Deposition Of Nitric Acid Research Articles

Modeling Indoor Inorganic Aerosol Concentrations During the ATHLETIC Campaign with IMAGES.

In 2018, the ATHLETIC campaign was conducted at the University of Colorado Dal Ward Athletic Center and characterized dynamic indoor air composition in a gym environment. Among other parameters, inorganic particle and gas-phase species were alternatingly measured in the gym's supply duct and weight room. The Indoor Model of Aerosols, Gases, Emissions, and Surfaces (IMAGES) uses the inorganic aerosol thermodynamic equilibrium model, ISORROPIA, to estimate the partitioning of inorganic aerosols and corresponding gases. In this study herein, measurements from the ATHLETIC campaign were used to evaluate IMAGES' performance. Ammonia emission rates, nitric acid deposition, and particle deposition velocities were related to observed occupancy, which informed these rates in IMAGES runs. Initially, modeled indoor inorganic aerosol concentrations were not in good agreement with measurements. A parametric investigation revealed that lowering the temperature or raising the relative humidity used in the ISORROPIA model drove the semivolatile species more toward the particle phase, substantially improving modeled-measured agreement. One speculated reason for these solutions is that aerosol water was enhanced by increasing the RH or decreasing the temperature. Another is that thermodynamic equilibrium was not established in this indoor setting or that the thermodynamic parametrizations in ISORROPIA are less accurate for typical indoor settings. This result suggests that applying ISORROPIA indoors requires further careful experimental validation.

Acid deposition at higher acidity weakens the antagonistic responses during the co-decomposition of two Asteraceae invasive plants

Co-invasion by two invasive plant species (IPS) can occur in the same habitat. Diversified acid deposition may change the co-invasion process by altering litter decomposition and plant-soil feedback signalling. This study examined the co-decomposition of two Asteraceae IPS (Solidago canadensis L. and Bidens pilosa L.) on litter decomposition rate, soil enzyme activities, and soil N-fixing bacterial communities under diversified acid deposition (mixed acid deposition at pH 5.6 and at pH 4.5, sulfuric acid at pH 4.5, and nitric acid at pH 4.5). B. pilosa litter degraded faster than S. canadensis litter. Acid deposition at higher acidity accelerated the decomposition rate of both pure S. canadensis litter and the equally mixed litters from the two Asteraceae IPS. Antagonistic responses may occur during the co-decomposition of the two Asteraceae IPS with mixed acid deposition, regardless of the pH, as well as with nitric acid deposition at pH 4.5; in contrast, there may be neutral responses for the co-decomposition process with sulfuric acid at pH 4.5. The type of acid deposited may be one of the key factors affecting the intensity of the mixing effect affecting the co-decomposition. Acid deposition at higher acidity weakened the antagonistic responses for the co-decomposition of the two Asteraceae IPS compared with the response to weak acids. Together, these results indicate that acid deposition at higher acidity could facilitate the co-invasion of the two Asteraceae IPS mainly through accelerated litter decomposition as well as weakened antagonistic responses for co-decomposition.

Study on Roasting for Selective Lithium Leaching of Cathode Active Materials from Spent Lithium-Ion Batteries

Recently, many studies have been conducted on the materialization of spent batteries. In conventional cases, lithium is recovered from an acidic solution through the leaching and separation of valuable metals; however, it is difficult to remove impurities because lithium is recovered in the last step. Cathode active materials of lithium-ion batteries comprise oxides with lithium, such as LiNixCoyMnzO2 and LiCoO2. Thus, lithium should be converted into a compound that can be leached in deionized water for selective lithium leaching. Recent studies on the leaching and recovery of Li2CO3 through a carbon reduction reaction show low economic efficiency, due to the solubility of Li2CO3 at room temperature being as low as 13 g/L. This paper proposes a method of roasting after nitric acid deposition for selective lithium leaching and recovery to LiNO3. Based on experiments involving the varying of the amount of nitric acid, roasting temperature, and solid–liquid ratio, optimal values were found to be dipping in 10 M HNO3 2 mL/g, roasting at 275 °C, and deionized water with a solid–liquid ratio of 10 mL/g, respectively. Over 80% Li leaching was possible under these conditions. IC analysis confirmed that the purity was 97% lithium nitrate.

