臭氧对颗粒物中有机组分形成的关键作用

基于2019年10月广东省鹤山大气超级监测站的观测数据分析了臭氧浓度特征与单颗粒气溶胶中的有机物组分.结果表明,PM_2.5中OC的含量显著大于EC,OC/EC比值为0.7～10.4,其中,OC/EC>2的比例占91%,表明有机碳主要来自二次生成.高臭氧浓度下二次组分(Sec)单颗粒和老化有机无机碳(ECOC-aged)单颗粒的数浓度显著增加,Sec和ECOC-aged单颗粒中含乙酸根(⁵⁹CH₃CO₂^-)和乙醛酸(⁷³C₂HO₃^-)的单颗粒数浓度呈单峰分布,两种有机单颗粒的增加都发生在下午臭氧浓度升高光化学反应较强的时段,表明大气氧化性增强有利于含氧有机物的生成.此外,Sec单颗粒中两种有机单颗粒的峰值出现在16:00,而ECOC-aged单颗粒中两种有机单颗粒的峰值出现在18:00之后,这种差异产生的原因可能与含氧有机物氧化形成的过程有关,ECOC-aged粒子中的含氧有机物主要来自...     

针铁矿/H_2O_2体系对染料橙黄Ⅱ光化学脱色的实验研究

以针铁矿(α-FeOOH)为光催化剂,在金属卤灯(λ≥365 nm)照射下,对α-FeOOH与H2O2组成的非均相Fenton体系内橙黄Ⅱ的脱色进行了研究。考察了初始pH值、α-FeOOH用量、H2O2浓度和反应时间对橙黄Ⅱ脱色过程的影响。结果表明,在α-FeOOH用量为0.3 g/L,H2O2浓度为6 mmol/L,pH 3.0时,橙黄Ⅱ的脱色效果最好,光照90 min后脱色率达到99.4%。橙黄Ⅱ的光降解反应动力学符合Langmuir-Hinshelwood(L-H)动力学方程。对不同时间溶液中的总有机碳(TOC)监测,结果表明体系中橙黄Ⅱ的矿化率较低,通过对溶液中铁(Fe2+和总铁)溶出的测定,说明可能的反应涉及针铁矿表面的铁循环。     

Effects of building aspect ratio, diurnal heating scenario, and wind speed on reactive pollutant dispersion in urban street canyons

A photochemistry coupled computational fluid dynamics (CFD) based numerical model has been developed to model the reactive pollutant dispersion within urban street canyons, particularly integrating the interrelationship among diurnal heating scenario (solar radiation affections in nighttime, daytime, and sun-rise/set), wind speed, building aspect ratio (building-height-to-street-width), and dispersion of reactive gases, specifically nitric oxide (NO), nitrogen dioxide (NO₂) and ozone (O₃) such that a higher standard of air quality in metropolitan cities can be achieved. Validation has been done with both experimental and numerical results on flow and temperature fields in a street canyon with bottom heating, which justifies the accuracy of the current model. The model was applied to idealized street canyons of different aspect ratios from 0.5 to 8 with two different ambient wind speeds under different diurnal heating scenarios to estimate the influences of different aforementioned parameters on the chemical evolution of NO, NO₂ and O₃. Detailed analyses of vertical profiles of pollutant concentrations showed that different diurnal heating scenarios could substantially affect the reactive gases exchange between the street canyon and air aloft, followed by respective dispersion and reaction. Higher building aspect ratio and stronger ambient wind speed were revealed to be, in general, responsible for enhanced entrainment of O₃ concentrations into the street canyons along windward walls under all diurnal heating scenarios. Comparatively, particular attention can be paid on the windward wall heating and nighttime uniform surface heating scenarios.     

表层土壤中有机污染物的光化学行为

本文首先简要介绍了光化学反应的基本原理。然后 ,重点介绍了研究表层土壤中有机污染物光化学行为的实验方法 ,影响光化学行为的因素及影响机理 ,光化学反应与吸附、迁移等的互相作用。最后阐述了这方面存在的问题 ,并且提出了一些建议     

A model for tropospheric multiphase chemistry: application to one cloudy event during the CIME experiment

A multiphase box model for a remote environment of the troposphere has been developed with an explicit chemistry for both gas and aqueous phase. The model applied to a set of measurements performed by Voisin et al. (2000) during the European CIME experiment for a cloud event on 13th December 1997 at the top of the Puy de Dôme (France). The results of the simulation are compared to the measurements in order to follow the evolution of the ambient chemical composition as a function of the pH and of the varying water content. After verifying that the model retrieves the main features observed in the behavior of species in the cloud droplets, a detailed analysis of the simulated chemical regime is performed. It essentially discusses the sources and sinks of radical in aqueous phase, the relative importance of the oxidation pathways of volatile organic compounds by the main radicals and the conversion of S(IV) into S(VI) which seems to be influenced by the presence of peroxonitric acid, HNO₄, in aqueous phase in the environmental conditions that are considered with low H₂O₂. These numerical results are then compared with the theoretical study from Herrmann et al. (2000), who proposed a slightly different mechanism, including C2 chemistry and transition metal chemistry whereas they neglect some reaction pathways, such as the one involving OHCH₂O₂ radical. This double confrontation between model results and both real experimental data and numerical results from Herrmann et al. (1999c) underlines limitations of such modeling approach that does not include any dynamical or microphysical coupling but also demonstrates its capability to identify the main oxidants or reactants in aqueous phase in real environmental conditions more realistic than a purely theoretical approach. The originality of this study resides in the explicit and exhaustive ways the chemical reactions are treated in aqueous phase and in a first attempt to compare such a detailed chemical scheme to real environmental conditions.     

