Quantifying atmospheric N deposition in dryland ecosystems: A test of the Integrated Total Nitrogen Input (ITNI) method.

Estimating nitrogen (N) deposition to terrestrial ecosystems is complicated by the multiple forms and routes of N loading from the atmosphere. We used the integrated total nitrogen input (ITNI) method, which is based on the principle of isotope dilution within a plant-liquid-sand system, to quantify N inputs to coastal sage scrub ecosystems in Riverside, California. Using the ITNI method, we measured atmospheric N deposition of 29.3 kg N ha-1 yr-1 over a range of aboveground plant biomass of 228 to 424 g m-2. From 85 to 96% of the atmospheric N inputs were taken up by plants in the ITNI modules with most of the assimilation mediated by, and stored in, aboveground biomass. Parallel measurements using conventional approaches yielded deposition rates of 25.2 kg N ha-1 yr-1 when using the inferential method and 4.8 kg N ha-1 yr-1 using throughfall collectors. The relatively low throughfall estimates were attributed to canopy retention of inorganic N, low rainfall, and to the fact that the throughfall flux data did not include organic N and stomatal uptake of N gases. Also, during dry periods, frequent watering of ITNI modules may have increased stomatal conductance and led to overestimates of N deposition. Across published studies that used the ITNI method, areal N deposition rates varied by ~40-fold, were positively correlated with plant biomass and 90% of the variability in measured deposition rates can be explained by plant biomass production. The ITNI method offers a holistic approach to measuring atmospheric N deposition in arid ecosystems, although more study is needed to understand how watering rates effect N deposition measurements.

Nitrogenous air pollutants and ozone exposure in the central Sierra Nevada and White Mountains of California - Distribution and evaluation of ecological risks.

Ammonia (NH3), nitric oxide (NO), nitrogen dioxide (NO2), nitric acid (HNO3), and ozone (O3) were measured in summers of 2012 and 2013 with passive samplers. Nine monitoring sites were on W-E transect (511 to 3490 m) across central Sierra Nevada Mountains (SNM), and five sites on elevational gradient (1237 to 4346 m) in White Mountains (WM) of California. Levels of pollutants were similar in 2012 and 2013 in all sites. NH3, NO2, and HNO3 were highest near highly polluted Central Valley of California (CVC): maximum summer season means 7.8 µg m-3, 3.0 ppb, and 3.0 µg m-3, respectively. Regional background for NH3, NO2, and HNO3 in SNM occurred >20 km from CVC and >1500 m with seasonal averages: 2.1-4.8 µg m-3; 0.8-1.7 ppb; 1.0-1.8 µg m-3, respectively, during two seasons. Levels of NH3, NO2, and HNO3 in WM remote locations were similar: 1.2-3.3 µg m-3, 0.6-1.1 ppb, and 1.0-1.3 µg m-3, respectively. Seasonal mean O3 (38-60 ppb) in SNM did not change with distance from CVC nor elevation. In WM, O3 and NO mixing ratios were 41-61 ppb and 2.3-4.1 ppb, respectively, increasing with elevation. Even the lowest NH3 concentrations determined in this study were higher than NH3 continental background. This fact, as well as high values of Nreduced/Noxidized near CVC of 1.9 in 2012 and 2.0 in 2013, decreasing with distance to 0.7 in 2012 and 0.8 in 2013, show importance of NH3 emissions from CVC as a contributor to N deposition and ecological impacts in SNM. The phytotoxic O3 indices, AOT40 and W126, for selected sites on SNM and WM transects, showed high potential for negative O3 impacts on vegetation, including forest trees. CAPSULE: Elevated NH3, NO2, and HNO3 on the western slopes of the Sierra Nevada Mountains (SNM) near the Central Valley of California (CVC) decreased with distance from CVC and elevation to regional background levels also recorded at high elevation sites of the White Mountains (WM).

Joining empirical and modelling approaches to estimate dry deposition of nitrogen in Mediterranean forests.

