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.     

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.     

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.     

Near UV absorption spectra and photolysis products of difunctional organic nitrates: Possible importance as NO x reservoirs

Difunctional organic nitrates are important products of the atmospheric reaction of NO₃ radicals with unsaturated hydrocarbons about which relatively little is known. In a continuation of the investigation of the atmospheric chemistry of such compounds, the UV absorption spectra of the following organic dinitrates and keto nitrates have been quantitively measured in the gas phase at 298±2 K and atmospheric pressure: 1,2-propandiol dinitrate, CH₃CH(ONO₂)CH₂(ONO₂); 1,2-butandiol dinitrate, CH₃CH₂CH(ONO₂)CH₂(ONO₂); 2,3-butandiol dinitrate, CH₃CH(ONO₂)CH(ONO₂)CH₃;cis 1,4-dinitrooxy-2-butene, CH₂(ONO₂)CH=CHCH₂(ONO₂); 3,4-dinitrooxy-1-butene, CH₂(ONO₂CH(ONO₂)CH=CH₂; -nitrooxy acetone, CH₃COCH₂(ONO₂); 1-nitrooxy-2-butanone, CH₃CH₂COCH₂(ONO₂); 3-nitrooxy-2-butanone, CH₃CH(ONO₂)COCH₃.Although the UV spectra of the nitrates are all very similar in shape those of the keto nitrates are red-shifted compared to the dinitrates and in the spectral range of atmospheric interest (>290 nm) their absorption cross-sections are approximately a factor of 5 higher. The cross-sections of the dinitrates are a factor of 2 higher than those reported in the literature for the corresponding alkyl mononitrates.The UV absorption cross-sections of the difunctional nitrates were used in combination with solar actinic flux data to estimate photolysis frequencies and consequently atmospheric lifetimes for these compounds. The results indicate that for the saturated difunctional nitrates studied in this work photolysis will generally be somewhat some important than reaction with OH radicals as an atmospheric removal process. However, for unsaturated nitrates loss due to reaction with OH will dominate over photolysis as an atmospheric sink.Preliminary FT-IR analyses of the photolysis products of -nitrooxy acetone, 3-nitrooxy-2-butanone and 2,3-butandiol dinitrate using both mercury and fluorescent lamps indicate that NO₂ is released in the primary step. The further reactions of the radicals thus produced result in the formation of CO, aldehydes and PAN. The possible significance of the results for difunctional organic nitrate as reservoirs for reactive odd nitrogen NO _y in the atmosphere, especially during the night, is briefly discussed.     

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.     

Covariations in oceanic dimethyl sulfide,its oxidation products and rain acidity at Amsterdam Island in the Southern Indian Ocean

Simultaneous measurements of rain acidity and dimethyl sulfide (DMS) at the ocean surface and in the atmosphere were performed at Amsterdam Island over a 4 year period. During the last 2 years, measurements of sulfur dioxide (SO₂) in the atmosphere and of methane sulfonic acid (MSA) and non-sea-salt-sulfate (nss-SO₄ ^2-) in rainwater were also performed. Covariations are observed between the oceanic and atmospheric DMS concentrations, atmospheric SO₂ concentrations, wet deposition of MSA, nss-SO₄ ^2-, and rain acidity. A comparable summer to winter ratio of DMS and SO₂ in the atmosphere and MSA in precipitation were also observed. From the chemical composition of precipitation we estimate that DMS oxidation products contribute approximately 40% of the rain acidity. If we consider the acidity in excess, then DMS oxidation products contribute about 55%.     

Multi-species chemical data assimilation with the Danish Eulerian hemispheric model: system description and verification

