Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

Uncertainty and sensitivity analyses of OH-initiated dimethyl sulphide (DMS) oxidation kinetics

A numerical experiment has been conducted on the OH-initiated tropospheric oxidation of DMS. This involved the selection of a set of reactions describing the OH-initiated oxidation kinetics and the conversion of the present level of uncertainty of the system into uncertainty ranges and distributions for the relevant system parameters (kinetic constants and initial concentrations). Uncertainties have been propagated through the model onto the output variables of interest. This has allowed (a) the uncertainty in model prediction to be quantified and compared with observations (uncertainty analysis) and (b) the relative importance of each input parameter in determining the output uncertainty to be quantified (sensitivity analysis). Output considered were the ratio of MSA/(SO₂ + H₂SO₄) concentration at a given time, the ratio SO₂/H₂SO₄, the total peroxynitrate species concentrations and the relative fraction of SO₂ and H₂SO₄ formed through the various pathways. Conditional upon the model and data assumptions underlying the experiment, the following main conclusions were drawn:

1. The possibility of direct formation of SO₃ without SO₂ as intermediate as suggested by Bandyet al. (1992) and Yinet al. (1990), involving direct thermal decomposition of CH₃SO₃ · does not seem to play a major role in the overall generation of sulphate. This is relevant to the issue of gas to particle conversion over remote areas.
2. Reaction of CH₃SOO · intermediate may be the most important pathway to the formation of SO₂.
3. The dominating peroxynitrate is CH₃S(O)₂O₂NO₂.

Through sensitivity analysis the kinetic constants have been identified which — because of their uncertainty and of their impact on the output — mostly contribute to the output uncertainty.     

The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry

The aqueous phase acid-catalyzed reaction of methanol (CH₃OH) with nitric acid (HNO₃) to yield methyl nitrate (CH₃ONO₂) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH₃OH] = 0.00005–0.005 M and [HNO₃] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH₃OH and HNO₃ concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k _obs [CH₃OH][HNO₃], where k _obs  = 2.337 × 10⁻¹³(exp(0.3198*wt.% H₂SO₄)) when the solubility of CH₃ONO₂ in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H₂SO₄, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at     

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.     

Spectroscopic measurements of atmospheric carbon monoxide and methane. 2: Seasonal variations and long-term trends

A spectroscopic technique for measuring CO and CH₄ contents is described and the latitudinal distributions of these gases are presented. Carbon monoxide abundance decreases southward, having two local maxima: in midlatitudes and in the tropics. The slope of latitude dependence varies according to the season of the year. The difference in CH₄ content does not exceed the accuracy of the method (±8%).     

中美大气化学联合考察实验结果的初步分析与比较

根据临安区域本底站观测资料分析结果得出,中国中纬度地区秋、冬季O₃及其前体物NO_x等浓度偏高,可以对农作物和地表生态系统产生影响.观测结果表明:近地层大气O₃浓度主要决定于地面总辐射量控制下的光化学反应过程;O₃的生成受到前体物NO_x的控制,但O₃与NO_x存在着明显的非线性关系.从PEM-WESTA和B的实验及1995年的观测资料表明,O₃的生成效率随着NO_x浓度的增大而减小.尽管O₃的生成速率秋季比冬季的大,但由于秋季较高的NO_x抑制了过氧基的生成,因此冬季O₃的累积量几乎可以和秋季相比拟.在临安观测的NMHC和NO_x的比值比国外同纬度地区测值要大.这说明在临安本底站O₃的光化学生成中,NMHC不是控制物种.从而提示我们,在这些季节临安O₃光化学产物能够被NO_x浓度所控制.中美大气化学联合考察(PEM-WEST-B)实验期间,台湾省的卡盯站SO₂的平均浓度为0.29ppb,O₃的平均浓度为42.2ppb,可以认为此值为低纬度海岛的本底值.1994年PEM-WEST-B实验期间临安站的观测资料和台湾省的卡盯站资料相比,临安站SO₂的浓度约为卡盯站SO₂浓度的50倍左右,从而可以看出人类活动对大气本底的显着影响.     

