FT-IR product study of the OH-initiated oxidation of DMS in the presence of NOx

The influence of NO_x (NO+NO₂) concentrations on the product distribution of the OH-initiated oxidation of DMS has been studied at room temperature using total NO_x concentrations varying from 0 to ∼1800 ppbv (30–600 ppbv NO₂ and 140–1760 ppbv NO). Clear trends in the formation yields of the products SO₂, COS, MSA, MTF (methyl thiolformate), MSPN (methanesulphonyl peroxynitrate), DMSO and DMSO₂ have been observed with variation in NO_x. The presence of low levels of NO reduces the yields of both MTF and COS to zero. The formation yields of MSA and DMSO₂ increase with increasing NO_x concentration, whereas the yields of DMSO and SO₂ decrease. The following approximate changes in the yield, not corrected for possible loss processes, have been measured for variation of NO_x between 0 and ∼1800 ppbv: DMSO decreases from 20 to 3%S; DMSO₂ increases from 3 to 15%S, SO₂ decreases from 70 to 30%S and MSA increases from 4 to 17%S. Under the experiments conditions NO_x levels of several tens of ppbv are required before a perceptible change is observed in the MSA yield. If applicable to the atmosphere such a situation is only likely to be observed near coastal areas affected by pollution. MSPN (CH₃SO₂O₂NO₂) is observed as an oxidation product in the presence of NO₂ even at low levels (e.g. 60 ppbv). Its possible role as a NO_x reservoir in the troposphere is considered.     

Aerosol speciation and mass prediction from toluene oxidation under high NOx conditions

A kinetically based gas-particle partitioning box model is used to highlight the importance of parameter representation in the prediction of secondary organic aerosol (SOA) formation following the photo-oxidation of toluene. The model is initialized using experimental data from York University's indoor smog chamber and provides a prediction of the total aerosol yield and speciation. A series of model sensitivity experiments were performed to study the aerosol speciation and mass prediction under high NO_x conditions (VOC/NO_x = 0.2). Sensitivity experiments indicate vapour pressure estimation to be a large area of weakness in predicting aerosol mass, creating an average total error range of 70 μg m^?3 (range of 5–145 μg m^?3), using two different estimation methods. Aerosol speciation proved relatively insensitive to changes in vapour pressure. One species, 3-methyl-6-nitro-catechol, dominated the aerosol phase regardless of the vapour pressure parameterization used and comprised 73–88% of the aerosol by mass. The dominance is associated with the large concentration of 3-methyl-6-nitro-catechol in the gas-phase. The high NO_x initial conditions of this study suggests that the predominance of 3-methyl-6-nitro-catechol likely results from the cresol-forming branch in the Master Chemical Mechanism taking a significant role in secondary organic aerosol formation under high NO_x conditions. Further research into the yields and speciation leading to this reaction product is recommended.     

Unsaturated dicarbonyl products from the OH-initiated photo-oxidation of furan, 2-methylfuran and 3-methylfuran

This study presents the application of O-(2,3,4,5,6)-pentafluorobenzyl-hydroxylamine hydrochloride (PFBHA) on-fibre derivatisation Solid Phase Microextraction (SPME) to the sampling and quantification of the unsaturated 1,4-dicarbonyl products obtained in the photo-oxidation of furan, 2-methylfuran and 3-methylfuran with HONO: butenedial, 4-oxo-2-pentenal and 2-methylbutenedial, respectively. The use of Proton Transfer Reaction Mass Spectrometry (PTR-MS) is also considered and the advantages of the combined use of both methodologies is discussed. The 1,4 unsaturated dicarbonyl products sampled by SPME were quantified by GC-FID.The experiments were carried out in the EUPHORE outdoor simulation chambers. The results confirm that 1,4-dicarbonyls are the main products of the OH-initiated oxidation of furan and its methylated derivatives, a fact with environmental implications. Molar yields of (1.09 ± 0.41) and (0.90 ± 0.36) were obtained in two experiments of furan photo-oxidation. The yields of 4-oxo-2-pentenal and methylbutenedial were estimated to be (0.60 ± 0.24) and (0.83 ± 0.33) respectively, assuming the same SPME response factor as for butenedial. Furthermore, the unsaturated 1,4-dicarbonyls have also been identified in the chemical characterisation of the aerosols formed in the reactions. The yield of aerosols quantified were (8.5 ± 0.8)% in the photo-oxidation of furan, (1.85 ± 0.18)% in the photo-oxidation of 2-methylfuran and (5.5 ± 0.5)% in the photo-oxidation of 3-methylfuran, at the following concentrations of their precursors: 829 ± 249 ppbV and 748 ± 224 (in two furan experiments), 633 ± 190 in the 2-methylfuran and 641 ± 192 ppbV in the 3-methylfuran experiment.     

