Historical alteration in the nitrogen concentration and N natural abundance of mosses in Germany: Indication for regionally varying changes in atmospheric nitrogen deposition within the last 140 years

Historical alterations of nitrogen deposition in the western part of Germany were investigated by comparing nitrogen concentrations and ¹⁵N natural abundance of historical and recent samples of the two pleurocarpous mosses Pleurozium schreberi and Scleropodium purum. Pooling of the data revealed only slight tissue N increases over the past 140 years which were significant nevertheless. At closer examination on the single site level historical increases of N concentrations were found particularly for some sites in regions where agricultural activities were considerably intensified during the second half of the 20th century. The comparison of δ¹⁵N values showed a strong depletion of ¹⁵N natural abundance in areas currently heavily influenced by livestock management. This indicates an increased impact of NH_y compounds. However, the almost unchanged δ¹⁵N values in some low mountain range areas with only moderate intensification of agriculture point to a more or less constant ratio of NH_y/NO_x input over time. Significant correlations of both tissue N concentrations and ¹⁵N natural abundance between the two species justify the assumption that they use the same nitrogen source, probably atmospheric deposition.     

Atmospheric transport of urban-derived NH(x): Evidence from nitrogen concentration and delta(15)N in epilithic mosses at Guiyang, SW China

Nitrogen concentration and δ¹⁵N in 175 epilithic moss samples were investigated along four directions from urban to rural sites in Guiyang, SW China. The spatial variations of moss N concentration and δ¹⁵N revealed that atmospheric N deposition is dominated by NH_x-N from two major sources (urban sewage NH₃ and agricultural NH₃), the deposition of urban-derived NH_x followed a point source pattern characterized by an exponential decline with distance from the urban center, while the agricultural-derived NH_x was shown to be a non-point source. The relationship between moss N concentration and distance (y = 1.5e^−0.13x + 1.26) indicated that the maximum transporting distance of urban-derived NH_x averaged 41 km from the urban center, and it could be determined from the relationship between moss δ¹⁵N and distance [y = 2.54 ln(x) − 12.227] that urban-derived NH_x was proportionally lower than agricultural-derived NH_x in N deposition at sites beyond 17.2 km from the urban center. Consequently, the variation of urban-derived NH_x with distance from the urban center could be modeled as y = 56.272e^−0.116x − 0.481 in the Guiyang area.     

The use of experimental data and their uncertainty for assessing ozone photochemistry in the Eastern Iberian Peninsula

Observation-based methods are useful tools to explore the sensitivity of ozone concentrations to precursor controls. With the aim of assessing the ozone precursor sensitivity in two locations: Paterna (suburban) and Villar del Arzobispo (rural) of the Turia river basin in the east of Spain, the photochemical indicator O₃/NO_y and the Extent-of-Reaction (EOR) parameter have been calculated from field measurements. In Paterna, the O₃/NO_y ratio varied from 0 to 13 with an average value of 5.1 (SD 3.2), whereas the averaged value for the EOR was 0.43 (SD 0.14). In Villar del Arzobispo, the O₃/NO_y ratio changed from 5 to 30 with a mean value of 13.6 (SD 4.7) and the EOR gave an averaged value of 0.72 (SD 0.11). The results show two different patterns of ozone production as a function of the location. The suburban area shows a VOC-sensitive regime whereas the rural one shows a transition regime close to NO_x-sensitive conditions. No seasonal differences in these regimes are observed along the monitoring campaigns. Finally, an analysis of the influence of the measurement quality of NO_y, NO_x and O₃ on the uncertainty of the O₃/NO_y ratio and the EOR was performed showing that the uncertainty of O₃/NO_y is not dependent on either its value or the individual values of O₃ and NO_y but just on the quality of O₃ and NO_y measurements. The maximum uncertainty is 26% as long as the combined uncertainties of O₃ and NO_y remain below the 7.5%. The case of the EOR is different and its uncertainty depends on both the value of the EOR parameter and the individual concentration values of NO_y and NO_x. The uncertainty of the EOR estimation can be very high (>200%) if the combined uncertainties of both NO_y and NO_x are high (>7.5%), or especially, if u(NO_y) and u(NO_x) differ considerably from each other (>3.5%).     

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.     

