Contribution of Nitrate and Carbonaceous Species to PM2.5 Observed in Canadian Cities

ABSTRACT

At a variety of Canadian monitoring sites, carbonaceous compounds were estimated to account for an average of 50% of fine particle mass. These estimates were determined by subtracting the total fine particle mass associated with inorganic compounds from the total fine mass determined gravimetrically. This approach, which yields an upper limit estimate of the total amount of carbon-related mass was necessary since particulate carbon was not measured in the Canadian National Air Pollution Surveillance (NAPS) network. In this paper, total carbon estimates are evaluated against organic and elemental carbon measurements at locations in the Greater Vancouver area and Toronto. In addition, particle nitrate measurements at seven Canadian locations are used to determine the importance of nitrate relative to total mass and to examine the sampling artifacts due to the loss of particle nitrate from Teflon filters used in the NAPS di-chotomous samplers.

Measurements of organic and elemental carbon indicated that the total carbon estimation approach provides representative estimates of the average contribution by carbonaceous material to the total fine and coarse mass. The average total carbon among all Vancouver area measurements (N = 225) was 4.28 μg m^-3, while the estimated value was 4.34 μg m^-3. There was a larger discrepancy between Toronto total carbon measurements (12.1 μg m^-3) and estimates (8.8 μg m^-3), which is attributed in part to sampling of particles above 10 mm in diameter. However, the R² relating the measurements and estimates was about 0.71 for both areas. Linear regression slopes of 0.98 for Vancouver and 0.78 for Toronto (nonsignificant intercepts) indicate little bias in the Vancouver estimates, but a tendency for underestimation as the observed total carbon concentration increased in Toronto.

Annually, nitrate was responsible for 17% and 12% of the fine mass in the Vancouver area and Ontario, respectively. In contrast, at two rural locations in southern Quebec and Nova Scotia, only 6% of fine mass was associated with nitrate. Due to filter losses, nitrate concentrations determined through the NAPS dichot sampling were much lower than actual concentrations (0.44 μg m^-3 vs. 2.63 μg m^-3). As a result of these losses (attributed mostly to loss during laboratory storage), previous total carbon estimates for the Canadian NAPS sites were likely to have been overestimated on average by about 10%.     

Development of a Sample Equilibration System for the TEOM Continuous PM Monitor

ABSTRACT

In recent years, scientific discussion has included the influence of thermodynamic conditions (e.g., temperature, relative humidity, and filter face velocity) on PM retention efficiency of filter-based samplers and monitors. Method-associated thermodynamic conditions can, in some instances, dramatically influence the presence of particle-bound water and other light-molecular-weight chemical components such as particulate nitrates and certain organic compounds. The measurement of fine particle mass presents a new challenge for all PM measurement methods, since a relatively greater fraction of the mass is semi-volatile.

The tapered element oscillating microbalance (TEOM) continuous PM monitor is a U.S. Environmental Protection Agency (EPA) PM₁₀ equivalent method (EQPM-1090-079). Several hundred of these monitors are deployed throughout the United States. The TEOM monitor has the unique characteristic of providing direct PM mass measurement without the calibration uncertainty inherent in mass surrogate methods. In addition, it provides high-precision, near-real-time continuous data automatically. Much attention has been given to semi-volatile species retention of the TEOM method.

While using this monitor, it is desirable to maintain as low an operating temperature as practical and to remove unwanted particle-bound water. A new sample equilibration system (SES) has been developed to allow conditioning of the PM sample stream to a lower humidity and temperature level. The SES incorporates a special low-particle-loss Nafion dryer. This paper discusses the configuration and theory of the SES. Performance results include high time-resolved PM_2.5 data comparison between a 30 °C sample stream TEOM monitor with SES and a standard 50 °C TEOM monitor. In addition, 24-hr integrated data are compared with data collected using an EPA PM_2.5 Federal Reference Method (FRM)-type sampler. The SES is a significant development because it can be applied easily to existing TEOM monitors.     

