A Study of Ammonia Source at a Portland Cement Production Plant

A source and process sampling study was conducted at a dry process Portland Cement production plant. The study was performed to determine the nature of the formation of a highly visable plume related to the kiln emissions. One aspect of the study focused on the source or point of NH₃ within the production process. An extensive number of process solids from raw feeds to baghouse solids were collected and analyzed for NH₄ ⁺. Samples were analyzed for NH₄ ⁺ both by washing the solids with 0.1 N H₂SO₄ and by collecting NH₃ in impingers as it was evolved from heated solids. The results showed that NH₄ ⁺ was present in many process samples and that the collection efficiency of NH₄ ⁺ in the baghouse was related to baghouse temperature. The data also showed that NH₃ was derived from the shale used in the raw feed at this cement production plant.     

A Predictive Mechanism for Mercury Oxidation on Selective Catalytic Reduction Catalysts under Coal-Derived Flue Gas

Abstract

This paper introduces a predictive mechanism for elemental mercury (Hg⁰) oxidation on selective catalytic reduction (SCR) catalysts in coal-fired utility gas cleaning systems, given the ammonia (NH₃)/nitric oxide (NO) ratio and concentrations of Hg⁰ and HCl at the monolith inlet, the monolith pitch and channel shape, and the SCR temperature and space velocity. A simple premise connects the established mechanism for catalytic NO reduction to the Hg⁰ oxidation behavior on SCRs: that hydrochloric acid (HCl) competes for surface sites with NH₃ and that Hg⁰ contacts these chlorinated sites either from the gas phase or as a weakly adsorbed species. This mechanism explicitly accounts for the inhibition of Hg⁰ oxidation by NH₃, so that the monolith sustains two chemically distinct regions. In the inlet region, strong NH₃ adsorption minimizes the coverage of chlorinated surface sites, so NO reduction inhibits Hg⁰ oxidation. But once NH₃ has been consumed, the Hg⁰ oxidation rate rapidly accelerates, even while the HCl concentration in the gas phase is uniform. Factors that shorten the length of the NO reduction region, such as smaller channel pitches and converting from square to circular channels, and factors that enhance surface chlorination, such as higher inlet HCl concentrations and lower NH₃/NO ratios, promote Hg⁰ oxidation.

This mechanism accurately interprets the reported tendencies for greater extents of Hg⁰ oxidation on honeycomb monoliths with smaller channel pitches and hotter temperatures and the tendency for lower extents of Hg⁰ oxidation for hotter temperatures on plate monoliths. The mechanism also depicts the inhibition of Hg⁰ oxidation by NH₃ for NH₃/NO ratios from zero to 0.9. Perhaps most important for practical applications, the mechanism reproduces the reported extents of Hg⁰ oxidation on a single catalyst for four coals that generated HCl concentrations from 8 to 241 ppm, which covers the entire range encountered in the U.S. utility industry. Similar performance is also demonstrated for full-scale SCRs with diverse coal types and operating conditions.     

Comparison of titania nanotubes and titanium dioxide as supports of low-temperature selective catalytic reduction catalysts under sulfur dioxide poisoning

A series of iron–manganese oxide catalysts supported on TiO₂ and titanium nanotubes (TNTs) were studied for low temperature selective catalytic reduction (SCR) of NO with NH₃ in the presence of SO_2. The results showed that the specific surface area and the amount of Brønsted acid sites were highly correlated. The results also demonstrated that higher Mn⁴⁺/Mn³⁺ ratios and larger specific surface areas might be the main reasons for the excellent performance of MnFe-TNTs catalyst after SO₂ poisoning. The SO₂ poisoning effect could be minimized by reducing the GHSV, increasing the reaction temperature, or increasing the [NH₃]/[NO] molar ratio. The results also indicated that the formation of ammonium sulfate had a stronger effect on the NO conversion efficiency as compared to the formation of metal sulfate. Thus operating the low temperature SCR at above 230 ^oC to avoid the formation of ammonium sulfate would be the priority choice when SO₂ poisoning is a concerned issue.?Implications: Low-temperature selective catalytic reduction (SCR) has attracted increasing attention due to that it can reduce the energy consumption for the SCR process employed in industries such as steel plants and glass manufacturing plants. However, it also suffers from the sulfur dioxide (SO₂) poisoning problem. This study investigates the possibility of using titania nanotubes (TNTs) as the support of Mn/Fe bimetal oxide catalysts for low-temperature SCR to reduce the SO₂ poisoning. The results indicated that the MnFe-TNT catalyst can tolerate SO₂ for a longer time as compared with the MnFe-TiO₂ catalyst.     