An FTIR product study of the photooxidation of dimethyl disulfide

The products of the 254 nm photolysis of ppm levels of DMDS have been studied as a function of the O₂ partial pressure at 760 Torr (N₂ + O₂) and 298±2 K. The major sulfur containing compounds detected were SO₂ and CH₃SO₃H (methane sulfonic acid, MSA) and the major carbon containing compounds were CO, HCHO, CH₃OH and CH₃OOH (methyl hydroperoxide). Within the experimental error limits the observed sulfur and carbon balances were approximately 100%. CH₃OOH has been observed for the first time in such a photooxidation system. Its observation provides evidence for the formation of CH₃ radicals by the further oxidation of the CH₃S radicals formed in the primary photolysis step.From the behavior of the DMDS photolysis products as a function of the O₂ partial pressure, O₃ concentration and added OH radical source it is postulated that the further reactions of CH₃SOH (methyl sulfenic acid), formed in the reaction OH + CH₃SCCH₃ CH₃SOH + CH₃S, are the main source of MSA in the 254 nm photolysis of DMDS.Some of the possible implications of the results of this study for the degradation mechanisms of other atmospherically important organic sulfur compounds, in particular DMS, are briefly considered.     

Numerical Investigation of Gas Scavenging by Weak Precipitation

A one-dimensional cloud model with size-resolved microphysics and size-resolved aqueous-phase chemistry, driven by prescribed dynamics, has been used to study gas scavenging by weak precipitation developed from low-level, warm stratiform clouds. The dependence of the gas removal rate on the physical and chemical properties of precipitation has been explored under controlled initial conditions. It is found that the removal of four gaseous species (SO₂, NH₃, H₂O₂ and HNO₃) strongly depends on the total droplet surface area, regardless the mean size of droplets. The removal rates also correlate positively with the precipitation rate, especially for precipitation having a mean radius larger than 20 μm. The dependence of the scavenging coefficients on the total droplet surface area is stronger than on the precipitation rate. The removal rates of SO₂, NH₃ and H₂O₂ by precipitation strongly depend on the others' initial concentrations. When NH₃ (or H₂O₂) concentration is much lower than that of SO₂, the removal rate of SO₂ is then controlled by the concentration of H₂O₂ (or NH₃). The removal of NH₃ (or H₂O₂) also directly depends on the concentration of SO₂. NH₃ and H₂O₂ can also indirectly affect each other's removal rate through interaction with SO₂. The scavenging coefficient of SO₂ increases with the concentration ratio of NH₃ to SO₂ if the ratio is larger than 0.5, while the scavenging coefficient of NH₃ increases with the concentration ratio of SO₂ to NH₃ when the ratio is smaller than 1. The scavenging coefficient of H₂O₂ generally increases with the concentration ratio of SO₂ to H₂O₂. Although the Henry's law equilibrium approach seems to be able to simulate gas scavenging by cloud droplets, it causes large errors when used for simulating the scavenging of soluble gas species by droplets of precipitating sizes.     

Products and mechanisms of the gas phase reactions of NO3 with CH3SCH3, CD3SCD3, CH3SH and CH3SSCH3

Products and mechanisms of the reaction between the nitrate radical (NO₃) and three of the most abundant reduced organic sulphur compounds in the atmosphere (CH₃SCH₃, CH₃SH and CH₃SSCH₃), have been studied in a 480 L reaction chamber using in situ FT-IR and ion chromatography as analytical techniques. In the three reactions, methanesulphonic acid was found to be the most abundant sulphur containing product. In addition the stable products SO₂, H₂SO₄, CH₂O, and CH₃ONO₂ were identified and quantified and thionitric acid-S-methyl ester (CH₃SNO₂) was observed in the i.r. spectrum from all of the three reactions. Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction rate constant (k_H/k_D) of 3.8±0.6, indicating that hydrogen abstraction is the first step in the NO₃+CH₃SCH₃ reaction, probably after the formation of an inital adduct.Based on the products and intermediates identified, reaction mechanisms are proposed for the three reactions.     