Nitrogen burden from atmospheric deposition in East Asian oceans in 2010 based on high-resolution regional numerical modeling

East Asian oceans are possibly affected by a high nitrogen (N) burden because of the intense anthropogenic emissions in this region. Based on high-resolution regional chemical transport modeling with horizontal grid scales of 36 and 12 km, we investigated the N burden into East Asian oceans via atmospheric deposition in 2010. We found a high N burden of 2–9 kg N ha−1 yr−1 over the Yellow Sea, East China Sea (ECS), and Sea of Japan. Emissions over East Asia were dominated by ammonia (NH3) over land and nitrogen oxides (NOx) over oceans, and N deposition was dominated by reduced N over most land and open ocean, whereas it was dominated by oxidized N over marginal seas and desert areas. The verified numerical modeling identified that the following processes were quantitatively important over East Asian oceans: the dry deposition of nitric acid (HNO3), NH3, and coarse-mode (aerodynamic diameter greater than 2.5 μm) NO3−, and wet deposition of fine-mode (aerodynamic diameter less than 2.5 μm) NO3− and NH4+. The relative importance of the dry deposition of coarse-mode NO3− was higher over open ocean. The estimated N deposition to the whole ECS was 390 Gg N yr−1; this is comparable to the discharge from the Yangtze River to the ECS, indicating the significant contribution of atmospheric deposition. Based on the high-resolution modeling over the ECS, a tendency of high deposition in the western ECS and low deposition in the eastern ECS was found, and a variety of deposition processes were estimated. The dry deposition of coarse-mode NO3− and wet deposition of fine-mode NH4+ were the main factors, and the wet deposition of fine-mode NO3− over the northeastern ECS and wet deposition of coarse-mode NO3− over the southeastern ECS were also found to be significant processes determining N deposition over the ECS.

Automated, High-resolution Mobile Collection System for the Nitrogen Isotopic Analysis of NOx.

Nitrogen oxides (NOx = NO + NO2) are a family of atmospheric trace gases that have great impact on the environment. NOx concentrations directly influence the oxidizing capacity of the atmosphere through interactions with ozone and hydroxyl radicals. The main sink of NOx is the formation and deposition of nitric acid, a component of acid rain and a bioavailable nutrient. NOx is emitted from a mixture of natural and anthropogenic sources, which vary in space and time. The collocation of multiple sources and the short lifetime of NOx make it challenging to quantitatively constrain the influence of different emission sources and their impacts on the environment. Nitrogen isotopes of NOx have been suggested to vary amongst different sources, representing a potentially powerful tool to understand the sources and transport of NOx. However, previous methods of collecting atmospheric NOx integrate over long (week to month) time spans and are not validated for the efficient collection of NOx in relevant, diverse field conditions. We report on a new, highly efficient field-based system that collects atmospheric NOx for isotope analysis at a time resolution between 30 min and 2 hr. This method collects gaseous NOx in solution as nitrate with 100% efficiency under a variety of conditions. Protocols are presented for collecting air in urban settings under both stationary and mobile conditions. We detail the advantages and limitations of the method and demonstrate its application in the field. Data from several deployments are shown to 1) evaluate field-based collection efficiency by comparisons with in situ NOx concentration measurements, 2) test the stability of stored solutions before processing, 3) quantify in situ reproducibility in a variety of urban settings, and 4) demonstrate the range of N isotopes of NOx detected in ambient urban air and on heavily traveled roadways.