Major ionic compositions of fine particulate matter in an animal feeding operation facility and its vicinity

Animal feeding operations (AFOs) produce particulate matter (PM) and gaseous pollutants. Investigation of the chemical composition of PM_2.5 inside and in the local vicinity of AFOs can help to understand the impact of the AFO emissions on ambient secondary PM formation. This study was conducted on a commercial egg production farm in North Carolina. Samples of PM_2.5 were collected from five stations, with one located in an egg production house and the other four located in the vicinity of the farm along four wind directions. The major ions of NH₄⁺, Na⁺, K⁺, SO₄^2?, Cl^?, and NO₃^? were analyzed using ion chromatography (IC). In the house, the mostly abundant ions were SO₄^2?, Cl^?, and K⁺. At ambient stations, SO₄^2?, and NH₄⁺ were the two most abundant ions. In the house, NH₄⁺, SO₄^2?, and NO₃^? accounted for only 10% of the PM_2.5 mass; at ambient locations, NH₄⁺, SO₄^2?, and NO₃^? accounted for 36–41% of the PM_2.5 mass. In the house, NH₄⁺ had small seasonal variations indicating that gas-phase NH₃ was not the only major force driving its gas–particle partitioning. At the ambient stations, NH₄⁺ had the highest concentrations in summer. In the house, K⁺, Na⁺, and Cl^? were highly correlated with each other. In ambient locations, SO₄^2? and NH₄⁺ had a strong correlation, whereas in the house, SO₄^2? and NH₄⁺ had a very weak correlation. Ambient temperature and solar radiation were positively correlated with NH₄⁺ and SO₄^2?. This study suggests that secondary PM formation inside the animal house was not an important source of PM_2.5. In the vicinity, NH₃ emissions had greater impact on PM_2.5 formation.

ImplicationsThe chemical composition of PM_2.5 inside and in the local vicinity of AFOs showed the impact of the AFO emissions on ambient secondary PM_2.5 formation, and the fate and transport of air pollutants associated with AFOs. The results may help to manage in-house animal facility air quality, and to develop regional air quality control strategies and policies, especially in animal agriculture-concentrated areas.     

Effect of typhoon on atmospheric particulates in autumn in central Taiwan

Previous studies have suggested that the ongoing global climate change will likely increase the intensity and frequency of extreme weather, such as typhoons. Since the beginning of global warming, it has become necessary to understand the influence of typhoons on air quality. Rare data, especially particulate measurements data could be used to establish the relationship between the air pollution and typhoons. One of main limiting factors is that most of the previous chemical analyses of particulates used a relatively long sampling time, which could dilute the temporal impact of particulate characteristics and their sources. This work, depending more time-resolved measurements, focus on the characteristics and sources of high particulate matter levels and the influence of typhoons and the Pacific high system. Depending on the measurements, two pollutant groups were clearly identified in this work. The first pollutant group was the emissions from neighboring riverbeds under the strong circulation of the typhoon in the driest season and characterized as high coarse particle concentrations with high mass fraction of Ca²⁺. The second pollutant group was characterized as the formation and transport of secondary particles with prevalent ions of NH₄⁺, NO₃^?, and SO₄^2? and occurred in the sea-land breeze circulation under the influence the Pacific high system.     