The Impact of Precipitation Scavenging on the Transport of Trace Gases: A 3-Dimensional Model Sensitivity Study

With the global Chemistry-Transport model MATCHsensitivity simulations were performed to determinethe degree to which especially upward transport ofgases from the earth's surface is limited byconvective and large-scale precipitation scavenging.When only dissolution of species in the liquid phaseis taken into account, mixing ratio reductions in themiddle and upper troposphere by 10% arecalculated for gases with a Henry's Law constant H of10³ mol/l/atm. The removal increases to 50% forH = 10⁴ mol/l/atm, and to 90% for H =10⁵ mol/l/atm. We also consider scavenging by theice phase, which is generally much less efficient thanby the aqueous phase. In fact, rejection of gases fromfreezing water droplets may be a source of trace gasat higher altitudes.H₂O₂ and the strong acids (H₂SO₄,HNO₃, HCl, HBr, HI) have such large solubilitiesthat they become largely removed by precipitation.When significant concentrations of these gases andsulfate aerosol exist above the liquid water domain ofthe atmosphere, they have likely been produced thereor at higher altitudes, although some could have comefrom trace gas rejection from ice particles or fromevaporating hydrometeors. Several other gases areaffected by precipitation, but not strongly enough toprevent fractional transfer to the middle and uppertroposphere: e.g., HNO₄, HNO₂ at pH 5,CH₂O, the organic acids at pH 6,CH₃SOCH₃, HOCl, HOBr, and HOI. NH₃ islargely removed by liquid phase scavenging at pH 7 and SO₂ atpH 7. At pH less thanabout 6, upward transport of SO₂ should largelydepend on the efficiency of oxidation processes in thewater droplets by O₃ and H₂O₂.Most gases have solubilities which are too low forsignificant precipitation scavenging and aqueous phaseoxidation to occur. This holds, e.g., for O₃, CO,the hydrocarbons, NO, NO₂, HCN, CH₃CN,CH₃SCH₃, CH₃O₂H, CH₃CHOandhigher aldehydes, CH₃OH and higher alcohols,peroxyacetylnitrate (PAN), CH₃COCH₃ andother ketones (note that some of these are not listedin Table I because their solubilities are below 10mol/l/atm). Especially for the short-lived gases,transfer from the boundary layer to the middle andupper troposphere is actually promoted by the enhancedupward transport that occurs in clouds.     

The vertical sulfur dioxide distribution at the tropopause level

In 1978–1980 nine aircraft flights to an altitude of up to 15 km were made over western Europe. Sulfur dioxide was measured with a sensitive chemiluminescence method consisting of separate sampling and analysis stages and application of a wet chemical filter procedure (detection limit: 8 pptv SO₂).The measurements performed in the upper troposphere and lower stratosphere lead to some unexpected results: (a) the meteorological conditions at the tropopause level have an important influence on the observed SO₂ mixing ratio; (b) between the 500 mb and the actual tropopause level the SO₂ mixing ratio is found to be <100 pptv, and weak vertical gradients of SO₂ suggest only a small flux of tropospheric SO₂ into the stratosphere; (c) increasing SO₂ mixing ratios within the first kilometers of the stratosphere give strong support to a stratospheric source of SO₂.In the light of improved one-dimensional models considering the vertical distribution of stratospheric sulfur compounds (Crutzen, 1981; Turco et al. 1981) it can be shown that the oxidation of organic sulfur compounds (e.g., OCS, CS₂) seems to be a stratospheric source of SO₂. Furthermore, the flux calculations based on the SO₂ mixing ratios measured at the tropopause level indicate that the contribution of tropospheric (man-made) SO₂ to the stratospheric aerosol layer is of only minor importance.     

NUMERICAL SIMULATION OF ATMOSPHERIC METHANE TRENDS OVER THE LAST 150 YEARS*

A global two-dimensional chemistry model is developed to study long-term trends of CH₄ since industrial revolution.The sources of CH₄,CO and NO_x are parameterized as functions of latitude and time.With two long-term emission scenarios,long-term trends of CH₄ are simulated.The results have a good agreement with observation from ice cores.The modeled CH₄ increased from 760 ppbv in 1840 to 1611.9 ppbv in 1991, while the modeled number concentration of tropospheric OH decreased from 7.17×10⁵ cm^-3 in 1840 to 5.79×10⁵ cm^-3 in 1991.The increase of atmospheric CH₄ can be explained by the increase of emission of CH₄ and build-up because of decrease of OH radicals that remove CH₄ from the atmosphere.The model is also used to simulate the distribution of CH₄.Comparisons between the model results and observations show that the model can simulate both latitudinal distribution and seasonal variation of CH₄ well.     

