Determination of Atmospheric Nitrogen Input to Lake Greenwood,South Carolina: Part 2—Gaseous Measurements and Modeling

Abstract

The Reedy River branch of Lake Greenwood, SC, has repeatedly experienced summertime algal blooms, upsetting the natural system. A series of experiments were carried out to investigate atmospheric nitrogen (N) input into the lake. N was examined because of the insignificant phosphorus dry atmospheric flux and the unique nutrient demands of the dominant algae (Pithophora oedogonia) contributing to the blooms. Episodic atmospheric measurements during January and March 2001 have shown that the dry N flux onto the lake ranged from 0.9 to 17.4 kg N/ha-yr, and on average is caused by nitric acid (HNO₃; 31%), followed by nitrogen dioxide (NO₂; 23%), fine ammonium (NH₄ ⁺; 20%), coarse nitrate (NO₃ ^?; 16%), fine NO₃ ⁺ (5%), and coarse NH₄ ⁺ (5%). Similar measurements in Greenville, SC (the upper watershed of the Reedy River), showed that the dry N deposition flux there ranged from 1.4 to 9.7 kg N/ha-yr and was mostly caused by gaseous deposition (40% NO₂ and 40% HNO₃). The magnitude of this dry N deposition flux is comparable to wet N flux as well as other point sources in the area. Thermodynamic modeling showed low concentrations of ammonia, relative to the particulate NH₄ ⁺ concentrations.     

Deposition processes of ionic constituents to snow cover

Atmospheric deposition is an important removal process of aerosol particles and gases from the atmosphere. To elucidate the relative contributions of wet and dry processes and in-cloud and below-cloud scavenging based on deposition amounts in winter at Mt. Tateyama, central Japan, we obtained daily samples (December, 2006–March, 2007) of size-segregated aerosol particles and precipitation at Senjyugahara (SJ; 475 m a.s.l.) and vertical samples of spring snow cover at Murododaira (MR, 2450 m a.s.l., 13 km distance from SJ) on the western flank of Mt. Tateyama. The NH₄⁺ and nssSO₄^2? in aerosols were mostly found in the fine fraction (<2 μm), although Na⁺, NO₃^?, and nssCa²⁺ were mainly detected in the coarse fraction (>2 μm). Average ionic concentrations (μg g^?1) in precipitation at SJ were higher about 3.8 for Na⁺ and nssCa²⁺, 3.4 for NO₃^?, 3.7 for NH₄⁺, 2.5 for nssSO₄^2? than those at MR, whereas cumulative precipitation amounts at SJ and MR were, respectively, 84 and 175 cm of water equivalent. Wet and dry deposition amounts during the study period were estimated for sites using size-segregated aerosol data, winter averages of HNO₃, NH₃, and SO₂ concentrations, and dry deposition velocities. Particle-dry deposition comprised about 3% (Na⁺) to 11% (NH₄⁺) of the total deposition at MR. The maximum amounts of gas dry deposition were estimated, respectively, as 4, 13, and 3% of the total deposition at MR for NH₄⁺, NO₃^?, and nssSO₄^2?. The relative contributions of below-cloud scavenging (BCS) between MR and SJ were estimated as considering the wet only deposition amount at MR. Higher contributions of BCS were obtained for Na⁺ (56%) and nssCa²⁺ (45%), whereas BCSs for NH₄⁺, NO₃^?, and nssSO₄^2? were lower than 28%. Ionic constituents existing predominantly in the coarse fraction showed a large contribution of BCS.     

NH4+, NO3−, and SO42− in roadside and rural size-resolved particles and transformation of NO2/SO2 to nanoparticle-bound NO3−/SO42−