Time Trends and Seasonal Variation of the Rainwater Chemical Composition in Spain

Abstract

A multiple regression model was used to describe temporal variations of the concentrations of H⁺, SO₄ ^{2 -}, NO₃ ^- and NH₄ ⁺ in Spanish rainwater. The model included the effects of linear trend, annual cycle, and precipitation quantity simultaneously.

The model fit very well for SO₄ ^{2 -} and NO₃ ^-, with statistical evidence of annual cycle and effect of precipitation quantity for these two ions and for NH₄ ⁺, but not for H⁺. There is no trend for any ion, with the single exception of a decreasing trend for H⁺ in one of the stations used.     

Simultaneous nitrification and denitrification by Pseudomonas sp. Y-5 in a high nitrogen environment

Pseudomonas sp. Y-5, a strain with simultaneous nitrification and denitrification (SND) capacity, was isolated from the Wuhan Municipal Sewage Treatment Plant. This strain could rapidly remove high concentrations of inorganic nitrogen. Specifically, Pseudomonas sp. Y-5 removed 103 mg/L of NH₄⁺-N in 24 h without nitrate or nitrite accumulation when NH₄⁺-N was its sole nitrogen source. The NH₄⁺-N removal efficiency (RE) was 97.26%, and the average removal rate (RR) was 4.30 mg/L/h. Strain Y-5 also removed NO₃^?-N and NO₂^?-N even in aerobic conditions, with average RRs of 4.39 and 4.23 mg/L/h, respectively, and REs of up to 99.34% and 95.81% within 24 h. When cultured in SND medium (SNDM-1), strain Y-5 achieved an NH₄⁺-N RE of up to 97.80% and a total nitrogen (TN) RE of 93.01%, whereas NO₃^?-N was fully depleted in 48 h. Interestingly, high nitrite concentrations did not inhibit the nitrification capacity of Y-5 when grown in SNDM-2, the RE of NH₄⁺-N and TN reached 96.29% and 94.26%, respectively, and nitrite was consumed completely. Strain Y-5 also adapted well to high concentrations of ammonia (~401.68 mg NH₄⁺-N/L) or organic nitrogen (~315.12 mg TN/L). Our results suggested that Pseudomonas sp. Y-5 achieved efficient simultaneous nitrification and denitrification, thus demonstrating its potential applicability in the treatment of nitrogen-polluted wastewater.

     

The continuous field measurements of soluble aerosol compositions at the Taipei Aerosol Supersite,Taiwan

The characteristics of ambient aerosols, affected by solar radiation, relative humidity, wind speed, wind direction, and gas–aerosol interaction, changed rapidly at different spatial and temporal scales. In Taipei Basin, dense traffic emissions and sufficient solar radiation for typical summer days favored the formation of secondary aerosols. In winter, the air quality in Taipei Basin was usually affected by the Asian continental outflows due to the long-range transport of pollutants carried by the winter monsoon. The conventional filter-based method needs a long time for collecting aerosols and analyzing compositions, which cannot provide high time-resolution data to investigate aerosol sources, atmospheric transformation processes, and health effects. In this work, the in situ ion chromatograph (IC) system was developed to provide 15-min time-resolution data of nine soluble inorganic species (Cl⁻, NO₂⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺). Over 89% of all particles larger than approximately 0.056 μm were collected by the in situ IC system. The in situ IC system is estimated to have a limit of detection lower than 0.3 μg m⁻³ for the various ambient ionic components. Depending on the hourly measurements, the pollutant events with high aerosol concentrations in Taipei Basin were associated with the local traffic emission in rush hour, the accumulation of pollutants in the stagnant atmosphere, the emission of industrial pollutants from the nearby factories, the photochemical secondary aerosol formation, and the long-range transport of pollutants from Asian outflows.     