Automated, High-resolution Mobile Collection System for the Nitrogen Isotopic Analysis of NO<sub>x</sub>

Nitrogen oxides (NOx = NO + NO2) are a family of atmospheric trace gases that have great impact on the environment. NOx concentrations directly influence the oxidizing capacity of the atmosphere through interactions with ozone and hydroxyl radicals. The main sink of NOx is the formation and deposition of nitric acid, a component of acid rain and a bioavailable nutrient. NOx is emitted from a mixture of natural and anthropogenic sources, which vary in space and time. The collocation of multiple sources and the short lifetime of NOx make it challenging to quantitatively constrain the influence of different emission sources and their impacts on the environment. Nitrogen isotopes of NOx have been suggested to vary amongst different sources, representing a potentially powerful tool to understand the sources and transport of NOx. However, previous methods of collecting atmospheric NOx integrate over long (week to month) time spans and are not validated for the efficient collection of NOx in relevant, diverse field conditions. We report on a new, highly efficient field-based system that collects atmospheric NOx for isotope analysis at a time resolution between 30 min and 2 hr. This method collects gaseous NOx in solution as nitrate with 100% efficiency under a variety of conditions. Protocols are presented for collecting air in urban settings under both stationary and mobile conditions. We detail the advantages and limitations of the method and demonstrate its application in the field. Data from several deployments are shown to 1) evaluate field-based collection efficiency by comparisons with in situ NOx concentration measurements, 2) test the stability of stored solutions before processing, 3) quantify in situ reproducibility in a variety of urban settings, and 4) demonstrate the range of N isotopes of NOx detected in ambient urban air and on heavily traveled roadways.

The allelopathic effects of invasive plant Solidago canadensis on seed germination and growth of Lactuca sativa enhanced by different types of acid deposition.

Invasive species can exhibit allelopathic effects on native species. Meanwhile, the types of acid deposition are gradually changing. Thus, the allelopathic effects of invasive species on seed germination and growth of native species may be altered or even enhanced under conditions with diversified acid deposition. This study aims to assess the allelopathic effects (using leaves extracts) of invasive plant Solidago canadensis on seed germination and growth of native species Lactuca sativa treated with five types of acid deposition with different SO4(2-) to NO3(-) ratios (1:0, sulfuric acid; 5:1, sulfuric-rich acid; 1:1, mixed acid; 1:5, nitric-rich acid; 0:1, nitric acid). Solidago canadensis leaf extracts exhibited significantly allelopathic effects on germination index, vigor index, and germination rate index of L. sativa. High concentration of S. canadensis leaf extracts also similarly exhibited significantly allelopathic effects on root length of L. sativa. This may be due to that S. canadensis could release allelochemicals and then trigger allelopathic effects on seed germination and growth of L. sativa. Acid deposition exhibited significantly negative effects on seedling biomass, root length, seedling height, germination index, vigor index, and germination rate index of L. sativa. This may be ascribed to the decreased soil pH values mediated by acid deposition which could produce toxic effects on seedling growth. Sulfuric acid deposition triggered more toxic effects on seedling biomass and vigor index of L. sativa than nitric acid deposition. This may be attributing to the difference in exchange capacity with hydroxyl groups (OH(-)) between SO4(2-) and NO3(-) as well as the fertilizing effects mediated by nitric deposition. All types of acid deposition significantly enhanced the allelopathic effects of S. canadensis on root length, germination index, vigor index, and germination rate index of L. sativa. This may be due to the negatively synergistic effects of acid deposition and S. canadensis on seed germination and growth of L. sativa. The ratio of SO4(2-) to NO3(-) in acid deposition was an important factor that profoundly affected the allelopathic effects of S. canadensis on the seed germination and growth of L. sativa possibly because the difference in exchange capacity with hydroxyl groups (OH(-)) between SO4(2-) and NO3(-) as well as the fertilizing effects triggered by nitric deposition. Thus, the allelopathic effects of invasive species on seed germination and growth of native plants might be enhanced under increased and diversified acid deposition.

Photosynthetic and growth responses of Schima superba seedlings to sulfuric and nitric acid depositions.

