Characteristics of ozone and ozone precursors (VOCs and NOx) around a petroleum refinery in Beijing, China

A field measurement campaign for ozone and ozone precursors(VOCs and NOx) was conducted in summer 2011 around a petroleum refinery in the Beijing rural region. Three observation sites were arranged, one at southwest of the refinery as the background, and two at northeast of the refinery as the downwind receptors. Monitoring data revealed the presence of serious surface O3 pollution with the characteristics of high average daily mean and maximum concentrations(64.0 and 145.4 ppbV in no-rain days, respectively) and multi-peak diurnal variation. For NOx, the average hourly concentrations of NO2 and NO were in the range of 20.5–46.1 and 1.8–6.4 ppbV, respectively. For VOC measurement, a total of 51 compounds were detected. Normally, TVOCs at the background site was only dozens of ppbC, while TVOCs at the downwind sites reached several hundreds of ppbC. By subtracting the VOC concentrations at background, chemical profiles of VOC emission from the refinery were obtained, mainly including alkanes(60.0% ± 4.3%), alkenes(21.1% ± 5.5%) and aromatics(18.9% ± 3.9%). Moreover, some differences in chemical profiles for the same measurement hours were observed between the downwind sites; the volume ratios of alkanes with low reactivity and those of alkenes with high reactivity respectively showed an increasing trend and a decreasing trend. Finally, based on temporal and spatial variations of VOC mixing ratios, their photochemical degradations and dispersion degradations were estimated to be 0.15–0.27 and 0.42–0.62, respectively, by the photochemical age calculation method, indicating stronger photochemical reactions around the refinery.     

Electrochemical or UV-photochemical oxidation of industrial wastes containing polar aromatic sulphonates

BACKGROUND AND INTENTION: Aromatic sulphonates other than surfactants and their hydroxy and amino-derivatives are important intermediates for the production of azo dyes. Their production on a large scale can be detrimental for the environment, if the by-products of their synthesis are not disposed of appropriately. An industrial waste, the organic components of which were mainly amino and hydroxy-substituted aromatic sulphonates, seriously endangers the environment close to an dismissed Italian industrial site. Inorganic sulphates and chlorides contained in the waste seriously hinder its disposal by incineration, since they corrode furnace walls. In this work, preliminary exploration of aqueous-phase electrochemically and photochemically induced oxidation techniques have been performed as possible alternatives to incineration. METHODS: Electrochemically-induced oxidation was experimented on individual aromatic sulphonates and on an industrial waste by electrolysing them between smooth platinum electrodes at low temperature (5 degrees C) and high current densities (0.4 A/cm2) with aqueous 0.5 M NaHSO4 electrolyte. Photochemically-induced oxidation was performed by irradiating individual aromatic sulphonates or industrial waste with a 500 W mercury lamp in the presence of sodium peroxydisulphate. RESULTS AND DISCUSSION: After 200 min electrodegradation, 90% of the original compounds disappeared, while 50% Total Organic Carbon (TOC) of an industrial waste was removed from solution after 10 hours. After 180 min UV-photodegradation, 90% of two test aromatic sulphonates disappeared, while 65% of TOC of industrial waste was removed after 5 hours. CONCLUSIONS: Two methods, electrochemical and UV-persulphate oxidation of an industrial waste, were used in order to propose a disposal procedure alternative to incineration. Electrodegradation with smooth Pt anode in 0.5 M NaHSO4 at 5 degrees C halved TOC concentration within 10 hours, while persulphate-assisted UV-photochemical oxidation with a 500 W high pressure Hg lamp abated two-thirds of TOC concentration after 5 hours. Energetic consumption of electrodegradation was 0.33 kWh/g TOC, while that of photooxidation was larger than 2 kWh/g TOC. Although both techniques can be considered efficient from a purely chemical point of view, since both are capable of wet-oxidising the aromatic sulphonates and the industrial waste, electrodegradation seems more promising than a photochemical degradation if economical considerations are also taken into account. Considering also that neither cell design nor catalyst were optimised in this preliminary study, the energy yield of electrodegradation seems likely to be largely improved.     