The Use of Ambient Measurements To Identify which Precursor Species Limit Aerosol Nitrate Formation

ABSTRACT

A thermodynamic equilibrium model was used to investigate the response of aerosol NO₃ to changes in concentrations of HNO₃, NH₃, and H₂SO₄. Over a range of temperatures and relative humidities (RHs), two parameters provided sufficient information for indicating the qualitative response of aerosol NO₃. The first was the excess of aerosol NH₄ ⁺ plus gas-phase NH₃ over the sum of HNO₃, particulate NO₃, and particulate SO₄ ^2- concentrations. The second was the ratio of particulate to total NO₃ concentrations. Computation of these quantities from ambient measurements provides a means to rapidly analyze large numbers of samples and identify cases in which inorganic aerosol NO₃ formation is limited by the availability of NH₃. Example calculations are presented using data from three field studies. The predictions of the indicator variables and the equilibrium model are compared.     

人工湿地植物泌氧与污染物降解耗氧关系研究

实验采用静态水培方法研究了香蒲(Typha orientalis)、芦苇(Phragmites australis)和水葱(Scirpus validus)3种常见湿地水生植物潜在泌氧能力、去污效果,并对水生植物泌氧量与污染物降解耗氧量进行了计算分析,从而阐明湿地植物泌氧与污染物降解耗氧之间的关系。结果表明,3种植物泌氧能力由大到小依次为:芦苇香蒲水葱,其中,芦苇比放氧速率、面积泌氧率均最高,分别为3.36 mg O2/(g.d)和4.35 g O2/(m2.d)。植物对湿地系统中污染物的去除有重要影响,各植物系统COD去除速率在3.46~3.77 g/(m2.d)之间;NH4+-N去除速率在0.07~0.13 g/(m2.d);TN去除速率在0.25~0.27 g/(m2.d);TP去除速率均为0.09 g/(m2.d);均好于无植物空白系统。计算表明,各植物体系泌氧量在0.48~0.55 g O2/d之间;各植物体系COD、NH4+-N耗氧量在0.41~0.46 g O2/d之间;植物净泌氧量在0.02~0.12 g O2/d之间。植物泌氧量与COD、NH4+-N耗氧量呈显著正相关关系。若应用人工湿地处理城镇生活污水,各植物体系COD最大去除负荷在3.81~4.35 g/(m2.d)之间,NH4+-N最大去除负荷在0.83~0.95 g/(m2.d)之间,最大水力负荷在1.65~1.89 cm/d之间。     

Atmospheric concentrations of ammonia and ammonium at an agricultural site in the southeast United States

In this study, we present ∼1 yr (October 1998–September 1999) of 12-hour mean ammonia (NH₃), ammonium (NH₄⁺), hydrochloric acid (HCl), chloride (Cl⁻), nitrate (NO₃⁻), nitric acid (HNO₃), nitrous acid (HONO), sulfate (SO₄²⁻), and sulfur dioxide (SO₂) concentrations measured at an agricultural site in North Carolina's Coastal Plain region. Mean gas concentrations were 0.46, 1.21, 0.54, 5.55, and 4.15 μg m⁻³ for HCl, HNO₃, HONO, NH₃, and SO₂, respectively. Mean aerosol concentrations were 1.44, 1.23, 0.08, and 3.37 μg m⁻³ for NH₄⁺, NO₃⁻, Cl⁻, and SO₄²⁻, respectively. Ammonia, NH₄⁺, HNO₃, and SO₄²⁻ exhibit higher concentrations during the summer, while higher SO₂ concentrations occur during winter. A meteorology-based multivariate regression model using temperature, wind speed, and wind direction explains 76% of the variation in 12-hour mean NH₃ concentrations (n=601). Ammonia concentration increases exponentially with temperature, which explains the majority of variation (54%) in 12-hour mean NH₃ concentrations. Dependence of NH₃ concentration on wind direction suggests a local source influence. Ammonia accounts for >70% of NH_x (NH_x=NH₃+NH₄⁺) during all seasons. Ammonium nitrate and sulfate aerosol formation does not appear to be NH₃ limited. Sulfate is primarily associated ammonium sulfate, rather than bisulfate, except during the winter when the ratio of NO₃⁻–NH₄⁺ is ∼0.66. The annual average NO₃⁻–NH₄⁺ ratio is ∼0.25.     