Direct and indirect effects of ammonia, ammonium and nitrate on phosphatase activity and carbon fluxes from decomposing litter in peatland

Here we investigate the response of soils and litter to 5 years of experimental additions of ammonium (NH₄), nitrate (NO₃), and ammonia (NH₃) to an ombrotrophic peatland. We test the importance of direct (via soil) and indirect (via litter) effects on phosphatase activity and efflux of CO₂. We also determined how species representing different functional types responded to the nitrogen treatments. Our results demonstrate that additions of NO₃, NH₄ and NH₃ all stimulated phosphatase activity but the effects were dependent on species of litter and mechanism (direct or indirect). Deposition of NH₃ had no effect on efflux of CO₂ from Calluna vulgaris litter, despite it showing signs of stress in the field, whereas both NO₃ and NH₄ reduced CO₂ fluxes. Our results show that the collective impacts on peatlands of the three principal forms of nitrogen in atmospheric deposition are a result of differential effects and mechanisms on individual components.     

Possible particulate nitrite formation and its atmospheric implications inferred from the observations in Seoul,Korea

Simultaneous measurements of gaseous species and fine-mode, particulate inorganic components were performed at the University of Seoul, Seoul in Korea. In the simultaneous measurements, a certain level of nitrous acid (HONO) was observed in the gas-phase, indicating possible heterogeneous HONO production on the surface of the ambient aerosols. On the other hand, high particulate nitrite (NO^2?) concentrations of 1.41(±2.26) μg/m³ were also measured, which sometimes reached 18.54 μg/m³. In contrast, low HONO-to-NO₂ ratios of 0.007(±0.006) were observed in Seoul. This indicates that a significant fraction of HONO is dissolved in atmospheric aerosols. Around the Seoul site, sufficient alkalinity may have been provided to the atmospheric aerosols from the excessive presence of NH₃ in the gas-phase. Due to the alkaline particulate conditions (defined in this study as a particle pH >～3.29), the HONO molecules produced at the surface of the atmospheric aerosols appeared to have been converted into particulate nitrite, thereby preventing their further participation in the atmospheric O₃/NO_y/HO_x photochemical cycles. It was estimated that a minimum average of 65% of HONO was captured by alkaline, anthropogenic, urban particles in the Seoul measurements.     

The characterization of water-soluble inorganic ions in PM2.5 during a winter period in Xi'an,China

The characteristics of water-soluble inorganic ions (WSIIs) during a winter period in a suburb of Xi'an, China, were investigated. Our results show that the total mass concentration of the dominant WSIIs (8) was 91.27 µg m^–3, accounting for 50.1% of the total mass concentration of PM_2.5 (particulates with a size of 2.5 µm or less). Secondary inorganic aerosols (SO₄^2?, NO₃^? and NH₄⁺) were the most abundant ions, accounting for up to 95.12% of the total ions. By using the anion and cation equivalence ratio method, PM_2.5 was shown to have weak alkalinity, and the chemical forms of WSIIs were mainly (NH₄)₂SO₄ and NH₄NO₃. The sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) suggested that larger proportions of SO₄^2? and NO₃^? were formed by gas-phase SO₂ and NO₂ in the sampling site. Ratio analysis also indicated that anthropogenic sources significantly contributed to WSII pollution. Among the anthropogenic sources, fixed pollution sources were found to be dominant over mobile sources.     

原位水解生成的羟基氧化铁凝聚吸附除磷效能与机制简

将不同摩尔比Fe³⁺与OH^-（[Fe³⁺]：[OH^-]=1：0、1：1、1：2和1：3）反应获得原位水解生成的羟基氧化铁（in situ FeO_xH_y）,研究了具有不同水解程度的羟基氧化铁对凝聚吸附除磷效能与机制。研究显示,In situ FeO_xH_y对磷的去除率随铁投量增大而升高,且均在中性pH范围内具有最佳除磷效果;在相同铁投量条件下,磷去除率随着[OH^-]：[Fe³⁺]的升高而降低;当体系碱度较低时（pH<6）,引入OH^-可促进Fe³⁺水解而提高除磷效果。4种羟基氧化铁均可在15 s内可快速吸附磷,且吸附过程符合准二级动力学模型;Freundlich模型均可很好地描述磷在4种羟基氧化铁表面的吸附行为。磷酸盐吸附后,In situ FeO_xH_y表面Zeta电位明显降低,且[Fe³⁺]：[OH^-]为1：0的羟基氧化铁降低最为显著。结合MINITEQ计算软件磷酸盐、铁盐形态分析结果显示,对于碱度较低的体系,通过投加一定量OH^-可促进Fe³⁺水解,进而使得其更易与水中H₂PO₄^-与HPO₄^2-结合,生成具有多核羟基的磷酸铁络合物,进而提高除磷效果。     

Size partitioning of particulate inorganic nitrogen species between the fine and coarse mode ranges and its implication to their deposition on the surface ocean