γ-FeOOH-草酸系统中橙黄I的光化学脱色

以8W黑光灯为光源,γ-FeOOH为催化剂,加入草酸构成光化学Fenton体系,研究了这一体系中橙黄I的光化学脱色动力学;考察了橙黄I的初始浓度、初始pH值和草酸初始浓度对橙黄I光化学脱色降解的影响.结果表明,草酸能显著促进橙黄I的脱色与降解,橙黄I光化学脱色一级动力学常数随草酸浓度的增大呈先升后降的趋势,最佳草酸初始浓度为1·8mmol·L-1;溶液pH值的变化也显著影响橙黄I的脱色.光化学反应过程中Fe2+和总Fe的浓度也随草酸浓度与反应时间的变化而变化.     

A Sensitivity Analysis of Ozone Formation to Ambient Air Composition by Means of Photochemical Models

The prediction of the atmospheric concentration of ozoneand of other photochemical pollutants represents one of themajor scientific challenges in the study of urban airquality. To this aim, photochemical models are widelyapplied as support tools for regulatory purposes, but theirresults are known to be affected by several uncertainties,in boundary conditions, geographical and meteorologicaldata and the chemical composition of emission and ambientair as well. Also the mechanism selected to describe theurban chemistry may lead to large differences in the modelresults. In this work, the influence of ambient air composition onthe results of photochemical model has been studied using a simple Lagrangian trajectory model coupled with different chemical sub-models (CB-IV and a simplified version of EMEP). To this aim a parametric sensitivity study of ozone with respect to its precursors' concentration was performed withreference to the same meteorological conditions and by simulatingdifferent scenarios characterized by specific emitted pollutantsconcentration. Rather than analyzing sensitivity by changing initial composition, an analytical local sensitivity concept has been applied; this allowed evaluation the influence of initial concentration on the predicted ozone concentration andto discriminate between VOC-sensitive and NOx-sensitive kineticregimes. Finally, these results have been successfully comparedwith those obtained applying the concept of photochemical indicators (i.e. O₃/NOy and H₂O₂/HNO₃ ratios).     

Review of the influencing factors of secondary organic aerosol formation and aging mechanism based on photochemical smog chamber simulation methods

The formation and aging mechanism of secondary organic aerosol (SOA) and its influencing factors have attracted increasing attention in recent years because of their effects on climate change, atmospheric quality and human health. However, there are still large errors between air quality model simulation results and field observations. The currently undetected components during the formation and aging of SOA due to the limitation of current monitoring techniques and the interactions among multiple SOA formation influencing factors might be the main reasons for the differences. In this paper, we present a detailed review of the complex dynamic physical and chemical processes and the corresponding influencing factors involved in SOA formation and aging. And all these results were mainly based the studies of photochemical smog chamber simulation. Although the properties of precursor volatile organic compounds (VOCs), oxidants (such as OH radicals), and atmospheric environmental factors (such as NO_x, SO₂, NH₃, light intensity, temperature, humidity and seed aerosols) jointly influence the products and yield of SOA, the nucleation and vapor pressure of these products were found to be the most fundamental aspects when interpreting the dynamics of the SOA formation and aging process. The development of techniques for measuring intermediate species in SOA generation processes and the study of SOA generation and aging mechanism in complex systems should be important topics of future SOA research.     

