Investigation of the Ultraviolet Photolysis Method for the Determination of Organic Nitrogen in Aerosol Samples

Abstract

The research objective was to adapt the ultraviolet (UV)photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2² factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 °C occurred at pH 2.0 with a 24-hr irradiance period at concentrations < µM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH₄ ⁺), but urea released a near equimolar ratio of NH₄ ⁺ and nitrate (NO₃ ^?). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM₁₀ were 78.1 ± 29.2 nmol-Nm^?3and 8.3 ± 4.9 nmol-Nm^?3, respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 ± 5.7%, and the majority of the DON (79.1 ± 18.2%) was found in the fine particulate matter (PM_2.5) fraction. The average concentrations of DIN and DON in the PM_2.5 fraction were 54.4 ± 25.6 nmol-Nm^?3 and 6.5 ± 4.4 nmol-Nm^?3, respectively.     

Use of carbon-based composites to enhance performance of TiO<Subscript>2</Subscript> for the simultaneous removal of nitrates and organics from aqueous environments

The simultaneous photocatalytic removal of nitrate from aqueous environment in presence of organic hole scavenger using TiO₂ has long been explored. However, the use of unmodified TiO₂ in such reaction resulted in non-performance or release of significant amount of undesirable reaction products in the process, a problem that triggered surface modification of TiO₂ for enhanced photocatalytic performance. Previous studies focused on decreasing rate of charge carrier recombination and absorption of light in the visible region. Yet, increasing active sites and adsorption capacity by combining TiO₂ with a high surface area adsorbent such as activated carbon (AC) remains unexploited. This study reports the potential of such modification in simultaneous removal of nitrates and oxalic acid in aqueous environment. The adsorptive behaviour of nitrate and oxalic acid on TiO₂ and TiO₂/AC composites were studied. The Langmuir adsorption coefficient for nitrate was four times greater than that of oxalic acid. However, the amount of oxalic acid adsorbed was about 10 times greater than the amount of nitrate taken up. Despite this advantage, the materials did not appear to produce more active photocatalysts for the simultaneous degradation of nitrate and oxalic acid. The photocatalytic activity of TiO₂ and its carbon-based composites was improved by combination with Cu₂O particles. Consequently, 2.5 Cu₂O/TiO₂ exhibited the maximum photocatalytic performance with 57.6 and 99.8% removal of nitrate and oxalic acid, respectively, while selectivity stood at 45.7, 12.4 and 41.9% for NH₄⁺, NO₂^? and N₂, respectively. For the carbon based, 2.5 Cu₂O/TiO₂-20AC showed removal of 12.7% nitrate and 80.3% oxalic acid and achieved 21.6, 0 and 78.4% selectivity for NH₄⁺, NO₂^? and N₂, respectively. Using the optimal AC loading (20 wt%) resulted in significant decrease in the selectivity for NH₄⁺ with no formation of NO₂^?, which unveils that selectivity for N₂ and low/no selectivity for undesirable products can be manipulated by controlling the rate of consumption of oxalic acid. In contract, no nitrate reduction was observed with Cu₂O promoted TiO₂-T and its TiO₂-(T)-20AC, which may be connected to amorphous nature of TiO₂-T and perhaps served as charge carrier trapping sites that impeded activity.     

A long-path infra-red study of Los Angeles smog

Gaseous air pollutants have been measured in Los Angeles smog by the method of long-path infra-red absorption spectroscopy. A Fourier transform spectrometer operated at 0.25cm⁻¹ resolution was used in conjunction with a 1260-m optical path folded along a base path of 23 m. Detection sensitivities were in the parts-per-billion range. Compounds measured included NH₃, CO, H₂CO, HCOOH, CH₃OH, HNO₃, NO, NO₂, O₃, peroxyacetyl nitrate, alkyl nitrates and various hydrocarbons. The rise and fall of pollutant concentrations is reported in detail for the smoggy two-day period of 26 and 27 June 1980. Reactive hydrocarbons and nitrogen oxides were oxidized during the daytime, yielding ozone, aldehyde, nitric acid and peroxyacetyl nitrate. The observed gaseous reaction products only accounted for about 20 % of the nitrogen oxides that disappeared during the day. It is deduced that the “missing” 80% of the nitrogen was removed heterogeneously into aerosol particles or on surfaces at ground level.     