This study investigates ammonium, nitrate, and sulfate (NH₄⁺, NO₃^?, and SO₄^2?) in size-resolved particles (particularly nano (PM_0.01–0.056)/ultrafine (PM_0.01–0.1)) and NO_x/SO₂ collected near a busy road and at a rural site. The average (mass) cumulative fraction of secondary inorganic aerosols (SO₄^2?+NO₃^?+NH₄⁺) in nano or ultrafine particles at the roadside was found to be three to four times that at the rural site. The above three secondary inorganic aerosol species were present in similar cumulative fractions in particles of size 1–18 μm at both sites; however, dissimilar fractions were observed for Cl^?, Na⁺, and K⁺. The nitrogen ratios (NRs: NR = NO₃^??N/(NO₃^??N + NO₂–N)), sulfur ratios (SRs: SR = SO₄^2??S/(SO₄^2??S + SO₂–S)), dNR/D_P (derivative of NR with respect to D_P (particle diameter)), and dSR/D_P (derivative of SR with respect to D_P) at the roadside were higher than those at the rural site for nano/ultrafine particles. At both sites (particularly the roadside), the nanoparticles had significantly higher dNR/D_P and dSR/D_P values than differently sized particles, implying that NO₃^?/SO₄^2? (from NO₂/SO₂ transformation or NO₃^?/SO₄^2? deposition) were present on these particles.     

Source apportionment of particulate matter at urban mixed site in Indonesia using PMF

A receptor model of positive matrix factorization (PMF) was used to identify the emission sources of fine and coarse particulates in Bandung, a city located at about 150 km south-east of Jakarta. Total of 367 samples were collected at urban mixed site, Tegalega area, in Bandung City during wet and dry season in the period of 2001–2007. The samples of fine and coarse particulate matter were collected simultaneously using dichotomous samplers and mini-volume samplers. The Samples from dichotomous Samplers were analyzed for black carbon and elements while samples from mini-volume samplers were analyzed for ions. The species analyzed in this study were Na, Mg, Al, Si, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Pb, Cl^?, NO₃^?, SO₄^2?, and NH₄⁺. The data were then analyzed using PMF to determine the source factors. Different numbers of source factors were found during dry and wet season. During dry season, the main source factors for fine particles were secondary aerosol (NH₄)₂SO₄, electroplating industry, vehicle emission, and biomass burning, while for coarse particles, the dominant source factors were electroplating industry, followed by aged sea salt, volcanic dust, soil dust, and lime dust. During the wet season, the main source factors for fine particulate matter were vehicle emission and secondary aerosol. Other sources detected were biomass burning, lime dust, soil and volcanic dust. While for coarse particulate matter, the main source factors were sulphate-rich industry, followed by lime dust, soil dust, industrial emission and construction dust.     

Changes in soil inorganic nitrogen as related to atmospheric nitrogenous pollutants in southern California

The deposition of nitrogenous pollutants has serious implications for ecosystem function and stability. Research in temperate ecosystems has indicated a wide range of ecological responses, yet very little is known about arid ecosystems. In this study, measurements of atmospheric and soil concentrations of the plant-available NO^-₃ and NH⁺₄ were evaluated to identify a potential gradient in nitrogen (N) deposition. The evaluations were conducted in coastal sage scrub, a semi-arid vegetation type native to the lower elevations of southern California.The summer atmospheric concentrations of nitrate (NO^-₃) and ammonium (NH⁺₄) were determined at five locations on the Perris Plain of southern California. The atmospheric influences varied from direct interception of pollution generated in the Los Angeles Basin at the northern end of the gradient to a site 70 km south lacking any direct Los Angeles influence. The summer atmospheric concentrations of NO^-₃ varied more than three-fold along the gradient. Ammonium concentrations followed a similar pattern, but the gradient was less steep. Winter concentrations were very low for both compounds. The summer soil surface NO^-₃ concentrations were near the detection limits at low pollution sites but in the range of 50–60 μg N g^-1 soil under highly polluted conditions. Wet deposition was found to be a minor contributor of plant-available N, suggesting that dry deposition may be a consequential source of plant-available N.The detection of significant changes in inorganic, plant-available N in the upper layer of soils is enhanced by the unique environmental conditions and vegetation of southern California. This study suggests that the coastal sage scrub ecosystem is experiencing significant changes in N fertility that may contribute to changes in plant species composition. The data also show that this semi-arid ecosystem provides a unique opportunity to assess many physical, chemical and biological responses to dry deposition alone.     

