Nabin Upadhyay

Chemical Speciation of PM2.5 and PM10 in South Phoenix, AZ

ABSTRACT Phoenix, AZ, experiences high particulate matter (PM) episodes, especially in the wintertime. The spatial variation of the PM concentrations and resulting differences in exposure is of particular concern. In this study, PM2.5 (PM with aerodynamic diameter <2.5 μm) and PM10 (PM with aerodynamic diameter <10 μm) samples were collected simultaneously from the east and west sides of South Phoenix and at a control site in Tempe and analyzed for trace elements and bulk elemental and organic carbon. Measurements showed that although PM2.5 concentrations had similar trends in temporal scale across all sites, concentrations of PM10 did not. The difference in PM10 concentrations and fluctuation across the three sites suggest effects of a local soil source as evidenced by high concentrations of Al, Ca, and Fe in PM10. K and anthro pogenic elements (e.g., Cu, Pb, and Zn) in PM2.5 samples on January 1 were strikingly high, suggesting the influence of New Years fireworks. Concentrations of toxic elements (e.g., Pb) in the study presented here are not different from similar studies in other U.S. cities. Application of principal component analysis indicated two broad categories of emission sources—soil and combustion—together accounting for 80 and 90% of variance, respectively, in PM2.5 and PM10. The soil and combustion components explained approximately 60 and 30% of the variance in PM10, respectively, whereas combustion sources dominated PM2.5 (>50% variance). Many elements associated with anthropogenic sources were highly enriched, with enrichment factors in PM2.5 an order of magnitude higher than in PM10 relative to surface soil composition in the study area. IMPLICATIONS This study investigates the variability of PM10 and PM2.5 mass concentrations and speciation between two sites in southern Phoenix, representative of a lower income part of the city, and a comparison site in nearby Tempe, with a higher income lower minority population. The results indicate similar temporal trends in PM2.5 concentrations and sources, although lower overall concentrations in Tempe. For PM10, the highest concentrations and a unique temporal variability at one South Phoenix site suggest a particular influence of local dust sources.

Synthetic musk emissions from wastewater aeration basins.

Wastewater aeration basins at publicly owned treatment works (POTWs) can be emission sources for gaseous or aerosolized sewage material. In the present study, particle and gas phase emissions of synthetic musks from covered and uncovered aeration basins were measured. Galaxolide (HHCB), tonalide (AHTN), and celestolide (ADBI) were the most abundant, ranging from 6704 to 344,306 ng m(-3), 45-3816 ng m(-3), and 2-148 ng m(-3) in the gas phase with particle phase concentrations 3 orders of magnitude lower. The musk species were not significantly removed from the exhaust air by an odor control system, yielding substantial daily emission fluxes (∼ 200 g d(-1) for HHCB) into the atmosphere. However, simple dispersion modeling showed that the treatment plants are unlikely to be a major contributor to ambient air concentrations of these species. Emission of synthetic musk species during wastewater treatment is a substantial fate process; more than 14% of the influent HHCB is emitted to the atmosphere in a POTW as opposed to the <1% predicted by an octanol-water partition coefficient and fugacity-based US EPA fate model. The substantial atmospheric emission of these compounds is most likely due to active stripping that occurs in the aeration basins by bubbling air through the sludge.

Chemical characterization of coarse particulate matter in the Desert Southwest – Pinal County Arizona, USA

The Desert Southwest Coarse Particulate Matter Study was undertaken to further our understanding of ambient concentrations and the composition of fine and coarse particles in rural, arid environments. Sampling was conducted in Pinal County, Arizona between February 2009 and February 2010. The goals of this study were to: (1) chemically characterize the coarse and fine fraction of the ambient particulate matter in terms of mass, ions, elements, bulk organic and elemental carbon; (2) examine the temporal and spatial variability of particles within the area using a series of three sampling locations and use this information to determine the contribution of local vs. regional sources; (3) collect, re–suspend, and chemically characterize various crustal sources within the area to identify differences which may isolate them (crustal sources) as independent sources, and; (4) use a receptor based modeling approach to identify particle sources and the relative impact of each on ambient PM concentrations. This work reviews the study objectives, design, site descriptions, and measurement techniques relevant to this research effort and presents the general characteristics of PM during the study period. This unique dataset will support efforts to reduce PM10 and PM2.5 concentrations in the area to below the National Ambient Air Quality Standards (NAAQS) for these pollutants. Coarse particle concentrations are, on average, approximately 5 times fine particle mass concentrations within the region. Coarse particle concentrations in Pinal County are highest during spring and fall seasons, consistent with the tilling and harvesting seasons while fine particles concentrations are highest during fall. Crustal material is the dominant component of coarse particle composition, representing 50% of the mass on average followed closely by organic matter representing 15%. Fine particles still contain a significant crustal fraction (30%) but organic matter dominates at 37% of the particle mass.

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 PM2.5 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.

Characterization of aerosol emissions from wastewater aeration basins

The emission of particulate matter (PM10 and PM2.5) and ammonia (NH3) by aeration processes at wastewater treatment plants (WWTPs) with and without odor control units was examined. Local concentrations of PM2.5, PM10, and NH3 at the aeration basins were within urban ranges. Emission fluxes of NH3 and PM2.5 for a medium-sized WWTP were determined to be 136 g day−1 and 43 g day−1, respectively, which are not substantial emission fluxes for urban environments. Odor control treatment using a granulated activated carbon bed reduced aerosol and NH3 emissions substantially. Detection of sterols, in particular the fecal sterol campesterol, in the PM clearly demonstrates aerosolization of wastewater components in the aeration process. The presence of campesterol in PM2.5 at a remote fenceline location in a WWTP facility illustrates that wastewater components are aerosolized in the fine PM fraction and transported beyond the facilities. Implications: Wastewater treatment plants are potential emission sources of particulate matter and gases. This study characterized particulate matter emissions from aeration basins and quantified emissions fluxes of particulate matter and NH3. While fine and coarse particles as well as NH3 are being emitted, the overall emissions are small compared to other urban sources. However, fecal steroid presence in particles at the fence of a treatment plant demonstrates that wastewater material is getting aerosolized and transported beyond the facilities.

Source identification of coarse particles in the Desert Southwest, USA using Positive Matrix Factorization

The Desert Southwest Coarse Particulate Matter Study was undertaken to further our understanding of the spatial and temporal variability and sources of fine and coarse particulate matter (PM) in rural, arid, desert environments. Sampling was conducted between February 2009 and February 2010 in Pinal County, AZ near the town of Casa Grande where PM concentrations routinely exceed the U.S. National Ambient Air Quality Standards (NAAQS) for both PM10 and PM2.5. In this desert region, exceedances of the PM10 NAAQS are dominated by high coarse particle concentrations, a common occurrence in this region of the United States. This work expands on previously published measurements of PM mass and chemistry by examining the sources of fine and coarse particles and the relative contribution of each to ambient PM mass concentrations using the positive matrix factorization receptor model (Clements et al., 2014). Coarse particles within the region were apportioned to nine sources including primary biological aerosol particles (PBAPs - 25%), crustal material (20%), re-entrained road dust (11%), feedlot (11% at the site closest to a cattle feedlot), secondary particles (10%), boron-rich crustal material (9%), and transported soil (6%), with minor contributions from ammonium nitrate, and salt (considered to be NaCl). Fine particles within the region were apportioned to six sources including motor vehicles (37%), road dust (29%), lead-rich (10%), with minor contributions from brake wear, crustal material, and salt. These results can help guide local air pollution improvement strategies designed to reduce levels of PM to below the NAAQS.