Chemical Transformations of Nitrogen Oxides While Sampling Combustion Products

The present study reviews the sampling environments and chemical transformations of nitrogen oxides that may occur within probes and sample lines while sampling combustion products. Experimental data are presented for NO_x transformations in silica and 316 stainless steel tubing when sampling simulated combustion products in the presence of oxygen, carbon monoxide, and hydrogen. A temperature range of 25° to 400°C is explored. In the absence of CO and H₂, 316 stainless steel is observed to promote the reduction of nitrogen dioxide to nitric oxide at temperatures in excess of 300°C, and silica is found to be passive to chemical transformation. In the presence of CO, reduction of N0₂ to NO is observed in 316 stainless steel at temperatures in excess of 100°C, and reduction of NO₂ to NO in silica is observed at 400°C. In the presence of H₂, NO₂ is reduced to NO in 316 stainless steel at 200°C and NO_x is removed at temperatures exceeding 200°C. In silica, the presence of H₂ promotes the reduction of NO₂ to NO at 300°C and the removal of NO_x above 300°C.     

Standard Reference Gases and Analytical Procedures for Use in Gas Turbine Exhaust Measurements

This paper is directed to people who are involved in the measurement of gas turbine exhaust emissions and as a consequence in the establishment of standard reference gases and attendant analytical procedures.

Several problems exist in connection with the establishment of these standards:

A number of standard reference gases have been developed by the National Bureau of Standards for use in the automotive industry which are also suitable for gas turbine exhaust measurements. However, there is a need for additional standard reference materials such as NO in nitrogen, intermediate levels of CO₂ in air, and higher concentrations of CO in nitrogen and propane in air.

There is difficulty in maintaining certain reference materials with confidence in assay, particularly due to instability in the cylinder.

Instrumental operational problems with flame ionization detector type units exist. Of particular importance is the difference in response per carbon atom in different organic molecules and the difference in response of a test sample as a function of the oxygen content of the sample.

Instrumental method problems such as converter efficiency in chemiluminescence units measuring NO₂ and calibration techniques involving CO to CH₄ conversion, also must be considered.

A number of problems occur in the use of wet chemical reference methods such as the phenoldisulfonic acid method for the determination of NO_x. These include both efficiency of collection, conversion of NO to NO₂, and subsequent analysis.

This paper considers the development of standards for the measurement of NO_x, CO, CO₂, total hydrocarbons, and O₂ and reviews the state-of-the-art with respect to these problems and their resolution.     

Odor Threshold Measurement by Dynamic Olfactometry: Significant Operational Variables

Abstract

Combustion flue gases of three different industrial boilers firing miscellaneous fuels were monitored for a twoweek period. Nitric oxide (NO), sulfur dioxide (SO₂), carbon monoxide (CO), carbon dioxide (CO₂), and total hydrocarbons (CxHy) were continuously measured using single-component gas analyzers in parallel with a lowresolution Fourier Transform Infrared (FTIR) gas analyzer. Hydrogen chloride (HCl) was measured continuously using the FTIR analyzer and semi-continuously using a traditional liquid-absorption technique. Nitrous oxide (N₂O), nitrogen dioxide (NO₂), and water vapor (H₂O) were continuously measured using the FTIR analyzer only. Laboratory tests were conducted prior to the field measurements to assess the detection limits of the different measurement methods for each gas component. No significant differences were found between the results of the low-resolution FTIR analyzer and the single-component analyzers or the liquid absorption method.     