Deposition of sulphur,nitrogen and acidity in precipitation over Ireland: chemistry,spatial distribution and long-term trends

The chemical composition of pollutant species in precipitation sampled daily or weekly at 10 sites in Ireland for the five-year period, 1994–1998, is presented. Sea salts accounted for 81% of the total ionic concentration. Approximately 50% of the SO₄²⁻ in precipitation was from sea-salt sources. The proportion of sea salts in precipitation decreased sharply eastwards. In contrast, the concentration of NO₃⁻ and the proportion of non-sea-salt SO₄²⁻ increased eastwards reflecting the closer proximity to major emission sources. The mean (mol_c) ratio of SO₄²⁻:NO₃⁻ was 1.6 for all sites, indicating that SO₄²⁻ was the major acid anion.The spatial correlation between SO₄²⁻, NO₃⁻ and NH₄⁺ concentrations in precipitation was statistically significant. The regional trend in NO₃⁻ concentration was best described by linear regression against easting. SO₄²⁻ concentration followed a similar pattern. However, the regression was improved by inclusion of elevation. Inclusion of northing in the regression did not significantly improve any of the relationships except for NH₄⁺, indicating a significant increase in concentrations from northwest to southeast.The spatial distribution of deposition fluxes showed similar gradients increasing from west and southwest to east and northeast. However, the pattern of deposition shows the influence of precipitation volume in determining the overall input. Mean depositions of sulphur and nitrogen in precipitation were ≈30 ktonnes S yr⁻¹ and 48 ktonnes N yr⁻¹ over the five-year period, 1994–1998, for Ireland.Least-squares linear regression analysis indicated a slight decreasing trend in precipitation concentrations for SO₄²⁻ (20%), NO₃⁻ (13%) and H⁺ (24%) and a slight increasing trend for NH₄⁺ (15%), over the period 1991–1998.     

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3

TiO₂-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH₃ with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn⁴⁺, displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO₂ catalysts were important for the low-temperature SCR at 80～160 and 200～350 °C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO₂ oxidation at low temperatures.

Implications: Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO_x). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO₂ catalysts.     

Ambient suspended particulate matters and related chemical species study in central Taiwan,Taichung during 1998–2001

Ambient suspended particulate (PM_2.5, PM_2.5–10, TSP) was collected from June 1998 to February 2001 in Taichung, central Taiwan. In addition, the related water-soluble ionic species (Cl⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺) and metallic species (Fe, Zn, Pb, Ni) were also analyzed in this study. The results showed that the concentrations of particulate mass are higher in the traffic site (CCRT) than the other sampling sites in this study. Also, the fine particle (PM_2.5) concentration is the dominant species of the total suspended particles in Taichung, central Taiwan. The dominant species for PM_2.5 are sulfate and ammonium at all sampling sites during the period of 1998–2001. The results of diurnal variation at THUC sampling site are also discussed in this study. Overall, acidic and secondary aerosol (Cl⁻, NO₃⁻, SO₄²⁻ and NH₄⁺) is a more serious air pollutant issue in southern and central Taiwan than at several sites around the world. Therefore, ambient suspended particulate monitoring in Taichung, central Taiwan will be continuing in our following study to provide more information for the government to formulate environmental strategy.     