The tropospheric distribution of formaldehyde during TROPOZ II

A series of 149 measurements of the HCHO mixing ratio were made between 0 and 10 km altitude and 70° N to 60° S latitude during TROPOZ II. The data show a vertical decrease of the HCHO mixing ratio with altitude at all latitudes and a broad latitudinal maximum in the HCHO mixing ratio between 30° N and 30° S at all altitudes. The measured mixing ratios of HCHO are considerably higher than those expected from CH₄ oxidation alone, but agree broadly with the average latitude by altitude distribution of HCHO derived by a 2D model including emissions of C₁–C₇ hydrocarbons. A number of the regional scale deviations of the measured HCHO distribution from the average modelled one can be explained in terms of the local wind field.     

Carboxylic monoacids in the air of mayombe forest (Congo): Role of the forest as a source or sink

In the tropical rain forests of the Congo during the dry season, from June to September 1987, carboxylic acid partial pressures (P _gas) in the air above the canopy, at ground level, and at the boundary layer, were estimated from water samples such as fog and rainwater. The concentrations of these acids were also measured in the sap of tree leaves. Tree leaves act as a sink or as a source if the acid P _gas is greater of lower than the acid concentrations in molecular form in sap. For each of these soluble gases, there is a value of P _gas where the exchange is nul. This is called the compensation point. Values of the compensation point for some tree leaves were evaluated according to Henry's law. Henry's law coefficients at ppm levels were redetermined for formic (HCOOH), acetic (CH₃COOH), propionic (CH₃CH₂COOH), and isobutyric (CH₃CH(CH₃)COOH) acids.By comparison of P _gas and compensation points, it is concluded that the forest was a potential source for these acids. The soil-or the litter-acts as a significant source of a carboxylic acid of C₃ or C₄ atoms in the aliphatic chain. This carboxylic acid, not yet fully characterized, could play an important role in the rain acidity in forested zones of the equatorial areas.The direct emission of these carboxylic acids by vegetation was the main source in the boundary layer above the forest. The average emissions were 3.1×10⁹, 7.8×10⁹, and 8.4×10⁹ molecules cm^-2 s^-1 for HCOOH, CH₃COOH, and CH₃CH₂COOH, respectively. The savanna is an exogenous source of HCOOH and CH₃CH₂COOH during moderately rainy days for 30% of the time. The ozonolysis of isoprene seems to be a small source of HCOOH.     

Study of a high SO2 event observed over an urban site in western India

Continuous measurements of SO₂, NO_x and O₃ along with sampling based measurements of CO, CH₄, NMHCs and CO₂ were carried out during May, 2010 at Ahmedabad. The diurnal variations of SO₂ in ambient air exhibited elevated values during the night and lower levels during the sunlit hours. The mean concentration of SO₂ during the study period was 0.95 ± 0.88 ppbv. However, the ambient SO₂ exceeded 17 ppbv in the night of 20 May, 2010. On the same day, tropospheric columnar SO₂ from OMI showed almost 350% increase corroborating the surface observations over an extended height regime. This was also the highest columnar value of SO₂ during the summer of 2010. Columnar loadings were also found to be high for formaldehyde, precipitable water vapor and aerosol optical depth on 20 May. Elevated concentrations were also recorded for other trace gases like NO₂ and O₃. Analysis of related data of trace gases indicated characteristics of fresh emissions with dominant contributions from mobile sources during the study period. However, SO₂/NO₂ ratio of 0.36 during the event period on 20th May connotes non-local influences. Analyses of meteorological parameters suggest combined impacts of transport and inversion causing higher levels of SO₂ and other pollutants during 20?C21 May. Episodes of such enhancements may perturb chemical and radiative balance of the atmosphere.     