Biofiltration of Trichloroethylene-Contaminated Air: A Pilot Study

Abstract

This project demonstrated the biofiltration of a trichloroethylene (TCE)-contaminated airstream generated by air stripping groundwater obtained from several wells located at the Anniston Army Depot, Anniston, AL. The effects of several critical process variables were investigated to evaluate technical and economic feasibility, define operating limits and preferred operating conditions, and develop design information for a full-scale biofilter system. Long-term operation of the demonstration biofilter system was conducted to evaluate the performance and reliability of the system under variable weather conditions. Propane was used as the primary substrate necessary to induce the production of a nonspecific oxygenase. Results indicated that the process scheme used to introduce propane into the biofiltration system had a significant impact on the observed TCE removal efficiency. TCE degradation rates were dependent on the inlet contaminant concentration as well as on the loading rate. No microbial inhibition was observed at inlet TCE concentrations as high as 87 parts per million on a volume basis.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): Overview and Statistical Considerations

Abstract

Average concentrations of particulate matter with an aerodynamic diameter less than or equal to 2.5 μm (PM_2.5) in Steubenville, OH, have decreased by more than 10 μg/m³ since the landmark Harvard Six Cities Study¹ associated the city’s elevated PM_2.5 concentrations with adverse health effects in the 1980s. Given the promulgation of a new National Ambient Air Quality Standard (NAAQS) for PM_2.5 in 1997, a current assessment of PM_2.5 in the Steubenville region is warranted. The Steubenville Comprehensive Air Monitoring Program (SCAMP) was conducted from 2000 through 2002 to provide such an assessment. The program included both an outdoor ambient air monitoring component and an indoor and personal air sampling component. This paper, which is the first in a series of four that will present results from the outdoor portion of SCAMP, provides an overview of the outdoor ambient air monitoring program and addresses statistical issues, most notably autocorrelation, that have been overlooked by many PM_2.5 data analyses. The average PM_2.5 concentration measured in Steubenville during SCAMP (18.4 μg/m³) was 3.4g/m³ above the annual PM_2.5 NAAQS. On average, sulfate and organic material accounted for ～31% and 25%, respectively, of the total PM_2.5 mass. Local sources contributed an estimated 4.6 μg/m³ to Steubenville’s mean PM_2.5 concentration. PM_2.5 and each of its major ionic components were significantly correlated in space across all pairs of monitoring sites in the region, suggesting the influence of meteorology and long-range transport on regional PM_2.5 concentrations. Statistically significant autocorrelation was observed among time series of PM_2.5 and component data collected at daily and 1-in-4-day frequencies during SCAMP. Results of spatial analyses that accounted for autocorrelation were generally consistent with findings from previous studies that did not consider autocorrelation; however, these analyses also indicated that failure to account for autocorrelation can lead to incorrect conclusions about statistical significance.     

Ozone and Other Air Quality-Related Variables Affecting Visibility in the Southeast United States

Abstract

An analysis of ozone (O₃) concentrations and several other air quality-related variables was performed to elucidate their relationship with visibility at five urban and semi-urban locations in the southeast United States during the summer seasons of 1980-1996. The role and impact of O₃ on aerosols was investigated to ascertain a relationship with visibility. Regional trend analysis over the 1980s reveals an increase in maximum O₃ concentration coupled with a decrease in visibility. However, a similar analysis for the 1990s shows a leveling-off of both O₃ and visibility; in both cases, the results were not statistically significant at the 5% level. A case study of site-specific trends at Nashville, TN, followed similar trends. To better understand the relationships between O₃ concentration and visibility, the analysis was varied from yearly through daily to hourly averaged values. This increased temporal resolution showed a statistically significant inverse relationship between visibility and O₃. Site-specific hourly r² values ranged from 0.02 to 0.43. Additionally, by performing back-trajectory analysis, it was found that the visibility degraded by air mass migration over polluted areas.     

Beryllium-7 Measurements in the Houston and Phoenix Urban Areas: An Estimation of Upper Atmospheric Ozone Contributions

