Improving Estimates of Sulfur, Nitrogen, and Ozone Total Deposition through Multi-Model and Measurement-Model Fusion Approaches.

Earth system and environmental impact studies need high quality and up-to-date estimates of atmospheric deposition. This study demonstrates the methodological benefits of multimodel ensemble and measurement-model fusion mapping approaches for atmospheric deposition focusing on 2010, a year for which several studies were conducted. Global model-only deposition assessment can be further improved by integrating new model-measurement techniques, including expanded capabilities of satellite observations of atmospheric composition. We identify research and implementation priorities for timely estimates of deposition globally as implemented by the World Meteorological Organization.

Nitrogen and triple oxygen isotopes in near-road air samples using chemical conversion and thermal decomposition.

RATIONALE: The determination of triple oxygen (δ(18)O and δ(17)O) and nitrogen isotopes (δ(15)N) is important when investigating the sources and atmospheric paths of nitrate and nitrite. To fully understand the atmospheric contribution into the terrestrial nitrogen cycle, it is crucial to determine the δ(15)N values of oxidised and reduced nitrogen species in precipitation and dry deposition. METHODS: In an attempt to further develop non-biotic methods and avoid expensive modifications of the gas-equilibration system, we have combined and modified sample preparation procedures and analytical setups used by other researchers. We first chemically converted NO(3)(-) and NH(4)(+) into NO(2)(-) and then into N(2)O. Subsequently, the resulting gas was decomposed into N(2) and O(2) and analyzed by isotope ratio mass spectrometry (IRMS) using a pre-concentration system equipped with a gold reduction furnace. RESULTS: The δ(17)O, δ(18)O and δ(15)N values of nitrate and nitrite samples were acquired simultaneously in one run using a single analytical system. Most importantly, the entire spectrum of δ(17)O, δ(18)O and/or δ(15)N values was determined from atmospheric nitrate, nitric oxide, ammonia and ammonium. The obtained isotopic values for air and precipitation samples were in good agreement with those from previous studies. CONCLUSIONS: We have further advanced chemical approaches to sample preparation and isotope analyses of nitrogen-bearing compounds. The proposed methods are inexpensive and easily adaptable to a wide range of laboratory conditions. This will substantially contribute to further studies on sources and pathways of nitrate, nitrite and ammonium in terrestrial nitrogen cycling.

Author Correction: Global and regional trends of atmospheric sulfur.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Global and regional trends of atmospheric sulfur.

The profound changes in global SO2 emissions over the last decades have affected atmospheric composition on a regional and global scale with large impact on air quality, atmospheric deposition and the radiative forcing of sulfate aerosols. Reproduction of historical atmospheric pollution levels based on global aerosol models and emission changes is crucial to prove that such models are able to predict future scenarios. Here, we analyze consistency of trends in observations of sulfur components in air and precipitation from major regional networks and estimates from six different global aerosol models from 1990 until 2015. There are large interregional differences in the sulfur trends consistently captured by the models and observations, especially for North America and Europe. Europe had the largest reductions in sulfur emissions in the first part of the period while the highest reduction came later in North America and East Asia. The uncertainties in both the emissions and the representativity of the observations are larger in Asia. However, emissions from East Asia clearly increased from 2000 to 2005 followed by a decrease, while in India a steady increase over the whole period has been observed and modelled. The agreement between a bottom-up approach, which uses emissions and process-based chemical transport models, with independent observations gives an improved confidence in the understanding of the atmospheric sulfur budget.

Baseline ambient gaseous ammonia concentrations in the Four Corners area and eastern Oklahoma, USA.

Ambient ammonia monitoring using Ogawa passive samplers was conducted in the Four Corners area and eastern Oklahoma, USA during 2007. The resulting data will be useful in the multipollutant management of ozone, nitrogen oxides, and visibility (atmospheric regional haze) in the Four Corners area, an area with growing oil/gas production and increasing coal-based power plant construction. The passive monitoring data also add new ambient ammonia concentration information for the U.S. and will be useful to scientists involved in present and future visibility modeling exercises. Three week integrated passive ammonia samples were taken at five sites in the Four Corners area and two sites in eastern Oklahoma from December, 2006 through December, 2007 (January, 2008 for two sites). Results show significantly higher regional background ammonia concentrations in eastern Oklahoma (1.8 parts per billion (ppb) arithmetic mean) compared to the Four Corners area (0.2 ppb arithmetic mean). Annual mean ammonia concentrations for all Four Corners area sites for the 2007 study ranged from 0.2 ppb to 1.5 ppb. Peak ambient ammonia concentrations occurred in the spring and summer in both areas. The passive samplers deployed at the Stilwell, Oklahoma site compared favorably with other passive samplers and a continuous ammonia monitoring instrument.

Evaluation and Intercomparison of Five North American Dry Deposition Algorithms at a Mixed Forest Site.