Ammonium,Nitrate and Nitrite Nitrogen and Nitrate Reductase Enzyme Activity in Groundnut (Arachis hypogaea L.) Fields After Diazinon,Imidacloprid and Lindane Treatments

Impacts of diazinon (O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate), imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] and lindane (1,2,3,4,5.6-hexachlorocyclohexane) treatments on ammonium, nitrate, and nitrite nitrogen and nitrate reductase enzyme activities were determined in groundnut (Arachis hypogaea L.) field for three consecutive years (1997 to 1999). Diazinon was applied for both seed- and soil-treatments but imidacloprid and lindane were used for seed treatments only at recommended rates. Diazinon residues persisted for 60 days in both the cases. Average half-lives (t_1/2) of diazinon were found 29.3 and 34.8 days respectively in seed and soil treatments. In diazinon seed treatment, NH₄ ⁺, NO₃ ^?, and NO₂ ^? nitrogen and nitrate reductase activity were not affected. Whereas, diazinon soil treatment indicated significant increase in NH₄ ⁺-N in a 1-day sample, which continued until 90 days. Some declines in NO₃ ^?N were found from 15 to 60 days. Along with this decline, significant increases in NO₂ ^?N and nitrate reductase activity were found between 1 and 30 days. Imidacloprid and lindane persisted for 90 and 120 days with average half-lives (t_1/2) of 40.9 and 53.3 days, respectively. Within 90 days, imidacloprid residues lost by 73.17% to 82.49% while such losses for lindane residues were found 78.19% to 79.86 % within 120 days. In imidacloprid seed-treated field, stimulation of NO₃ ^?N and the decline in NH₄ ⁺NO₂ ^?-N and nitrate reductase enzyme activity were observed between 15 to 90 days. However, lindane seed treatment indicated significant increases in NH₄ ⁺-N, NO₂ ^?-N and nitrate reductase activity and some adverse effects on NO₃ ^?N between 15 and 90 days.     

Monitoring Deposition of Nitrogen-Containing Compounds in a High-Elevation Forest Canopy

Measurements of airborne (gaseous and aerosol), cloud water, and precipitation concentrations of nitrogen compounds were made at Mt. Mitchell State Park (Mt. Gibbs, ~2006 m MSL), North Carolina, during May through September of 1988 and 1989, An annular denuder system was used to ascertain gaseous (nitric acid, nitrous acid, and ammonia) and particulate (nitrate and ammonium) nitrogen species, and a chemiluminescence nitrogen oxides analyzer was used to measure nitric oxide and nitrogen dioxide. Measurements of NO₃ ^? and NH₄ ⁺ ions in cloud and rain water samples were made during the same time period. Mean concentrations of gaseous nitric acid, nitrous acid, and ammonia were 1.14 μg/m³, 0.3 μg/m³, and 0.62 μg/m³ for 1988, and 1.40 μg/m³,0.3 μg/m³, and 1.47 μg/m³ for 1989, respectively. Fine particulate nitrate and ammonium ranged from 0.02 to 0.21 μg/m³ and 0.01 to 4.72 μg/m³ for 1988, and 0.1 to 0.78 μg/m³ and 0.24 to 2.32 μg/m³ for 1989, respectively. The fine aerosol fraction was dominated by ammonium sulfate particles. Mean concentrations of nitrate and ammonium ions in cloud water samples were 238 and 214 μmol/l in 1988, and 135 and 147 μmol/l in 1989, respectively. Similarly, the concentrations of NO₃ and NH₄ ⁺ in precipitation were 26.4 and 14.0 μmol/l in 1988, and 16.6 and 15.2 μmol/l in 1989, respectively. The mean total nitrogen deposition due to wet, dry, and cloud deposition processes was estimated as ~30 and ~40 kg N/ha/year (i.e., ~10 and ~13 kg N/ha/growing season) for 1988 and 1989. Based on an analytical analysis, deposition to the forest canopy due to cloud interception, precipitation, and dry deposition processes was found to contribute ~60, ~20, and ~20 percent, respectively, of the total nitrogen deposition.     

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.     