Satellite retrievals of atmospheric composition provide a wealth of data on a global scale. These complement results from atmospheric chemistry-transport models (CTMs), and can be combined using data assimilation. We present two assimilation schemes coupled to the Danish Eulerian Hemispheric Model (DEHM), a three-dimensional, off-line CTM with full photochemistry: a variant on the ensemble Kalman filter and the three-dimensional variational scheme. The aim of this paper is to describe the two schemes and present an initial assessment of their impacts on model skill. Retrievals of multiple atmospheric trace gases are assimilated, namely: NO₂ tropospheric column densities, CH₄ total column densities, and partial column concentrations of O₃, CO and CH₄; these data are retrieved from four satellite sensors. Data for each species are assimilated independently of one another, and other species are only adjusted indirectly via the model’s chemistry and dynamics. Assimilation results are compared with measurements from surface monitoring stations and other satellite retrievals, and preliminary validation results are presented.Reference simulations (without assimilation) grossly underestimate surface CO concentrations, and both assimilation schemes eliminate this large and systematic model bias. The assimilation improves the spatial correlation of modelled CO with surface observations, and improves the spatial correlation between forecasts and retrievals for CO, NO₂ and O₃. Results for CH₄ show a loss of skill due to a mismatch in model bias between two assimilated CH₄ data-sets. Finally, we discuss differences in methodology and results between this paper and a recent study on multi-species chemical data assimilation. Joint optimisation of initial conditions and emission rates offers a promising direction for improving modelled boundary-layer concentrations.     

Measurements of Atmospheric Concentrations of Reduced Sulphur Compounds in the All Saints Bay Area in Bahia,Brazil

Atmospheric concentrations of several reduced sulphur compounds (H₂S, COS, CH₃SH, CH₃SCH₃, CS₂) originating from both natural and anthropogenic sources were measured at a number of locations in the All Saints Bay area and Reconcavo Baiano, Brazil.The volatile reduced sulphur compounds were collected by pre-concentration using cryo-tubes. Analysis of these compounds was carried out at a later date using gas chromatography with a flame photometric detector. In areas dominated by biogenic sources, the COS concentration varied between 0.5 and 1.0 ppbv, consistent with its normal global distribution in the atmosphere.Areas without direct industrial influence showed low atmospheric concentrations for all volatile sulphur compounds ( 0.25 ppb_v).The anthropogenic influence of the Petrochemical Complex in Camaçari resulted in relatively high levels of some reduced sulphur compounds, such as COS (8 ppb_v), CH₃SH (1.50 ppb_v), H₂S (1.35 ppb_v) and CS₂ (0.3 ppb_v). In mangrove areas, the H₂S concentrations (0.2 ppb_v) were almost twice as high as those in the air masses arriving from the Atlantic Ocean. The maximum H₂S concentrations were found in the industrial area of the Petrochemical Complex in Camaçari, but did not reach the limit of human perception (0.14 ppb_v) and rarely reached the typical recognizable smelling level (0.40 ppb_v). Industrial emissions from the Landulfo Alves Refinery increased the COS, DMS and CS₂ concentrations to 2.0, 0.55 and 0.2 ppb_v, respectively.     

Seasonal Variations of CH_4 Emissions in the Yangtze River Delta Region of China Are Driven by Agricultural Activities

Developed regions of the world represent a major atmospheric methane(CH_4) source, but these regional emissions remain poorly constrained. The Yangtze River Delta(YRD) region of China is densely populated(about 16% of China's total population) and consists of large anthropogenic and natural CH_4 sources. Here, atmospheric CH_4 concentrations measured at a 70-m tall tower in the YRD are combined with a scale factor Bayesian inverse(SFBI) modeling approach to constrain seasonal variations in CH_4 emissions. Results indicate that in 2018 agricultural soils(AGS, rice production) were the main driver of seasonal variability in atmospheric CH_4 concentration. There was an underestimation of emissions from AGS in the a priori inventories(EDGAR—Emissions Database for Global Atmospheric Research v432 or v50), especially during the growing seasons. Posteriori CH_4 emissions from AGS accounted for 39%(4.58 Tg, EDGAR v432) to 47%(5.21 Tg, EDGAR v50) of the total CH_4 emissions. The posteriori natural emissions(including wetlands and water bodies) were1.21 Tg and 1.06 Tg, accounting for 10.1%(EDGAR v432) and 9.5%(EDGAR v50) of total emissions in the YRD in2018. Results show that the dominant factor for seasonal variations in atmospheric concentration in the YRD was AGS,followed by natural sources. In summer, AGS contributed 42%(EDGAR v432) to 64%(EDGAR v50) of the CH_4 concentration enhancement while natural sources only contributed about 10%(EDGAR v50) to 15%(EDGAR v432). In addition, the newer version of the EDGAR product(EDGAR v50) provided more reasonable seasonal distribution of CH_4 emissions from rice cultivation than the old version(EDGAR v432).     