Simultaneous removal of NOx,SO2, and Hg from flue gas in FGD absorber with oxidant injection (NaClO2)– full-scale investigation

ABSTRACT

This article presents the results of an industrial-scale study (on 400 MW_e lignite fired unit) of simultaneous NO_x, SO₂, and Hg^T removal in FGD absorber with oxidant injection (NaClO₂) into flue gas. It was confirmed that the injection of sodium chlorite upstream the FGD (Flue Gas Desulfurization) absorber oxidize NO to NO₂, Hg⁰ to Hg²⁺, and enhancing NO_x and Hg^T removal efficiency from exhaust gas in FGD absorber. Mercury removal efficiency grows with the rise of degree of oxidation NO to NO₂ and was limited by the phenomenon of re-emission. For NO_x removal the most critical parameters is slurry pH and temperature. There was no negative effect on sulfur dioxide removal efficiency caused by oxidant injection in tested FGD absorber. Based on the data provided, NO_x and Hg^T emissions can be reduced by adjusting the FGD absorber operating parameters combined with oxidant injection.     

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

Absorption of NO and NO2 in Caprolactam Tetrabutyl Ammonium Halide Ionic Liquids

ABSTRACT

To explore environmentally benign solvents for the absorption of NO and NO₂, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO₂ was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO₂ in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO₂ decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO₂ was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO₂.

IMPLICATIONS Basic ionic liquids with amino groups were synthesized and used to capture CO₂, SO₂, and H₂S, and to promote hydrogenation of CO₂. In this paper, the authors used caprolactam tetrabutyl ammonium halide ionic liquid (IL) as absorbing medium in which NO_x could be absorbed. NO_x desorbed from the absorbent could be efficiently reduced by right catalysts at high temperature. The absorbed NO and NO₂ gas could be desorbed at higher temperature, allowing the ionic liquids to be reused several times without loss of capability. It was believed that caprolactam tetrabutyl ammonium bromide (CPL-TBAB) ILs may be useful for NO_x removal reagent for pollution control.     

Uranyl–water-containing complexes: solid-state UV-MALDI mass spectrometric and IR spectroscopic approach for selective quantitation

Since primary environmental concept for long storage of nuclear waste involved assessment of water in uranium complexes depending on migration processes, the paper emphasized solid-state matrix-assisted laser desorption/ionization (MALDI) mass spectrometric (MS) and IR spectroscopic determination of UO₂(NO₃)₂·6H₂O; UO₂(NO₃)₂·3H₂O, α-, β-, and γ-UO₃ modifications; UO₃·xH₂O (x?=?1 or 2); UO₃·H₂O, described chemically as UO₂(OH)₂, β- and γ-UO₂(OH)₂ modifications; and UO₄·2H₂O, respectively. Advantages and limitation of vibrational spectroscopic approach are discussed, comparing optical spectroscopic data and crystallographic ones. Structural similarities occurred in α–γ modifications of UO₃, and UO₂(OH)₂ compositions are analyzed. Selective speciation achieved by solid-state mass spectrometry is discussed both in terms of its analytical contribution for environmental quality assurance and assessment of radionuclides, and fundamental methodological interest related the mechanistic complex water exchange of UO₃·H₂O forms in the gas phase. In addition to high selectivity and precision, UV-MALDI-MS, employing an Orbitrap analyzer, was a method that provided fast steps that limited sample pretreatment techniques for direct analysis including imaging. Therefore, random and systematic errors altering metrology and originating from the sample pretreatment stages in the widely implemented analytical protocols for environmental sampling determination of actinides are significantly reduced involving the UV-MALDI-Orbitrap-MS method. The method of quantum chemistry is utilized as well to predict reliably the thermodynamics and nature of U–O bonds in uranium species in gas and condensed phases.     

