NO removal by reducing agents and additives in the selective non-catalytic reduction (SNCR) process

The effect of the additives on the selective non-catalytic reduction (SNCR) reaction has been determined in a three-stage laboratory scale reactor. The optimum reaction temperature is lowered and the reaction temperature window is widened with increasing concentrations of the gas additives (CO, CH4). The optimum reaction temperature is lowered and the maximum NO removal efficiency decreases with increasing the concentration of alcohol additives (CH3OH, C2H5OH). The addition of phenol lowers the optimum reaction temperature about 100-150 degrees C similar to that of the toluene addition. The volatile organic compounds (VOCs: C6H5OH, C7H8) can be utilized in the SNCR process to enhance NO reduction and removed at the same time. A previously proposed simple kinetic model can successfully apply the NO reduction by NH3 and the present additives.     

Experimental and modeling study of the effect of CO and H2 on the urea DeNO(x) process in a 150kW laboratory reactor

An experimental and modeling investigation has been performed to study the effect of process additives, H2 and CO on NO(x) removal from flue gases by a selective non-catalytic reduction process using urea as a reducing agent. Experiments were performed with a flow reactor in which flue gas was generated by the combustion of propane in air at 3% excess oxygen and the desired levels of initial NO(x) (500ppm) were achieved by doping the flame with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 850 to 1200 degrees C for investigation of the effects of the process additives on the performance of aqueous urea DeNO(x). Subsequently, computational kinetic modeling with SENKIN code was performed to analyze the performance of urea providing a direct comparison of modeling prediction with experimental measurements. With CO addition, a downwards shift of 215 degrees C in the peak reduction temperature from 1125 to 910 degrees C was observed during the experimentation while the kinetic modeling suggests it to be 150 degrees C, i.e. from 1020 to 870 degrees C. The addition of H2 impairs the peak NO(x) reduction but suggests a low temperature application of the process. A downward shift of 250 degrees C in the peak reduction temperature, from 1020 to 770 degrees C, was observed during kinetic modeling studies. The kinetic modeling shows a good qualitative agreement with the experimental observations and reveals additional information about the process.     

Formation characteristics of aerosol particles from pulverized coal pyrolysis in high-temperature environments

The formation characteristics of aerosol particles from pulverized coal pyrolysis in high temperatures are studied experimentally. By conducting a drop-tube furnace, fuel pyrolysis processes in industrial furnaces are simulated in which three different reaction temperatures of 1000, 1200, and 1400 degrees C are considered. Experimental observations indicate that when the reaction temperature is 1000 degrees C, submicron particles are produced, whereas the particle size is dominated by nanoscale for the temperature of 1400 degrees C. Thermogravimetric analysis of the aerosol particles stemming from the pyrolysis temperature of 1000 degrees C reveals that the thermal behavior of the aerosol is characterized by a three-stage reaction with increasing heating temperature: (1) a volatile-reaction stage, (2) a weak-reaction stage, and (3) a soot-reaction stage. However, with the pyrolysis temperature of 1400 degrees C, the volatile- and weak-reaction stages almost merge together and evolve into a chemical-frozen stage. The submicron particles (i.e., 1000 degrees C) are mainly composed of volatiles, tar, and soot, with the main component of the nanoscale particles (i.e., 1400 degrees C) being soot. The polycyclic aromatic hydrocarbons (PAHs) contained in the aerosols are also analyzed. It is found that the PAH content in generated aerosols decreases dramatically as the pyrolysis temperature increases.     

