Increasing importance of deposition of reduced nitrogen in the United States.

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.

Passive ammonia monitoring in the United States: comparing three different sampling devices.

The need for ambient gaseous ammonia (NH(3)) measurements has increased in the last decade as reactive NH(3) concentrations and deposition fluxes show little change even with tightening standards on nitrogen oxides (NO(x)) emissions. Currently, there are several networks developing methods for adding NH(3) measurements in the U.S. Gaseous NH(3) measurements will provide scientists and policymakers data which can be used to estimate ecosystem inputs, validate air quality models including trends and regional variability, and evaluate changes to the environment based on additional emission reduction requirements and estimates of critical nitrogen load exceedances. The passive samplers described in this paper were deployed in duplicate or triplicate and collocated with annular denuders or continuous instruments to determine their accuracy. The samplers assessed included the Adapted Low-Cost Passive High Absorption (ALPHA), Radiello(®), and Ogawa passive samplers. The median relative percent differences (MRPD) between the reference method and passive samplers for the ALPHA, Radiello(®) and Ogawa were -2.4%, -37% and -44%, respectively. The precision between duplicate samplers for the ALPHA and Ogawa samplers, was 7% and 6%, respectively. Triplicate Radiello(®) precision was assessed using the coefficient of variation (CV). The CV for the Radiello(®) samplers was 10%. This article discusses the statistical results from these studies.

A statistical comparison of active and passive ammonia measurements collected at Clean Air Status and Trends Network (CASTNET) sites.

Atmospheric concentrations of ammonia (NH3) are not well characterized in the United States due to the sparse number of monitors, the relatively short lifetime of NH3 in the atmosphere, and the difficulty in measuring non-point source emissions such as fertilized agricultural land. In this study, we compare measured weekly concentrations of NH3 collected by two denuder systems with a bi-weekly passive NH3 sampler used by the National Atmospheric Deposition Program's (NADP) Ammonia Monitoring Network (AMoN). The purpose of the study was to verify the passive samplers used by AMoN and characterize any uncertainties introduced when using a bi-weekly versus weekly sampling time period. The study was conducted for 1 year at five remote Clean Air Status and Trends Network (CASTNET) sites. Measured ambient NH3 concentrations ranged from 0.03 µg NH3 m(-3) to 4.64 µg NH3 m(-3) in upstate New York and northwest Texas, respectively, while dry deposition estimates ranged from 0.003 kg N ha(-1) wk(-1) to 0.47 kg N ha(-1) wk(-1). Results showed that the bi-weekly passive samplers performed well compared to annular denuder systems (ADS) deployed at each of the five CASTNET sites, while the MetOne Super SASS Mini-Parallel Plate Denuder System (MPPD) was biased low when compared to the ADS. The mean relative percent difference (MRPD) between the ADS and MPPD and the ADS and AMoN sampler was -38% and -9%, respectively. Precision of the ADS and MPPD was 5% and 13%, respectively, while the precision of the passive samplers was 5%. The results of this study demonstrate that the NH3 concentrations measured by AMoN are comparable to the ADS and may be used to supplement the high-time resolution measurements to gain information on spatial gradients of NH3, long-term trends and seasonal variations in NH3 concentrations.