In Mediterranean areas, dry deposition is a major component of the total atmospheric N input to natural habitats, particularly to forest ecosystems. An innovative approach, combining the empirical inferential method (EIM) for surface deposition of NO3- and NH4+ with stomatal uptake of NH3, HNO3 and NO2 derived from the DO3SE (Deposition of Ozone and Stomatal Exchange) model, was used to estimate total dry deposition of inorganic N air pollutants in four holm oak forests under Mediterranean conditions in Spain. The estimated total deposition varied among the sites and matched the geographical patterns previously found in model estimates: higher deposition was determined at the northern site (28.9 kg N ha-1 year-1) and at the northeastern sites (17.8 and 12.5 kg N ha-1 year-1) than at the central-Spain site (9.4 kg N ha-1 year-1). On average, the estimated dry deposition of atmospheric N represented 77% ±â€¯2% of the total deposition of N, of which surface deposition of gaseous and particulate atmospheric N averaged 10.0 ±â€¯2.9 kg N ha-1 year-1 for the four sites (58% of the total deposition), and stomatal deposition of N gases averaged 3.3 ±â€¯0.8 kg N ha-1 year-1 (19% of the total deposition). Deposition of atmospheric inorganic N was dominated by the surface deposition of oxidized N in all the forests (means of 54% and 42% of the dry and total deposition, respectively). The relative contribution of NO2 to dry deposition averaged from 19% in the peri-urban forests to 11% in the most natural site. During the monitoring period, the empirical critical loads provisionally proposed for ecosystem protection (10-20 kg N ha-1 year-1) was exceeded in three of the four studied forests.

On-road emissions of ammonia: An underappreciated source of atmospheric nitrogen deposition.

We provide updated spatial distribution and inventory data for on-road NH3 emissions for the continental United States (U.S.) On-road NH3 emissions were determined from on-road CO2 emissions data and empirical NH3:CO2 vehicle emissions ratios. Emissions of NH3 from on-road sources in urbanized regions are typically 0.1-1.3tkm-2yr-1 while NH3 emissions in agricultural regions generally range from 0.4-5.5tkm-2yr-1, with a few hotspots as high as 5.5-11.2tkm-2yr-1. Counties with higher vehicle NH3 emissions than from agriculture include 40% of the U.S. POPULATION: The amount of wet inorganic N deposition as NH4+ from the National Atmospheric Deposition Program (NADP) network ranged from 37 to 83% with a mean of 58.7%. Only 4% of the NADP sites across the U.S. had <45% of the N deposition as NH4+ based on data from 2014 to 2016, illustrating the near-universal elevated proportions of NH4+ in deposition across the U.S. Case studies of on-road NH3 emissions in relation to N deposition include four urban sites in Oregon and Washington where the average NH4-N:NO3-N ratio in bulk deposition was 2.3. At urban sites in the greater Los Angeles Basin, bulk deposition of NH4-N and NO3-N were equivalent, while NH4-N:NO3-N in throughfall under shrubs ranged from 0.6 to 1.7. The NH4-N:NO3-N ratio at 7-10 sites in the Lake Tahoe Basin averaged 1.4 and 1.6 in bulk deposition and throughfall, and deposition of NH4-N was strongly correlated with summertime NH3 concentrations. On-road emissions of NH3 should not be ignored as an important source of atmospheric NH3, as a major contributor to particulate air pollution, and as a driver of N deposition in urban and urban-affected regions.

In situ assay of nitrate reductase activity using portable water bath.

In environmental research (i.e., plant ecophysiology, environmental microbiology, and environmental chemistry), some assays require incubation of samples at controlled temperature and darkness. Until now, due to a lack of equipment providing such possibility in situ, researchers had to move collected samples to the laboratory for incubation. Obviously, a delayed incubation and the ex situ conditions could seriously affect the assays' results. A good example of analysis where water bath use is needed is the nitrate reductase activity (NRA) in vivo assay where plant tissue samples are incubated in buffer solution at a predetermined temperature. We designed a transportable water bath with a temperature control which enables in situ measurements in many types of environmental studies. The presented device is small in size featuring a thermally insulated chamber and an electronically controlled thermostat system powered by a 12-V battery. Due to its modular design, it can be transported comfortably in difficult terrain. The incubation process can be carried out continuously in stable temperature and darkness. In order to examine the field usability of the presented device, we conducted measurements of plant nitrate reductase activity in difficult field conditions. The in situ assays were carried out at high altitudes in the Karkonosze mountains, SW Poland. The NRA was studied in two alpine species (Deschampsia caespitosa and Homogyne alpina). Our results showed low NR activity in H. alpina (mean 0.31 µM NO2 g-1 DW h-1) and higher NRA in D. caespitosa (mean 2.7 µM NO2 g-1 DW h-1). The obtained results were highly reproducible and had small variability (low standard error values).