Gas-phase terpene oxidation products: a review

Terpenes are emitted in large quantities from vegetation into the troposphere, where they react readily with ozone, OH and NO₃ radicals leading to a number of oxidation products. The current knowledge about gas-phase terpene oxidation products is reviewed. Their formation and decomposition pathways, their products and their relevance for the troposphere, and their chemical analysis are discussed. Data on oxidation kinetics, and product yields is presented for 23 terpenes and 65 oxidation products. A total of 84 references are quoted.     

Surface ozone and NOx concentrations at a high altitude Mediterranean site,Greece

Ozone was measured in six- and NO_x in five sampling periods in 1996–97, mostly during summer, at a 1070 m altitude site in northern Peloponnese. Mean values in each sampling period ranged from 43–48 ppb exceeding the European Union 24 h plant protection standard. The background ozone concentration of 43 ppb derived from the correlation of ozone with NO^′_x also exceeded the EU plant protection standard. Ozone exhibited maxima in the afternoon and minima during the night; in certain 24–48 h periods, however, the ozone concentrations remained practically constant; in these short periods air mass back trajectories indicated air masses which originated in north Africa. NO^′_x concentrations had maximum of 24 h around noon. Their mean concentrations ranged from 0.5–0.7 ppb, smaller than respective concentrations in north-central Europe.     

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.     

反应条件对等离子体脱除吸附于Cu-Ce/AC表面NOx的影响

以放电等离子体协同催化法对吸附在Cu-Ce/AC上的NOx进行脱除,研究了不同的放电条件和添加水蒸气对脱除NOx的影响。结果表明,对于同轴圆筒形反应器,催化剂量一定时,放电长度增加,吸附态NOx去除率先升高后下降;放电电压增大,吸附态NOx去除率升高,原因在于放电反应区内能量密度和活性粒子分布状态改变。根据NOx程序升温脱附（TPD）,TPD低温位（x更容易被放电等离子体脱除,放电长度和放电电压能够影响不同吸附位上NOx的去除效率。适宜条件下,吸附态NOx去除率最高达到93.3%。循环吸附-等离子体脱除NOx进行10次后,NOx脱除率在92%以上。在混合气中添加5%水蒸气提高了等离子体对吸附态NOx的去除率,但导致循环吸附-等离子体脱除NOx效率下降。原因是H2O与NOx竞争吸附带来的负面效应大于等离子体中H2O提供自由基与吸附态NOx反应所带来的正面效应。     

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。     

Oxidation of ofloxacin by Oxone/Co2+: identification of reaction products and pathways

Oxidative degradation of ofloxacin (OFX) by sulfate free radicals (SO₄ ^??) in the UV/Oxone/Co²⁺oxidation process was investigated for the first time, with a special focus upon identifying the transformation products as well as understanding the reaction pathways. Thirteen main compounds were identified after the initial transformation of OFX; the detailed structural information of which were characterized by high-performance liquid chromatography–high resolution mass spectrometry and MS fragmentation analysis. The degradation pathways mainly encompassed ring openings at both the piperazinyl substituent and the quinolone moiety, indicating that the usage of SO₄ ^?? aided the oxidative degradation of OFX to undergo more facile routes compared to those in previous reports by using OH^?/h⁺ as the oxidant, where the initial transformation attacks were mainly confined to the piperazine moiety. Moreover, in this study, smart control over the pH conditions of the oxidation system via different modes of Oxone dosage resulted in the selective degradation of the functional sites of OFX molecule, where it was shown that the SO₄ ^??-driven destruction of the quinolone moiety of OFX molecule favored the neutral pH conditions. This would be beneficial for the reduction of bacterial resistance against quinolones in the aqueous environment.     