Gaseous and particulate water-soluble organic and inorganic nitrogen in rural air in southern Scotland

Simultaneous daily measurements of water-soluble organic nitrogen (WSON), ammonium and nitrate were made between July and November 2008 at a rural location in south-east Scotland, using a ‘Cofer’ nebulizing sampler for the gas phase and collection on an open-face PTFE membrane for the particle phase. Average concentrations of NH₃ were 82 ± 17 nmol N m^?3 (error is s.d. of triplicate samples), while oxidised N concentrations in the gas phase (from trapping NO₂ and HNO₃) were smaller, at 2.6 ± 2.2 nmol N m^?3, and gas-phase WSON concentrations were 18 ± 11 nmol N m^?3. The estimated collection efficiency of the nebulizing samplers for the gas phase was 88 (±8) % for NH₃, 37 (±16) % for NO₂ and 57 (±7) % for WSON; reported average concentrations have not been corrected for sampling efficiency. Concentrations in the particle phase were smaller, except for nitrate, at 21 ± 9, 10 ± 6 and 8 ± 9 nmol N m^?3, respectively. The absence of correlation in either phase between WSON and either (NH₃ + NH₄⁺) or NO₃^? concentrations suggests atmospheric WSON has diverse sources. During wet days, concentrations of gas and particle-phase inorganic N were lower than on dry days, whereas the converse was true for WSON. These data represent the first reports of simultaneous measurements of gas and particle phase water-soluble nitrogen compounds in rural air on a daily basis, and show that WSON occurs in both phases, contributing 20–25% of the total water-soluble nitrogen in air, in good agreement with earlier data on the contribution of WSON to total dissolved N in rainfall in the UK.     

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 (PM_2.5). 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 PM_2.5 sulfate (SO₄^2-), nitrate (NO₃^?) and ammonium, and gaseous nitric acid (HNO₃) and ammonia (NH₃). The model approximately reproduced PM_2.5 SO₄^2? concentration, but clearly overestimated PM_2.5 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 PM_2.5 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 PM_2.5 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.     

Elevated nitrogen isotope ratios of tropical Indian aerosols from Chennai: Implication for the origins of aerosol nitrogen in South and Southeast Asia

To better understand the origins of aerosol nitrogen, we measured concentrations of total nitrogen (TN) and its isotope ratios (δ¹⁵N) in tropical Indian aerosols (PM₁₀) collected from Chennai (13.04°N; 80.17°E) on day- and night-time basis in winter and summer 2007. We found high δ¹⁵N values (+15.7 to +31.2‰) of aerosol N (0.3–3.8 μg m^?3), in which NH₄⁺ is the major species (78%) with lesser contribution from NO₃^? (6%). Based on the comparison of δ¹⁵N in Chennai aerosols with those reported for atmospheric aerosols from mid-latitudes and for the particles emitted from point sources (including a laboratory study), as well as the δ¹⁵N ratios of cow-dung samples (this study), we found that the atmospheric aerosol N in Chennai has two major sources; animal excreta and bio-fuel/biomass burning from South and Southeast Asia. We demonstrate that a gas-to-particle conversion of NH₃ to NH₄HSO₄ and (NH₄)₂SO₄ and the subsequent exchange reaction between NH₃ and NH₄⁺ are responsible for the isotopic enrichment of ¹⁵N in aerosol nitrogen.     