Analysis of the air pollution climate at a central urban background site

Measurements of air pollutants from a background site in central London are analysed. These comprise hourly data for CO, NO, NO₂, O₃, SO₂ and PM₁₀ from 1996 to 2008 and particle number count from 2001 to 2008. The data are analysed in terms of long-term trends, annual, weekly and diurnal cycles, and autocorrelation and cross-correlation functions. CO, NO and NO₂ show a typical traffic-associated pattern with two daily peaks and lesser concentrations at the weekend. Particle number count and PM₁₀ show a similar cycle, but with smaller amplitude. Ozone has an annual cycle with a maximum in May, influenced by the spring maximum in background ozone, but the diurnal and weekly cycles are dominated by losses through reaction with nitric oxide. Particle number count shows a minimum corresponding with maximum air temperatures in August, whereas the CO, NO NO₂ and SO₂ show a minimum in June/July. There is a lower particle count to NO_x ratio at the background site compared to a central London kerbside site (Marylebone Road) and a seasonal pattern in particle count to NO_x and PM₁₀ ratios consistent with loss of nanoparticles by evaporation during atmospheric transport. Sulphur dioxide peaks in the morning in summer, but at midday in winter consistent with emissions from elevated sources mixing down from aloft as the diurnal mixed layer deepens. Implications for epidemiological studies of air quality and health are discussed. Sulphur dioxide, carbon monoxide, nitric oxide and nitrogen dioxide show clear downward trends over the measurement period, PM₁₀ declines initially before levels stabilised, and ozone concentrations increased.     

Development of a Method for the Analysis of NO2 and NH3 by NO-Measuring Instruments

Adaptation of available instruments to the analysis of NO₂ and NH₃ became important with the introduction of the Federal Constant Volume Sampling procedure for exhaust analysis in 1970. Two instruments, the NO optical detector (NOOD) and the non-dispersive infrared analyzer (ND1R), are both fast and accurate. The use of a system of two converters in conjunction with either of these instruments permits the analysis of a gas stream for NO, NO₂, and NH₃. NO is measured on the gas stream before conversion; NO₂ is determined after the gas stream has passed over a C-Mo converter at 475°C; and NH₃ is determined after the gas has been conducted over a C-Cu converter.     

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.     

Selective Reduction of Nitrogen Oxides In Combustion Flue Gases

The body of Information presented in this paper is directed to those Individuals concerned with the removal of NO_x in combustion flue gases. A catalytic process for the selective reduction of nitrogen oxides by ammonia has been investigated. Efforts were made toward the development of catalysts resistant to SO_x poisoning. Nitrogen oxides were reduced over various metal oxide catalysts in the presence or absence of SO_x(SO₂ and SO₃). Catalysts consisting of oxides of base metals (for example, Fe₂O₃) were easily poisoned by SO₃, forming sulfates of the base metals. A series of catalysts which are not susceptible to the SO_x poisoning has been developed. The catalysts possess a high activity and selectivity over a wide range of temperatures, 250—450°C. The catalysts were tested in a pilot plant which treated a flue gas containing 110-150 ppm NO_x, 660-750 ppm SO₂, and 40-90 ppm SO₃. The pilot plant was operated at 350°C and at a space velocity of 10,000 h^-1. The removal of nitrogen oxides was more than 90% for several months.

A mechanism of the NO-NH₃ reaction has also been investigated. It is found that NO reacts with NH₃ at a 1:1 mole ratio in the presence of oxygen and the reaction is completely inhibited by the absence of oxygen. The experimental data show that the NO-NH₃ reaction in the presence of oxygen is represented byNO + NH₃ + 1/4 O₂ = N₂ + 3/2 H₂O.     

The Effects of Liquid Water Addition In Gas Turbine Combustors

The addition of liquid water, in quantities equivalent to the mass of fuel consumed, exerts thermal and chemical effects upon the combustion process in a gas turbine engine. The thermal influence is produced by the vaporizalion and heating of the water and its vapor. The final temperature is reduced and the concentrations of NO _x , O, OH, CO are lower than standard combustion concentrations. Chemically, the additional H₂O participates in reactions producing the aforementioned species. However, the lower temperature overrides this influence. These effects have been assessed for different fuel states, i.e., for pre-mixed combustion and for liquid fuel undergoing vaporization and mixing.     