Conversion of nitrogen oxides on commercial photocatalytic dispersion paints

In the present study, photocatalytic reactions of nitrogen oxides (NO_x = NO + NO₂) were studied on commercial TiO₂ doped facade paints in a flow tube photoreactor under simulated atmospheric conditions. Fast photocatalytic conversion of NO and NO₂ was observed only for the photocatalytic paints and not for non-catalytic reference paints. Nitrous acid (HONO) was formed in the dark on all paints studied, however, it efficiently decomposes under irradiation only on the photocatalytic samples. Thus, it is concluded that photocatalytic paint surfaces do not represent a daytime source of HONO, in contrast to other recent studies on pure TiO₂ surfaces. As main final product, the formation of adsorbed nitric acid/nitrate anion (HNO₃/NO₃^?) was observed with near to unity yield. In addition, traces of H₂O₂ were observed in the gas phase only in the presence of O₂. Formation of the greenhouse gas nitrous oxide (N₂O) could be excluded. The uptake kinetics of NO, NO₂ and HONO was very fast under atmospheric conditions (e.g. γ(NO + TiO₂) > 10^?5). Thus, the uptake on urban surfaces (painted houses, etc.) will be limited by transport. For a hypothetically painted street canyon, an average reduction of nitrogen oxide levels of ca. 5% is estimated. Since the harmful HNO₃/NO₃^? is formed on the surface of the photoactive paints, whereas it is formed in the gas phase in the atmosphere, the use of photocatalytic paints may also help to reduce acid deposition, e.g. on plants, or nitric acid related health issues.     

Physicochemical factors and sources of particulate matter at residential urban environment in Kuala Lumpur

Long-term measurements (2004–2011) of PM₁₀ (particulate matter with an aerodynamic diameter <10 μm) and trace gases (carbon monoxide [CO], ozone [O₃], nitrogen oxide [NO], oxides of nitrogen [NO_x], nitrogen dioxide [NO₂], sulfur dioxide [SO₂], methane [CH₄], nonmethane hydrocarbon [NMHC]) have been conducted to study the effect of physicochemical factors on the PM₁₀ concentration. In addition, this study includes source apportionment of PM₁₀ in Kuala Lumpur urban environment. An advanced principal component analysis (PCA) technique coupled with absolute principal component scores (APCS) and multiple linear regression (MLR) has been applied. The average annual concentration of PM₁₀ for 8 yr is 51.3 ± 25.8 μg m^?3, which exceeds the Recommended Malaysian Air Quality Guideline (RMAQG) and international guideline values. Detail analysis shows the dependency of PM₁₀ on the linear changes of the motor vehicles in use and the amount of biomass burning, particularly from Sumatra, Indonesia, during southwesterly monsoon. The main sources of PM₁₀ identified by PCA-APCS-MLR are traffic combustion (28%), ozone coupled with meteorological factors (20%), and windblown particles (1%). However, the apportionment procedure left 28.0 μg m^?3, that is, 51% of PM₁₀ undetermined.

Implications: Air quality is always a top concern around the globe. Especially in the South Asian regions, measures are not yet sufficient; as revealed in our studies, the concentrations of particulate matters exceed the tolerable limits. Long-term data analysis and characterization of particular matters and their sources will aid the policy makers and the concerned authority to adapt measures and policies according to the circumstances. Additionally, similar intensive studies will give insight about future implications of air quality management.     

Effect of PM2.5 chemical constituents on atmospheric visibility impairment

PM_2.5 sampling was conducted at a curbside location in Delhi city for summer and winter seasons, to evaluate the effect of PM_2.5 and its chemical components on the visibility impairment. The PM_2.5 concentrations were observed to be higher than the National Ambient Air Quality Standards (NAAQS), indicating poor air quality. The chemical constituents of PM_2.5 (the water-soluble ionic species SO₄^2-, NO₃^?, Cl^?, and NH₄⁺, and carbonaceous species: organic carbon, elemental carbon) were analyzed to study their impact on visibility impairment by reconstructing the light extinction coefficient, b_ext. The visibility was found to be negatively correlated with PM_2.5 and its components. The reconstructed b_ext showed that organic matter was the largest contributor to b_ext in both the seasons which may be attributed to combustion sources. In summer season, it was followed by elemental carbon and ammonium sulfate; however, in winter, major contributions were from ammonium nitrate and elemental carbon. Higher elemental carbon in both seasons may be attributed to traffic sources, while lower concentrations of nitrate during summer, may be attributed to volatility because of higher atmospheric temperatures.