Atmospheric nitrogen fluxes at the Belgian coast: 2004–2006

Daily and seasonal variations in dry and wet atmospheric nitrogen fluxes have been studied during four campaigns between 2004 and 2006 at a coastal site of the Southern North Sea at De Haan (Belgium) located at coordinates of 51.1723° N and 3.0369° E. Concentrations of inorganic N-compounds were determined in the gaseous phase, size-segregated aerosol (coarse, medium, and fine), and rainwater samples. Dissolved organic nitrogen (DON) was quantified in rainwater. The daily variations in N-fluxes of compounds were evaluated with air-mass backward trajectories, classified into the main air-masses arriving at the sampling site (i.e., continental, North Sea, and Atlantic/UK/Channel).The three, non-episodic campaigns showed broadly consistent fluxes, but during the late summer campaign exceptionally high episodic N-deposition was observed. The average dry and wet fluxes for non-episodic campaigns amounted to 2.6 and 4.0 mg N m^?2 d^?1, respectively, whereas during the episodic late summer period these fluxes were as high as 5.2 and 6.2 mg N m^?2 d^?1, respectively.Non-episodic seasons/campaigns experienced average aerosol fluxes of 0.9–1.4 mg N m^?2 d^?1. Generally, the contribution of aerosol NH₄⁺ was more significant in the medium and fine particulate fractions than that of aerosol NO₃^?, whereas the latter contributed more in the coarse fraction, especially in continental air-masses. During the dry mid-summer campaign, the DON contributed considerably (～15%) to the total N-budget.Exceptionally high episodic aerosol-N inputs have been observed for the late summer campaign, with especially high deposition rates of 3.6 and 2.9 mg N m^?2 d^?1 for Atlantic/UK/Channel and North Sea-continental (mixed) air-masses, respectively. During this pollution episode, the flux of NH₄⁺ was dominating in each aerosol fraction/air-mass, except for coarse continental aerosols. High deposition of gaseous-N was also observed in this campaign with an average total N-flux of 2–2.5-times higher than in other campaigns.     

High concentrations and dry deposition of reactive nitrogen species at two sites in the North China Plain

Atmospheric concentrations of major reactive nitrogen (N_r) species were quantified using passive samplers, denuders, and particulate samplers at Dongbeiwang and Quzhou, North China Plain (NCP) in a two-year study. Average concentrations of NH₃, NO₂, HNO₃, pNH₄⁺ and pNO₃⁻ were 12.0, 12.9, 0.6, 10.3, and 4.7 μg N m⁻³ across the two sites, showing different seasonal patterns of these N_r species. For example, the highest NH₃ concentration occurred in summer while NO₂ concentrations were greater in winter, both of which reflected impacts of N fertilization (summer) and coal-fueled home heating (winter). Based on measured N_r concentrations and their deposition velocities taken from the literature, annual N dry deposition was up to 55 kg N ha⁻¹. Such high concentrations and deposition rates of N_r species in the NCP indicate very serious air pollution from anthropogenic sources and significant atmospheric N input to crops.     

Study of size distribution of atmospheric aerosol at Agra

Measurements on size distribution of atmospheric aerosol were made at Dayalbagh, Agra during July to September 1998. A 4-stage cascade particle sampler (CPS - 105) which fractionates particles in sizes ranging between 0.7 and >10.9 μm, was used. Samples were collected on Whatman 41 filters. The filters were analyzed for the major water-soluble ions. The anions (F, Cl, NO₃ and SO₄) were analyzed by Dionex DX-500 ion chromatograph while atomic absorption and colorimetric techniques were used for the analysis of cations (Na, K, Ca and Mg) and NH₄, respectively. The average mass of aerosol was found to be 131.6 μg m⁻³ and aerosol composition was found to be influenced by terrigeneous sources. The mass size distribution of total aerosol and the ions NH₄, Cl, NO₃, K, Ca, Mg, SO₄ and Na was bimodal while that of F was unimodal. SO₄, F, K and NH₄ dominated in the fine mode while Ca, Mg, Cl and NO₃ were in abundance in coarse fraction. Na was found in both coarse as well as fine mode. Coarse mode SO₄ and NO₃ have been ascribed to contribution from re-suspension of soil and formation by heterogeneous oxidation on soil derived particles. Preponderance of K in fine mode is attributed to emissions from vegetation and from burning of plant materials. Ca, Mg, Cl and NO₃ are largely soil derived and hence dominate in coarse fraction. Equivalent ratios of NH₄/(SO₄+NO₃) were calculated for both fine and coarse aerosols. The coarse mode ratio varied between 0.7 and 1.4 while in fine mode it ranged between 1.4 and 1.9. It shows that aerosol is basic, the basicity of coarse mode is due to higher concentration of soil-derived alkaline components while the basicity in fine mode is due to neutralization of acidity by NH₃.     

