter (PM2.5) and black carbon (BC) during summer 2011 and winter 2012. Multivariate linear regression models were used to examine contributions from both outdoor concentrations and indoor sources. In the models, an outdoor infiltration component explained 10 to 39% of variability in indoor air pollution for PM2.5, and 33 to 42% for BC. For both PM2.5 models and the summer BC model, smoking was a stronger predictor than outdoor pollution, as greater pollutant concentration increases were identified. For winter BC, the model was explained by outdoor pollution and an open windows modifier. In both seasons, indoor concentrations for both PM2.5 and BC were consistently higher than residence-specific outdoor concentration estimates. Mean indoor PM2.5 was higher, on average, during summer (25.8±22.7μg/m3) than winter (18.9±13.2μg/m3). Contrary to the study's hypothesis, outdoor concentrations accounted for only little to moderate variability (10 to 42%) in indoor concentrations; a much greater proportion of PM2.5 was explained by cigarette smoking. Outdoor infiltration was a stronger predictor for BC compared to PM2.5, especially in winter. Our results suggest that, even in industrial communities of high outdoor pollution concentrations, indoor activities – particularly cigarette smoking – may play a larger role in shaping indoor exposures

Fine-Scale Source Apportionment Including Diesel-Related Elemental and Organic Constituents of PM2.5 across Downtown Pittsburgh

Health effects of fine particulate matter (PM2.5) may vary by composition, and the characterization of constituents may help to identify key PM2.5 sources, such as diesel, distributed across an urban area. The composition of diesel particulate matter (DPM) is complicated, and elemental and organic carbon are often used as surrogates. Examining multiple elemental and organic constituents across urban sites, however, may better capture variation in diesel-related impacts, and help to more clearly separate diesel from other sources. We designed a “super-saturation” monitoring campaign of 36 sites to capture spatial variance in PM2.5 and elemental and organic constituents across the downtown Pittsburgh core (~2.8 km2). Elemental composition was assessed via inductively-coupled plasma mass spectrometry (ICP-MS), organic and elemental carbon via thermal-optical reflectance, and organic compounds via thermal desorption gas-chromatography mass-spectrometry (TD-GCMS). Factor analysis was performed including all constituents—both stratified by, and merged across, seasons. Spatial patterning in the resultant factors was examined using land use regression (LUR) modelling to corroborate factor interpretations. We identified diesel-related factors in both seasons; for winter, we identified a five-factor solution, describing a bus and truck-related factor [black carbon (BC), fluoranthene, nitrogen dioxide (NO2), pyrene, total carbon] and a fuel oil combustion factor (nickel, vanadium). For summer, we identified a nine-factor solution, which included a bus-related factor (benzo[ghi]fluoranthene, chromium, chrysene, fluoranthene, manganese, pyrene, total carbon, total elemental carbon, zinc) and a truck-related factor (benz[a]anthracene, BC, hopanes, NO2, total PAHs, total steranes). Geographic information system (GIS)-based emissions source covariates identified via LUR modelling roughly corroborated factor interpretations

Spatial Patterns in Rush-Hour vs. Work-Week Diesel-Related Pollution across a Downtown Core

Despite advances in monitoring and modelling of intra-urban variation in multiple pollutants, few studies have attempted to separate spatial patterns by time of day, or incorporated organic tracers into spatial monitoring studies. Due to varying emissions sources from diesel and gasoline vehicular traffic, as well as within-day temporal variation in source mix and intensity (e.g., rush-hours vs. full-day measures), accurately assessing diesel-related air pollution within an urban core can be challenging. We allocated 24 sampling sites across downtown Pittsburgh, Pennsylvania (2.8 km2) to capture fine-scale variation in diesel-related pollutants, and to compare these patterns by sampling interval (i.e., “rush-hours” vs. “work-week” concentrations), and by season. Using geographic information system (GIS)-based methods, we allocated sampling sites to capture spatial variation in key traffic-related pollution sources (i.e., truck, bus, overall traffic densities). Programmable monitors were used to collect integrated work-week and rush-hour samples of fine particulate matter (PM2.5), black carbon (BC), trace elements, and diesel-related organics (polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes), in summer and winter 2014. Land use regression (LUR) models were created for PM2.5, BC, total elemental carbon (EC), total organic carbon (OC), elemental (Al, Ca, Fe), and organic constituents (total PAHs, total hopanes), and compared by sampling interval and season. We hypothesized higher pollution concentrations and greater spatial contrast in rush-hour, compared to full work-week samples, with variation by season and pollutant. Rush-hour sampling produced slightly higher total PM2.5 and BC concentrations in both seasons, compared to work-week sampling, but no evident difference in spatial patterns. We also found substantial spatial variability in most trace elements and organic compounds, with comparable spatial patterns using both sampling paradigms. Overall, we found higher concentrations of traffic-related trace elements and organic compounds in rush-hour samples, and higher concentrations of coal-related elements (e.g., As, Se) in work-week samples. Mean bus density was the strongest LUR predictor in most models, in both seasons, under each sampling paradigm. Within each season and constituent, the bus-related terms explained similar proportions of variance in the rush-hour and work-week samples. Rush-hour and work-week LUR models explained similar proportions of spatial variation in pollutants, suggesting that the majority of emissions may be produced during rush-hour traffic across downtown. Results suggest that rush-hour emissions may predominantly shape overall spatial variance in diesel-related pollutants

Assessment of Spatial Variability across Multiple Pollutants in Auckland, New Zealand

Spatial saturation studies using source-specific chemical tracers are commonly used to examine intra-urban variation in exposures and source impacts, for epidemiology and policy purposes. Most such studies, however, has been performed in North America and Europe, with substantial regional combustion-source contributions. In contrast, Auckland, New Zealand, a large western city, is relatively isolated in the south Pacific, with minimal impact from long-range combustion sources. However, fluctuating wind patterns, complex terrain, and an adjacent major port complicate pollution patterns within the central business district (CBD). We monitored multiple pollutants (fine particulate matter (PM2.5), black carbon (BC), elemental composition, organic diesel tracers (polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes), and nitrogen dioxide (NO2)) at 12 sites across the ~5 km2 CBD during autumn 2014, to capture spatial variation in traffic, diesel, and proximity to the port. PM2.5 concentrations varied 2.5-fold and NO2 concentrations 2.9-fold across the CBD, though constituents varied more dramatically. The highest-concentration constituent was sodium (Na), a distinct non-combustion-related tracer for sea salt (µ = 197.8 ng/m3 (SD = 163.1 ng/m3)). BC, often used as a diesel-emissions tracer, varied more than five-fold across sites. Vanadium (V), higher near the ports, varied more than 40-fold across sites. Concentrations of most combustion-related constituents were higher near heavy traffic, truck, or bus activity, and near the port. Wind speed modified absolute concentrations, and wind direction modified spatial patterns in concentrations (i.e., ports impacts were more notable with winds from the northeast)