Implications: The chemical constituents of PM_2.5 that majorly effect the visibility impairment are organic matter and elemental carbon, both of which are products of combustion processes. Secondary formations that lead to ammonium sulfate and ammonium nitrate production also impair the visibility.     

电化学氧化法去除超高盐榨菜废水中的氨氮

采用电化学氧化法去除超高盐榨菜废水中的氨氮,阳极为Ti/RuO2-TiO2-IrO2-SnO2网状电极,阴极为网状钛电极,考察了电流密度、电解时间、极板间距、初始pH以及极水比对氨氮去除率的影响,并分析了电流密度对氨氮能耗和阳极效率的影响。结果表明,在初始氨氮浓度为472.73 mg/L,电流密度为156 mA/cm2,极板间距为1.5 cm,极水比为0.8dm2/L,原水pH为4.3～5.0时,电解30 min和60 min时氨氮的去除率分别为89.75%和99.94%,电解30 min时,氨氮能耗最低为96 kWh/kg,阳极效率最高为8.47 g/(h.m2.A)。     

Monthly variations in nitrogen isotopes of ammonium and nitrate in wet deposition at Guangzhou,south China

Monthly nitrogen isotopes of ammonium and nitrate in wet deposition in the city of Guangzhou, and the causes of their variability, are reported in this paper. Nitrate δ¹⁵N showed nearly constant values around zero in the dry season (October to April), but oscillating values from negative to positive in the rainy season (May to September). By contrast, ammonium δ¹⁵N displayed lower values during the rainy season than in the dry season. The rural area north of the city was considered as the prominent source of ammonium and nitrate in spring and early summer (May and June), as suggested by their concurrent negative isotopic trends and higher NH₄⁺/NO₃^? ratios. From July to September, different dominating sources from the city, i.e., fossil fuel combustion for nitrate, and sewage and waste emission for ammonium, caused disparate δ¹⁵N trends of the two species, showing positive nitrate δ¹⁵N, but still negative ammonium δ¹⁵N. During the cool dry season, the high values of ammonium δ¹⁵N and concurrently low NH₄⁺/NO₃^? ratios suggested the decrease in NH₃ volatilization and relatively important thermogenic origin of ammonium, but the intermediate nitrate δ¹⁵N values around zero may be a result of a balanced emission of NO_x from the city and the rural areas. The isotopic effects of chemical conversion of NO_x to nitrate and washout of nitrate were ruled out as significant causes of nitrate δ¹⁵N variability, but ammonium washout, during which ¹⁵N is assumed to be preferentially removed, may partly contribute to the ammonium δ¹⁵N variability.     

Nitrate removal under different ecological remediation measures in Taihu Lake: a 15 N mass-balance approach

Ecological remediation is an important measure for the protection of lake water quality in removing nutrients, such as nitrate (NO₃ ^?). In this study, four bioremediation processes (bare sediment, immobilized nitrogen cycling bacteria (INCB) added, Elodea nuttallii added, E. nuttallii-INCB assemblage) were operated at a lab to elucidate the effect of macrophyte appearance and INCB addition on NO₃ ^? removal and achieve the optimal processes for biomediation. ¹⁵?N-NO₃ solution was added to microcosms to identify the key nitrogen transformation processes responsible for NO₃ ^? removal. Results showed that nitrate removal was significantly enhanced after the addition of INCB and E. nuttallii. In the treatments with INCB added, E. nuttallii added, and INCB and E. nuttallii-INCB assemblage, nitrate removal ratio achieved 94.74, 98.76, and 99.15 %, respectively. In contrast, only 23.47 % added nitrate was removed in the control. Plant uptake and denitrification played an important role in nitrogen removal. The water quality was substantially improved by the addition of INCB and macrophyte that can accelerate denitrification and promote nitrogen assimilation of plants. The results indicated that plant uptake and microbial denitrification were key processes for nitrate removal.     

