Bret A. Schichtel

Revised Algorithm for Estimating Light Extinction from IMPROVE Particle Speciation Data

Abstract The Interagency Monitoring of Protected Visual Environments (IMPROVE) particle monitoring network consists of approximately 160 sites at which fine particulate matter (PM2.5) mass and major species concentrations and course particulate matter (PM10) mass concentrations are determined by analysis of 24-hr duration sampling conducted on a 1-day-in-3 schedule. A simple algorithm to estimate light extinction from the measured species concentrations was incorporated in the 1999 Regional Haze Rule as the basis for the haze metric used to track haze trends. A revised algorithm was developed that is more consistent with the recent atmospheric aerosol literature and reduces bias for high and low light extinction extremes. The revised algorithm differs from the original algorithm in having a term for estimating sea salt light scattering from Cl - ion data, using 1.8 instead of 1.4 for the mean ratio of organic mass to measured organic carbon, using site-specific Rayleigh scattering based on site elevation and mean temperature, employing a split component extinction efficiency associated with large and small size mode sulfate, nitrate and organic mass species, and adding a term for nitrogen dioxide (NO2) absorption for sites with NO2 concentration information. Light scattering estimates using the original and the revised algorithms are compared with nephelometer measurements at 21 IMPROVE monitoring sites. The revised algorithm reduces the underprediction of high haze periods and the overprediction of low haze periods compared with the performance of the original algorithm. This is most apparent at the hazier monitoring sites in the eastern United States. For each site, the PM10 composition for days selected as the best 20% and the worst 20% haze condition days are nearly identical regardless of whether the basis of selection was light scattering from the original or revised algorithms, or from nephelometer-measured light scattering.

Haze trends over the United States, 1980-1995

The patterns and trends of haze over the United States for the period of 1980–1995 are presented. Haze measurements are based on human visual range observations at 298 synoptic meteorological stations operated by the United States Weather Service. There was a significant (B10%) decline in haziness over the 15-yr period. The reductions were evident throughout the eastern United States as well as over the hazy air basins of California. During the same period, in the eastern United States sulfur emissions also declined by about 10%. However, a causality for the reductions has not been established. This report is an update of an earlier survey of haze patterns and trends from 1950 to 1980. r 2001 Elsevier Science Ltd. All rights reserved.

Uncertainties in PM2.5 Gravimetric and Speciation Measurements and What We Can Learn from Them

ABSTRACT The U.S. Environmental Protection Agency (EPA) and the federal land management community (National Park Service, United States Fish and Wildlife Service, United States Forest Service, and Bureau of Land Management) operate extensive particle speciation monitoring networks that are similar in design but are operated for different objectives. Compliance (mass only) monitoring is also carried out using federal reference method (FRM) criteria at approximately 1000 sites. The Chemical Speciation Network (CSN) consists of approximately 50 long-term-trend sites, with about another 250 sites that have been or are currently operated by state and local agencies. The sites are located in urban or suburban settings. The Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network consists of about 181 sites, approximately 170 of which are in nonurban areas. Each monitoring approach has its own inherent monitoring limitations and biases. Determination of gravimetric mass has both negative and positive artifacts. Ammonium nitrate and other semivolatiles are lost during sampling, whereas, on the other hand, measured mass includes particle-bound water. Furthermore, some species may react with atmospheric gases, further increasing the positive mass artifact. Estimating aerosol species concentrations requires assumptions concerning the chemical form of various molecular compounds, such as nitrates and sulfates, and organic material and soil composition. Comparing data collected in the various monitoring networks allows for assessing uncertainties and biases associated with both negative and positive artifacts of gravimetric mass determinations, assumptions of chemical composition, and biases between different sampler technologies. All these biases are shown to have systematic seasonal characteristics. Unaccounted-for particle-bound water tends to be higher in the summer, as does nitrate volatilization. The ratio of particle organic mass divided by organic carbon mass (Roc) is higher during summer and lower during the winter seasons in both CSN and IMPROVE networks, and Roc is lower in urban than nonurban environments. IMPLICATIONS Particulate matter less than 2.5 microns in size (PM2.5) National Ambient Air Quality Standards (NAAQS) are based on gravimetric analysis of particulate matter collected on a Teflon substrate, using federal reference methodologies, whereas compliance under the Regional Haze Rule (RHR) is based on atmospheric extinction, derived from measurements of individual aerosol species. Gravimetric mass can be over- or underestimated because of volatilization issues and water retention by inorganic species, whereas species-specific estimates of mass are dependent on assumptions concerning their detailed chemical composition. Over- or underestimation of aerosol species or gravimetric mass could result in violation of standards or failure to meet visibility goals established under the RHR.