Formate species in the low-temperature oxidation of dimethyl ether

The oxidation of dimethyl ether (DME, 340 ppm in 10% O2) has been studied experimentally in an atmospheric pressure laminar flow reactor in the temperature range from 240 degrees C to 700 degrees C for residence times in the range 2-4 s. The influence of nitric oxide additions up to 620 ppm to the feed gases has also been investigated. Products of reaction were determined by FTIR. In the absence of NO, reaction is first detected at about 260 degrees C. The products in the low-temperature region include formaldehyde (HCHO), and formic acid (HCOOH). The addition of NO leads to the appearance of methyl formate (CH3OCHO). While the overall behaviour of the system can be explained qualitatively in terms of typical low-temperature hydrocarbon ignition, recently published chemical kinetic models for DME ignition do not allow for the formation of these formate species. We find no experimental evidence for the formation of hydroperoxymethyl formate (HPMF, HOOCH2OCHO) which is predicted by the models to be a significant stable intermediate at temperatures below 350 degrees C. Since both formic acid and methyl formate have potentially harmful health effects, these observations may have significant implications for use of DME as a diesel fuel.     

Computational modelling of NOx removal by selective non-catalytic reduction

This paper presents the results of computational kinetic modelling of the removal of nitrogen oxides (NO_x) from flue gases by selective non-catalytic reduction (SNCR) process using urea as a reducing agent. CHEMKIN and SENKIN computer codes were used with latest reaction mechanism parameters for simulated conditions in an isothermal plug flow reactor. Flue gas initial conditions were simulated as 70 litres/min propane containing 500 ppm background NO_x. A range of molar ratios was studied at optimum temperature. Carbon monoxide and hydrogen were investigated as potential enhancers to lower the temperature window. The modelling results suggested that the optimum temperature for peak reduction was around 1075°C with optimum molar ratios of 1.5. Hydrogen was found to be an efficient enhancer. The optimum residence time was found to be about 80 milliseconds.     

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

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

Bacteria additives to the changes in gaseous mass transfer from stored swine manure

Abstract

A bacteria additives treatment experiment in assessing the changes in gaseous mass transfer from stored swine manure is presented. The experiment is tested for ammonia, methane, hydrogen sulfide, and carbon dioxide emission data sampled from pilot swine manure columns and analyzed by GC/MS. The result shows that bacteria additives slightly reduce the methane and carbon dioxide releases, while the same additives do not show any effect on the reduction of ammonia. The hydrogen sulfide contents of stored swine manure continued to be low. Gas concentrations emitted from treated and untreated stored swine manure were: 3.76 and 2.2 ppm for methane, 0.35 and 0.11 ppm for ammonia, and 1000 and 470 ppm for carbon dioxide, respectively. A simple model to estimate gas emission rates is also developed from the viewpoint of two‐film resistance theory. The average emission rates calculated from the model for methane, ammonia, and carbon dioxide are respectively: 0.01, 0.0005, and 13.98 g/min from untreated stored manure; while 0.07, 0.096, and 0.55 g/min from treated manure. The emission model also indicates that for most gaseous pollutants of environmental concern, liquid phase transfer coefficient controls the rate of volatile compounds emitted from stored swine manure and gas phase transfer coefficient has insignificant effect in the calculation of overall mass transfer coefficient.     

Surface properties and catalytic performance of La(1-x)Sr(x)FeO(3) perovskite-type oxides for methane combustion

La(1-x)Sr(x)FeO(3) (x=0.0-1.0) perovskites were prepared and tested for the combustion of methane. X-ray diffraction (XRD) patterns revealed the presence of a single perovskite structure for substitutions 0x0.3, however Fe(2)O(3), SrCO(3) and SrFeO(3) phases were observed for substitutions x>0.3. The results of activity test indicate that with La(1-x)Sr(x)FeO(3) as the catalyst, the combustion of methane can take place at low temperatures around 400 degrees C. Partial substitution of La with Sr increases the activity and an optimal substitution fraction (x=0.5) exists in the La(1-x)Sr(x)FeO(3) catalysts. Catalyst activity can be well correlated to the product of the specific surface area and atomic ratio of Fe to La+Sr on the catalyst surface. Experimental results of O(2)-TPD and CH(4)-TPD in the range of 350-500 degrees C indicate that the amount of oxygen desorbed from the La(1-x)Sr(x)FeO(3) catalysts is far larger than that of methane. Therefore, it can be proposed that the catalytic oxidation of CH(4) over these catalysts proceeds with the surface reaction between CH(4) in the gas phase and the adsorbed O(2). Addition of water vapor or CO(2) to the feed inhibited catalyst activity, but the inhibition was reversible and became negligible at high reaction temperature.     

