Katherine B. Benedict

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.

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.

Rocky Mountain National Park reduced nitrogen source apportionment

Excess wet and dry deposition of nitrogen-containing compounds are a concern at a number of national parks. The Rocky Mountain Atmospheric Nitrogen and Sulfur Study Part II (RoMANS II) campaign was conducted from November 2008 to November 2009 to characterize the composition of reactive nitrogen and sulfur deposited in Rocky Mountain National Park (RMNP). RoMANS II identified reduced nitrogen as the major contributor to reactive nitrogen deposition in RMNP, making up over 50% of the total. Motivated by this finding, the particulate source apportionment technology within the Comprehensive Air Quality Model with extensions was used here to estimate source apportionment of reduced nitrogen concentrations at RMNP. Source apportionment results suggest that approximately 40% of reduced nitrogen deposition to RMNP comes from ammonia sources within Colorado. However, the model evaluation also suggests that this number could be underrepresenting ammonia sources in eastern Colorado due to the difficulty of capturing upslope airflow on the eastern side of the Continental Divide with meteorological models. Emissions from California, the western model boundary, and the Snake River Valley in Idaho, the next three most influential sources, contribute approximately 15%, 8%, and 7%, respectively, to total reduced nitrogen measured in RMNP. Within Colorado, about 61%, 26%, and 13% of the total Colorado contribution comes from sources to the east of the Continental Divide, sources to the west of the Continental Divide, and from the park itself.

Meteorological and Back Trajectory Modeling for the Rocky Mountain Atmospheric Nitrogen and Sulfur Study II

The Rocky Mountain Atmospheric Nitrogen and Sulfur (RoMANS II) study with field operations during November 2008 through November 2009 was designed to evaluate the composition and sources of reactive nitrogen in Rocky Mountain National Park, Colorado, USA. As part of RoMANS II, a mesoscale meteorological model was utilized to provide input for back trajectory and chemical transport models. Evaluation of the models ability to capture important transport patterns in this region of complex terrain is discussed. Previous source-receptor studies of nitrogen in this region are also reviewed. Finally, results of several back trajectory analyses for RoMANS II are presented. The trajectory mass balance (TrMB) model, a receptor-based linear regression technique, was used to estimate mean source attributions of airborne ammonia concentrations during RoMANS II. Though ammonia concentrations are usually higher when there is transport from the east, the TrMB model estimates that, on average, areas to the west contribute a larger mean fraction of the ammonia. Possible reasons for this are discussed and include the greater frequency of westerly versus easterly winds, the possibility that ammonia is transported long distances as ammonium nitrate, and the difficulty of correctly modeling the transport winds in this area.

Impact of Front Range sources on reactive nitrogen concentrations and deposition in Rocky Mountain National Park

Human influenced atmospheric reactive nitrogen (RN) is impacting ecosystems in Rocky Mountain National Park (ROMO). Due to ROMO’s protected status as a Class 1 area, these changes are concerning, and improving our understanding of the contributions of different types of RN and their sources is important for reducing impacts in ROMO. In July–August 2014 the most comprehensive measurements (to date) of RN were made in ROMO during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ). Measurements included peroxyacetyl nitrate (PAN), C1–C5 alkyl nitrates, and high-time resolution NOx, NOy, and ammonia. A limited set of measurements was extended through October. Co-located measurements of a suite of volatile organic compounds provide information on source types impacting ROMO. Specifically, we use ethane as a tracer of oil and gas operations and tetrachloroethylene (C2Cl4) as an urban tracer to investigate their relationship with RN species and transport patterns. Results of this analysis suggest elevated RN concentrations are associated with emissions from oil and gas operations, which are frequently co-located with agricultural production and livestock feeding areas in the region, and from urban areas. There also are periods where RN at ROMO is impacted by long-range transport. We present an atmospheric RN budget and a nitrogen deposition budget with dry and wet components. Total deposition for the period (7/1–9/30) was estimated at 1.58 kg N/ha, with 87% from wet deposition during this period of above average precipitation. Ammonium wet deposition was the dominant contributor to total nitrogen deposition followed by nitrate wet deposition and total dry deposition. Ammonia was estimated to be the largest contributor to dry deposition followed by nitric acid and PAN (other species included alkyl nitrates, ammonium and nitrate). All three species are challenging to measure routinely, especially at high time resolution.