Particulate Matter in California: Part 2—Spatial,Temporal, and Compositional Patterns of PM2.5, PM10–2.5, and PM10

Abstract

Geographic and temporal variations in the concentration and composition of particulate matter (PM) provide important insights into particle sources, atmospheric processes that influence particle formation, and PM management strategies. In the nonurban areas of California, annual-average PM_2.5 and PM₁₀ concentrations range from 3 to 10 [H9262]g/m³ and from 5 to 18 µg/m³, respectively. In the urban areas of California, annual-averages for PM_2.5 range from 7 to 30 [H9262]g/m³, with observed 24-hr peaks reaching levels as high as 160 [H9262]g/m³. Within each air basin, exceedances are a mixture of isolated events as well as periods of elevated PM_2.5 concentrations that are more prolonged and regional in nature. PM_2.5 concentrations are generally highest during the winter months. The exception is the South Coast Air Basin, where fairly high values occur throughout the year. Annual-average PM_2.5 mass, as well as the concentrations of major components, declined from 1988 to 2000. The declines are especially pronounced for the sulfate (SO₄ ^2?) and nitrate (NO₃ ^?) components of PM_2.5 and PM₁₀ and correlate with reductions in ambient levels of oxides of sulfur (SO_x) and oxides of nitrogen (NO_x). Annual averages for PM_10–2.5 and PM₁₀ exhibited similar downwind trends from 1994 to 1999, with a slightly less pronounced decrease in the coarse fraction.     

Effect of inorganic and organic solutes on zero-valent aluminum-activated hydrogen peroxide and persulfate oxidation of bisphenol A

The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO₃^? (no inhibition)?<?Cl^? (250 mg/L)?=?SO₄^2??<?PO₄^3? for HP/ZVA and Cl^? (250 mg/L; no inhibition)?<?NO₃^??<?SO₄^2??<?PO₄^3? for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.     

A Combustion Method for the Determination of Solvent Vapors at Low Concentrations in Air

The nitrogen-containing products of smog chamber reactions have been the subject of much controversy. Concern has arisen over nitrogen products because of the almost universally poor nitrogen balance reported for irradiated mixtures of hydrocarbons and nitrogen oxides. Some possible nitrogen-containing products, such as molecular nitrogen, nitrous oxide, and nitroolefins have been investigated and shown to be unimportant. The nitrogen products most often measured are peroxyacetyl nitrate and residual nitrogen dioxide. These two products rarely comprise more than 70% of the initial nitrogen at the end of an experiment, and often account for less than 50%. Previous experiments in which total nitrate was determined in the gas phase and on the vessel walls at the end of irradiation have shown very good nitrogen balances. The assumption has been made that the nitrate arises from nitric acid formed on the walls by adsorbed N₂O₅.

In the work reported here, all major nitrogen-containing compounds have been monitored continuously for the first time. Nitric oxide and nitrogen dioxide have been monitored by chemilumines-cence and automated Saltzman techniques. Methyl, ethyl, and peroxyacetyl nitrate have been determined by gas chromatogra-phy. Two methods, one continuous and one integrated, have been specially developed to measure nitric acid both in the smog chambers and in the atmosphere. Continuous determination of these compounds yields good nitrogen balances throughout the irradiations.

Profiles of the nitrogen-containing species from irradiated HC/ NO_x mixtures are discussed in terms of nitrogen products and nitrogen balance. Differences in product distribution for different hydrocarbon systems are also considered. Using rate information from the nitrogen compound profiles, important reactions leading to nitrogen-containing products are identified. Interference with the chemiluminescent technique by HON0₂, PAN, and C₂H₅ONO₂ is discussed.     

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.

     

Quantifying nitrate sources in a large reservoir for drinking water by using stable isotopes and a Bayesian isotope mixing model

Drinking water reservoirs are threatened globally by anthropogenic nitrogen pollution. Hydrochemistry and isotopes were analyzed to identify spatial and temporal varieties of main nitrate sources in a large drinking water reservoir in East China. The results showed that NO₃^? was the main nitrogen form in both the dry and wet seasons, but dissolved organic nitrogen (DON) was increased in the wet season. The δ¹⁵N-NO₃^? values (+?1.3‰ to +?11.8‰) and δ¹⁸O-NO₃^? values (+?2.5‰ to +?13.5‰), combined with principal component analysis (PCA), indicated that chemical fertilizer was the main nitrate source during the dry season, while chemical fertilizer, soil N, and sewage/manure were the main nitrate sources during the wet season in the Qiandao Lake area. And, the nitrate isotopes showed the significant nitrification and assimilation in the Qiandao Lake area. A Bayesian isotopic mixing model (Stable Isotope Analysis in R) was applied to the spatial and seasonal trends in the proportional contribution of four NO₃^? sources (chemical fertilizer (CF), soil nitrogen (SN), sewage and manure (SM), and atmospheric deposition (AD)) in the Qiandao Lake area. It was revealed that CF was the most important nitrate source in the dry season, accounting for 53.4% with 19.2% of SM and 18.9% of SN, while the contribution of SN increased in the wet season, accounting for 31.6%, followed by CF (30.8%) and then SM (24.2%). The main nitrate sources in the urban area, rural area, and central lake area were CF and SN, accounting for 66.1% in the urban area, 71.7% in the rural area, and 68.2% in the central lake area. Measures should be made to improve chemical fertilizer use efficiency and to reduce nitrogen loss in the Qiandao Lake area.