Influence of HCl on oxidation of gaseous elemental mercury by dielectric barrier discharge process

The influence of HCl on the oxidation of gaseous elemental mercury (Hg0) has been investigated using a dielectric barrier discharge (DBD) plasma process, where the temperature of the plasma reactor and the composition of gas mixtures of HCl, H2O, NO, and O2 in N2 balance have been varied. We observe that Cl atoms and Cl2 molecules, created by the DBD process, play important roles in the oxidation of Hg0 to HgCl2. The addition of H2O to the gas mixture of HCl in N2 accelerates the oxidation of Hg0, although no appreciable effect of H2O alone on the oxidation of Hg0 has been observed. The increase of the reaction temperature in the presence of HCl results in the reduction of Hg0 oxidation efficiency probably due to the deterioration of the heterogeneous chemical reaction of Hg0 with chlorinated species on the reactor wall. The presence of NO shows an inhibitory effect on the oxidation of Hg0 under DBD of 16% O2 in N2, indicating that NO acts as an O and O3 scavenger. At the composition of Hg0 (280 microg m(-3)), HCl (25 ppm), NO (204 ppm), O2 (16%) and N2 (balance) and temperature 90 degrees C, we obtain the nearly complete oxidation of Hg0 at a specific energy density of 8 J l(-1). These results lead us to suggest that the DBD process can be viable for the treatment of mercury released from coal-fired power plants.     

Acceleration of the Fe(III)EDTA(-) reduction rate in BioDeNO(x) reactors by dosing electron mediating compounds

BioDeNO(x), a novel technique to remove NO(x) from industrial flue gases, is based on absorption of gaseous nitric oxide into an aqueous Fe(II)EDTA(2-) solution, followed by the biological reduction of Fe(II)EDTA(2-) complexed NO to N(2). Besides NO reduction, high rate biological Fe(III)EDTA(-) reduction is a crucial factor for a succesful application of the BioDeNO(x) technology, as it determines the Fe(II)EDTA(2-) concentration in the scrubber liquor and thus the efficiency of NO removal from the gas phase. This paper investigates the mechanism and kinetics of biological Fe(III)EDTA(-) reduction by unadapted anaerobic methanogenic sludge and BioDeNO(x) reactor mixed liquor. The influence of different electron donors, electron mediating compounds and CaSO(3) on the Fe(III)EDTA(-) reduction rate was determined in batch experiments (21mM Fe(III)EDTA(-), 55 degrees C, pH 7.2+/-0.2). The Fe(III)EDTA(-) reduction rate depended on the type of electron donor, the highest rate (13.9mMh(-1)) was observed with glucose, followed by ethanol, acetate and hydrogen. Fe(III)EDTA(-) reduction occurred at a relatively slow (4.1mMh(-1)) rate with methanol as the electron donor. Small amounts (0.5mM) of sulfide, cysteine or elemental sulfur accelerated the Fe(III)EDTA(-) reduction. The amount of iron reduced significantly exceeded the amount that can be formed by the chemical reaction of sulfide with Fe(III)EDTA(-), suggesting that the Fe(III)EDTA(-) reduction was accelerated via an auto-catalytic process with an unidentified electron mediating compound, presumably polysulfides, formed out of the sulfur additives. Using ethanol as electron donor, the specific Fe(III)EDTA(-) reduction rate was linearly related to the amount of sulfide supplied. CaSO(3) (0.5-100mM) inhibited Fe(III)EDTA(-) reduction, probably because SO(3)(2-) scavenged the electron mediating compound.     