Ground-level air pollution changes during a boreal wildland mega-fire.

The 2011 Richardson wildland mega-fire in the Athabasca Oil Sands Region (AOSR) in northern Alberta, Canada had large effects on air quality. At a receptor site in the center of the AOSR ambient PM2.5, O3, NO, NO2, SO2, NH3, HONO, HNO3, NH4+ and NO3- were measured during the April-August 2011 period. Concentrations of NH3, HNO3, NO2, SO2 and O3 were also monitored across the AOSR with passive samplers, providing monthly summer and bi-monthly winter average values in 2010, 2011 and 2012. During the fire, hourly PM2.5 concentrations >450µgm-3 were measured at the AMS 1 receptor site. The 24-h National Ambient Air Quality Standard (NAAQS) of 35µgm-3 and the Canada Wide Standard (CWS) of 30µgm-3 were exceeded on 13days in May and 7days in June. During the fire emission periods, sharp increases in NH3, HONO, HNO3, NH4+, NO3- and total inorganic reactive N concentrations occurred, all closely correlated with the PM2.5 changes. There were large differences in the relative contribution of various N compounds to total inorganic N between the no-fire emission and fire emission periods. While in the absence of fires NO and NO2 dominated, their relative contribution during the fires was ~2 fold smaller, mainly due to increased NH3, NH4+ and NO3-. Concentrations of HONO and HNO3 also greatly increased during the fires, but their contribution to the total inorganic N pool was relatively small. Elevated NH3 and HNO3 concentrations affected large areas of northern Alberta during the Richardson Fire. While NH3 and HNO3 concentrations were not at levels considered toxic to plants, these gases contributed significantly to atmospheric N deposition. Generally, no significant changes in O3 and SO2 concentrations were detected and their ambient concentrations were below levels harmful to human health or sensitive vegetation.

Atmospheric dry deposition of sulfur and nitrogen in the Athabasca Oil Sands Region, Alberta, Canada.

Due to the potential ecological effects on terrestrial and aquatic ecosystems from atmospheric deposition in the Athabasca Oil Sands Region (AOSR), Alberta, Canada, this study was implemented to estimate atmospheric nitrogen (N) and sulfur (S) inputs. Passive samplers were used to measure ambient concentrations of ammonia (NH3), nitrogen dioxide (NO2), nitric acid/nitrous acid (HNO3/HONO), and sulfur dioxide (SO2) in the AOSR. Concentrations of NO2 and SO2 in winter were higher than those in summer, while seasonal differences of NH3 and HNO3/HONO showed an opposite trend, with higher values in summer. Concentrations of NH3, NO2 and SO2 were high close to the emission sources (oil sands operations and urban areas). NH3 concentrations were also elevated in the southern portion of the domain indicating possible agricultural and urban emission sources to the southwest. HNO3, an oxidation endpoint, showed wider ranges of concentrations and a larger spatial extent. Concentrations of NH3, NO2, HNO3/HONO and SO2 from passive measurements and their monthly deposition velocities calculated by a multi-layer inference model (MLM) were used to calculate dry deposition of N and S. NH3 contributed the largest fraction of deposited N across the network, ranging between 0.70-1.25kgNha(-1)yr(-1), HNO3/HONO deposition ranged between 0.30-0.90kgNha(-1)yr(-1), and NO2 deposition between 0.03-0.70kgNha(-1)yr(-1). During the modeled period, average dry deposition of the inorganic gaseous N species ranged between 1.03 and 2.85kgNha(-1)yr(-1) and SO4-S deposition ranged between 0.26 and 2.04kgha(-1)yr(-1). Comparisons with co-measured ion exchange resin throughfall data (8.51kgSha(-1)yr(-1)) indicate that modeled dry deposition combined with measured wet deposition (1.37kgSha(-1)yr(-1)) underestimated S deposition. Gas phase NH3 (71%) and HNO3 plus NO2 (79%) dry deposition fluxes dominated the total deposition of NH4-N and NO3-N, respectively.

