Gas and Particulate Products Distribution from the Photooxidation of α-Humulene in the Presence of NOx, Natural Atmospheric Air and Sunlight

The photooxidation of -humulene in the presence of NO_x, natural sunlight, and rural background air was investigated using a combination of gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). Identification and quantification of gas and particulate reaction products were reported over the course of the reaction. The daytime photooxidation was carried out in a large outdoor smog chamber (190 m³). A wide range of ring retaining and ring opening products in the gas and particle phase are reported. On average, measured gas and particle phase products accounted for 44% of the reacted -humulene carbon. Measurements show that a number of reaction products with low vapor pressures (e.g. 3-seco--humulone aldehyde, 7-seco--humulone aldehyde, -humulal aldehyde, -humulene 3-oxide or -humulene 7-oxide, -humulaic/alic acid isomers, and 3-seco--14-hydroxyhumulone aldehyde) were found in the early stage of the reaction and may play an important role in the early formation of secondary organic aerosol. A detailed mechanism is proposed to account for most products observed in this investigation.     

海水中溶解有机磷的测定方法

磷和氮一样,都是海洋环境中的重要生源要素,其在水环境中的时空分布控制着海洋生态系统中的初级生产过程.在大洋或深海区,氮的供应相对不足常是初级生产的制约因素,但在浅海区,特别是河口和海湾,由于农业施肥、城市污水及大气干湿沉降等的作用,氮/磷比值常远高于Redfield比值,从而使磷成为初级生产的制约因素[1-6].     

海洋溢油的风化过程研究

水体中石油的分布与归宿取决于溢油风化.在溢油扩散漂移的同时,发生油类蒸发与溶解过程.石油烃在光能的激发和微量金属离子的催化下会发生氧化反应.石油入海后,在风、浪的作用下很容易发生乳化作用.油膜和分散液滴可附在海洋中悬浮颗粒物上沉淀,溶解的烃类吸附在固体颗粒物上沉淀.石油烃类的生物化学作用为其决定性降解作用.油的风化是许多不同过程的综合过程,它们是同时发生,互相影响的.未来需要在组成、性质和行为相互关系的研究基础上进行.在分子水平上系统研究溢油风化过程对于溢油事故发生后肇事者的确定、危害评价以及生物修复效果评估等具有重要的指导意义.     

Determination of Secondary Organic Aerosol Products from the Photooxidation of Toluene and their Implications in Ambient PM2.5

A laboratory study was carried out to investigate the secondary organic aerosol products from photooxidation of the aromatic hydrocarbon toluene. The laboratory experiments consisted of irradiating toluene/propylene/NO_x/air mixtures in a smog chamber operated inthe dynamic mode and collecting submicron secondary organic aerosol samples through a sampling train that consisted of an XAD denuder and a Zefluor^TM filter. Oxidation products in the filter extracts were treated using O-(2,3,4,5,6,-pentafluorobenzyl)-hydroxylamine (PFBHA) to derivatize carbonyl groups followed by treatment with N,O-Bis(trimethylsilyl)-acetamide (BSTFA) to derivatize OH groups. The derivatized products were detected with a positive chemical ionization (CI) gas chromatography ion trap mass spectroscopy (GC-ITMS) system. The results of the GC-ITMS analyses were consistent with the previous studies that demonstrated the formation of multi-functional oxygenates. Denuder results showed that many of these same compounds were present in the gas, as well as, the particle phase. Moreover, evidence was found for a series of multifunctional acids produced as higher order oxidation products of the toluene/NO_x system. Products having nearly the same mass spectrumwere also found in the ambient environment using identical analytical techniques. These products having multiple acid and alcoholic-OH moieties have substantially lower volatility than previously reported SOA products of the toluene photooxidation and might serve as an indicator for aromatic oxidation in the ambient atmosphere.     

古全球变化与非等时韵律沉积及前寒武纪条带状铁矿建造形成的终止

前寒武纪各种地质记录表明了太古代—元古代早期古全球环境具有显著的陆少洋多和大气富ＣＯ２、贫Ｏ２的特征。ＢＩＦｓ大气－海洋系统中Ｆｅ２＋的氧化是导致铁质发生沉淀的一个重要过程，在前寒武纪早期缺Ｏ２的环境，生物－无氧氧化和日光－紫外线为主的宇宙射线光致氧化作用产生的直接非生物－无氧氧化过程，在前寒武纪早期缺Ｏ２环境对Ｆｅ２＋的氧化可能起着重要的和主导的作用。ＢＩＦｓ条带状矿石的宏、微观ＳｉＯ２或Ｆｅ２Ｏ３／Ｆｅ３Ｏ４单层厚度非等厚性表征了硅、铁供给非等量性与交替淀积非等时性的韵律堆积。文章提出了一种与地球自转速率有关的日长年际变化（古ＥＬＮｉｎｏ事件）－硅铁临界饱和浓度模式，从统一的地球动力学条件和不同类型ＢＩＦｓ的成因联系解析了这种韵律堆积的机制。元古代早—中期大气－海洋系统发生了Ｏ２增多和ＣＯ２减少的古全球变化，导致了２．２～１．８Ｇａ之间大气圈平流层古臭氧层的形成。古臭氧层大幅度消减日光－紫外线对地球表面的强烈辐射，不仅使全球性由日光－紫外线光致氧化作用直接产生的Ｆｅ２＋非生物－缺氧氧化过程消失，而且也保证了生命演化的延续和生物进入多样性繁衍。与其伴随的全球性巨厚碳酸盐建造，导致了上壳岩下伏的地球早期富铁?     