Coarse–fine and day–night differences of water-soluble ions in atmospheric aerosols collected in Christchurch and Auckland,New Zealand

The water-soluble ions in fine (PM_<2.5) and coarse (PM_2.5−10) atmospheric aerosols collected in Christchurch during winter 2001, spring 2000 and summer 2001, and in Auckland during winter 2001 have been studied in terms of coarse–fine and day–night differences. Although the chemical characteristics of the coarse particles were similar in both cities, those of the fine particles collected in the Christchurch winter were significantly different, as manifested by higher concentrations of nss-K⁺, nss-Cl⁻, nss-Ca²⁺, nss-SO₄²⁻, NO₃⁻ and NH₄⁺. It was found that nighttime PM₁₀ and nss-K⁺ concentrations were much higher than their daytime concentrations in the Christchurch winter but a clear day–night difference was not apparent in the Auckland winter. Moreover, in the winter, sea-salt ions did not show a day–night difference; however, nss-SO₄²⁻ had opposite day–night variation in the two cities. An ion balance calculation has shown that in most samples, coarse particles can be neutral or alkaline, however, fine particles can be neutral or acidic. The possibility of ammonium salts existing in the fine particles collected in the Christchurch winter is discussed and it is concluded that a variety of ammonium salts were present. Equivalent ratios suggest that the fine particles may be significantly aged in the Christchurch winter.The evidence from our soluble ion study strongly suggests that wood and coal burning and secondary aerosols make a significant contribution to fine particulate mass in the Christchurch atmosphere. Thus, home-heating, a sheltered geographic location and relatively calm atmospheric condition are thought to be the major causes for the serious atmospheric particulate pollution in the Christchurch winter.     

Atmospheric phosphorus deposition at a montane site: Size distribution,effects of wildfire,and ecological implications

The dry deposition of atmospheric particulate matter can be a significant source of phosphorus (P) to oligotrophic aquatic ecosystems, including high-elevation lakes. In this study, measurements of the mass concentration and size distribution of aerosol particles and associated particulate P are reported for the southern Sierra Nevada, California, for the period July–October, 2008. Coarse and fine particle samples were collected with Stacked Filter Units and analyzed for Total P (TP) and inorganic P (IP) using a digestion-extraction procedure, with organic P (OP) calculated by difference. Particle size-resolved mass and TP distributions were determined concurrently using a MOUDI cascade impactor. Aerosol mass concentrations were significantly elevated at the study site, primarily due to transport from offsite and emissions from local and regional wildfires. Atmospheric TP concentrations ranged from 11 to 75 ng m^?3 (mean = 37 ± 16 ng m^?3), and were typically dominated by IP. Phosphorus was concentrated in the coarse (>1 μm diameter) particle fraction and was particularly enriched in the 1.0–3.2 μm size range, which accounted for 30–60% of the atmospheric TP load. Wildfire emissions varied widely in P content, and may be related to fire intensity. The estimated dry depositional flux of TP for each daily sampling period ranged between 7 and 118 μg m^?2 d^?1, with a mean value of 40 ± 27 μg m^?2 d^?1. Relative rates of dry deposition of N and P in the Sierra Nevada are consistent with increasing incidence of N limitation of phytoplankton growth and previously observed long-term eutrophication of lakes.     

Nitrate facilitates cadmium uptake, transport and accumulation in the hyperaccumulator Sedum plumbizincicola