Fe(Ⅲ)/丙酮酸钠体系光解过程中生成的 Fe(Ⅱ)浓度和·OH的浓度变化

以日光灯和金属卤化物灯为主要光源,以Fe(Ⅲ)/丙酮酸钠体系光化学过程中产生的Fe(Ⅱ)和·OH为主要检测对象,探讨了Fe(Ⅲ)/丙酮酸钠体系光解过程中生成的Fe(Ⅱ)和·OH的浓度变化.结果表明,Fe(Ⅲ)/丙酮酸钠体系的光解过程不仅能产生Fe(Ⅱ)和·OH;在丙酮酸钠过量的情况下,光解过程还存在着Fe(Ⅲ)/Fe (Ⅱ)的循环;Fe(Ⅱ)浓度和·OH累积浓度均在pH 3.00时最大;体系的光化学过程中会伴随pH的升高;初始Fe(Ⅲ)浓度和初始丙酮酸钠浓度的提高都有利于Fe(Ⅱ)浓度和·OH累积浓度的提高.     

Aqueous free radical chemistry of mercury in the presence of iron oxides and ambient aerosol

The effect of goethite (α-FeOOH), hematite (α-Fe₂0₃) and maghemite (γ-Fe₂0₃) on the aqueous photoreduction of divalent mercury with organic acids (oxalate, formate and acetate) is investigated. Laboratory photochemistry experiments with synthetic iron oxides and simulated sunlight were performed to assess the role of the oxides on the photoreduction. Ambient aerosol was also collected and introduced as the solid phase to compare its effect with that of synthetic oxides. It is observed that the presence of various iron oxides or aerosol particles enhances the photoreduction. It is also found that the hydroxyl radicals produced in the hematite-oxalate systems can re-oxidize the reduced mercury back to Hg(II). Based on the experimental observations, mechanisms responsible for the Hg(II) reduction are proposed. The kinetics of Hg⁰ oxidation by hydroxyl radicals was also studied by a steady-state kinetic technique using nitrate photolysis as the * OH radical source. The second-order rate constant is determined to be 2.0 × 10⁹ M⁻ s⁻¹. The implications of the studied reactions on the atmospheric chemistry of mercury are discussed.     

天然水体中亚硝酸根和硝酸根的光化学研究进展

综述了近年来亚硝酸根和硝酸根 (NO-2 /NO-3 )在天然水体中的环境光化学研究进展。重点介绍了NO-2 /NO-3 光解生成活性氧 (如羟基 )的机理及其影响因素 ,探讨了NO-2 /NO-3 光解引发天然水体中有机物反应的环境意义 ,并据此提出了本领域今后的研究方向     

济南市区近地面臭氧浓度变化特征

利用2003年9月～2004年8月一年内的O3连续自动监测数据,对济南市大气中O3浓度的频率分布、日变化、季变化等特征进行分析。实验结果表明,O3小时平均浓度达到《环境空气质量标准》(GB3095-1996)二级标准的频率为98.67%;O3浓度在一天中呈明显的单峰型变化规律,14:00左右达到日最高值;四季的O3浓度日变化均呈单峰型,夏季高O3浓度值出现频率较多,冬季浓度普遍较低,春季的平均浓度最高;在所监测的一年周期内,O3浓度呈现明显的单峰型变化规律:秋季逐渐降低,冬季达到最低,春季升高,夏季最高。     

Determination of hydroxyl radicals with salicylic acid in aqueous nitrate and nitrite solutions

The qualitative and quantitative analyses of reactive oxygen species are essential to determine their steady-state concentration and related reaction mechanisms in environmental aquatic systems. In this study, salicylic acid was employed as an innovative molecular probe of hydroxyl radical(OH) generated in aqueous nitrate and nitrite solutions through photochemical reactions. Kinetic studies showed that the steady-state concentrations of OH in aqueous NO3^-(10 mmol/L, pH=5) and NO2^ (10 mmol/L, pH=5) solutions under ultraviolet irradiation were at a same magnitude, 10v-15 mol/L. Apparent quantum yields of OH at 313 nm were measured as 0.011 and 0.07 for NO3^- and NO2^ respectively, all comparable to the results of previous studies.