Emission estimates of methyl chloride from industrial sources in China based on high frequency atmospheric observations

Methyl Chloride (CH₃Cl) is a chlorine-containing trace gas in the atmosphere contributing significantly to stratospheric ozone depletion (Carpenter et al. 2014). In the global CH₃Cl budget, the atmospheric CH₃Cl emissions is predominantly maintained by natural sources, of which magnitudes have been relatively well-constrained. However, significant uncertainties still remain in the CH₃Cl emission strengths from anthropogenic sources. High-frequency and high-precision in situ measurements of atmospheric CH₃Cl concentrations obtained since 2008 at Gosan station (a remote background site in the East Asia) reveal significant pollution events superimposed on the seasonally varying regional background levels. Back trajectory statistics showed that air masses corresponding to the observed CH₃Cl enhancement largely originated from regions of intensive industrial activities in China. Based on an inter-species correlation method, estimates of CH₃Cl emissions from manufacturing industries including coal combustion, use of feedstocks, or process agents in chemical production for China (2008–2012) are 297 ± 71 Gg yr.^?1 in 2008 to 480 ± 99 Gg yr.^?1 in 2009, followed by a gradual decrease of about 25% between 2009 and 2012 (398 ± 92 Gg yr.^?1 for 2010; 286 ± 68 Gg yr.^?1 for 2011; 358 ± 92 Gg yr.^?1 for 2012). The annual average of industrial CH₃Cl emissions for 2008–2012 (363 ± 85 Gg yr.^?1) in China is comparable to the known total global anthropogenic CH₃Cl emissions accounting only for coal combustion and indoor biofuel use. This may suggest that unless emissions from the chemical industry are accounted for, global anthropogenic emissions of CH₃Cl have been substantially underestimated. In particular, since industrial production and use of CH₃Cl have not been regulated under the Montreal Protocol (MP) or its successor amendments, continuous monitoring of Chinese CH₃Cl outflow is important to properly evaluate its anthropogenic emissions.     

A nocturnal atmospheric loss of CH<Subscript>2</Subscript>I<Subscript>2</Subscript> in the remote marine boundary layer

Ocean emissions of inorganic and organic iodine compounds drive the biogeochemical cycle of iodine and produce reactive ozone-destroying iodine radicals that influence the oxidizing capacity of the atmosphere. Di-iodomethane (CH₂I₂) and chloro-iodomethane (CH₂ICl) are the two most important organic iodine precursors in the marine boundary layer. Ship-borne measurements made during the TORERO (Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOC) field campaign in the east tropical Pacific Ocean in January/February 2012 revealed strong diurnal cycles of CH₂I₂ and CH₂ICl in air and of CH₂I₂ in seawater. Both compounds are known to undergo rapid photolysis during the day, but models assume no night-time atmospheric losses. Surprisingly, the diurnal cycle of CH₂I₂ was lower in amplitude than that of CH₂ICl, despite its faster photolysis rate. We speculate that night-time loss of CH₂I₂ occurs due to reaction with NO₃ radicals. Indirect results from a laboratory study under ambient atmospheric boundary layer conditions indicate a k _CH2I2+NO3 of ≤4 × 10^?13 cm³ molecule^?1 s^?1; a previous kinetic study carried out at ≤100 Torr found k _CH2I2+NO3 of 4 × 10^?13 cm³ molecule^?1 s^?1. Using the 1-dimensional atmospheric THAMO model driven by sea-air fluxes calculated from the seawater and air measurements (averaging 1.8 +/? 0.8 nmol m^?2 d^?1 for CH₂I₂ and 3.7 +/? 0.8 nmol m^?2 d^?1 for CH₂ICl), we show that the model overestimates night-time CH₂I₂ by >60 % but reaches good agreement with the measurements when the CH₂I₂ + NO₃ reaction is included at 2–4 × 10^?13 cm³ molecule^?1 s^?1. We conclude that the reaction has a significant effect on CH₂I₂ and helps reconcile observed and modeled concentrations. We recommend further direct measurements of this reaction under atmospheric conditions, including of product branching ratios.     