Global topics and novel approaches in the study of air pollution, climate change and forest ecosystems.

Research directions from the 27th conference for Specialists in Air Pollution and Climate Change Effects on Forest Ecosystems (2015) reflect knowledge advancements about (i) Mechanistic bases of tree responses to multiple climate and pollution stressors, in particular the interaction of ozone (O3) with nitrogen (N) deposition and drought; (ii) Linking genetic control with physiological whole-tree activity; (iii) Epigenetic responses to climate change and air pollution; (iv) Embedding individual tree performance into the multi-factorial stand-level interaction network; (v) Interactions of biogenic and anthropogenic volatile compounds (molecular, functional and ecological bases); (vi) Estimating the potential for carbon/pollution mitigation and cost effectiveness of urban and peri-urban forests; (vii) Selection of trees adapted to the urban environment; (viii) Trophic, competitive and host/parasite relationships under changing pollution and climate; (ix) Atmosphere-biosphere-pedosphere interactions as affected by anthropospheric changes; (x) Statistical analyses for epidemiological investigations; (xi) Use of monitoring for the validation of models; (xii) Holistic view for linking the climate, carbon, N and O3 modelling; (xiii) Inclusion of multiple environmental stresses (biotic and abiotic) in critical load determinations; (xiv) Ecological impacts of N deposition in the under-investigated areas; (xv) Empirical models for mechanistic effects at the local scale; (xvi) Broad-scale N and sulphur deposition input and their effects on forest ecosystem services; (xvii) Measurements of dry deposition of N; (xviii) Assessment of evapotranspiration; (xix) Remote sensing assessment of hydrological parameters; and (xx) Forest management for maximizing water provision and overall forest ecosystem services. Ground-level O3 is still the phytotoxic air pollutant of major concern to forest health. Specific issues about O3 are: (xxi) Developing dose-response relationships and stomatal O3 flux parameterizations for risk assessment, especially, in under-investigated regions; (xxii) Defining biologically based O3 standards for protection thresholds and critical levels; (xxiii) Use of free-air exposure facilities; (xxiv) Assessing O3 impacts on forest ecosystem services.

Ozone distribution in remote ecologically vulnerable terrain of the southern Sierra Nevada, CA.

Ozone concentration spatial patterns remain largely uncharacterized across the extensive wilderness areas of the Sierra Nevada, CA, despite being downwind of major pollution sources. These natural areas, including four national parks and four national forests, contain forest species that are susceptible to ozone injury. Forests stressed by ozone are also more vulnerable to other agents of mortality, including insects, pathogens, climate change, and ultimately fire. Here we analyze three years of passive ozone monitor data from the southern Sierra Nevada and interpolate landscape-scale spatial and temporal patterns during the summer-through-fall high ozone concentration period. Segmentation analysis revealed three types of ozone exposure sub-regions: high, low, and variable. Consistently high ozone exposure regions are expected to be most vulnerable to forest mortality. One high exposure sub-region has been documented elsewhere as being further vulnerable to increased drought and fire potential. Identifying such hot-spots of forest vulnerability has utility for prioritizing management.

Status of the Southern Carpathian forests in the long-term ecological research network.