Control strategies of atmospheric mercury emissions from coal-fired power plants in China

Atmospheric mercury (Hg) emission from coal is one of the primary sources of anthropogenic discharge and pollution. China is one of the few countries in the world whose coal consumption constitutes about 70% of total primary energy, and over half of coals are burned directly for electricity generation. Atmospheric emissions of Hg and its speciation from coal-fired power plants are of great concern owing to their negative impacts on regional human health and ecosystem risks, as well as long-distance transport. In this paper, recent trends of atmospheric Hg emissions and its species split from coal-fired power plants in China during the period of 2000-2007 are evaluated, by integrating each plant's coal consumption and emission factors, which are classified by different subcategories of boilers, particulate matter (PM) and sulfur dioxide (SO2) control devices. Our results show that the total Hg emissions from coal-fired power plants have begun to decrease from the peak value of 139.19 t in 2005 to 134.55 t in 2007, though coal consumption growing steadily from 1213.8 to 1532.4 Mt, which can be mainly attributed to the co-benefit Hg reduction by electrostatic precipitators/fabric filters (ESPs/FFs) and wet flue gas desulfurization (WFGD), especially the sharp growth in installation of WFGD both in the new and existing power plants since 2005. In the coming 12th five-year-plan, more and more plants will be mandated to install De-NO(x) (nitrogen oxides) systems (mainly selective catalytic reduction [SCR] and selective noncatalytic reduction [SNCR]) for minimizing NO(x) emission, thus the specific Hg emission rate per ton of coal will decline further owing to the much higher co-benefit removal efficiency by the combination of SCR + ESPs/FFs + WFGD systems. Consequently, SCR + ESPs/FFs + WFGD configuration will be the main path to abate Hg discharge from coal-fired power plants in China in the near future. However advanced specific Hg removal technologies are necessary for further reduction of elemental Hg discharge in the long-term.     

Evaluation of gas emissions from coal stockpile

Gas emissions of carbon dioxide, methane, dimethylsulfide, carbon monoxide and oxygen from a coal stockpile in Velenje were determined. Gases from the coal stockpile were collected in Alltech Standard sampling bags and then analysed using a capillary gas chromatograph and electrochemical sensors. A flame ionisation detector equipped with a Zr/Ni catalytic reactor was used for the determination of methane and carbon dioxide. Dimethylsulfide was detected with a flame photometric detector, and the concentrations of carbon monoxide and oxygen were determined by use of electrochemical sensors. The results showed that the main influence on gas emissions is related to the ambient temperature. Emissions of carbon dioxide during summer 2001 (average temperature during sampling period was 24 degrees C) were approximately 30-times higher than during winter 2002 (average temperature during sampling period was -2 degrees C) and were also influenced by the oxygen concentration. Carbon dioxide is mainly formed by oxidation of coal. Methane and dimethylsulfide are desorbed from coal, and are present in higher concentrations in stockpile emissions when stockpiles are renewed. The dimethylsulfide concentration, in contrast to laboratory experiments in stockpile emissions, falls immediately due to photo-degradation.     

The interfacial mass transfer resistances of the ozone dry deposition over the field soil of Taichung County in Taiwan

This study aims to design a dry deposition chamber and to measure ozone depletion over the Taichung field soil. This study seeks to verify the phenomena by an experimental and mathematical model. It is demonstrated that interfacial mass transfer resistances of ozone dry deposition involve reactive resistance (R(sr)) and kinetic resistance (R(sk)). It reveals the chemical reaction (O3 + NO --> NO2) to produce the reactive resistance, and verifies that the interfacial mass transfer resistances depend on nitrogen oxide emission and soil temperature. It shows that the interfacial mass transfer resistances are reduced with increasing soil temperature (T(S)). The model profiles are smaller than the observed data within a relative error of 15%. The reactive resistance decreases exponentially with increasing soil temperature; R(sr)(-1) (cm x sec(-1)) = 0.0001 exp (0.1455T(S)). The kinetic resistance decreases linearly with increasing soil temperature; R(sk)(-1)(cm x sec(-1)) = 0.0108T(S) + 1.4012. This model is more accurate with higher soil temperature and larger ozone concentration. Results are consistent with thermodynamics and reaction kinetics. Ozone dry deposition over agricultural soil causes conversion of nitrogen oxide (NO) to nitrogen dioxide (NO2).     

