OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels

Dimethylsulphide (DMS) gas phase oxidation with OH radicals was investigated by long path FT-IR spectroscopy and by ion chromatography (IC) and HPLC-MS2 to quantify the reaction products and evaluate heterogeneous processes. The experiments were performed considering two different NOx (NO2+NO) levels. The initial concentration of NO2 was varied from 24 ppbV (NOx=1 ppmV) to 953 ppbV (NOx=10 ppmV). Photolysis of H2O2 was used as the OH-radical source. SO2, dimethylsulphoxide (DMSO), dimethylsulphone (DMSO2), methanesulphonic acid (MSA), methanesulphinic acid (MSIA) and methane sulphonyl peroxynitrate (MSPN) were identified as the main sulphur-containing products. The results indicate that higher NOx levels play a significant role in the chemistry of CH3S(O)x radical, influencing both the SO2/MSPN ratio and the amount of the sulphur species in the condensed phase, and that the NO2/NO ratio could influence the trends in the molar yields of the different products. For this reason the NOx content results a limiting parameter when on measure DMS in atmospheric environment.     

Measurements of acetone and other gas phase product yields from the OH-initiated oxidation of terpenes by proton-transfer-reaction mass spectrometry (PTR-MS)

The atmospheric oxidation of several terpenes appears to be a potentially relevant source of acetone in the atmosphere. Proton-transfer-reaction mass spectrometry was used as an on-line analytical method in a chamber study to measure acetone and other gas phase products from the oxidation of α- and β-pinene initiated by OH radicals in air and in the presence of NO_x.Acetone may be formed promptly, following attack by the OH radical on the terpene, via a series of highly unstable radical intermediates. It can also be formed by slower processes, via degradation of stable non-radical intermediates such as pinonaldehyde and nopinone.Primary acetone and pinonaldehyde molar yields of 11±2% (one σ) and 34±9% (one σ), respectively, were found from the reaction between α-pinene and the OH radical. After all α-pinene had been consumed, an additional formation of acetone due to the degradation of stable non-radical intermediates was observed. The total amount of acetone formed was 15±2% (one σ) of the reacted α-pinene. An upper limit of 12±3% (one σ) for the acetone molar yield from the oxidation of pinonaldehyde was established.From the reaction between β-pinene and the OH radicals, primary acetone and nopinone molar yields of 13±2% (one σ) and 25±3% (one σ), respectively, were observed. Additional amounts of acetone were formed by the further degradation of the primary product, such as the most abundant product nopinone. The total amount of acetone formed was 16±2% (one σ) of the reacted β-pinene. An upper limit of 12±2% (one σ) for the acetone molar yield from the oxidation of nopinone was established.The observed product yields from α- and β-pinene are in good agreement with other studies using mass-spectrometric and gas chromatographic analytical techniques, but differ significantly from previous studies using spectroscopic methods. Possible reasons for the discrepancies are discussed.     

A kinetic mechanism for predicting secondary organic aerosol formation from toluene oxidation in the presence of NOx and natural sunlight

A kinetic mechanism to predict secondary organic aerosol (SOA) formation from the photo-oxidation of toluene was developed. Aerosol phase chemistry that includes nucleation, gas–particle partitioning and particle-phase reactions as well as the gas-phase chemistry of toluene and its degradation products were represented. The mechanism was evaluated against experimental data obtained from the University of North Carolina (UNC) 270 m³ dual outdoor aerosol smog chamber facility. The model adequately simulates the decay of toluene, the nitric oxide (NO) to nitrogen dioxide (NO₂) conversion and ozone formation. It also provides a reasonable prediction of SOA production under different conditions that range from 15 to 300 μg m⁻³. Speciation of simulated aerosol material shows that up to 70% of the aerosol mass comes from oligomers and polymers depending on initial reactant concentrations. The dominant particle-phase species predicted by the mechanism are glyoxal oligomers, ketene oligomers from the photolysis of the toluene OH reaction product 2-methyl-2,4-hexadienedial, organic nitrates, methyl nitro-phenol analogues, C7 organic peroxides, acylperoxy nitrates and for the low-concentration experiments, unsaturated hydroxy nitro acids.     