A continuing rise in acid deposition can cause forest degradation. In China, acid deposition has converted gradually from sulfuric acid deposition (SAD) to nitric acid deposition (NAD). However, the differing responses of photosynthesis and growth to depositions of sulfuric vs. nitric acid have not been well studied. In this study, 1-year-old seedlings of Schima superba, a dominant species in subtropical forests, were treated with two types of acid deposition SO4 (2-)/NO3 (-) ratios (8:1 and 0.7:1) with two applications (foliar spraying and soil drenching) at two pH levels (pH 3.5 and pH 2.5) over a period of 18months. The results showed that the intensity, acid deposition type, and spraying method had significant effects on the physiological characteristics and growth performance of seedlings. Acid deposition at pH 2.5 via foliar application reduced photosynthesis and growth of S. superba, especially in the first year. Unlike SAD, NAD with high acidity potentially alleviated the negative effects of acidity on physiological properties and growth, probably due to a fertilization effect that improved foliar nitrogen and chlorophyll contents. Our results suggest that trees were damaged mainly by direct acid stress in the short term, whereas in the long term, soil acidification was also likely to be a major risk to forest ecosystems. Our data suggest that the shift in acid deposition type may complicate the ongoing challenge of anthropogenic acid deposition to ecosystem stability.

Highway contributions to reactive nitrogen deposition: tracing the fate of vehicular NOx using stable isotopes and plant biomonitors

While epidemiologists have long acknowledged that automobile emissions create corridors of increased NOx concentrations near highways, the influence of these emissions on dry nitrogen (N) deposition and effects on surrounding ecosystems are not well-characterized. This study used stable isotopes in plant tissue and dry N deposition to examine the extent of N deposition from automobile emissions along a roadside transect spanning 400 m perpendicular to a moderately trafficked highway (33,000 vehicles per day). Passive samplers were deployed monthly for four months at six stations to collect dry deposition of nitric acid (HNO3) and nitrogen dioxide (NO2), analyzed for concentration and natural abundance isotopic composition (δ15N). Agrostis perennans (bentgrass) and Panicum virgatum (switchgrass) were deployed as biomonitors to examine relative sources of N to plant tissue. Both NO2 flux and δ15N–NO2 values were significantly higher close to the road indicating a high proportion of automobile-sourced N is deposited near-road. Further, this near-road deposition occurred primarily as NO2 prior to oxidation to HNO3, as HNO3 fluxes were an order of magnitude lower than NO2 fluxes and were highest midway through the transect. Plant tissue δ15N values were higher near the road, signifying the influence of automobile emissions on plant tissue composition. Importantly, N flux near the road was four times higher than background N flux measured at the nearest regional dry deposition monitoring locations. We extrapolated these results to demonstrate that the observed spatial patterns of concentrated N deposition impact our understanding of regional N deposition to watersheds when applied to a metropolitan area.

Sensitivity analyses of factors influencing CMAQ performance for fine particulate nitrate

Improvement of air quality models is required so that they can be utilized to design effective control strategies for fine particulate matter (PM2.5). The Community Multiscale Air Quality modeling system was applied to the Greater Tokyo Area of Japan in winter 2010 and summer 2011. The model results were compared with observed concentrations of PM2.5 sulfate (SO42-), nitrate (NO3−) and ammonium, and gaseous nitric acid (HNO3) and ammonia (NH3). The model approximately reproduced PM2.5 SO42− concentration, but clearly overestimated PM2.5 NO3− concentration, which was attributed to overestimation of production of ammonium nitrate (NH4NO3). This study conducted sensitivity analyses of factors associated with the model performance for PM2.5 NO3− concentration, including temperature and relative humidity, emission of nitrogen oxides, seasonal variation of NH3 emission, HNO3 and NH3 dry deposition velocities, and heterogeneous reaction probability of dinitrogen pentoxide. Change in NH3 emission directly affected NH3 concentration, and substantially affected NH4NO3 concentration. Higher dry deposition velocities of HNO3 and NH3 led to substantial reductions of concentrations of the gaseous species and NH4NO3. Because uncertainties in NH3 emission and dry deposition processes are probably large, these processes may be key factors for improvement of the model performance for PM2.5 NO3−.Implications: The Community Multiscale Air Quality modeling system clearly overestimated the concentration of fine particulate nitrate in the Greater Tokyo Area of Japan, which was attributed to overestimation of production of ammonium nitrate. Sensitivity analyses were conducted for factors associated with the model performance for nitrate. Ammonia emission and dry deposition of nitric acid and ammonia may be key factors for improvement of the model performance.

Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN) above a Ponderosa pine forest

Abstract. During the Biosphere Effects on AeRosols and Photochemistry EXperiment 2007 (BEARPEX-2007), we observed eddy covariance (EC) fluxes of speciated acyl peroxy nitrates (APNs), including peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN) and peroxymethacryloyl nitrate (MPAN), above a Ponderosa pine forest in the western Sierra Nevada. All APN fluxes are net downward during the day, with a median midday PAN exchange velocity of −0.3 cm s−1; nighttime storage-corrected APN EC fluxes are smaller than daytime fluxes but still downward. Analysis with a standard resistance model shows that loss of PAN to the canopy is not controlled by turbulent or molecular diffusion. Stomatal uptake can account for 25 to 50% of the observed downward PAN flux. Vertical gradients in the PAN thermal decomposition (TD) rate explain a similar fraction of the flux, suggesting that a significant portion of the PAN flux into the forest results from chemical processes in the canopy. The remaining "unidentified" portion of the net PAN flux (~15%) is ascribed to deposition or reactive uptake on non-stomatal surfaces (e.g. leaf cuticles or soil). Shifts in temperature, moisture and ecosystem activity during the summer – fall transition alter the relative contribution of stomatal uptake, non-stomatal uptake and thermochemical gradients to the net PAN flux. Daytime PAN and MPAN exchange velocities are a factor of 3 smaller than those of PPN during the first two weeks of the measurement period, consistent with strong intra-canopy chemical production of PAN and MPAN during this period. Depositional loss of APNs can be 3–21% of the gross gas-phase TD loss depending on temperature. As a source of nitrogen to the biosphere, PAN deposition represents approximately 4–19% of that due to dry deposition of nitric acid at this site.

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.

Secondary acidification: Changes in gas‐aerosol partitioning of semivolatile nitric acid and enhancement of its deposition due to increased emission and concentration of SOx

Secondary acidification, or the indirect enhancement of semivolatile air pollutant deposition associated with increased SO42− concentrations, is shown to occur in general air pollution using data collected from six stations of the Acid Deposition Monitoring Network in East Asia (EANET) in Japan. This effect was first detected as a result of volcanic SO2 plumes in our previous studies. Results indicate that as SO42− concentration increases, gas‐aerosol partitioning of nitric acid shifts to the gas phase, increasing the HNO3 gas concentration. Since the dry and wet deposition rates of HNO3 gas are very high, deposition can be enhanced even when the emission of NOx remains unchanged. In western Japan, the indirect effect for wet deposition is most apparent from spring to autumn, when the Asian continental outflow carries sulfate‐rich contaminated air masses. However, it is not pronounced in air masses containing abundant sea‐salt particles and related cation components in aerosols. In areas such as forests or farmlands with low surface resistance, dry deposition of nitric acid is more pronounced than wet deposition as the dry deposition velocity of HNO3 gas is high. Increased dry deposition of t‐NO3 due to the indirect effect and consequent vegetation damage is thus of considerable concern in such regions. The deposition of other semivolatile components, such as hydrochloric acid and ammonia, can be altered and can also induce secondary acidification.

Increase in tropospheric nitrogen dioxide over China observed from space

Emissions from fossil fuel combustion and biomass burning reduce local air quality and affect global tropospheric chemistry. Nitrogen oxides are emitted by all combustion processes and play a key part in the photochemically induced catalytic production of ozone, which results in summer smog and has increased levels of tropospheric ozone globally. Release of nitrogen oxide also results in nitric acid deposition, and--at least locally--increases radiative forcing effects due to the absorption of downward propagating visible light. Nitrogen oxide concentrations in many industrialized countries are expected to decrease, but rapid economic development has the potential to increase significantly the emissions of nitrogen oxides in parts of Asia. Here we present the tropospheric column amounts of nitrogen dioxide retrieved from two satellite instruments GOME and SCIAMACHY over the years 1996-2004. We find substantial reductions in nitrogen dioxide concentrations over some areas of Europe and the USA, but a highly significant increase of about 50 per cent-with an accelerating trend in annual growth rate-over the industrial areas of China, more than recent bottom-up inventories suggest.