The Southeastern Aerosol Research and Characterization Study,Part 3: Continuous Measurements of Fine Particulate Matter Mass and Composition

Abstract

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM_2.5) mass is performed using a dried, 30 °C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO₄ ^2? via reduction to SO₂; (2) NH₄ ⁺ and NO₃ ^? via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO₂, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM_2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM_2.5 components indicates the need to better understand the continuous composition of the unmeasured “other” category, because it contributes a significant fraction to total mass during periods of high PM_2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO₂ conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH₃ to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Identification of brake wear particles and derivation of a quantitative tracer for brake dust at a major road

Traffic-generated air pollutant emissions can be classified into exhaust and non-exhaust emissions. Increased attention is focussing on non-exhaust emissions as exhaust emissions are progressively limited by regulations. To characterise metal-rich emission from abrasion processes, size-segregated analysis of atmospheric aerosol particles sampled with micro-orifice uniform deposit impactors (MOUDI) in March 2007 in London was performed. The samples were collected at a roadside and a background site and were analysed for Al, Ba, Cu, Fe, Sb, Ti, V, Zn, Ca²⁺, K⁺, Mg²⁺, Na⁺, and NH₄⁺. Most components showed a clear roadside increment, which was evident as a higher mass concentration and a change in the size distribution. In particular, Fe, Cu, Ba, and Sb correlated highly, indicative of a common traffic-related source. Using complementary information on the fleet composition, vehicle number and average speed, the brake wear emission was calculated using the EMEP/CORINAIR emission database. The total PM₁₀ and barium emission of the traffic was determined by ratio to NO_x whose source strength was estimated from published emission factors. Barium was found to comprise 1.1% of brake wear (PM₁₀) particles from the traffic fleet as a whole, allowing its use as a quantitative tracer of brake wear emissions at other traffic-influenced sites.     

Ionic composition of wet precipitation over the southern slope of central Himalayas,Nepal

Severe atmospheric pollution transported to Himalayas from South Asia may affect fragile ecosystem and can be harmful for human health in the region. In order to understand the atmospheric chemistry in the southern slope of central Himalayas, where the data is limited, precipitation has been sampled at four sites: Kathmandu (1,314 m), Dhunche (2,065 m), Dimsa (3,078 m), and Gosainkunda (4,417 m) in Nepal for over a 1-year period characterized by an urban, rural, and remote sites, respectively. HCO₃ ^? is the dominant anion, while the NH₄ ⁺ is the dominant cation in precipitation at the four sites. Generally, most of ions (e.g., SO₄ ^2?, NO₃ ^?, NH₄ ⁺, HCO₃ ^?, and Ca²⁺) have higher concentrations in urban site compared to the rural sites. Neutralization factor calculation showed that precipitation in the region is highly neutralized by NH₄ ⁺ and Ca²⁺. Empirical orthogonal function and correlation analysis indicated that the precipitation chemistry was mostly influenced by crustal, anthropogenic, and marine sources in Nepal. Among different sites, urban area was mostly influenced by anthropogenic inputs and crustal dusts, whereas remote sites were mostly from marine and crustal sources. Seasonal variations show higher ionic concentrations during non-monsoon seasons mainly due to limited precipitation amount. On the other hand, lower ionic concentrations were observed during monsoon season when higher amount of precipitation washes out aerosols. Thus, precipitation chemistry from this work can provide a useful database to evaluate atmospheric environment and its impacts on ecosystem in the southern slope of central Himalayas, Nepal.     

Organic nitrogen in precipitation over Eastern North America

A measurement technique was developed to reliably quantify organic nitrogen (ON) in ambient, wet-only precipitation. Samples were frozen during collection and subsequently divided into two aliquots. One set was stored at −170°C and analyzed for total N (TN) via high-temperature combustion to NO and detection by chemiluminescence; the other set was sterilized with CHCl₃, stored refrigerated, and analyzed for NH₄⁺ by automated colorimetry and for NO₃⁻, and NO₂⁻ by ion chromatography. ON was inferred by difference. Analysis of paired, untreated aliquots stored for 30 and 41 days at different temperatures revealed substantial conversion of NH₄⁺ to ON at room temperature and significant losses (16% and 23%) of NH₄⁺ (presumably to biota growing on bottle walls) in refrigerated samples. Analytes in frozen and sterilized samples were stable. Volume-weighted ON concentrations for precipitation sampled at Charlottesville, Virginia (VA), Newark, Delaware (DE), and New Castle, New Hampshire (NH; 3.1, 4.2, and 0.6 μM N, respectively) and corresponding contributions to volume-weighted TN (6.5%, 7.8%, and 2.6%, respectively) are at the lower limit of published values for eastern North America and elsewhere. Methodological differences contribute to the apparent variability among these reported sample statistics. Volume-weighted ON concentrations were generally highest during spring and were lowest during summer. Due to the combined influence of unmeasured ON and loss of NH₄⁺ from inadequately preserved samples, current estimates for the wet deposition of atmospheric N to eastern North America based on data from national networks may be underestimated by 10–20%.     