北京地区对流层低层臭氧及硫酸盐气溶胶的时空分布

基于OMI/Aura卫星资料,分析了北京地区2007~2016年近10a对流层O₃浓度（0~3km）、硫酸盐气溶胶光学厚度（0~2km）、SO₂（边界层以内）柱浓度时空演变特征.结果表明,近10a来北京地区O₃浓度总体呈现上升趋势,最低值在2007年,浓度为33.65 μg/m³;硫酸盐气溶胶污染总体变化呈现先下降后增长的趋势,2007年硫酸盐气溶胶污染最为严重,2011年污染最轻,对应的AOD值为0.252,但在2014年以后,硫酸盐气溶胶污染又出现增长趋势;SO₂浓度在2007~2016年总体呈现下降的变化趋势,且下降趋势明显,最高值为2007年,最低值出现在2016年,最低值比最高值降低了60.42%,但在2011年污染出现反弹.北京O₃季节变化明显,夏季高、春秋次之、冬季低;硫酸盐气溶胶污染季节特征与O₃相同;SO₂污染主要集中在冬季,采暖期污染程度高于非采暖期.     

基于观测的臭氧污染研究方法

总结了国内外研究中常用的基于外场观测的臭氧污染成因分析方法。区域传输和本地生成的相对贡献以及臭氧与前体物的非线性关系是研究臭氧污染和制定控制对策的两个关键科学问题。基于对观测数据的分析,常见的量化区域传输和本地生成贡献的方法包括背景点测量法、TCEQ区域背景臭氧估算法和主成分分析区域背景臭氧估算法;用于诊断臭氧光化学生成机制的方法包括光化学指示剂比值法和基于观测的化学模型。本文对上述方法的原理和应用情况进行了总结,并对其优缺点和适用条件进行了评述,以期为环境监测资料的深入科学分析提供参考和借鉴。     

三氯乙醛的光降解反应研究

研究了太阳光照下,水溶液中FeC l3-三氯乙醛的光化学反应速率,采用紫外分光光度计定时对含有不同浓度Fe（Ⅲ）的溶液进行实验测定,并根据三氯乙醛标准溶液曲线进行分析。实验结果表明,在波长为480nm的紫外光照射下：室内自然光下含有Fe（Ⅲ）和室外太阳光下不含Fe（Ⅲ）的三氯乙醛溶液中,三氯乙醛的浓度基本保持不变;但在室外太阳光下含有Fe（Ⅲ）的三氯乙醛溶液中,三氯乙醛的浓度随着Fe（Ⅲ）浓度的增加而减小。由此表明,Fe（Ⅲ）是三氯乙醛光化学反应的催化剂,FeC l3-三氯乙醛的光化学反应随着Fe（Ⅲ）浓度的增加而加快。     

异戊二烯和甲苯二次有机示踪物的臭氧非均相氧化

本文基于相对速率法,通过烟雾箱实验测定了异戊二烯和甲苯二次有机示踪物的臭氧非均相氧化的有效速率常数,考察了不同条件(相对湿度和混合状态等)对示踪物臭氧非均相氧化过程的影响,并且分析了由于示踪物被氧化所引起的二次源解析的不确定性.结果表明,赤藓糖醇(analogue of 2-methyl erythritol,AME)和2,3-二羟基-4-氧代戊酸(2,3-dihydroxy-4-oxopentanoic acid,DHOPA)的有效速率常数分别为(4. 60±0. 66)×10-19cm~3·(molecule·s)~(-1)和(6. 57±0. 51)×10-19cm~3·(molecule·s)~(-1);考虑到示踪物不稳定引起的不确定性,采用示踪物产率法解析二次源会对异戊二烯和甲苯二次生成气溶胶低估约16. 5%～44. 8%和18. 3%～47. 3%.     

焦炭负载型纳米TiO2光催化剂的制备优化试验及其降解效果分析

以焦炭为载体,Na2SiO3为粘结剂制备了负载型纳米TiO2光催化剂,通过单因素试验和正交试验优化出制备该光催化剂的最佳条件,研究分析了该催化剂在紫外灯辐照下降解亚甲基蓝染料废水的效果及影响因素。试验结果表明,煅烧3h,粘结剂浓度为20％wt,煅烧温度为400℃时制备的负载型纳米TiO2光催化剂的降解效果最好,达到80．88％。