Characteristics of penicillin bacterial residue

A hybrid selective noncatalytic reduction/selective catalytic reduction (SNCR/SCR) system that uses two types of technology, low-temperature SCR process and SNCR process, was designed to develop nitrogen oxide (NO_x) reduction technology. SCR was conducted with space velocity (SV) = 2400 hr^?1 and hybrid SNCR/SCR with SV = 6000 hr^?1, since the study focused on reducing the amount of catalyst and both achieved 98% NO_x reduction efficiency. Characteristics of NO_x reduction by NH₃ were studied for low-temperature SCR system at 150 °C using Mn-V₂O₅/TiO₂ catalyst. Mn-added V₂O₅/TiO₂ catalyst was produced, and selective catalyst reduction of NO_x by NH₃ was experimented. NO_x reduction rate according to added Mn content in Mn-V₂O₅/TiO₂ catalyst was studied with varying conditions of reaction temperature, normalized stoichiometric ratio (NSR), SV, and O₂ concentration. In the catalyst experiment according to V₂O₅ concentration, 1 wt.% V₂O₅ catalyst showed the highest NO_x reduction rate: 98% reduction at temperature window of 200~250 °C. As a promoter of the V₂O₅ catalyst, 5 wt.% Mn was added, and the catalyst showed 47~90% higher efficiency even with low temperatures, 100~200 °C. Mn-V₂O₅/TiO₂ catalyst, prepared by adding 5 wt.% Mn in V₂O₅/TiO₂ catalyst, showed increments of catalyst activation at 150 °C as well as NO_x reduction. Mn-V₂O₅/TiO₂ catalyst showed 8% higher rate for NO_x reduction compared with V₂O₅/TiO₂ catalyst in 150 °C SCR. Thus, (5 wt.%)Mn-(1 wt.%)V₂O₅/TiO₂ catalyst was applied in SCR of hybrid SNCR/SCR system of low temperature at 150 °C. Low-temperature SCR hybrid SNCR/SCR (150 °C) system and hybrid SNCR/SCR (350 °C) showed 91~95% total reduction rate with conditions of SV = 2400~6000 hr^?1 SCR and 850~1050 °C SNCR, NSR = 1.5~2.0, and 5% O₂. Hybrid SNCR/SCR (150 °C) system proved to be more effective than the hybrid SNCR/SCR (350 °C) system at low temperature.

Implications:?NO_x control is very important, since they are the part of greenhouse gases as well as the cause of acid rain and ozone hole. A technology, so-called hybrid SNCR/SCR process, was tested using Mn-V₂O₅/TiO₂ monolithic catalyst for NO_x reduction, and the method is promising. The results of this study would provide some ideas to parties such as policy makers, environmental engineers, and so on.     

Characterization and reactivity of natural manganese ore catalysts in the selective catalytic oxidation of ammonia to nitrogen

Natural manganese ore (NMO) catalysts were characterized and tested in the selective catalytic oxidation of ammonia to nitrogen oxides under dilute conditions. Also, the oxidation of ammonia (NH(3)) was carried out using pure MnO(2), Mn(2)O(3) for comparing with the activity. It is found that the activity of NMO was similar to that of MnO(2) at low temperature below 150 degrees C but above this temperature, the activity of these catalysts showed the difference. In the course of NH(3) oxidation, N(2), NO, N(2)O and H(2)O were produced. But the quantity of NO(2) produced in this experiment was negligible. At temperature below 250 degrees C, selectivity into N(2) from NH(3) oxidation was in the order, NMO > MnO(2) > Mn(2)O(3). This is the reverse of activity of these manganese oxides. Also the characterization of NH(3) oxidation was proposed and supported by the effect of space velocity, inlet O(2) and NH(3) concentration. The increase of space velocity remarkably influenced not only the conversion but also selectivity into N(2). The higher the reaction temperature was, the higher the effect of inlet O(2) and NH(3) concentration on the reaction rate was. By introducing NO during NH(3) oxidation reaction, the possibility of NMO as selective catalytic reduction catalyst at low temperature was studied and showed positive results.     