In order to discuss the dry deposition fluxes of atmospheric fixed nitrogen species, observations of aerosol chemistry including nitrate (NO₃^?) and ammonium (NH₄⁺) were conducted at two islands, Rishiri Island and Sado Island, over the Sea of Japan. Although the atmospheric concentrations of particulate NH₄⁺–N showed higher values than those of particulate NO₃^?–N at both sites, the dry deposition fluxes of the particulate NO₃^?–N were estimated to be higher than those of the particulate NH₄⁺–N. This was caused by the difference of particle sizes between the particulate NO₃^? and NH₄⁺; NH₄⁺ was almost totally contained in fine particles (d < 2.5 μm) with smaller deposition velocity, whereas NO₃^? was mainly contained in coarse particles (d > 2.5 μm) with greater deposition velocity. Fine mode NO₃^? was strongly associated with fine mode sea-salt and mineral particles, of which higher concentrations shifted the size of particulate NO₃^? toward the fine mode range. This size shift would decrease the dry deposition flux of the fixed nitrogen species on coastal waters and accelerate atmospheric transport of them to the remote oceanic areas.     

Assessment of the Ozone-Nitrogen Oxide-Volatile Organic Compound Sensitivity of Mexico City through an Indicator-Based Approach: Measurements and Numerical Simulations Comparison

Abstract

The ozone (O₃) sensitivity to nitrogen oxides (NO_x, or nitric oxide [NO] + nitrogen dioxide [NO₂]) versus volatile organic compounds (VOCs) in the Mexico City metropolitan area (MCMA) is a current issue of scientific controversy. To shed light on this issue, we compared measurements of the indicator species O₃/NO_y (where NO_y represents the sum of NO + NO₂ + nitric acid [HNO₃] + peroxyacetyl nitrate [PAN] + others), NO_y, and the semiempirically derived O₃/NO_{z surrogate} (where NO_{z surrogate} is the derived surrogate NO_z, and NO_z represents NO_x reaction products, or NO_y – NO_x) with results of numerical predictions reproducing the transition regimes between NO_x and VOC sensitivities. Ambient air concentrations of O₃, NO_x, and NO_y were measured from April 14 to 25, 2004 in one downwind receptor site of photo-chemically aged air masses within Mexico City. MCMA-derived transition values for an episode day occurring during the same monitoring period were obtained through a series of photochemical simulations using the Multiscale Climate and Chemistry Model (MCCM). The comparison between the measured indicator species and the simulated spatial distribution of the indicators O₃/NO_y, O₃/NO_{z surrogate}, and NO_y in MCMA suggest that O₃ in this megacity is likely VOC-sensitive. This is in opposition to past studies that, on the basis of the observed morning VOC/NO_x ratios, have concluded that O₃ in Mexico City is NO_x-sensitive. Simulated MCMA-derived sensitive transition values for O₃/NO_y, hydrogen peroxide (H₂O₂)/HNO₃, and NO_y were found to be in agreement with threshold criteria proposed for other regions in North America and Europe, although the transition crossover for O₃/NO_z and O₃/HNO₃ was not consistent with values reported elsewhere. An additional empirical evaluation of weekend/weekday differences in average maximum O₃ concentrations and 6:00- to 9:00-a.m. NO_x and NO levels registered at the same site in April 2004 indirectly confirmed the above results. A preliminary conclusion is that additional reductions in NO_x emissions in MCMA might cause an increase in presently high O₃ levels.     

NOx Removal with Combined Selective Catalytic Reduction and Selective Noncatalytic Reduction: Pilot-Scale Test Results

Pilot-scale tests were conducted to develop a combined nitrogen oxide (NO_x) reduction technology using both selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR). A commercially available vanadium- and titanium-based composite honeycomb catalyst and enhanced urea (NH₂CONH₂) were used with a natural-gas-fired furnace at a NO_x concentration of 110 ppm. Changes in SNCR chemical injection temperature and stoichiometry led to varying levels of post-furnace ammonia (NH₃), which acts as the reductant feed to the downstream SCR catalyst. The urea-based chemical could routinely achieve SNCR plus SCR total NO_x reductions of 85 percent with less than 3 ppm NH₃ slip at reductant/NO_x stoichiometries ranging from about 1.5 to 2.5 and SCR space velocities of 18,000 to 32,000 h^?1. This pilot-scale research has shown that SNCR and SCR can be integrated to achieve high NO_x removal. SNCR provides high temperature reduction of NO_x followed by further removal of NO_x and minimization of NH₃ slip by a significantly downsized (high-space velocity) SCR.     