To quantify differences between dry deposition algorithms commonly used in North America, five models were selected to calculate dry deposition velocity (V d) for O3 and SO2 over a temperate mixed forest in southern Ontario, Canada, where a 5-year flux database had previously been developed. The models performed better in summer than in winter with correlation coefficients for hourly V d between models and measurements being approximately 0.6 and 0.3, respectively. Differences in mean V d values between models were on the order of a factor of 2 in both summer and winter. All models produced lower V d values than the measurements of O3 in summer and SO2 in summer and winter, although the measured V d may be biased. There was not a consistent tendency in the models to overpredict or underpredict for O3 in winter. Several models produced magnitudes of the diel variation of V d (O3) comparable to the measurements, while all models produced slightly smaller diel variations than the measurements of V d (SO2) in summer. A few models produced larger diel variations than the measurements of V d for O3 and SO2 in winter. Model differences were mainly due to different surface resistance parameterizations for stomatal and nonstomatal uptake pathways, while differences in aerodynamic and quasi-laminar resistances played only a minor role. It is recommended to use ensemble modeling results for ecosystem impact assessment studies, which provides mean values of all the used models and thus can avoid too much overestimations or underestimations.

Factors affecting stomatal uptake of ozone by different canopies and a comparison between dose and exposure.

Measured ozone (O(3)) and carbon dioxide (CO(2)) concentrations and fluxes over five different canopies (mixed coniferous-deciduous forest, deciduous forest, corn, soybean and pasture) in the eastern USA were analyzed to investigate the stomatal uptake of O(3). It was found that the ambient O(3) concentration levels had little effect on stomatal conductance. However, the accumulated stomatal uptake of O(3), upon reaching a threshold value on any given day, appears to reduce the rate of further O(3) uptake substantially. This may explain why the maximum O(3) deposition velocity often appeared in the early morning hours over some forest canopies. Substantially reduced CO(2) fluxes over wet canopies compared to dry canopies suggest that stomata were likely partially or totally blocked by water droplets or films when canopies were wet. By using a big-leaf dry deposition model, measured O(3) fluxes were separated into stomatal and non-stomatal portions. It was estimated that stomatal uptake contributed 55-75% of the total daytime O(3) fluxes and 40-60% of the total daytime plus nighttime fluxes, depending on canopy type. This suggests that about half of the total O(3) flux occurred through the non-stomatal pathway. At three locations (deciduous forest, corn and soybean sites), O(3) concentrations of 30-60 ppb and of 60-85 ppb contributed equally to the accumulated stomatal fluxes, while at the other two locations (mixed coniferous-deciduous forest and pasture sites), concentrations of 30-60 ppb contributed twice as much as those from 60 to 85 ppb.

Dry deposition of O3 and SO2 estimated from gradient measurements above a temperate mixed forest.

Vertical profiles of O3 and SO2 concentrations were monitored at the Borden Forest site in southern Ontario, Canada from May 2008 to April 2013. A modified gradient method (MGM) was applied to estimate O3 and SO2 dry deposition fluxes using concentration gradients between a level above and a level below the canopy top. The calculated five-year mean (median) dry deposition velocity (Vd) were 0.35 (0.27) and 0.59 (0.54) cm s(-1), respectively, for O3 and SO2. Vd(O3) exhibited large seasonal variations with the highest monthly mean of 0.68 cm s(-1) in August and the lowest of 0.09 cm s(-1) in February. In contrast, seasonal variations of Vd(SO2) were smaller with monthly means ranging from 0.48 (May) to 0.81 cm s(-1) (December). The different seasonal variations between O3 and SO2 were caused by the enhanced SO2 uptake by snow surfaces in winter. Diurnal variations showed a peak value of Vd in early morning in summer months for both O3 and SO2. Canopy wetness increased the non-stomatal uptake of O3 while decreasing the stomatal uptake. This also applied to SO2, but additional factors such as surface acidity also played an important role on the overall uptake.

Assessing the recovery of lakes in southeastern Canada from the effects of acidic deposition.

Reductions in North American sulfur dioxide (SO2) emissions promoted expectations that aquatic ecosystems in southeastern Canada would soon recover from acidification. Only lakes located near smelters that have dramatically reduced emissions approach this expectation. Lakes in the Atlantic provinces, Quebec and Ontario affected only by long-range sources show a general decline in sulfate (SO4(2-)) concentrations, but with a relatively smaller compensating increase in pH or alkalinity. Several factors may contribute to the constrained (or most likely delayed) acidity response: declining base cation concentrations, drought-induced mobilization of SO4(2-), damaged internal alkalinity generation mechanisms, and perhaps increasing nitrate or organic anion levels. Monitoring to detect biological recovery in southeastern Canada is extremely limited, but where it occurs, there is little evidence of recovery outside of the Sudbury/Killarney area. Both the occurrence of Atlantic salmon in Nova Scotia rivers and the breeding success of Common Loons in Ontario lakes are in fact declining although factors beyond acidification also play a role. Chemical and biological models predict that much greater SO2 emission reductions than those presently required by legislation will be needed to promote widespread chemical and latterly, biological recovery. It may be unrealistic to expect that pre-industrial chemical and biological conditions can ever be reestablished in many lakes of southeastern Canada.