Intramolecular distribution of stable nitrogen and oxygen isotopes of nitrous oxide emitted during coal combustion

The intramolecular distribution of stable isotopes in nitrous oxide that is emitted during coal combustion was analyzed using an isotopic ratio mass spectrometer equipped with a modified ion collector system (IRMS). The coal was combusted in a test furnace fitted with a single burner and the flue gases were collected at the furnace exit following removal of SO(x), NO(x), and H2O in order to avoid the formation of artifact nitrous oxide. The nitrous oxide in the flue gases proved to be enriched in 15N relative to the fuel coal. In air-staged combustion experiments, the staged air ratio was controlled over a range of 0 (unstaged combustion), 20%, and 30%. As the staged air ratio increased, the delta15N and delta18O of the nitrous oxide in the flue gases became depleted. The central nitrogen of the nitrous oxide molecule, N(alpha), was enriched in 15N relative to that occupying the end position of the molecule, N(beta), but this preference, expressed as delta15N(alpha)-delta15N(beta), decreased with the increase in the staged air ratio. Thermal decomposition and hydrogen reduction experiments carried out using a tube reactor allowed qualitative estimates of the kinetic isotope effects that occurred during the decomposition of the nitrous oxide and quantitative estimates of the extent to which the nitrous oxide had decomposed. The site preference of nitrous oxide increased with the extent of the decomposition reactions. Assuming that no site preference exists in nitrous oxide before decomposition, the behavior of nitrous oxide in the test combustion furnace was analyzed using the Rayleigh equation based on a single distillation model. As a result, the extent of decomposition of nitrous oxide was estimated as 0.24-0.26 during the decomposition reaction governed by the thermal decomposition and as 0.35-0.38 during the decomposition reaction governed by the hydrogen reduction in staged combustion. The intramolecular distribution of nitrous oxide can be a valuable parameter to estimate the extent of decomposition reaction and to understand the reaction pathway of nitrous oxide at the high temperature.     

Effects of NO2 and SO2 on selective catalytic reduction of nitrogen oxides by ammonia

The selective catalytic reduction (SCR) characteristics of NO and NO(2) over V(2)O(5)-WO(3)-MnO(2)/TiO(2) catalyst using ammonia as a reducing agent have been determined in a fixed-bed reactor at 200-400 degrees C. The presence of NO(2) enhances the SCR activity at lower temperatures and the optimum ratio of NO(2)/NO(x) is found to be 0.5. During the SCR reactions, there are some side reactions occurred such as ammonia oxidation and N(2)O formation. At higher temperatures, the selective catalytic oxidation of ammonia and the nitrous oxide formation compete with the SCR reactions. The denitrification (DeNO(x)) conversion decreases at lower temperatures but it increases at higher temperatures with increasing SO(2) concentration. The presence of SO(2) in the feeds inhibits N(2)O formation.     

Selective catalytic oxidation of ammonia over copper-cerium composite catalyst

This work considers the oxidation of ammonia (NH3) by selective catalytic oxidation (SCO) over a copper (Cu)-cerium (Ce) composite catalyst at temperatures between 150 and 400 degrees C. A Cu-Ce composite catalyst was prepared by coprecipitation of copper nitrate and cerium nitrate at various molar concentrations. This study also considers how the concentration of influent NH3 (500-1000 ppm), the space velocity (72,000-110,000 hr(-1)), the relative humidity (12-18%) and the concentration of oxygen (4-20%) affect the operational stability and the capacity for removing NH3. The effects of the O2 and NH3 content of the carrier gas on the catalyst's reaction rate also are considered. The experimental results show that the extent of conversion of NH3 by SCO in the presence of the Cu-Ce composite catalyst was a function of the molar ratio. The NH3 was removed by oxidation in the absence of Cu-Ce composite catalyst, and approximately 99.2% NH3 reduction was achieved during catalytic oxidation over the Cu-Ce (6:4, molar/molar) catalyst at 400 degrees C with an O2 content of 4%. Moreover, the effect of the initial concentration and reaction temperature on the removal of NH3 in the gaseous phase was also monitored at a gas hourly space velocity of less than 92,000 hr(-1).     