Abstract

Natural radionuclides have been proposed as a means of assessing the transport of ozone (O₃) and aerosols in the troposphere. Beryllium-7 (⁷Be) is produced in the upper troposphere and lower stratosphere by the interaction of cosmogenic particles with atmospheric nitrogen and oxygen. ⁷Be has a 53.29-day half-life (478 keV γ) and is known to attach to fine particles in the atmosphere once it is formed. It has been suggested that O₃ from aloft can be transported into rural and urban regions during stratospheric–tropospheric folding events leading to increased background levels of O₃ at the surface. ⁷Be can be used as a tracer of upper atmospheric air parcels and the O₃ associated with them. Aerosol samples with a 2.5-µm cutoff were collected during 12-hr cycles (day/night) for a 30-day period at Deer Park, TX, near Houston, in August– September of 2000, and at Waddell, AZ, near Phoenix, in June–July of 2001. A comparison of ⁷Be levels with 12-hr O₃ averages and maxima shows little correlation. Comparison of nighttime and daytime O₃ levels indicate that during the day, when mixing is anticipated to be higher, the correlation of ⁷Be with O₃ in Houston is approximately twice that observed at night. This is consistent with mixing and with the anticipated loss of O₃ by reaction with nitric oxide (NO) and dry deposition. At best, 30% of the O₃ variance can be explained by the correlation with ⁷Be for Houston, less than that for Phoenix where no significant correlation was seen. This result is consistent with the intercept values obtained for ⁷Be correlations with either O₃ 24-hr averages or O₃ 12-hr maxima and is also in the range of the low O₃ levels (25 ppb) observed at Deer Park during a tropical storm event where the O₃ is attributable primarily to background air masses. That is, maximum background O₃ level contributions from stratospheric sources aloft are estimated to be in the range of 15–30 ppb in the Houston, TX, and Phoenix, AZ, area, and levels above these are because of local tropospheric photochemical production.     

Characterization of summertime coarse particulate matter in the Desert Southwest—Arizona,USA

A year-long study was conducted in Pinal County, AZ, to characterize coarse (2.5 – 10 μm aerodynamic diameter, AD) and fine (< 2.5 μm AD) particulate matter (PMc and PMf, respectively) to further understand spatial and temporal variations in ambient PM concentrations and composition in rural, arid environments. Measurements of PMc and PMf mass, ions, elements, and carbon concentrations at one-in-six day resolution were obtained at three sites within the region. Results from the summer of 2009 and specifically the local monsoon period are presented.

The summer monsoon season (July – September) and associated rain and/or high wind events, has historically had the largest number of PM₁₀ NAAQS exceedances within a year. Rain events served to clean the atmosphere, decreasing PMc concentrations resulting in a more uniform spatial gradient among the sites. The monsoon period also is characterized by high wind events, increasing PMc mass concentrations, possibly due to increased local wind-driven soil erosion or transport. Two PM₁₀ NAAQS exceedances at the urban monitoring site were explained by high wind events and can likely be excluded from PM₁₀ compliance calculations as exceptional events. At the more rural Cowtown site, PM₁₀ NAAQS exceedances were more frequent, likely due to the impact from local dust sources.

PM mass concentrations at the Cowtown site were typically higher than at the Pinal County Housing and Casa Grande sites. Crustal material was equal to 52-63% of the PMc mass concentration on average. High concentrations of phosphate and organic carbon found at the rural Cowtown were associated with local cattle feeding operations. A relatively high correlation between PMc and PMf (R²?=?0.63) indicated that the lower tail of the coarse particle fraction often impacts the fine particle fraction, increasing the PMf concentrations. Therefore, reductions in PMc sources will likely also reduce PMf concentrations, which also are near the value of the 24-hr PM_2.5 NAAQS.

Implications: In the desert southwest, summer monsoons are often associated with above average PM₁₀ (<10 μm AD) mass concentrations. Competing influences of monsoon rain and wind events showed that rain suppresses ambient concentrations while high wind increase them. In this region, the PMc fraction dominates PM₁₀ and crustal sources contribute 52-63% to local PMc mass concentrations on average. Cattle feedlot emissions are also an important source and a unique chemical signature was identified for this source. Observations suggest monsoon wind events alone cannot explain PM₁₀ NAAQS exceedances, thus requiring these values to remain in compliance calculations rather than being removed as exceptional wind events.     