The aims of this study are to investigate whether and how the nitrogen form (nitrate (NO₃ ^–) versus ammonium (NH₄ ⁺)) influences cadmium (Cd) uptake and translocation and subsequent Cd phytoextraction by the hyperaccumulator species Sedum plumbizincicola. Plants were grown hydroponically with N supplied as either NO₃ ^– or NH₄ ⁺. Short-term (36 h) Cd uptake and translocation were determined innovatively and quantitatively using a positron-emitting ¹⁰⁷Cd tracer and positron-emitting tracer imaging system. The results show that the rates of Cd uptake by roots and transport to the shoots in the NO₃ ^– treatment were more rapid than in the NH₄ ⁺ treatment. After uptake for 36 h, 5.6 (0.056 μM) and 29.0 % (0.290 μM) of total Cd in the solution was non-absorbable in the NO₃ ^– and NH₄ ⁺ treatments, respectively. The local velocity of Cd transport was approximately 1.5-fold higher in roots (3.30 cm h^?1) and 3.7-fold higher in shoots (10.10 cm h^?1) of NO₃ ^–- than NH₄ ⁺-fed plants. Autoradiographic analysis of ¹⁰⁹Cd reveals that NO₃ ^– nutrition enhanced Cd transportation from the main stem to branches and young leaves. Moreover, NO₃ ^– treatment increased Cd, Ca and K concentrations but inhibited Fe and P in the xylem sap. In a 21-day hydroponic culture, shoot biomass and Cd concentration were 1.51 and 2.63 times higher in NO₃ ^–- than in NH₄ ⁺-fed plants. We conclude that compared with NH₄ ⁺, NO₃ ^– promoted the major steps in the transport route followed by Cd from solution to shoots in S. plumbizincicola, namely its uptake by roots, xylem loading, root-to-shoot translocation in the xylem and uploading to the leaves. S. plumbizincicola prefers NO₃ ^– nutrition to NH₄ ⁺ for Cd phytoextraction.     

Canopy leaching of nutrients and metals in a mountain spruce forest

Precipitation and throughfall fluxes of major ions, nutrients (C, N, P), and metals (Al, Fe, Mn), and the chemical composition of litter fall and living plant tissue in Norway spruce stands (the Bohemian Forest; Czech Republic), were used to evaluate how microbial processes and decay of plant tissue in canopies influence canopy leaching (CL) of elements. Proton exchange for Mg²⁺, Ca²⁺, and K⁺ in decaying biomass and co-transport of Ca²⁺ and K⁺ out of plant cells with organic acid anions were the most likely processes contributing to CL of base cations. The CL of total P and N (and also NO₃^?) was minor. Important proportions of the N and P mineral forms were transformed to organic forms by microbial processes (primary and bacterial production), with the respective CL of ?13.9 and 16.4 mmol m^?2 yr^?1 for NH₄⁺ and organic N, and ?0.33 and 0.22 mmol m^?2 yr^?1 for dissolved reactive P (DRP) and organic P. Most of particulate P and N in throughfall (～90%) originated from microbial DRP and NH₄⁺ transformations, but particulate C mostly came from the fragmentation of plant tissue (58%). Among metals, CL was not observed for Al, was small for Fe (0.3 mmol m^?2 yr^?1), and greatest for Mn (0.9 mmol m^?2 yr^?1) due to leaching from decaying tissue by acidic precipitation.     

The Contribution of Sulfate and Nitrate to Atmospheric Fine Particles During Winter Inversion Fogs in Cache Valley,Utah

Abstract

Air pollutants were collected in Logan, Cache County, UT, in February 1993 during two periods of atmospheric inversion accompanied by fog. The following atmospheric species were determined: (1) gaseous SO₂, NO₂ (semi-quantitatively),HNO3, NH3, and HF; (2) fine particulate SO₄ ⁼, NO₃ ^-, NH₄ ⁺, F–, H⁺, C, Si, S, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Pb, Se, Br, and Sr, and; (3) fine particulate mass, which was calculated. The major components of fine particulate matter were carbonaceous material, ammonium nitrate, and ammonium sulfate, while the soil component was small. Calculated, fine particulate mass averaged 80 μg/m³ and reached concentrations as high as 120 μg/m³. SO₂/So_x and NO₂/NO_y mole ratios generally varied between 0.2 and 0.1 during inversions. These ratios also showed moderate but consistent diurnal patterns. The emission inventory for Cache County indicates sources of SO₂ and NO_x but not significant amounts of primary sulfate and nitrate. The observations reported here indicate there is significant conversion of SO₂ and NO_x in the presence of excess oxidants to sulfuric and nitric acid that are neutralized by excess ammonia.     