Behaviour and dynamics of di-ammonium phosphate in bauxite processing residue sand in Western Australia—I. NH<Subscript>3</Subscript> volatilisation and residual nitrogen availability

Background, aim and scope

Australia is the largest producer of bauxite in the world, with an annual output of approximately 62 million metric dry tons in 2007. For every tonne of alumina, about 2 tonnes of highly alkaline and highly saline bauxite-processing residue are produced. In Western Australia, Alcoa World Alumina, Australia (Alcoa) produces approximately 15 MT of residue annually from its refineries (Kwinana, Pinjarra and Wagerup). The bauxite-processing residue sand (BRS) fraction represents the primary material for rehabilitating Alcoa’s residue disposal areas (RDAs). However, the inherently hostile characteristics (high alkalinity, high salinity and poor nutrient availability) of BRS pose severe limitations for establishing sustainable plant cover systems. Alcoa currently applies 2.7 t ha^?1 of di-ammonium phosphate ((NH₄)₂HPO₄; DAP)-based fertiliser as a part of rehabilitation of the outer residue sand embankments of its RDAs. Limited information on the behaviour of the dominant components of this inorganic fertiliser in highly alkaline BRS is currently available, despite the known effects of pH on ammonium (NH₄) and phosphorus (P) behaviour. The aim of this study was to quantify the effects of pH on NH₃ volatilisation and residual nitrogen (N) in BRS following DAP applications.

Methods

The sponge-trapping and KCl-extraction method was used for determining NH₃ volatilisation from surface-applied DAP in samples of BRS collected from each of Alcoa’s three Western Australia Refineries (Kwinana, Pinjarra, Wagerup) under various pH conditions (pH 4, 7, 9 and 11). Following cessation of volatilisation, the residual N was extracted from BRS using 2 M KCl and concentrations of NH ₄ ⁺ –N and NO ₃ ^? –N were determined by flow injection analysis.

Results

The quantities of NH₃ volatilised increased dramatically as the pH increased from 4 to 11. Much of the N lost as NH₃ (up to 95.2%) occurred within a short period (24 h to 7 days), particularly for the pH 9 and 11 treatments. Concentrations of residual NH ₄ ⁺ –N recovered in DAP-treated BRS at the end of the experiment decreased with increasing pH. This finding was consistent with increasing loss of N via volatilisation as pH increased. The concentration of NO ₃ ^? –N was very low due to no nitrification in BRS.

Discussion

The pH was a key driver for NH₃ volatilisation from DAP-treated BRS and primarily controlled N dynamics in BRS. Results indicate that NH₄ not adsorbed by BRS was highly susceptible to volatilisation. The likely lack of nitrifying bacteria did not allow conversion of ammonium to nitrate, thereby further exacerbating the potential for loss via volatilisation

Conclusions

It was demonstrated that the pH is the key factor controlling the loss of inorganic N from BRS. Although volatilisation was considerably lower at pH 4, achieving this pH reduction in the field is not possible at present. Findings from this study highlight the need to better understand which forms of N fertiliser are most suitable for use in highly alkaline BRS.

Recommendation and perspectives

Although pH reduction is the most likely means of stopping NH₃ volatilisation in BRS, it is economically and operationally unfeasible to add sufficient acidity for adequately lowering pH in the BRS for revegetation. More attention on forms of fertilisers more suitable to highly alkaline, microbially inert soil conditions appears to be warranted.

     

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.