Aerosol species concentrations and source apportionment of ammonia at Rocky Mountain National Park

Changes in ecosystem function at Rocky Mountain National Park (RMNP) are occurring because of emissions of nitrogen and sulfate species along the Front Range of the Colorado Rocky Mountains, as well as sources farther east and west. The nitrogen compounds include both oxidized and reduced nitrogen. A year-long monitoring program of various oxidized and reduced nitrogen species was initiated to better understand their origins as well as the complex chemistry occurring during transport from source to receptor. Specifically, the goals of the study were to characterize the atmospheric concentrations of nitrogen species in gaseous, particulate, and aqueous phases (precipitation and clouds) along the east and west sides of the Continental Divide; identify the relative contributions to atmospheric nitrogen species in RMNP from within and outside of the state of Colorado; identify the relative contributions to atmospheric nitrogen species in RMNP from emission sources along the Colorado Front Range versus other areas within Colorado; and identify the relative contributions to atmospheric nitrogen species from mobile sources, agricultural activities, and large and small point sources within the state of Colorado. Measured ammonia concentrations are combined with modeled releases of conservative tracers from ammonia source regions around the United States to apportion ammonia to its respective sources, using receptor modeling tools.

Implications: Increased deposition of nitrogen in RMNP has been demonstrated to contribute to a number of important ecosystem changes. The rate of deposition of nitrogen compounds in RMNP has crossed a crucial threshold called the “critical load.” This means that changes are occurring to park ecosystems and that these changes may soon reach a point where they are difficult or impossible to reverse. Several key issues need attention to develop an effective strategy for protecting park resources from adverse impacts of elevated nitrogen deposition. These include determining the importance of previously unquantified nitrogen inputs within the park and identification of important nitrogen sources and transport pathways.     

A Framework for Responding to Coral Disease Outbreaks that Facilitates Adaptive Management

Predicted increases in coral disease outbreaks associated with climate change have implications for coral reef ecosystems and the people and industries that depend on them. It is critical that coral reef managers understand these implications and have the ability to assess and reduce risk, detect and contain outbreaks, and monitor and minimise impacts. Here, we present a coral disease response framework that has four core components: (1) an early warning system, (2) a tiered impact assessment program, (3) scaled management actions and (4) a communication plan. The early warning system combines predictive tools that monitor the risk of outbreaks of temperature-dependent coral diseases with in situ observations provided by a network of observers who regularly report on coral health and reef state. Verified reports of an increase in disease prevalence trigger a tiered response of more detailed impact assessment, targeted research and/or management actions. The response is scaled to the risk posed by the outbreak, which is a function of the severity and spatial extent of the impacts. We review potential management actions to mitigate coral disease impacts and facilitate recovery, considering emerging strategies unique to coral disease and more established strategies to support reef resilience. We also describe approaches to communicating about coral disease outbreaks that will address common misperceptions and raise awareness of the coral disease threat. By adopting this framework, managers and researchers can establish a community of practice and can develop response plans for the management of coral disease outbreaks based on local needs. The collaborations between managers and researchers we suggest will enable adaptive management of disease impacts following evaluating the cost-effectiveness of emerging response actions and incrementally improving our understanding of outbreak causation.     

A Question of Boundaries: The Importance of “Revenuesheds” for Watershed Protection1

Patterson, Lauren A., Jeffrey Hughes, Glenn Barnes, and Stacey I. Berahzer, 2012. A Question of Boundaries: The Importance of “Revenuesheds” for Watershed Protection. Journal of the American Water Resources Association (JAWRA) 48(4): 838‐848. DOI: 10.1111/j.1752‐1688.2012.00655.x Abstract: Watersheds transcend jurisdictional boundaries; raising important questions of who should pay for watershed protection, and how can watershed governance be funded? The responsibility and cost for watershed protection has progressively devolved to local governments, resulting in additional negative externalities and financing challenges. Watershed governance structures have formed at the scale of the watershed, but they often lack the financing mechanisms needed to achieve policy goals. Financing mechanisms via local governments provide a reliable source of revenue and the flexibility to address watershed specific issues. We develop a “revenueshed” approach to access the initial challenges local governments face when seeking to finance trans‐jurisdictional watershed governance. The revenueshed approach engages local governments into discussion and implementation of financial strategies for collaborative watershed governance. Legislation places water quality regulations primarily on local governments inside the watershed. The revenueshed approach extends the financial and stewardship discussion to include local governments outside the watershed that benefit from the watershed. We applied the revenueshed approach to the Mills River and Upper Neuse watersheds in North Carolina. Mills River had a partnership governance seeking revenue for specific projects, whereas the Upper Neuse sought long‐term financial stability to meet new water quality legislation.