Ag~+改性复合钛铌酸钾盐对二甲基硫醚和乙硫醇吸附与光催化氧化研究

采用高温固相法合成具有不同Nb/Ti摩尔比的复合钛铌酸钾盐,通过Ag+离子交换对其进行改性。在静态下评价了Ag+改性复合钛铌酸钾盐对二甲基硫醚(DMS)和乙硫醇(EM)的吸附与紫外光催化氧化作用,使用红外光谱技术对催化剂表面滞留物种进行表征。结果表明,Ag+改性复合钛铌酸钾盐对DMS的吸附作用力比EM弱。随着Nb/Ti摩尔比增加,Ag+改性复合钛铌酸钾盐对EM的吸附作用力增强。在紫外光辐射下,Ag+改性的复合钛铌酸钾盐将DMS氧化为亚砜、砜和硫酸盐,而EM则被氧化为磺酸和单齿硫酸盐。     

The mutagenic activity of irradiated C2H4/NOx mixtures in the presence of diethylhydroxylamine

Mixtures of ethylene and oxides of nitrogen were irradiated in the absence and presence of diethylhydroxylamine. As previously reported, the presence of diethylhydroxylamine inhibited the photo-oxidation of the hydrocarbon and nitric oxide and the onset of ozone formation. Once the diethylhydroxylamine completely reacted, the ozone rose more rapidly, but to a lower level than in the absence of diethylhydroxylamine. Peroxyacetyl nitrate was also produced with the addition of diethylhydroxylamine. The reaction mixtures were tested for total mutagenic activity by gas phase exposure to Salmonella typhimurium strain TA100. A significantly greater mutagenic activity was observed in the irradiated ethylene/diethylhydroxylamine/oxides of nitrogen mixture relative to the irradiated ethylene/oxides of nitrogen mixture. At most, 30% of the observed response could be accounted for by known reaction products.     

Aerobic and anaerobic abiotic oxidation of squalene in the presence of hydroperoxides

Abiotic oxidation of squalene in the presence of hydroperoxysterols was studied in seawater under aerobic and anaerobic conditions. This ubiquitous isoprenoid alkene is quickly degraded in the presence of oxygen and its oxidation results mainly in the production of tertiary alcohols and to a lesser extent of epoxides and secondary alcohols. Although the degradation of squalene logically slows down under anaerobic conditions, a significant oxidation affording similar products than in the case of aerobic degradation has been observed. These results show that hydroperoxysterols, which seem to be well preserved in Recent sediments, could contribute to the oxidation of unsaturated lipids (such as squalene) in sedimentary environments under oxic and anoxic conditions.     

Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether (, E_a/R=580 (±560) K), n-butyl acetate ( (±0.4)×10⁹ M⁻¹ s⁻¹, E_a/R=1000 (±200) K), acetone ( (±0.05)×10⁹ M⁻¹ s⁻¹, E_a/R=1400 (±500) K), methyl ethyl ketone (, E_a/R=1200 (±200) K), methyl iso-butyl ketone (, E_a/R=1200 (±300) K) and methylglyoxal (, E_a/R=1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.     

臭氧定量氧化联合湿法吸收同时脱硫脱硝

采用臭氧定量氧化NO,并结合湿法吸收进行脱硫脱硝实验研究。吸收实验选取3种常见碱性吸收液,采用鼓泡法进行NOx脱除效果对比,最终选定0.05 mol·L-1的Ca（OH）2乳浊液为吸收液。考察了NO和NO2不同配比下的吸收效果,当氧化度为60%（NO2/NO物质的量比1.3）时,吸收效果最佳。臭氧氧化实验结果表明,O3/NO物质的量比为0.6时能达到最佳氧化度,碱液吸收NOx脱除效率能达到76%,SO2脱除效率达100%。当改进鼓泡方式后,最佳氧化度条件下NOx脱除效率提高到85%。碱液pH对该法脱硝效率有影响,SO2的存在对NOx的脱除有一定促进作用。     

电弧放电产生NOx及其对亚硫酸铵的氧化

将脱硫塔产生的高浓度亚硫酸铵氧化为硫酸铵是氨法脱硫研究的一个难点。利用二氧化氮(NO2)的氧化性,可以有效氧化高浓度的亚硫酸铵。空气中电弧放电可以产生氮氧化物(NOx),本研究采用高频交流电源,不锈钢针-针电极,研究了放电间距、气体流量、湿度和O2含量等参数对产物NOx的浓度和NO2/NOx比值的影响,并对产物气体做了红外分析和光谱分析。实验结果表明,放电间距增大有利于NOx浓度和NO2/NOx的提高,气体流量和湿度的增大使NOx浓度和NO2/NOx降低,O2含量为50%和60%时NO2浓度和NO2/NOx分别达到最大值。产物NOx对亚硫酸铵的氧化速率最高可达0.0264 mol/(L·min)。     