Total deposition of nitrogen on Swiss long-term forest ecosystem research (LWF) plots: comparison of the throughfall and the inferential method

Abstract The total deposition of nitrogen was estimated at 10 plots in the Swiss Long-Term Forest Ecosystem Research Programme for 1 year (1999/2000) using two methods: (1) the throughfall method, using bulk precipitation and throughfall measurements as input data for the canopy budget model; and (2) the inferential method, based on measurements of ammonia and nitrogen dioxide with passive samplers and deposition velocities taken from literature. The inferential method was coupled with a regression model deriving the other terms of the total deposition of nitrogen (wet deposition, dry deposition of nitric acid and dry deposition of particulate nitrogen) from measurements of the bulk deposition of nitrogen. The two methods gave estimates of the total deposition that correlated significantly with each other, in the range of 5–38 kg ha −1 a −1 , but the inferential method tended to yield higher estimates than those obtained with the throughfall method (median difference +2.4 kg ha −1 a −1 ). In view of the overall agreement of the two methods, the use of passive samplers in the open, coupled with the measurement of bulk deposition, appears, under certain conditions, to be an interesting alternative to the throughfall method.

Gas-particle interactions above a Dutch heathland: III. Modelling the influence of the NH<sub>3</sub>-HNO<sub>3</sub>-NH<sub>4</sub>NO<sub>3</sub> equilibrium on size-segregated particle fluxes

Abstract. Micrometeorological measurements of size-segregated particle number fluxes above Dutch heathlands and forests have repeatedly shown simultaneous apparent emission of particles with a diameter (Dp)<0.18 µm and deposition of larger particles when measured with optical particle counters. In order to assess whether this observation may be explained by the equilibrium reaction of ammonia (NH3), nitric acid (HNO3) and ammonium (NH4+), a new numerical model is developed to predict the vertical concentration and flux profiles of the different species as modified by the interaction of equilibration and surface/atmosphere exchange processes. In addition to former studies, the new approach explicitly models the height-dependence of the NH4+ and total aerosol size-distribution. Using this model, it is demonstrated that both gas-to-particle conversion (gtpc) and aerosol evaporation can significantly alter the apparent surface exchange fluxes, and evoke the observed bi-directional particle fluxes under certain conditions. Thus, in general, the NH3-HNO3-NH4NO3 equilibrium needs to be considered when interpreting eddy-covariance particle fluxes. Applied to an extensive dataset of simultaneous flux measurements of particles and gases at Elspeet, NL, the model reproduces the diurnal pattern of the bi-directional exchange well. In agreement with the observation of fast NH4+ deposition, slow nitric acid deposition (both as measured by the aerodynamic gradient method) and small concentration products of NH3×HNO3 at this site, this study suggests that NH4+ evaporation at this site significantly alters surface exchange fluxes.

Experimentally derived estimates of nitric acid dry deposition velocity and viscous sub-layer resistance at a conifer forest

Daytime dry deposition of nitric acid to a conifer forest with a LAI of 5.3 was measured using the relaxed eddy accumulation technique. The observations indicate a mean friction velocity of 0.45 m s � 1 and a mean dry deposition velocity (vd) of 7.5 cm s � 1 , with approximately equal aerodynamic (ra) and non-aerodynamic resistances (rb+rc). Mean ra is 10 s m � 1 , while mean rb+rc (derived from the difference between the observed vd and a value derived based solely on ra) is 13.2 s m � 1 . Assuming the surface resistance (rc) is zero, the viscous sub-layer resistance (rb) from a number of models capture the mean observationally derived value to within 740%, but the models underestimate the variability inherent in the measurements. This discrepancy between the modeled and observed sample-to-sample variability of rb does not appear to be accounted for by leaf wetness, stomatal opening or an additional dependence on friction velocity. r 2004 Elsevier Ltd. All rights reserved.