Variability in the primary emissions and secondary gas and particle formation from vehicles using bioethanol mixtures

Bioethanol for use in vehicles is becoming a substantial part of global energy infrastructure because it is renewable and some emissions are reduced. Carbon monoxide (CO) emissions and total hydrocarbons (THC) are reduced, but there is still controversy regarding emissions of nitrogen oxides (NO_x), aldehydes, and ethanol; this may be a concern because all these compounds are precursors of ozone and secondary organic aerosol (SOA). The amount of emissions depends on the ethanol content, but it also may depend on the engine quality and ethanol origin. Thus, a photochemical chamber was used to study secondary gas and aerosol formation from two flex-fueled vehicles using different ethanol blends in gasoline. One vehicle and the fuel used were made in the United States, and the others were made in Brazil. Primary emissions of THC, CO, carbon dioxide (CO₂), and nonmethane hydrocarbons (NMHC) from both vehicles decreased as the amount of ethanol in gasoline increased. NO_x emissions in the U.S. and Brazilian cars decreased with ethanol content. However, emissions of THC, CO, and NO_x from the Brazilian car were markedly higher than those from the U.S. car, showing high variability between vehicle technologies. In the Brazilian car, formation of secondary nitrogen dioxide (NO₂) and ozone (O₃) was lower for higher ethanol content in the fuel. In the U.S. car, NO₂ and O₃ had a small increase. Secondary particle (particulate matter [PM]) formation in the chamber decreased for both vehicles as the fraction of ethanol in fuel increased, consistent with previous studies. Secondary to primary PM ratios for pure gasoline is 11, also consistent with previous studies. In addition, the time required to form secondary PM is longer for higher ethanol blends. These results indicate that using higher ethanol blends may have a positive impact on air quality.

Implications: The use of bioethanol can significantly reduce petroleum use and greenhouse gas emissions worldwide. Given the extent of its use, it is important to understand its effect on urban pollution. There is a controversy on whether there is a reduction or increase in PM emission when using ethanol blends. Primary emissions of THC, CO, CO₂, NO_x, and NMHC for both cars decreased as the fraction of ethanol in gasoline increased. Using a photochemical chamber, the authors have found a decrease in the formation of secondary particles and the time required to form secondary PM is longer when using higher ethanol blends.     

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.     

A new measurement method for nitrogen oxides in the air using an annular diffusion scrubber coated with titanium dioxide

A new convenient measurement method of nitrogen oxides (NO_x) in the ambient air was developed. The collection of NO_x is performed by an annular diffusion scrubber coated with a mixture of titanium dioxide (TiO₂) and hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) and the analysis is carried out by ion chromatography with conductivity detection. Under ultraviolet light (UV) illumination, TiO₂ produces reactive oxygen species such as super oxide (O₂⁻), hydroxyl radical (OH·) and peroxyhydroxyl radical (HO₂·), by which nitric oxide (NO) is oxidized to nitrogen dioxide (NO₂), and is further oxidized to nitric acid (HNO₃). The yielded HNO₃ and NO₂ are effectively adsorbed on the surface of TiO₂ and hydroxyapatite. The collection efficiencies of NO and NO₂ by the annular diffusion scrubber coated with the catalysts under UV illumination are higher than 98%, respectively, at the air flow rate of 0.2–1.0 l min⁻¹. After the collection of NO_x, by feeding deionized water into the annular diffusion scrubber, HNO₃ and NO₂ which adsorbed on the catalysts are extracted as forms of nitrite ion (NO₂⁻) and nitrate ion (NO₃⁻). The extraction efficiencies of NO and NO₂ are almost 100%. The activity of the washed catalysts can be completely recovered by drying with the purified air. Further, a simultaneous separated measurement of NO and NO₂ can be performed by utilizing the UV illumination dependence. This method was applied to the measurement of NO_x in the ambient air. The NO_x concentration measured by this method was in good agreement with that obtained using the chemiluminescence NO_x analyzer.     