TiO2光催化氧化脱除模拟烟气中的NOx

采用P25纳米TiO2为催化剂,对NOx浓度360 mg/m3的模拟烟气进行了光催化氧化实验研究,以期为此种方法在电厂烟气脱硝方面的应用提供依据。经SEM、XRD等表征手段,探讨了催化剂晶型尺寸对光催化的作用。实验考察了光催化反应过程规律以及负载量、光照度、NO初始浓度、O2含量、相对湿度和停留时间对光催化氧化效率的影响。结果表明,光催化反应是瞬态到稳态的过程,其催化效率与上述影响因子有密切关系。实验最优条件下NOx的脱除率为46%,但只需适当提高氧化效能,便能达到理想的效果。     

Photocatalytic oxidation of NOx gases using TiO2: a surface spectroscopic approach

The bandgap of solid-state TiO2 (3.2 eV) enables it to be a useful photocatalyst in the ultraviolet (lambda < 380 nm) region of the spectrum. A clean TiO2 surface in the presence of sunlight therefore enables the removal of harmful NOx gases from the atmosphere by oxidation to nitrates. These properties, in addition to the whiteness, relative cheapness and non-toxicity, make TiO2 ideal for the many de-NOX catalysts that are currently being commercially exploited both in the UK and Japan for concrete paving materials in inner cities. There is need, however, for further academic understanding of the surface reactions involved. Hence, we have used surface specific techniques, including X-ray photoelectron spectroscopy and Raman spectroscopy, to investigate the NOx adsorbate reaction at the TiO2 substrate surface.     

Aqueous phase oxidation of sulfites by ozone in the presence of iron and manganese

The oxidation of sulfur^IVspecies by ozone in aqueous solution was studied at 295 K, with pH between 4 and 6, pO₃ between 0.3 and 2.0 ppm (v), S^IV between 5 × 10⁻⁶ and 1 × 10⁻⁶ M, and Fe and Mn between 1 × 10⁻⁴and 5 × 10⁻⁶ M. Throughout this range the oxidation rates were simultaneously first order in S^IV and pO₃, and in the absence of added Fe or Mn displayed a rate coefficient equal to 0.12 + 0.02 mm⁻¹ ppm (v)⁻¹. With added Fe or Mn at concentrations above 10⁻⁵ M the rate coefficients each show maxima near to pH 4.5 of 0.27± 05 × 10⁵M⁻¹ min⁻¹ ppm⁻¹and 0.68 ±.08 × 10⁵M⁻¹ min⁻¹ ppm⁻¹. respectively. Near this pH the rates were first order with respect to concentrations of the metal ions. A phosphate citrate buffer system at 10⁻⁴ M slows the Fe catalyzed oxidation. No non-additive effect of simultaneous catalysis by Fe and Mn was observed.     

Photocatalytic oxidation of NOx using composite sheets containing TiO2 and a metal compound

The photocatalytic oxidation of nitrogen oxides (NO(x)) over titanium dioxide (TiO(2)) sheets containing metal compounds (MCs) had been studied. Calcium oxide (CaO), magnesium oxide (MgO), calcium carbonate (CaCO(3)), aluminium oxide (Al(2)O(3)) and ferric oxide (Fe(2)O(3)) were used as MCs. Al(2)O(3) and Fe(2)O(3) added to the TiO(2) sheet did not affect the photooxidation of nitrogen oxides (NO(x)). The CaO sheet treated with TiO(2) sol had the greatest efficiency as a NO(x) remover under UV irradiation. It is believed that CaO has a high adsorptivity for nitrogen dioxide (NO(2)) and nitric acid (HNO(3)). The amount of NO(x) removed by a TiO(2) sheet including MC showed a tendency to increase with increasing pH of the MC suspension, i.e. there is a good correlation between the alkalinity of the MC and the retention of NO(2) and HNO(3).     

