A review of measurements of air-surface exchange of reactive nitrogen in natural ecosystems across North America.

This review summarizes the state of the science of measurements of dry deposition of reactive nitrogen (Nr) compounds in North America, beginning with current understanding of the importance of dry deposition at the U.S. continental scale followed by a review of micrometeorological flux measurement methods. Measurements of Nr air-surface exchange in natural ecosystems of North America are then summarized, focusing on the U.S. and Canada. Drawing on this synthesis, research needed to address the incompleteness of dry deposition budgets, more fully characterize temporal and geographical variability of fluxes, and better understand air-surface exchange processes is identified. Our assessment points to several data and knowledge gaps that must be addressed to advance dry deposition budgets and air-surface exchange modeling for North American ecosystems. For example, recent studies of particulate (NO3-) and gaseous (NOx, HONO, peroxy nitrates) oxidized N fluxes challenge the fundamental framework of unidirectional flux from the atmosphere to the surface employed in most deposition models. Measurements in forest ecosystems document the importance of in-canopy chemical processes in regulating the net flux between the atmosphere and biosphere, which can result in net loss from the canopy. These results emphasize the need for studies to quantify within- and near-canopy sources and sinks of the full suite of components of the Nr chemical system under study (e.g., NOy or HNO3-NH3-NH4NO3). With respect to specific ecosystems and geographical locations, additional flux measurements are needed particularly in agricultural regions (NH3), coastal zones (NO3- and organic N), and arid ecosystems and along urban to rural gradients (NO2). Measurements that investigate non-stomatal exchange processes (e.g., deposition to wet surfaces) and the biogeochemical drivers of bidirectional exchange (e.g., NH3) are considered high priority. Establishment of long-term sites for process level measurements of reactive chemical fluxes should be viewed as a high priority long-term endeavor of the atmospheric chemistry and ecological communities.

Long-term trends of wet inorganic nitrogen deposition in Rocky Mountain National Park: Influence of missing data imputation methods and associated uncertainty.

Excess reactive nitrogen (Nr) deposition is occurring in Rocky Mountain National Park and impacting sensitive ecosystems. In 2006, the National Park Service, State of Colorado, and Environmental Protection Agency established the goal to reduce Nr deposition to below the ecosystem critical load by 2032. Progress is tracked using 5-year averages of annual wet inorganic nitrogen (IN) deposition measured at Loch Vale, Colorado, by the National Atmospheric Deposition Program (NADP). This remote high alpine site is challenging to operate, and large fractions of the annual precipitation, at times >40%, had invalid IN concentrations. Annual wet IN deposition is calculated using the NADP protocol, which replaces missing concentrations with the annual precipitation-weighted mean (PWM) concentration of valid samples. This protocol does not account for seasonal variations in IN concentrations and the inverse relationship between concentration and precipitation amounts. Invalid samples occurred more frequently in the winter and at high and low precipitation amounts, and the NADP protocol generally overestimated annual deposition rates, by as much as 20%. Here, a new method for imputing missing weekly IN concentrations that accounts for their seasonal and precipitation dependence is introduced. Using a bootstrapping analysis shows that the new method reduced the errors in the annual deposition rates by about 30% compared to the NADP protocol and the biases were near zero. The overall trend in the wet IN deposition rates was found to be flat from 1990 to 2017, but the nitrate contribution decreased about 33%, which was offset by a nearly equal increase in ammonium wet deposition. These trends are consistent with known changes in nitrate and ammonium precursor emissions. The long-term trends in the annual IN deposition rates were similar using both data imputation methods, but the 2013-2017 average was about 10% smaller using the new method.

Improved apportionment of ambient PM constituents to sources in Tampa, FL, with pseudo-deterministic receptor model-II.

In 2005, Park et al. developed a new Pseudo-Deterministic Receptor Model (PDRM) to apportion SO2 and ambient particulate matter (PM) constituents to local sources near Tampa Bay. Ambient pollutant measurements were fit to products of emission rates and dispersion factors constrained with a Gaussian Plume Model for individual sources. Although highly successful, ambient pollutant concentrations were affected by numerous contributing sources at a variety of distances and trajectories were complicated by shifting winds. In this work, we expanded the data set, modified the basic bilinear Gaussian filter equation to constrain solutions based on composition and temporal profiles of key marker species, and implemented a hierarchical approach to applying constraints in order of most-to-least stringent. To account for shifting winds and differing transport times for ground and elevated components of plumes from distant sources, a multiple-height trajectory method was implemented. These changes allowed the number of unknowns to be expanded, such that temporal profiles of the Gaussian dispersion terms could also be extracted from the data. Fits for all species were substantially improved, as was agreement with literature sources for both emission rates and source-particle compositions.