Major air pollutants in Bursa,Turkey: their levels,temporal changes,interactions, and sources

Bursa is one of the largest cities of Turkey and it hosts 17 organized industrial zones. Parallel to the increase in population, rapidly growing energy consumption, and increased numbers of transport vehicles have impacts on the air quality of the city. In this study, regularly calibrated automatic samplers were employed to get the levels of air pollution in Bursa. The concentrations of CH₄ and N-CH₄ as well as the major air pollutants including PM₁₀, PM_2.5, NO, NO₂, NO_x, SO₂, CO, and O₃, were determined for 2016 and 2017 calendar years. Their levels were 1641.62?±?718.25, 33.11?±?5.45, 42.10?±?10.09, 26.41?±?9.01, 19.47?±?16.51, 46.73?±?16.56, 66.23?±?32.265, 7.60?±?3.43, 659.397?±?192.73, and 51.92?±?25.63 µg/m³ for 2016, respectively. Except for O₃, seasonal concentrations were higher in winter and autumn for both years. O₃, CO, and SO₂ had never exceeded the limit values specified in the regulations yet PM₁₀, PM_2.5, and NO₂ had violated the limits in some days. The ratios of CO/NO_x, SO₂/NO_x, and PM_2.5/PM₁₀ were examined to characterize the emission sources. Generally, domestic and industrial emissions were dominated in the fall and winter seasons, yet traffic emissions were effective in spring and summer seasons. As a result of the correlation process between O_x and NO_x, it was concluded that the most important source of O_x concentrations in winter was NO_x and O₃ was in summer.     

On-Road,In-Use Gaseous Emission Measurements by Remote Sensing of School Buses Equipped with Diesel Oxidation Catalysts and Diesel Particulate Filters

Abstract

A remote sensing device was used to obtain on-road and in-use gaseous emission measurements from three fleets of schools buses at two locations in Washington State. This paper reports each fleet’s carbon monoxide (CO), hydrocarbon (HC), nitric oxide (NO), and nitrogen dioxide (NO₂) mean data. The fleets represent current emission retrofit technologies, such as diesel particulate filters and diesel oxidation catalysts, and a control fleet. This study shows that CO and HC emissions decrease with the use of either retrofit technology when compared with control buses of the same initial emission standards. The CO and HC emission reductions are consistent with published U.S. Environmental Protection Agency verified values. The total oxides of nitrogen (NO_x), NO, and the NO₂/NO_x ratio all increase with each retrofit technology when compared with control buses. As was expected, the diesel particulate filters emitted significantly higher levels of NO₂ than the control fleet because of the intentional conversion of NO to NO₂ by these systems. Most prior research suggests that NO_x emissions are unaffected by the retrofits; however, these previous studies have not included measurements from retrofit devices on-road and after nearly 5 yr of use. Two 2006 model-year buses were also measured. These vehicles did not have retrofit devices but were built to more stringent new engine standards. Reductions in HCs and NO_x were observed for these 2006 vehicles in comparison to other non-retrofit earlier model-year vehicles.     

Control of Diesel Gaseous and Particulate Emissions with a Tube-Type Wet Electrostatic Precipitator

Abstract

In this study, experiments were performed with a bench-scale tube-type wet electrostatic precipitator (wESPs) to investigate its effectiveness for the removal of mass- and number-based diesel particulate matter (DPM), hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NO_x) from diesel exhaust emissions. The concentration of ozone (O₃) present in the exhaust that underwent a nonthermal plasma treatment process inside the wESP was also measured. A nonroad diesel generator operating at varying load conditions was used as a stationary diesel emission source. The DPM mass analysis was conducted by means of isokinetic sampling and the DPM mass concentration was determined by a gravimetric method. An electrical low-pressure impactor (ELPI) was used to quantify the DPM number concentration. The HC compounds, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) were collected on a moisture-free quartz filter together with a PUF/XAD/PUF cartridge and extracted in dichloromethane with sonication. Gas chromatography (GC)/mass spectroscopy (MS) was used to determine HC concentrations in the extracted solution. A calibrated gas combustion analyzer (Testo 350) and an O₃ analyzer were used for quantifying the inlet and outlet concentrations of CO and NO_x (nitric oxide [NO] + nitrogen dioxide [NO₂]), and O₃ in the diesel exhaust stream. The wESP was capable of removing approximately 67–86% of mass- and number-based DPM at a 100% exhaust volumetric flow rate generated from 0- to 75-kW engine loads. At 75-kW engine load, increasing gas residence time from approximately 0.1 to 0.4 sec led to a significant increase of DPM removal efficiency from approximately 67 to more than 90%. The removal of n-alkanes, 16 PAHs, and CO in the wESP ranged from 31 to 57% and 5 to 38%, respectively. The use of the wESP did not significantly affect NO_x concentration in diesel exhaust. The O₃ concentration in diesel exhaust was measured to be less than 1 ppm. The main mechanisms responsible for the removal of these pollutants from diesel exhaust are discussed.     