Measurements of atmospheric dimethyl sulfide and carbon disulfide in the western Atlantic boundary layer

Shipboard measurements of atmospheric dimethyl sulfide were made during two transects along the east coast of the United States and at several stations in the Gulf of Maine. Limited measurements of carbon disulfide and hydrogen sulfide are also reported. The mean DMS mixing ratio was 29 pptv (=25, n=84, median 19 pptv) during the Atlantic transects, and 101 pptv (=67, n=77, median 79 pptv) in the Gulf of Maine. Distinct diurnal variations were found in the DMS data from the transects. The meteorology of the study area appears to control day-to-day differences in the magnitude of these diurnal variations, although rapid daytime oxidation is suggested in some cases. Diurnal variations were also evident in near-shore stations in the Gulf of Maine due to nocturnal boundary-layer inversion. Diurnal variation was not evident at other sites in the Gulf due to large scale changes in the atmospheric circulation pattern, which effectively masked any effects due to oxidation processes. Model simulations confirm that the DMS levels and diurnal variation found during the transects are not consistent with atmospheric oxidation processes alone. Atmospheric CS₂ and H₂S mixing ratios were less than 3 pptv during the transects, except for a single period of higher CS₂ mixing ratios (reaching 11 pptv) during advection of continental air. Calculations of the flux of oceanic sulfur to the eastern United States show that the contribution of natural sulfur to the North American sulfur budget is small compared to anthropogenic sources.     

Synergistic Effects of Nitrogen Amendments and Ethylene on Atmospheric Methane Uptake under a Temperate Old-growth Forest

An increase in atmospheric nitrogen (N) deposition can promote soil acidification, which may increase the release of ethylene (C2H4) under forest floors. Unfortunately, knowledge of whether increasing N deposition and C2H4 releases have synergistic effects on soil methane (CH4) uptake is limited and certainly deserves to be examined. We conducted some field measurements and laboratory experiments to examine this issue. The addition of (NH4)2SO4 or NH4Cl at a rate of 45 kg N ha-1 yr-1 reduced the soil CH4 uptake under a temperate old-growth forest in northeast China, and there were synergistic effects of N amendments in the presence of C2H4 concentrations equal to atmospheric CH4 concentration on the soil CH4 uptake, particularly in the NH4Cl-treated plots. Effective concentrations of added C2H4 on the soil CH4 uptake were smaller in NH+4 -treated plots than in KNO3-treated plots. The concentration of ca 0.3 μl C2H4 L-1 in the headspace gases reduced by 20% soil atmospheric CH4 uptake in the NH4Cl-treated plots, and this concentration was easily produced in temperate forest topsoils under short-term anoxic conditions. Together with short-term stimulating effects of N amendments and soil acidification on C2H4 production from forest soils, our observations suggest that knowledge of synergistic effects of NH+4 , rather than NO3- , amendments and C2H4 on the in situ soil CH4 uptake is critical for understanding the role of atmospheric N deposition and cycling of C2H4 under forest floors in reducing global atmospheric CH4 uptake by forests. Synergistic functions of NH4+ -N deposition and C2H4 release due to soil acidification in reducing atmospheric CH4 uptake by forests are discussed.     

青藏高原大气甲烷浓度时空分布变化特征

利用瓦里关大气本底站甲烷观测数据对美国Aqua卫星的AIRS观测结果进行对比分析,并分析研究了2003~2012年青藏高原对流层大气甲烷的时空分布特征,结果表明:1)AIRS观测结果与近地面观测资料变化趋势一致,存在显著的正相关关系,突变时间比较一致,可以用于青藏高原区域的甲烷浓度特征分析。2)青藏高原对流层甲烷浓度在空间分布上存在显著的西北—东南走向的低值带及其南北侧存在4个固定的高值中心,分别位于阿里、那曲、山南和玉树。3)青藏高原甲烷浓度呈现显著随高度而降低的趋势,年平均甲烷浓度分别为1.810ppm(1 ppm=10-6)、1.797 ppm和1.781 ppm。在对流层中层和中上层,甲烷浓度基本呈现低值带最低、南北侧均高的山谷型分布特征。在对流层层顶,以低值带为分界线,呈现明显的南高北低特征。4)青藏高原甲烷浓度随时间呈缓慢上升趋势,平均速度为0.0018 ppm/a,夏季上升最快,秋季上升最慢。5)青藏高原甲烷存在明显的单峰型季节变化特征,夏秋季高,冬春季低,与东部地区冬、夏双峰型特征不同,随着高度上升季节变化更为明显。     