Air pollution, bulk precipitation, throughfall, soil condition, foliar nutrients, as well as forest health and growth were studied in 2006-2009 in a long-term ecological research (LTER) network in the Bucegi Mountains, Romania. Ozone (O(3)) was high indicating a potential for phytotoxicity. Ammonia (NH(3)) concentrations rose to levels that could contribute to deposition of nutritional nitrogen (N) and could affect biodiversity changes. Higher that 50% contribution of acidic rain (pH < 5.5) contributed to increased acidity of forest soils. Foliar N concentrations for Norway spruce (Picea abies), Silver fir (Abies alba), Scots pine (Pinus sylvestris), and European beech (Fagus sylvatica) were normal, phosphorus (P) was high, while those of potassium (K), magnesium (Mg), and especially of manganese (Mn) were significantly below the typical European or Carpathian region levels. The observed nutritional imbalance could have negative effects on forest trees. Health of forests was moderately affected, with damaged trees (crown defoliation >25%) higher than 30%. The observed crown damage was accompanied by the annual volume losses for the entire research forest area up to 25.4%. High diversity and evenness specific to the stand type's structures and local climate conditions were observed within the herbaceous layer, indicating that biodiversity of the vascular plant communities was not compromised.

Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California.

Two-week average concentrations of ozone (O3), nitric acid vapor (HNO3) and ammonia (NH3) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were determined with seasonal means for individual sites ranging between 62 and 88 ppb for O3, 1.0-3.8 microg m(-3) for HNO3, and 2.6-5.2 microg m(-3) for NH3. Calculated O3 exposure indices were very high, reaching SUM00-191 ppm h, SUM60-151 ppm h, and W126-124 ppm h. Calculated nitrogen (N) dry deposition ranged from 1.4 to 15 kg N ha(-1) for maximum values, and 0.4-8 kg N ha(-1) for minimum values; potentially exceeding Critical Loads (CL) for nutritional N. The U.S., California, and European 8 h O3 human health standards were exceeded during 104, 108, and 114 days respectively, indicating high risk to humans from ambient O3.

Estimating contribution of wildland fires to ambient ozone levels in National Parks in the Sierra Nevada, California.

Data from four continuous ozone and weather monitoring sites operated by the National Park Service in Sierra Nevada, California, are used to develop an ozone forecasting model and to estimate the contribution of wildland fires on ambient ozone levels. The analyses of weather and ozone data pointed to the transport of ozone precursors from the Central Valley as an important source of pollution in these National Parks. Comparisons of forecasted and observed values demonstrated that accurate forecasts of next-day hourly ozone levels may be achieved by using a time series model with historic averages, expected local weather and modeled PM values as explanatory variables. Results on fire smoke influence indicated occurrence of significant increases in average ozone levels with increasing fire activity. The overall effect on diurnal ozone values, however, was small when compared with the amount of variability attributed to sources other than fire.

Long-term (1992-2004) record of lead, cadmium, and zinc air contamination in Warsaw, Poland: determination by chemical analysis of moss bags and leaves of Crimean linden.

Between 1992 and 2004, air contamination with lead (Pb), cadmium (Cd), and zinc (Zn) in Warsaw, Poland, was monitored annually with moss (Sphagnum fallax) bags on a network of 230 sites covering the entire city. During the study the highest contamination was near the Warszawa Steel Mill, northwestern Warsaw. Lead concentrations in moss bags decreased in time, while those of Cd and Zn did not show clear trends. Between 1994 and 2004, Pb, Cd, and Zn were also monitored in the Crimean linden (Tilia Euchlora) foliage along the main city avenue and in a northwestern warsaw park. Lead concentrations decreased more near the avenue than in the park, indicating that the phasing-out of leaded gasoline had a major effect on reduced Pb contamination in Warsaw. At the same time, foliar concentrations of Cd and Zn in both areas decreased much less.

Image analysis of epicuticular damage to foliage caused by dry deposition of the air pollutant nitric acid.