Modelling the deposition of atmospheric oxidised nitrogen and sulphur to the United Kingdom using a multi-layer long-range transport model

Abstract Deposition of sulphur and oxidised nitrogen have been estimated for the United Kingdom (UK) for 1996 using an atmospheric transport model (FRAME, Fine Resolution Atmospheric Multi-pollutant Exchange). Firstly, the modelled deposition is compared with measurement based estimates of NEGTAP (National Expert Group on Transboundary Air Pollution). Secondly, the modelled wet deposition and surface air concentrations are compared with measurements from the UK's monitoring networks using linear regression. FRAME gives 65 and 102 ktonnes(kt) for oxidised nitrogen dry and wet UK deposition, respectively, compared with the NEGTAP estimation of 87 and 91 kt . The modelled contributions of sulphur dry and wet deposition are 138 and 200 kt , respectively, compared with the NEGTAP estimation of 125 and 171 kt . FRAME is found to perform well for nitrogen dioxide concentrations and nitrate wet deposition, but the concentration and subsequent dry deposition of nitric acid is underestimated. Deposition of sulphur and sulphur dioxide surface concentrations are coherent with the NEGTAP estimation but they are slightly overestimated by FRAME. The paper also emphasises the uncertainties associated with the model when used to assess the effects of abatement policies.

Removal of NOx and NOy in biomass burning plumes in the boundary layer over northern Australia

The Biomass Burning and Lightning Experiment Phase B (BIBLE‐B) aircraft measurement campaign was conducted over the western Pacific and Australia in August and September 1999. In situ aircraft measurements of carbon monoxide (CO), nitric oxide (NO), total reactive nitrogen (NOy), ozone (O3), nonmethane hydrocarbons (NMHCs), and other species were made during BIBLE‐B. Meteorological analysis shows that the trace gases emitted from biomass burning in northern Australia were mostly confined within the planetary boundary layer (below ∼3 km) by strong subsidence in the free troposphere. Removal processes of NOx (equal to measured NO + calculated NO2) and NOy in biomass burning plumes in the boundary layer are examined on the basis of correlation analysis. The photochemical lifetime of NOx in biomass burning plumes during the daytime is estimated to be 0.1 to 0.3 days using the correlations of NOx with short‐lived NMHCs and hydroxyl radical (OH) concentration calculated from a constrained photochemical model. Correlation of NOy with CO shows that ∼60% of the NOy molecules originating from biomass burning were removed in the boundary layer within 2–3 days. This result is consistent with dry deposition of nitric acid (HNO3) in the plumes. It is likely that only a small fraction of NOy emitted from biomass burning was exported from the boundary layer to the free troposphere during the BIBLE‐B period.

Soil Acidification Induced by Ammonium Sulphate Addition in a Norway Spruce Forest in Southwest Sweden

The contributions of different acidifying processes to the total protonload (TPL) of the soil in control plots (C) and ammonium sulphate treatedplots (NS) were studied in a Norway spruce stand in Southwest Sweden during 1988–1998. The annual deposition of inorganic nitrogen and sulphate was on average 18 kg N and 20 kg S ha-1. In addition the NS treated plots received 100 kg N and 114 kg S ha-1 annually. The amounts of nutrients added to the ecosystem by wet and dry deposition and the leaching at 50 cm depth were calculated. The net atmosphericproton load, the proton load by nitrogen transformations in the soil, the sulphate sorption/desorption in the soil and the excess base cation accumulation in biomass were calculated. There was no leaching of inorganic nitrogen from control plots during the study period. The net atmospheric proton deposition, originating from sulphuric and nitric acid deposition, was the main contributor to TPL in control plots. The addition of ammonium sulphate increased the leaching of ammonium, nitrate, sulphate, magnesium and calcium but not of potassium. The TPL in NS plots was about ten times that in control plots. The nitrogen transformation processes were the main contributors to TPL to NS soil, in the beginning by ammonium uptake and later also by nitrification. The pH decreased by 0.4 units in the mineral soil. The between-year variation in TPL during the eleven year period in C plots (200–1500 molc ha-1 yr-1) and in NS plots (1000–13000 molc ha-1 yr-1) was mainly dependent on the sorption or release of sulphate. Both in C and NS, the TPL was buffered mainly by dissolving solid aluminium compounds, most probably some Al(OH)3 phase.