Humic acids from oxidized coals I. Elemental composition, titration curves, heavy metals in HA samples, nuclear magnetic resonance spectra of HAs and infrared spectroscopy

The formation of humic acids (HAs) from bituminous coal was verified by laboratory oxidation. In a relatively short time the oxidation by air at temperature above 150 degrees C led to the formation of HAs. These HAs were compared with those isolated from oxidized bituminous coal from the vicinity of red bed bodies, from weathered bituminous coal, oxihumolite and lignite. For this the organic and inorganic elemental composition of HAs, apparent dissociation constants, metal-binding capacities, nuclear magnetic resonance and infrared spectra were determined and evaluated. With increasing temperature of laboratory oxidation of bituminous coal the percentage of aromaticity of HAs increases. HAs prepared from coal oxidized at 150 degrees C are characterized by an aromaticity index 78% while for HAs prepared at 250 and 300 degrees C by 95% aromaticity. The same index for HAs isolated from naturally oxidized bituminous coals is of about 87% whereas it is of about 50% for oxihumolite and lignite. The apparent dissociation constants (Kapp) are much higher in HAs isolated from oxihumolite and lignite (pKapp from 3.35 to 3.80) than those from oxidized bituminous coal samples (pKapp from 4.47 to 4.85). There is a good negative correlation between Pb-binding capacity and pKapp of all samples suggesting that metallic ions are bonded to acidic groups of HAs. Also contents of inorganic elements like Fe, Al, Si are much higher in HAs isolated from lignite and oxihumolite than those in HAs from oxidized bituminous coal. Thus, it seems that the temperatures below 150 degrees C and the long oxidation time are necessary conditions for the formation of HAs in oxidative altered bituminous coal deposited deeply under the earth surface.     

Assessment of the photochemistry of OH and NO3 on Jeju Island during the Asian-dust-storm period in the spring of 2001

In this study, we examined the influence of the long-range transport of dust particles and air pollutants on the photochemistry of OH and NO3 on Jeju Island, Korea (33.17 degrees N, 126.10 degrees E) during the Asian-dust-storm (ADS) period of April 2001. Three ADS events were observed during the periods of April 10-12, 13-14, and 25-26. Average concentration levels of daytime OH and nighttime NO3 on Jeju Island during the ADS period were estimated to be about 1x10(6) and 2x10(8) moleculescm(-3) ( approximately 9 pptv), respectively. OH levels during the ADS period were lower than those during the non-Asian-dust-storm (NADS) period by a factor of 1.5. This was likely to result from higher CO levels and the significant loading of dust particles, reducing the photolysis frequencies of ozone. Decreases in NO3 levels during the ADS period was likely to be determined mainly by the enhancement of the N2O5 heterogeneous reaction on dust aerosol surfaces. Averaged over 24 h, the reaction between HO2 and NO was the most important source of OH during the study period, followed by ozone photolysis, which contributed more than 95% of the total source. The reactions with CO, NO2, and non-methane hydrocarbons (NMHCs) during the study period were major sinks for OH. The reaction of N2O5 on aerosol surfaces was a more important sink for nighttime NO3 during the ADS due to the significant loading of dust particles. The reaction of NO3 with NMHCs and the gas-phase reaction of N2O5 with water vapor were both significant loss mechanisms during the study period, especially during the NADS. However, dry deposition of these oxidized nitrogen species and a heterogeneous reaction of NO3 were of no importance.