Effects of Monochromatic UV-Visible Light and Sunlight on Fe(III)-Catalyzed Oxidation of Dissolved Sulfur Dioxide

The effect of UV-visible light and natural sunlight on the Fe(III)-catalyzed oxidation of dissolved sulfur dioxide has been studied under the conditions representative for those of acidified atmospheric liquids. The experimental results have shown that both sunlight and UV-visible light enhance the rate of Fe(III)-catalyzed oxidation of aqueous sulfite with wavelength ranging from 300 to 575 nm. The light enhanced oxidation is mainly due to photochemical formation of OH radicals from Fe(OH)²⁺ complexes in the wavelength region below 420 nm and SO₃^•− free radicals from Fe(III) sulfite complexes above 420 nm in the absence of organic ligands. Like the Fe(III)-catalyzed thermal chemical oxidation, the Fe(III)-catalyzed photochemical oxidation is also first order with respect to sulfite ion concentration. The sunlight irradiation can increase the Fe(III)-catalyzed oxidation of S(IV) over 45%. The presence of organic complex ligands, such as oxalate, can completely inhibit the Fe-catalyzed oxidation of S(IV) in the dark. However, the photolysis of Fe(III)-oxalato complexes generates oxalate free radicals, leading to the formation of H₂O₂ and OH radicals and the oxidation of S(IV). The rate of Fe(III)-catalyzed oxidation of S(IV) species is found to increase with increasing light intensity. The effects of sunlight on the Fe(III)-catalyzed oxidation of S(IV) should be taken into account when predicting the daytime rates of sulfuric acid formation in atmospheric water droplets.     

Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development

Detailed theoretical (Part I, this article) and experimental (Part II) investigations are presented for the mechanism of the atmospheric photooxidation of dimethyl sulfide (CH₃SCH₃) and dimethyl disulfide (CH₃SSCH₃). In this paper, comprehensive mechanisms for the atmospheric chemistry of CH₃SCH₃ and CH₃SSCH₃ are developed based on fundamental considerations of all available kinetic and mechanistic information.     

Photooxidation of dimethyl sulfide and dimethyl disulfide. II: Mechanism evaluation

The mechanisms for atmospheric photooxidation of CH₃SCH₃ and CH₃SSCH₃ developed in Part I are evaluated by a series of outdoor smog chamber experiments. Measured product yields, including SO₂, H₂SO₄, CH₃SO₃H and HCHO, are reported. The predictions of the mechanisms developed in Part I are found to be in substantial agreement with the measured concentrations from the smog chamber. By comparison of mechanism predictions and observations, critical uncertainties in the mechanism are identified.     

Atmospheric chemistry of alkanes

The reactions of the alkanes under atmospheric conditions and in the presence of oxides of nitrogen are reviewed and evaluated. Particular emphasis is placed upon their subsequent reactions after the initial OH radical reaction under conditions where the alkyl peroxy radicals produced react predominantly with NO, rather than with HO₂ and/or RO₂ radicals. Methods are discussed for estimating the overall OH radical rate constants, the number of molecules of NO consumed per alkane molecule reacted, and the products formed and their yields.     

Primary Product Distribution from the Reaction of Hydroxyl Radicals with Toluene at ppb NOX Mixing Ratios

A study has been conducted to examine the OH-initiated degradation products of toluene in the presence of sub part-per-million levels of NO_X. The experiments were conducted in a dynamic reactor to minimize the conversion of the aromatic compounds while allowing a sufficient mass of products to be collected for analysis. The major primary products detected in the toluene system (with molar yields) include glyoxal (0.238), methylglyoxal (0.167), o-cresol (0.120), benzaldehyde (0.06), 4-oxo-2-pentenal (0.03), and p-cresol (0.03). Six other reaction products, most being ring cleavage products, were measured at yields below 3%. Corrections for secondary OH reactions with the products were made where necessary. The formation of the cresol isomers was found to be invariant to the NO₂ concentrations which indicates that under atmospheric conditions the initial hydroxycyclohexadienyl radical reaction with NO₂ is a minor process and that most of the reaction occurs with O₂. The product yields found in this study are expected to be representative of those that occur in the urban atmosphere at ambient NO₂ concentrations.