Nitric acid vapor is produced by the same photochemical processes that produce ozone. In the laboratory, concentrated nitric acid is a strong acid and a powerful oxidant. In the environment, where the concentrations are much lower, it is an innocuous source of plant nitrogen. As an air pollutant, which mode of action does dry deposition of nitric acid follow? We investigated the effects of dry deposition of nitric acid on the foliage of four tree species native to the western United States. A novel controlled environment, fumigation system enabled a four-week exposure at concentrations consistent with ambient diurnal patterns. Scanning electron microscopy and automated image analysis revealed changes in the epicuticular wax layer during fumigation. Exposure to nitric acid resulted in a reproducible suite of damage symptoms that increased with increasing dose. Each tree species tested exhibited a unique set of damage features, including cracks, lesions, and conformation changes to epicuticular crystallite structures. Dry deposition of atmospheric nitric acid caused substantial perturbation to the epicuticular surface of all four tree species investigated, consistent with the chemical oxidation of epicuticular waxes. Automated image analysis eliminated many biases that can trouble microscopy studies. Trade names and commercial enterprises or products are mentioned solely for information. No endorsements by the U.S. Department of Agriculture are implied.

Foliar loading and metabolic assimilation of dry deposited nitric acid air pollutants by trees.

Dry deposition of nitric acid vapor (HNO(3)) is a major contributor to eutrophication of natural ecosystems. Although soil fertilization by nitrogen deposition is considered to be the primary pathway for changes in plant nutrient status and shifts in ecological structure, the aerial portion of plants offer many times the surface area in which to collect atmospheric HNO(3). As much as 60% of deposited nitrogen may be retained in the canopy and not land on the soil surface below. Although uptake and assimilation appears to contribute to retention, only a small percentage of dry deposition is recovered in assimilated N pools. To test the importance of biological activity on the process and measurements of dry deposition, we used controlled environmental chambers to compare deposition to living and freeze-dried foliage of four tree species using (15)N-labeled HNO(3). In living trees, assimilation was determined by (15)N incorporation into free amino acids and proteins in leaves and roots. From 10% to 60% of the retained HNO(3) was incorporated into the biologically active nitrogen pool. The remainder was bound to foliar surfaces in an insoluble form in either living or freeze-dried foliage. The importance of the boundary layer conditions emerged as a primary factor controlling dry deposition characteristics and measurements.Trade names and commercial enterprises or products are mentioned solely for information. No endorsements by the U.S. Department of Agriculture are implied.

Evidence of enhanced atmospheric ammoniacal nitrogen in Hells Canyon national recreation area: implications for natural and cultural resources.

Agriculture releases copious fertilizing pollutants to air sheds and waterways of the northwestern United States. To evaluate threats to natural resources and historic rock paintings in remote Hells Canyon, Oregon and Idaho, deposition of ammonia (NH3), nitrogen oxides (NOx), sulfur dioxide (SO2), and hydrogen sulfide (H2S) at five stations along 60 km of the Snake River valley floor were passively sampled from July 2002 through June 2003, and ozone data and particulate chemistry were obtained from the Interagency Monitoring of Protected Visual Environments (IMPROVE) station at Hells Canyon. NH3 concentrations were high; biweekly averages peaked at 5-19 ppb in spring and summer and the nutrient-laden Snake River is a likely source. Fine particulate ammonium nitrate (NH4NO3) averaged 2.6 microg/m3 during the 20% of worst visibility days with winter drainage of air masses from the Snake River Basin and possibly long distance transport from southern California. Other pollutants were within background ranges. NH3 is corrosive to clay-based pictographs; nitrogen deposition can alter natural biotic communities and terrestrial ecosystem processes at levels reported here.

Contribution of ambient ozone to Scots pine defoliation and reduced growth in the Central European forests: a Lithuanian case study.

The study aimed to explore if changes in crown defoliation and stem growth of Scots pines (Pinus sylvestris L.) could be related to changes in ambient ozone (O(3)) concentration in central Europe. To meet this objective the study was performed in 3 Lithuanian national parks, close to the ICP integrated monitoring stations from which data on meteorology and pollution were provided. Contribution of peak O(3) concentrations to the integrated impact of acidifying compounds and meteorological parameters on pine stem growth was found to be more significant than its contribution to the integrated impact of acidifying compounds and meteorological parameters on pine defoliation. Findings of the study provide statistical evidence that peak concentrations of ambient O(3) can have a negative impact on pine tree crown defoliation and stem growth reduction under field conditions in central and northeastern Europe where the AOT40 values for forests are commonly below their phytotoxic levels.