Tissue S/N ratios and stable isotopes (δS and δN) of epilithic mosses (Haplocladium microphyllum) for showing air pollution in urban cities in Southern China

In urban cities in Southern China, the tissue S/N ratios of epilithic mosses (Haplocladium microphyllum), varied widely from 0.11 to 0.19, are strongly related to some atmospheric chemical parameters (e.g. rainwater SO₄²⁻/NH₄⁺ ratios, each people SO₂ emission). If tissue S/N ratios in the healthy moss species tend to maintain a constant ratio of 0.15 in unpolluted area, our study cities can be divided into two classes: class I (S/N > 0.15, S excess) and class II (S/N < 0.15, N excess), possibly indicative of stronger industrial activity and higher density of population, respectively. Mosses in all these cities obtained S and N from rainwater at a similar ratio. Sulphur and N isotope ratios in mosses are found significantly linearly correlated with local coal δ³⁴S and NH₄⁺-N wet deposition, respectively, indicating that local coal and animal NH₃ are the major atmospheric S and N sources.     

PM2.5–10, PM2.5 and associated water-soluble inorganic species at a coastal urban site in the metropolitan region of Rio de Janeiro

The concentrations of PM_2.5−10, PM_2.5 and associated water-soluble inorganic species (WSIS) were determined in a coastal site of the metropolitan region of Rio de Janeiro, Southeastern Brazil, from October 1998 to September 1999 (n=50). Samples were dissolved in water and analyzed for major inorganic ions. The mean (± standard deviation; median) concentrations of PM_2.5−10 and PM_2.5 were, respectively, 26 (± 16; 21) μg m⁻³ and 17 (± 13; 14) μg m⁻³. Their mean concentrations were 1.7–1.8 times higher in dry season (May–October) than in rainy season (November–April). The WSIS comprised, respectively, 34% and 28% of the PM_2.5−10 and PM_2.5 masses. Chloride, Na⁺ and Mg²⁺ were the predominant ions in PM_2.5−10, indicating a significant influence of sea-salt aerosols. In PM_2.5, SO₄²⁻ (∼97% nss-SO₄²⁻) and NH₄⁺ were the most abundant ions and their equivalent concentration ratio (SO₄²⁻/NH₄⁺ ∼1.0) suggests that they were present as (NH₄)₂SO₄ particles. The mean concentration of (NH₄)₂SO₄ was 3.4 μg m⁻³. The mean equivalent PM_2.5 NO₃⁻ concentration was eight times smaller than those of SO₄²⁻ and NH₄⁺. The PM_2.5 NO₃⁻ concentration in dry season was three times higher than in rainy season, probably due to reaction of NaCl (sea salt) with HNO₃ as a result of higher levels of NO_y during the dry season and/or reduced volatilization of NH₄NO₃ due to lower wintertime temperature. Chloride depletion was observed in both size ranges, although more pronouncely in PM_2.5.     

First Europe-wide correlation analysis identifying factors best explaining the total nitrogen concentration in mosses

In this study, the indicative value of mosses as biomonitors of atmospheric nitrogen (N) depositions and air concentrations on the one hand and site-specific and regional factors which explain best the total N concentration in mosses on the other hand were investigated for the first time at a European scale using correlation analyses. The analyses included data from mosses collected from 2781 sites across Europe within the framework of the European moss survey 2005/6, which was coordinated by the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (ICP Vegetation). Modelled atmospheric N deposition and air concentration data were calculated using the Unified EMEP Model of the European Monitoring and Evaluation Programme (EMEP) of the Convention on Long-range Transboundary Air Pollution (CLRTAP). The modelled deposition and concentration data encompass various N compounds. In order to assess the correlations between moss tissue total N concentrations and the chosen predictors, Spearman rank correlation analysis and Classification and Regression Trees (CART) were applied. The Spearman rank correlation analysis showed that the total N concentration in mosses and modelled N depositions and air concentrations are significantly correlated (0.53 ≤ r_s ≤ 0.68, p < 0.001). Correlations with other predictors were lower than 0.55. The CART analysis indicated that the variation in the total N concentration in mosses was best explained by the variation in NH₄⁺ concentrations in air, followed by NO₂ concentrations in air, sampled moss species and total dry N deposition. The total N concentrations in mosses mirror land use-related atmospheric concentrations and depositions of N across Europe. In addition to already proven associations to measured N deposition on a local scale the study at hand gives a scientific prove on the association of N concentration in mosses and modelled deposition at the European scale.