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。     

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.     

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。     

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.     

厌氧硫酸盐还原-氨氧化的研究

采用厌氧序批式反应器,在无机营养条件下培养历时354 d,成功实现了SO42-和NH4+的同步生物去除。结果表明,提高进水的TN负荷有利于促进硫酸盐还原-氨氧化的发生,当进水TN负荷提高到120 mg/(L·d)时,对TN的平均去除速率和硫酸盐硫的平均去除速率达到了最大,分别为64.43 mg/(L·d)和44.82 mg/(L·d);在同步生物脱氮除硫前期生成了大量的NO3--N,平均浓度为53.88 mg/L,远大于由Anammox反应生成的量,推测部分NO3-是直接由NH4+和SO42-发生氧化还原反应生成。该体系中存在单质硫的自养反硝化,可以解释反应后期硫酸盐重生成的现象。     

Preparation of the Mn/Co mixed oxide catalysts for low-temperature CO oxidation reaction

The Mn/Co mixed powders with various Mn/Co molar ratios were prepared by the coprecipitation method and used in low-temperature CO oxidation. The physicochemical characteristics of these powders were characterized using the Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM) analyses. The results demonstrated that the Mn/Co molar ratio significantly affected both the textural and catalytic properties and the sample with a Mn/Co = 1:1 possessed a BET area of 123.7 m²g⁻¹ with a small mean pore size of 6.44 nm. The catalytic results revealed that the pure cobalt and manganese catalysts possessed the low catalytic activity and the pure Co catalyst is not active at temperatures lower than 140 °C. The highest catalytic activity was observed for the catalyst with a Mn/Co = 1. The obtained results showed that the incorporation of Pd into the Mn/Co catalyst significantly enhanced the catalytic activity for oxidation of carbon monoxide and the highest CO conversion was observed for the catalyst with 1 wt.% Pd and this catalyst exhibited a CO conversion of 100% at 80 ^°C.

     

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).     

NO对厌氧氨氧化反应的影响

通过在厌氧氨氧化塔式生物滤池内通入不同浓度的NO气体,探究NO对厌氧氨氧化反应的影响。当NO进气浓度升高至4 018 mg·m-3,NO2--N进水浓度降低至20 mg·L-1时,NO-N在电子受体中的比例升高至78.8%,NO去除速率最高达165.8 mg·d-1,证明厌氧氨氧化菌可以利用NO-N为电子受体进行厌氧氨氧化反应脱除NO。在这一过程中,TN去除负荷与不通入NO时相比下降了74.3%,NO3--N生成∶NH4+-N消耗比从0.26下降至0.13。当NO进气浓度升高至8 036 mg·m-3时,NO对厌氧氨氧化菌产生了抑制,TN去除负荷和NO消耗速率分别下降了47.1%和69.6%,同时NO2--N在电子受体中的比例升高至56.9%。实验证明,提高NO2--N进水浓度能降低高浓度NO对厌氧氨氧化菌的抑制性。     

FeAlOx/MMT催化Fenton反应降解高浓度苯酚废水

以蒙脱土为载体制备负载型Fe/Al复合氧化物(FeAlOx/MMT)用于催化Fenton反应降解高浓度苯酚废水。实验结果表明,活性相FeAlOx中Fe/Al摩尔比为0.22时制备所得催化剂对Fenton反应具有最佳活性,且Fe/Al复合氧化物并未嵌入蒙脱土层间。在低温和高pH条件下催化体系存在诱导期,诱导期内FeAlOx/MMT缓释出Fe离子并进而由Fe离子催化溶液中的Fenton反应。通过对非均相催化降解苯酚废水的动力学研究发现,H2O2初始浓度、溶液的pH和反应温度对COD降解效率具有显著影响。调节降解过程中的温度序列和氧化剂引入程序能够缓解高温和高双氧水浓度双重因素耦合导致的HO.自消耗。在优化的降解条件下使用理论用量的H2O2可使得1 g/L的苯酚废水中苯酚降解率达到100%,而COD的降解率则达到97%。