用于臭氧氧化烟气脱硝与烟气余热回收的一体化实验台

锅炉烟气中的NOx是大气污染的重要原因之一。针对燃气锅炉NOx超低排放的要求、以及烟气中大量余热被浪费的现状,提出了烟气脱硝与余热回收一体化的新方法,搭建了一体化实验台,在逆流式烟气喷淋塔中,进行了采用臭氧氧化烟气脱硝、并同时回收烟气余热的实验研究。研究了O3/NO摩尔比、液气比、碱液吸收对脱硝效果的影响,并对脱硝与余热回收的耦合关系进行了分析。在实验室实验的基础上,进一步进行了实际工程的中试研究。结果表明,烟气脱硝与余热回收一体化是可行的,实验台实验中,当烟气温度为83.0 ℃、喷淋水温度为46.4 ℃、液气比为14.8 m3·L-1、O3/NO摩尔比为1.6时,脱硝率为30%,同时回收烟气余热量18.5 kW。     

Effects of particle acidity and UV light on secondary organic aerosol formation from oxidation of aromatics in the absence of NOx

Recent laboratory observations have shown that particle acidity increases secondary organic aerosol (SOA) yields. However, these studies have mainly focused on biogenic precursors such as isoprene and terpenes. In this paper, the effects of particle acidity on the SOA yields from aromatic precursors under both dark and UV–visible light conditions were characterized through controlled chamber experiments. SOA was produced from oxidation of toluene and 1,3,5-trimethylbenzene (135-TMB) with OH radicals created by ozonolysis of 2-methyl-2-butene (MB). Particle acidity, described with proton concentrations, varied with inorganic seed aerosol composition and humidity (20–52%). Overall, in the presence of acidic seeds, greater increases in SOA yields were observed for the toluene system than the 135-TMB system. UV irradiation reduced SOA yields for both toluene and 135-TMB systems to different extents.     

Modeling study of the potential importance of heterogeneous surface reactions for NOx transformations in plumes

A parametric model of gas-particle surface reactions is incorporated into a reactive plume model and used to assess the potential importance of heterogeneous surface reactions on gas phase plume chemistry. Heterogeneous loss of the following species is found to be potentially significant: H₂O₂, PAN, NO₃, N₂O₅, OH, HO₂ and in cold weather HO₂NO₂. This simple model is unable to account for equilibrium/capacity effects in the condensed phase and therefore cannot be used for SO₂ and HNO₃ reaction with aerosol surface.     

我国氮氧化物排放因子的修正和排放量计算:2000年

根据我国城市的发展状况 ,采用城市分类的方法 ,将我国 2 6 1个地级市按照人口数量分为 5个类别。每类城市选取一个典型城市进行实地调查 ,对我国燃烧锅炉和机动车的NOx 的排放因子进行了修正 ,提出了适合我国目前排放水平的各类城市的固定源和移动源的排放因子。并依据 2 0 0 0年中国大陆地区的电站锅炉、工业锅炉和民用炉具的燃料消耗量和机动车保有量 ,以地级市为基本单位 ,估算了 2 0 0 0年我国各地区的NOx 排放量 ,分析了分地区、分行业、分燃料类型的NOx 排放特征。 2 0 0 0年我国NOx 排放总量为 11.12Mt,其中固定源占 6 0 .8% ;移动源占 39.2 %。NOx 排放在地域、行业和燃料类型上分布均不平衡。NOx 的排放主要集中在华东和华北地区 ,其排放量占全国排放量的一半以上。燃煤为最重要的NOx 排放源 ,其排放量占燃料型NOx 排放量的 72 .3%左右。     

Determination of sulfur oxides formed during the S(IV) oxidation in the presence of iron

The reaction products (i.e., sulfate (SO4(2-)) and dithionate (S2O6(2-))) of S(IV) oxidation in the presence of iron(III) under different experimental conditions were investigated. Ion-interaction chromatography was used for the separation of sulfate and dithionate using tetrabutylammonium hydroxide (TBAOH) as an ion-pair reagent. The chromatographic method was optimized by varying the composition of the mobile phase (i.e., concentration of TBAOH, acetonitrile and Na2CO3) and by varying the flow rate of the mobile phase. The method was successfully applied to the determination of dithionate formed during the S(IV) oxidation in the presence of Fe(III). In air-saturated solutions sulfate was observed as the only product, while in N2-saturated solutions dithionate was also determined, but it is the minor reaction product and represents about 4% of the total amount of oxidized HSO3- under the studied conditions.