Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide,hydrogen sulphide,aliphatic thiols and thiophenol

The reactions of OH radicals with SO₂, H₂S, thiophenol, and a series of aliphatic thiols (1–5 C-atoms) have been investigated in 201 and 381 reaction chambers at 1 atm total pressure and 300 K using a competitive kinetic technique. Initially, OH radicals were produced by photolysis of CH₃ONO/NO mixtures in air. Applying this OH source rate constants for OH with SO₂, H₂S, and thiophenol in synthetic air were determined to be (1.1±0.2)×10^-12, (5.5±0.8)×10^-12 and (1.1±0.2)×10^-11 cm³ s^-1, respectively. However, when this method was applied to the aliphatic thiols the rate constants obtained were found to be dependent on the partial pressures of O₂ and NO. These effects have been attributed to the built-up of a radical species, not yet identified, which leads to uncontrolled chain reactions in the system. Using the photolysis of H₂O₂ at wavelengths greater than 260 nm as the OH source in 1 atm N₂, rate constants for the 1–5 aliphatic thiols in the range 2.9 to 5.6×10^-11 cm³ s^-1 were obtained. The rate constants obtained in the present study are compared with recent literature values.     

The photo-oxidations of propyl acetates in synthetic air-HONO-NO x mixtures: Product formation studies and proposed kinetic mechanisms

The formation of products following the hydroxyl radical initiated photo-oxidations of n-and isopropyl acetates has been studied. Mixtures of synthetic air containing a few ppm of nitrous acid, nitric oxide, nitrogen dioxide and one of the propyl acetates were irradiated with sunlamps in a Teflon bag smog chamber. The decay of reactants and the formation of products was monitored by chemiluminescent analysis or by gas chromatography. The major primary products from the photo-oxidation of n-propyl acetate are acetaldehyde and propionaldehyde while from isopropyl acetate they are acetone and methyl nitrate. It was not possible to analyse for formaldehyde, an expected primary product in these systems. The nature and distribution of products indicate that a significant fraction of primary products arise from decomposition reactions of the alkoxy-type radicals generated following the initial attack of hydroxyl radicals on the esters. The derived reaction stoichiometries (molecules of NO oxidised per molecule of ester reacted) are also consistent with the proposed mechanisms.     