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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.     

Photochemical model performance for PM2.5 sulfate,nitrate, ammonium,and precursor species SO2, HNO3, and NH3 at background monitor locations in the central and eastern United States

Health studies have shown premature death is statistically associated with exposure to particulate matter <2.5 μm in diameter (PM2.5). The United States Environmental Protection Agency requires all States with PM2.5 non-attainment counties or with sources contributing to visibility impairment at Class I areas to submit an emissions control plan. These emission control plans will likely focus on reducing emissions of sulfur oxides and nitrogen oxides, which form two of the largest chemical components of PM2.5 in the eastern United States: ammonium sulfate and ammonium nitrate. Emission control strategies are simulated using three-dimensional Eulerian photochemical transport models.A monitor study was established using one urban (Detroit) and nine rural locations in the central and eastern United States to simultaneously measure PM2.5 sulfate ion (SO₄²⁻), nitrate ion (NO₃⁻), ammonium ion (NH₄⁺), and precursor species sulfur dioxide (SO₂), nitric acid (HNO₃), and ammonia (NH₃). This monitor study provides a unique opportunity to assess how well the modeling system predicts the spatial and temporal variability of important precursor species and co-located PM2.5 ions, which is not well characterized in the central and eastern United States.The modeling system performs well at estimating the PM2.5 species, but does not perform quite as well for the precursor species. Ammonia is under-predicted in the coldest months, nitric acid tends to be over-predicted in the summer months, and sulfur dioxide appears to be systematically over-predicted. Several indicators of PM2.5 ammonium sulfate and ammonium nitrate formation and chemical composition are estimated with the ambient data and photochemical model output. PM2.5 sulfate ion is usually not fully neutralized to ammonium sulfate in ambient measurements and is usually fully neutralized in model estimates. The model and ambient estimates agree that the ammonia study monitors tend to be nitric acid limited for PM2.5 nitrate formation. Regulatory strategies in this part of the country should focus on reductions in NO_X rather than ammonia to control PM2.5 ammonium nitrate.     

Feasibility of coupling a thermal/optical carbon analyzer to a quadrupole mass spectrometer for enhanced PM2.5 speciation

A thermal/optical carbon analyzer (TOA), normally used for quantification of organic carbon (OC) and elemental carbon (EC) in PM_2.5 (fine particulate matter) speciation networks, was adapted to direct thermally evolved gases to an electron impact quadrupole mass spectrometer (QMS), creating a TOA-QMS. This approach produces spectra similar to those obtained by the Aerodyne aerosol mass spectrometer (AMS), but the ratios of the mass to charge (m/z) signals differ and must be remeasured using laboratory-generated standards. Linear relationships are found between TOA-QMS signals and ammonium (NH₄⁺), nitrate (NO₃^?), and sulfate (SO₄^2-) standards. For ambient samples, however, positive deviations are found for SO₄^2-, compensated by negative deviations for NO₃^?, at higher concentrations. This indicates the utility of mixed-compound standards for calibration or separate calibration curves for low and high ion concentrations. The sum of the QMS signals across all m/z after removal of the NH₄⁺, NO₃^?, and SO₄^2- signals was highly correlated with the carbon content of oxalic acid (C?H?O?) standards. For ambient samples, the OC derived from the TOA-QMS method was the same as the OC derived from the standard IMPROVE_A TOA method. This method has the potential to reduce complexity and costs for speciation networks, especially for highly polluted urban areas such as those in Asia and Africa.

Implications: Ammonium, nitrate, and sulfate can be quantified by the same thermal evolution analysis applied to organic and elemental carbon. This holds the potential to replace multiple parallel filter samples and separate laboratory analyses with a single filter and a single analysis to account for a large portion of the PM_2.5 mass concentration.