Increasing importance of deposition of reduced nitrogen in the United States

Significance Human activities have greatly increased emissions of reactive forms of nitrogen to the atmosphere. This perturbation to the nitrogen cycle has produced large increases of nitrogen deposition to sensitive ecosystems. Over recent decades, attention has focused on wet and dry deposition of nitrate stemming from fossil fuel combustion emissions of nitrogen oxides. Successful decreases in nitrogen oxides emissions in the United States have substantially decreased nitrate deposition. By contrast, emissions of ammonia, an unregulated air pollutant, and resulting deposition of ammonium have grown. Expanded observations demonstrate that deposition of reactive nitrogen in the United States has shifted from a nitrate-dominated to an ammonium-dominated condition. Recognition of this shift is critical to formulating effective future policies to protect ecosystems from excess nitrogen deposition. Rapid development of agriculture and fossil fuel combustion greatly increased US reactive nitrogen emissions to the atmosphere in the second half of the 20th century, resulting in excess nitrogen deposition to natural ecosystems. Recent efforts to lower nitrogen oxides emissions have substantially decreased nitrate wet deposition. Levels of wet ammonium deposition, by contrast, have increased in many regions. Together these changes have altered the balance between oxidized and reduced nitrogen deposition. Across most of the United States, wet deposition has transitioned from being nitrate-dominated in the 1980s to ammonium-dominated in recent years. Ammonia has historically not been routinely measured because there are no specific regulatory requirements for its measurement. Recent expansion in ammonia observations, however, along with ongoing measurements of nitric acid and fine particle ammonium and nitrate, permit new insight into the balance of oxidized and reduced nitrogen in the total (wet + dry) US nitrogen deposition budget. Observations from 37 sites reveal that reduced nitrogen contributes, on average, ∼65% of the total inorganic nitrogen deposition budget. Dry deposition of ammonia plays an especially key role in nitrogen deposition, contributing from 19% to 65% in different regions. Future progress toward reducing US nitrogen deposition will be increasingly difficult without a reduction in ammonia emissions.

An aerosol climatology for a rapidly growing arid region (southern Arizona): Major aerosol species and remotely sensed aerosol properties

This study reports a comprehensive characterization of atmospheric aerosol particle properties in relation to meteorological and back trajectory data in the southern Arizona region, which includes two of the fastest growing metropolitan areas in the United States (Phoenix and Tucson). Multiple data sets (MODIS, AERONET, OMI/TOMS, MISR, GOCART, ground-based aerosol measurements) are used to examine monthly trends in aerosol composition, aerosol optical depth (AOD), and aerosol size. Fine soil, sulfate, and organics dominate PM2.5 mass in the region. Dust strongly influences the region between March and July owing to the dry and hot meteorological conditions and back trajectory patterns. Because monsoon precipitation begins typically in July, dust levels decrease, while AOD, sulfate, and organic aerosol reach their maximum levels because of summertime photochemistry and monsoon moisture. Evidence points to biogenic volatile organic compounds being a significant source of secondary organic aerosol in this region. Biomass burning also is shown to be a major contributor to the carbonaceous aerosol budget in the region, leading to enhanced organic and elemental carbon levels aloft at a sky-island site north of Tucson (Mt. Lemmon). Phoenix exhibits different monthly trends for aerosol components in comparison with the other sites owing to the strong influence of fossil carbon and anthropogenic dust. Trend analyses between 1988 and 2009 indicate that the strongest statistically significant trends are reductions in sulfate, elemental carbon, and organic carbon, and increases in fine soil during the spring (March-May) at select sites. These results can be explained by population growth, land-use changes, and improved source controls.

Deposition of reactive nitrogen during the Rocky Mountain Airborne Nitrogen and Sulfur (RoMANS) study.

Increases in reactive nitrogen deposition are a growing concern in the U.S. Rocky Mountain west. The Rocky Mountain Airborne Nitrogen and Sulfur (RoMANS) study was designed to improve understanding of the species and pathways that contribute to nitrogen deposition in Rocky Mountain National Park (RMNP). During two 5-week field campaigns in spring and summer of 2006, the largest contributor to reactive nitrogen deposition in RMNP was found to be wet deposition of ammonium (34% spring and summer), followed by wet deposition of nitrate (24% spring, 28% summer). The third and fourth most important reactive nitrogen deposition pathways were found to be wet deposition of organic nitrogen (17%, 12%) and dry deposition of ammonia (14%, 16%), neither of which is routinely measured by air quality/deposition networks operating in the region. Total reactive nitrogen deposition during the spring campaign was determined to be 0.45 kg ha(-1) and more than doubled to 0.95 kg ha(-1) during the summer campaign.