Transformations,Lifetimes, and Sources of NO2, HONO,and HNO3 in Indoor Environments

Recent research has demonstrated that nitrogen oxides are transformed to nitrogen acids in indoor environments, and that significant concentrations of nitrous acid are present in indoor air. The purpose of the study reported in this paper has been to investigate the sources, chemical transformations and lifetimes of nitrogen oxides and nitrogen acids under the conditions existing in buildings. An unoccupied single family residence was instrumented for monitoring of NO, NO₂, NO_y, MONO, HNO₃, CO, temperature, relative humidity, and air exchange rate. For some experiments, NO₂ and HONO were injected into the house to determine their removal rates and lifetimes. Other experiments investigated the emissions and transformations of nitrogen species from unvented natural gas appliances. We determined that HONO is formed by both direct emissions from combustion processes and reaction of NO₂ with surfaces present indoors. Equilibrium considerations influence the relative contributions of these two sources to the indoor burden of HONO. We determined that the lifetimes of trace nitrogen species varied in the order NO ~ HONO > NO₂ >HNO₃. The lifetimes with respect to reactive processes are on the order of hours for NO and HONO, about an hour for NO₂, and 30 minutes or less for HNO3. The rapid removal of NO₂ and long lifetime of HONO suggest that HONO may represent a significant fraction of the oxidized nitrogen burden in indoor air.     

Simultaneous Sulfur Dioxide and Nitrogen Dioxide Removal by Calcium Hydroxide and Calcium Silicate Solids

ABSTRACT

At conditions typical of a bag filter exposed to a coal-fired flue gas that has been adiabatically cooled with water, calcium hydroxide and calcium silicate solids were exposed to a dilute, humidified gas stream of nitrogen dioxide (NO₂) and sulfur dioxide (SO₂) in a packed-bed reactor. A prior study found that NO₂ reacted readily with surface water of alkaline and non-alkaline solids to produce nitrate, nitrite, and nitric oxide (NO). With SO₂ present in the gas stream, NO₂ also reacted with S(IV), a product of SO₂ removal, on the exterior of an alkaline solid. The oxidation of S(IV) to S(VI) by oxygen reduced the availability of S(IV) and lowered removal of NO₂. Subsequent acidification of the sorbent by the removal of NO₂ and SO₂ facilitated the production of NO. However, the conversion of nitrous acid to sulfur-nitrogen compounds reduced NO production and enhanced SO₂ removal. A reactor model based on empirical and semi-empirical rate expressions predicted rates of SO₂ removal, NO₂ removal, and NO production by calcium silicate solids. Rate expressions from the reactor model were inserted into a second program, which predicted the removal of SO₂ and NO_x by a continuous process, such as the collection of alkaline solids in a baghouse. The continuous process model, depending upon inlet conditions, predicted 30-40% removal for NO and 50-90% removal for SO₂. These x 2 results are relevant to dry scrubbing technology for combined SO₂ and NO_x removal that first oxidizes NO to NO₂ by the addition of methanol into the flue duct.