The Reaction of Unsaturated Aliphatic Oxygenates with Ozone

The reaction of ozone with unsaturated aliphatic oxygenates has been studied at ambient T (287–297 K) and p = 1 atm. of air (RH = 55 ± 10%) with sufficient cyclohexane added to scavenge the hydroxyl radical. Reaction rate constants, in units of 10-18 cm3 molecule-1 s-1, are 10.7 ± 1.4 for methyl trans-3-methoxy acrylate, 63.7 ± 9.9 for 4-hexen-3-one (predominantly the trans isomer), 125 ± 17 for trans-4-methoxy-3-buten-2-one, 148 ± 13 for cis-4-heptenal, 439 ± 37 for 3- methyl-2-buten-1-ol and 585 ± 132 for (cis + trans)-ethyl 1-propenyl ether. The influence of the oxygen-containing substituents on reactivity toward ozone is examined. Unsaturated ethers react with ozone faster than their alkene structural homologues; the reverse is observed for unsaturated esters and unsaturated carbonyls. Major reaction products have been identified by liquid chromatography with ultraviolet detection (LC-UV), particle beam-mass spectrometry (PB- MS) and gas chromatography-mass spectrometry (GC-MS) and are methyl formate and methyl glyoxylate from methyl trans-3-methoxy acrylate, acetaldehyde and 2-oxobutanal from 4-hexen-3-one, propanal and succinic dialdehyde from cis-4-heptenal, hydroxyacetaldehyde and acetone from 3-methyl-2-buten-1-ol, and ethyl formate and acetaldehyde from (cis + trans)-ethyl 1-propenyl ether. PB-MS and GC- MS were also employed to identify new reaction products and to confirm the structure of products tentatively identified in a previous study of the reaction of ozone with five unsaturated oxygenates (Grosjean and Grosjean, 1997a): formic acid and methyl glyoxylate from methyl acrylate, formic acid and formic acetic anhydride from vinyl acetate, 2-oxoethyl acetate and 3-oxopropyl acetate from cis-3-hexenyl acetate, ethyl formate and formic acid from ethyl vinyl ether, and methyl formate from trans-4-methoxy-3- buten-2-one. The nature and formation yields of the reaction products are consistent with (and supportive of) the reaction mechanism: O3 + R1R2C=CR3X (R1COR2 + R3C(X)OO) + (1 - )(R3COX + R1C(R2)OO), where R1, R2 and R3 = H or alkyl, X is the oxygen-containing substituent, R1COR2 and R3COX are the primary products and R1C(R2)OO and R3C(X)OO are the carbonyl oxide biradicals. The variations of the coefficient , which ranges from 0.25 to 0.61, are discussed in terms of the number and nature of alkyl and oxygen-containing substituents. Subsequent reactions of the alkyl-substituted biradicals R1C(R2)OO and of the biradicals R3C(X)OO that bear the oxygen-containing substituent are discussed. For the biradical CH3CHOO, the ratio ka/kb for the competing pathways of rearrangement to acetic acid (CH3CHOO CH3C(O)OH, reaction (a) and formation of an unsaturated hydroperoxide (CH3CHOO CH2=CH(OOH), reaction (b) is <0.25 for ethyl 1-propenyl ether and <0.27 for 4-hexen-3-one. Concentrations measured in co- located samples, one downstream of a water impinger and the other without water impinger, show the uptake in water impingers to be high (from 83.2 to >99.9%) and comparable to that for formaldehyde (98.4%) for formic acetic anhydride and for difunctional oxygenated compounds. Uptake in water impingers was lower (19–78%) for monofunctional aldehydes and ketones.     

The Mechanism of Reactive NO3 Uptake on Dry NaX (X=Cl, Br)

A simple kinetic mechanism of nitrate radicals uptake on dry sea-salt NaCl, NaBr surfaces is proposed. The mechanism includes adsorption/desorption equilibrium and unimolecular decomposition of the adsorbed complex: NO₃(g) + NaX(s) (NO₃-NaX)(s); (NO₃-NaX)(s) NaNO₃ + X(s) Two techniques were used: the matrix isolation ESR and mass spectrometry. The uptake coefficient () is found to be dependent on exposure time of salt to NO₃ for raw coating. The initial (t0) is higher than the observable steady-state _obs. At room temperature _obs is independent of [NO₃] at low [NO₃] = 3 × 10⁹ - 10¹¹ cm^-3, but it is inversely proportional to [NO₃] at concentrations higher than 10¹² cm^-3. At temperatures above 100 °C, _obs becomes independent of [NO₃] in a wider range of [NO₃]. An increased number of dislocations is supposed to exist in the case of raw coating. Due to a wide spread of the surface sites binding energy with the ionic lattice near dislocations, the part of surface complexes has lower binding energy and "burns" more rapidly. That burning determines the transition from (t0) down to _obs.The kinetic parameters and elementary rate coefficients are obtained. The recommended for low atmospheric NO₃ concentration are in the range of 0.002 ± 0.04 for NaCl and 0.1-0.3 for NaBr depending on a mechanism of the (t) relaxation.     

Dynamics of Ore-Forming Processesof the Stratabound Skarn Copper Depositsof Tongling, Anhui Province

The skarn and ore bodies of the stratabound skarn copper deposits of Tongling, Anhui Province, are both controlled by definite stratigraphic horizons, and they are concordant with the strata. They occur as layers and layer-like bodies in permeable carbonate rocks of the Middle-Upper Carboniferous Huanglong and Chuanshan Formations which are underlain by impermeable shale or siliceous rocks of the Upper Devonian Wutong Formation. The authors study the dynamics of ore-forming processes of the ore deposits with the dynamic model of coupled transport and reaction, and the following results are obtained: The salinity gradient and flow rate of the ore-forming fluids can both promote the mixing and reaction of juvenile water and formation water, and the permeable strata are favourable sites for the intense transport-reaction of mixing and the formation of deposits. (2) As isothermal transport-reaction took place along the bedding of strata, the moving transport-reaction front formed at the contact between the     