The distribution of acetaldehyde in the lower troposphere during TROPOZ II

A series of 72 measurements of the acetaldehyde (CH₃CHO) mixing ratio were made in the lower troposphere during TROPOZ II. These measurements are the first ever made of the background level of this trace gas in the free troposphere. The data show a vertical decrease of the CH₃CHO mixing ratio with increasing altitude and indicate higher CH₃CHO concentrations in the Northern Hemisphere — in general agreement with a model-derived average CH₃CHO distribution. Deviations of the observed CH₃CHO mixing ratios from the modelled mean distribution are correlated with similar deviations in the corresponding HCHO mixing ratios.     

The 1985 chlorine and fluorine inventories in the stratosphere based on ATMOS observations at 30° north latitude

The set of high-resolution infrared solar observations made with the Atmospheric Trace Molecule Spectroscopy (ATMOS)-Fourier transform spectrometer from onboard Spacelab 3 (30 April-1 May 1985) has been used to evaluate the total budgets of the odd chlorine and fluorine chemical families in the stratosphere. These budgets are based on volume mixing ratio profiles measured for HCl, HF, CH₃Cl, ClONO₂, CCl₄, CCl₂F₂, CCl₃F, CHClF₂, CF₄, COF₂, and SF₆ near 30° north latitude. When including realistic concentrations for species not measured by ATMOS, i.e., the source gases CH₃CCl₃ and C₂F₃Cl₃ below 25 km, and the reservoirs ClO, HOCl and COFCl between 15 and 40 km (five gases actually measured by other techniques), the 30° N zonal 1985 mean total mixing ratio of chlorine, Cl, was found to be equal to (2.58±0.10) ppbv (parts per billion by volume) throughout the stratosphere, with no significant decrease near the stratopause. The results for total fluorine indicate a slight, but steady, decrease of its volume mixing ratio with increasing altitude, around a mean stratospheric value of (1.15±0.12) ppbv. Both uncertainties correspond to one standard deviation. These mean springtime 1985 stratospheric budgets are commensurate with values reported for the tropospheric Cl and F concentrations in the early 1980s, when allowance is made for the growth rates of their source gases at the ground and the time required for tropospheric air to be transported into the stratosphere. The results are discussed with emphasis on conservation of fluorine and chlorine and the partitioning among source, sink, and reservoir gases throughout the stratosphere.     

Substitution of Natural Gas for Coal: Climatic Effects of Utility Sector Emissions

Substitution of natural gas for coal is one means of reducing carbon dioxide (CO₂) emissions. However, natural gas and coal use also results in emissions of other radiatively active substances including methane (CH₄), sulfur dioxide (SO₂), a sulfate aerosolprecursor, and black carbon (BC) particles. Will switching from coal to gas reduce the net impact of fossil fuel use on global climate? Using the electric utility sector as an example, changes in emissions of CO₂, CH₄,SO₂ and BC resulting from the replacement of coal by natural gas are evaluated, and their modeled net effect on global mean-annual temperature calculated. Coal-to-gas substitution initially produces higher temperatures relative to continued coal use. This warming is due to reduced SO₂ emissionsand possible increases in CH₄ emissions, and can last from 1 to 30years, depending on the sulfur controls assumed. This is followed by a net decrease in temperature relative to continued coal use, resulting from lower emissions of CO₂ and BC. The length of this period and the extent of the warming or cooling expected from coal-to-gas substitution is found to depend on key uncertainties and characteristics of the substitutions, especially those related to: (1) SO₂ emissions and consequentsulphate aerosol forcing; and (2) the relative efficiencies of the power plantsinvolved in the switch.     

Observation of DMSO and CH3S(O)OH from the gas phase reaction between DMS and OH

Products and mechanisms have been investigated for the reactions between dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) and the hydroxyl radical (OH) in the presence of NO_x. All of the experiments were performed in a 480 L reaction chamber, applying Fourier transform infrared spectroscopy (FT-IR) and ion chromatography as the analytical techniques.In addition to the sulfur containing products that are known to be produced from the gas phase reaction between DMS and OH (SO₂, dimethylsulfone, methylsulfonyl peroxynitrate, methanesulfonic acid, H₂SO₄), DMSO and methanesulfinic acid (CH₃S(O)OH) were also observed as products. Only SO₂, DMSO₂ and methylsulfonyl peroxynitrate were found as sulfur containing products in the reaction between DMSO and OH. Based on these new results we propose a mechanism for the atmospheric oxidation of DMS and DMSO by OH radical.