A diagnostic comparison of measured and model-predicted speciated VOC concentrations

This study compares speciated model-predicted concentrations (i.e., mixing ratios) of volatile organic compounds (VOCs) with measurements from the Photochemical Assessment Monitoring Stations (PAMS) network at sites within the northeastern US during June–August of 2006. Measurements of total non-methane organic compounds (NMOC), ozone (O₃), oxides of nitrogen (NO_x) and reactive nitrogen species (NO_y) are used for supporting analysis. The measured VOC species were grouped into the surrogate classes used by the Carbon Bond IV (CB4) chemical mechanism. It was found that the model typically over-predicted all the CB4 VOC species, except isoprene, which might be linked to overestimated emissions. Even with over-predictions in the CB4 VOC species, model performance for daily maximum O₃ was typically within ±15%. Analysis at an urban site in NY, where both NMOC and NO_x data were available, suggested that the reasonable ozone performance may be possibly due to compensating overestimated NO_x concentrations, thus modulating the NMOC/NO_x ratio to be in similar ranges as that of observations.     

Effects of high atmospheric CO2 concentration on root hydraulic conductivity of conifers depend on species identity and inorganic nitrogen source

We examined root hydraulic conductivity (L_p) responses of one-year-old seedlings of four conifers to the combined effects of elevated CO₂ and inorganic nitrogen (N) sources. We found marked interspecific differences in L_p responses to high CO₂ ranging from a 37% increase in P. abies to a 27% decrease in P. menziesii, but these effects depended on N source. The results indicate that CO₂ effects on root water transport may be coupled to leaf area responses under nitrate (NO₃⁻), but not ammonium (NH₄⁺) dominated soils. To our knowledge, this is the first study that highlights the role of inorganic N source and species identity as critical factors that determine plant hydraulic responses to rising atmospheric CO₂ levels. The results have important implications for understanding root biology in a changing climate and for models designed to predict feedbacks between rising atmospheric CO₂, N deposition, and ecohydrology.     

Technique for Measuring the Total Concentration of Gaseous Fixed Nitrogen Species

This paper reports the development of a rapid, continuous technique for analyzing fixed nitrogen species (NH₃, HCN, CH₃NH₂, etc.). The technique uses a platinum catalyst at low pressure in combination with a conventional chemiluminescent NO _x analyzer. Previous workers observed that conventional stainless steel catalysts, and platinum catalysts operated at atmospheric pressure, do not reliably convert NH₃ to NO. The most serious problem was the variation in the efficiency of these catalysts with operating conditions. Changes in temperature, gas composition, or X_NH3 could change the conversion efficiency from 99.9% to <30%. The new conversion technique, however, is quantitative up to several thousand ppm NH₃ in either O₂/He or O₂/CO₂/N₂.     

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.     

Analysis of the relationship between ambient levels of O3, NO2 and NO as a function of NOx in the UK

Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO_x, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O₃ and NO₂) varies with the level of NO_x, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NO_x-independent and NO_x-dependent contributions. The former is effectively a regional contribution which equates to the regional background O₃ level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO₂ emissions, (ii) the thermal reaction of NO with O₂ at high NO_x, and (iii) common-source emission of species which promote NO to NO₂ conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HO_x radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NO_x, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO₂ and O₃, are used to define expressions which describe the likely variation of annual mean NO₂ as a function of NO_x at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O₃.     

Nitrogen isotope variations in camphor (Cinnamomum Camphora) leaves of different ages in upper and lower canopies as an indicator of atmospheric nitrogen sources

Nitrogen isotopic composition of new, middle-aged and old camphor leaves in upper and lower canopies has been determined in a living area, near a motorway and near an industrial area (Jiangan Chemical Fertilizer Plant). We found that at sites near roads, more positive δ¹⁵N values were observed in the camphor leaves, especially in old leaves of upper canopies, and ?δ¹⁵N = δ¹⁵N_upper − δ¹⁵N_lower > 0, while those near the industrial area had more negative δ¹⁵N values and ?δ¹⁵N < 0. These could be explained by two isotopically different atmospheric N sources: greater uptake from isotopically heavy pools of atmospheric NO_x by old leaves in upper canopies at sites adjacent to roads, and greater uptake of ¹⁵N-depleted NH_y in atmospheric deposition by leaves at sites near the industrial area. This study presents novel evidence that ¹⁵N natural abundance of camphor leaves can be used as a robust indicator of atmospheric N sources.     

The use of ambient data to corroborate analyses of ozone control strategies

Data from environmental-chamber studies and photochemical box-model simulations were used to evaluate and revise a method for developing a qualitative understanding of the sensitivity of ozone formation at a particular time and place to changes in concentrations of volatile organic compounds (VOC) and oxides of nitrogen (NO_x). The revised method requires measurements of ozone, NO, and either NO_x or NO_y. The sensitivities of the method to biases in measurements were evaluated. The method potentially can be used for qualitative assessment of VOC versus NO_x limitation, comparison with the predictions of grid-based photochemical air-quality models, and evaluation of trends over time in the relative effectiveness of VOC versus NO_x controls.     

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.