A seasonal nitrogen deposition budget for Rocky Mountain National Park

Nitrogen deposition is a concern in many protected ecosystems around the world, yet few studies have quantified a complete reactive nitrogen deposition budget including all dry and wet, inorganic and organic compounds. Critical loads that identify the level at which nitrogen deposition negatively affects an ecosystem are often defined using incomplete reactive nitrogen budgets. Frequently only wet deposition of ammonium and nitrate are considered, despite the importance of other nitrogen deposition pathways. Recently, dry deposition pathways including particulate ammonium and nitrate and gas phase nitric acid have been added to nitrogen deposition budgets. However, other nitrogen deposition pathways, including dry deposition of ammonia and wet deposition of organic nitrogen, still are rarely included. In this study, a more complete seasonal nitrogen deposition budget was constructed based on observations during a year-long study period from November 2008 to November 2009 at a location on the east side of Rocky Mountain National Park (RMNP), Colorado, USA. Measurements included wet deposition of ammonium, nitrate, and organic nitrogen, PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 microm, nitrate, and ammonium) concentrations of ammonium, nitrate, and organic nitrogen, and atmospheric gas phase concentrations of ammonia, nitric acid, and NO2. Dry deposition fluxes were determined from measured ambient concentrations and modeled deposition velocities. Total reactive nitrogen deposition by all included pathways was found to be 3.65 kg N x ha(-1) yr(-1). Monthly deposition fluxes ranged from 0.06 to 0.54 kg N x ha(-1)yr(-1), with peak deposition in the month of July and the least deposition in December. Wet deposition of ammonium and nitrate were the two largest deposition pathways, together contributing 1.97 kg N x ha(-1)yr(-1) or 54% of the total nitrogen deposition budget for this region. The next two largest deposition pathways were wet deposition of organic nitrogen and dry deposition of ammonia; combined they contributed 1.37 kg N x ha(-1)yr(-1) or 37% of the total nitrogen deposition budget. To better understand the nitrogen cycle and key interactions between the atmosphere and biosphere we need to include as many sources and types of nitrogen as possible and understand their variability throughout the year. Here we examine the components of the nitrogen deposition budget to better understand the factors that influence the different deposition pathways and their seasonal variations.

Spatial and Temporal Trends in PM2.5 Organic and Elemental Carbon across the United States

The rural/remote IMPROVE network (Interagency Monitoring of Protected Visual Environments) and the Environmental Protection Agencys urban Chemical Speciation Network have measured PM2.5 organic (OC) and elemental carbon (EC) since 1989 and 2000, respectively. We aggregated OC and EC data from 2007 to 2010 at over 300 sites from both networks in order to characterize the spatial and seasonal patterns in rural and urban carbonaceous aerosols. The spatial extent of OC and EC was more regional in the eastern United States relative to more localized concentrations in the West. The highest urban impacts of OC and EC relative to background concentrations occurred in the West during fall and winter. Urban and rural carbonaceous aerosols experienced a large (although opposite) range in seasonality in the West compared to a much lower seasonal variability in the East. Long-term (1990–2010) trend analyses indicated a widespread decrease in rural TC (TC = OC

Directional Biases in Back Trajectories Caused by Model and Input Data

Abstract Back trajectory analyses are often used for source attribution estimates in visibility and other air quality studies. Several models and gridded meteorological datasets are readily available for generation of trajectories. The Big Bend Regional Aerosol and Visibility Observational (BRAVO) tracer study of July to October 1999 provided an opportunity to evaluate trajectory methods and input data against tracer concentrations, particulate data, and other source attribution techniques. Results showed evidence of systematic biases between the results of different back trajectory model and meteorological input data combinations at Big Bend National Park during the BRAVO. Most of the differences were because of the choice of meteorological data used as input to the trajectory models. Different back trajectories also resulted from the choice of trajectory model, primarily because of the different mechanisms used for vertical placement of the trajectories. No single model or single meteorological data set was found to be superior to the others, although rawinsonde data alone are too sparse in this region to be used as the only input data, and some combinations of model and input data could not be used to reproduce known attributions of tracers and simulated sulfate.

Characterization of the Winter Midwestern Particulate Nitrate Bulge

Abstract A previously unobserved multi-state region of elevated particulate nitrate concentration was detected as a result of the expansion of the Interagency Monitoring of Protected Visual Environments (IMPROVE) network of remote-area particulate matter (PM) speciation monitoring sites into the midwestern United States that began in 2002. Mean winter ammonium nitrate concentrations exceed 4 μg/m3 in a region centered in Iowa, which makes it responsible for as much as half of the particle light extinction. Before these observations, particulate nitrate in the United States was only observed to be a dominant component of the fine PM (PM2.5) in parts of California and some urban areas. Comparisons of the spatial patterns of particulate nitrate with spatial patterns of ammonia and nitrogen oxide emissions suggest that the nitrate bulge is the result of the high emissions of ammonia associated with animal agriculture in the Midwest. Nitrate episodes at several locations in the eastern United States are shown to be associated with transport pathways over the Midwest, suggesting long-range transport of either ammonia or ammonium nitrate. Thermodynamic equilibrium modeling conducted by others on data from the Midwest shows the relative importance of atmospheric ammonia and nitric acid in the production of PM2.5. This is a particular concern as the sulfur dioxide emissions in the United States are reduced, which increases the amount of ammonia available for ammonium nitrate production.