Oxygen Isotope Exchange Kinetics Between Coexisting Minerals and Water in the Aral Granite Pliiton of the Altay Mountains,Northern Xinjiang

Abstract Coexisting quartz, feldspar and biotite vary widely in their δ¹⁸O values and display a remarkable ¹⁸O / ¹⁶O disequilibrium relation; especially, a quartz–feldspar reversal (Δ ¹⁸O_{Quartz?feldspar}<0) exsists in the Aral granite pluton of the Altay Mountains, northern Xinjiang. The ¹⁸O / ¹⁶O exchange reaction definitely occurred between granite and water. Initial δ¹⁸O values of the granite and exotic fluid are evaluated by the mass balance consideration. The conventional method of discrimination between various magma derivations simply with δ¹⁸O values of either whole rock or separate minerals is misleading and unreliable. Experiments carried out by the authors show that the ¹⁸O / ¹⁶O exchange reaction is not accompanied by what geologists describe as petrological and mineralogical alteration effect. This decoupling relation implies that exchange reaction occurs at a relatively high temperature during subsolidus–postmagmatic cooling of magmas. The exchange mechanism is mainly diffusion–controlled. It is demonstrated through quantitative modelling that the hydrothermal system associated with the Aral pluton is long–lived (0.8—6 Ma), with a relatively high fluid flow rate (3 x 10^?14 mol. s^?1) and high W/ R ratio (0.79-6.14). This means that an intense flow and convection may exist at the midcrustal level of orogenic magmatic arcs.     

流体输运,化学反应与交代作用

在成矿及变质作用过程中， 体运移促使热量发生传输及周围岩石发生化学反应和交代作用。流体输过一化学反应耦合动力学方程能定量评价热液系统组分浓度、温度和流量函数的人演化，对于区域变质和交代韧性断裂带等变质系统，还可通过流体运称方向和时间积分流体能量来定量描述流体输运一化学反应耦合客观变持地体中水力破裂的形成与流体运移和失挥发分反应耦合过程有关。     

热液系统流体输运－化学反应耦合动力学综述

输运－反应模式通过连续质量守恒方程进行描述，它表示为主要组分的Ｎ＋Ｍ个耦合的非线性偏微分方程。这些方程可以通过有限差分或有限元等数值方法进行求解。利用准静态近似法，涉及平流、分子扩散和水动力弥散作用的地球化学系统的演化在时间上通过一系列静止状态模拟出来。模拟实际地质系统的动力学实验对输运－反应耦合动力学的应用具有十分重要的影响。     

Growth of monodisperse,submicron aerosol particles exposed to SO2, H2O2, and NH3

The growth of monodisperse particles (0.07 to 0.5 µm) exposed to SO₂ (0–860 ppb), H₂O₂ (0–150 ppb) and sometimes NH₃ (0–550 ppb) in purified air at 22 °C at relative humidities ranging from 25 to 75% were measured using the Tandem Differential Mobility Analyzer technique. The experiments were performed in a flow reactor with aqueous (NH₄)₂SO₄ and Na₂SO₄ droplets. For (NH₄)₂SO₄ droplets the fractional diameter growth was independent of size above 0.3 µm but decreased with decreasing size below that. When NH₃ was added the fractional growth increased with decreasing size. Measurements were compared with predictions of a model that accounts for solubility of the reactive gases, the liquid phase oxidation of SO₂ by H₂O₂, and ionic equilibria. Agreement between measured and predicted droplet growth is reasonable when the ionic strength effects are included. Theory and experiments suggest that NH₃ evaporation is responsible for the decrease in relative growth rates for small aqueous ammonium sulfate particles. The observed droplet growth rates are too slow to explain observed growth rates of secondary atmospheric sulfate particles.