Temperature-dependence of ultraviolet absorption cross-sections of alternative chlorofluoroethanes

The absorption cross-sections of HCFC-123 (CF₃–CHCl₂), HCFC-141b (CH₃–CFCl₂) and HCFC-142b (CH₃–CF₂Cl) are measured between 170 and 250 nm for temperatures ranging from 295 to 210 K with uncertainties between 2 and 4%. They are compared with other available determinations. Temperature effects are discussed and parametrical formulae are proposed to compute the absorption cross-section for wavelengths and temperatures useful in atmospheric modelling calculations. Photodissociation coefficients are presented and their temperature-dependence is discussed.     

A study of marine aerosols over the Pacific Ocean

Aerosol samples were collected on a Pacific cruise from 47°N to 55°S. Particle morphology, concentrations, and size distributions were analyzed with an electron microscope; elemental compositions of individual particles were determined with an X-ray energy spectrometer; and chemical compositions of bulk samples were measured with an ion chromatograph. Temporal and spatial variations of aerosol physico-chemical characteristics were studied in relation to ocean currents and atmospheric parameters. The results show that number and mass concentrations of primary particles depend mainly on surface wind speeds. However the ratios between the major ions, e.g., Na⁺, Cl^-, and Mg⁺⁺, are similar to the ratios in seawater regardless of location or meteorological conditions. The concentrations of secondary aerosols, e.g., non-seasalt sulfate, nitrate, and ammonium particles, show maxima at upwelling regions, such as along the California coast, at the Equator, and near the Chatham Rise where ascending motion brings nutrient-riched deep water into the surface layer. The number concentrations of small sulfate particles and large nitrate-coated particles showed diurnal variations with maxima in the early afternoon and minima at night, indicating that the particles are the products of photo-chemical reactions. Their precursor gases, e.g., CH₃SCH₃, NO, and NH₃ are known to be released from seawater in upwelling regions where biological activities thrive.     

Global Modelling of the Atmospheric Methyl Bromide Budget

A global three-dimensional chemical transport model has been used to identify and evaluate possible candidates for the `missing' surface source required to balance the atmospheric budget of methyl bromide. Both natural and anthropogenic emissions of methyl bromide are `coloured' in the model, thus allowing the global CH₃Br distribution to be broken-down into its source components. These coloured CH₃Br tracers are then combined in various ways to create one base-line emission scenario and five further plausible scenarios. The additional emission scenarios are specifically designed to test whether the geographical distribution and seasonal cycles of additional vegetation and/or increased biomass burning emissions are consistent with atmospheric observations of methyl bromide mixing ratios. Due to an imbalance in our current understanding of the methyl bromide budget, simulated CH₃Br mixing ratios from the base-line emission scenario are significantly lower than atmospheric measurements. Both the inclusion of a vegetation source in the tropics and a double strength biomass burning source substantially improve the agreement between model simulations and atmospheric measurements compared with the base-line emission scenario. While measurement data provides useful information on global fluxes and regional CH₃Br seasonal cycles, small differences between the simulated seasonal cycles of different emission scenarios makes it difficult to distinguish between the relative likelihoods of model scenarios containing a tropical vegetation source or an increased biomass burning source. Further measurements performed in continental mid-to-high northern latitudes, central-southern Africa and South America would be of particular benefit in future attempts to constrain the location and magnitude of the natural terrestrial sources of methyl bromide.     

Dimethylsulfide oxidation and the ratio of methanesulfonate to non sea-salt sulfate in the marine aerosol

A box model of DMS oxidation in the clean, low-NO _x marine atmospheric boundary layer has been used to predict the latitude dependence of the aerosol methanesulfonate to non sea-salt sulfate ratio. The observed latitude dependence of this ratio in the Southern Hemisphere can be reproduced reasonably well if the full suite of reactions proposed by Yin et al. (1990a) is employed, and a strong temperature dependence is specified in the rates of decomposition of CH₃SO₂ and CH₃SO₃ radicals.     

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.     

World-wide increase in tropospheric methane, 1978–1983

Tropospheric concentrations of methane in remote locations have averaged a yearly world-wide increase of 0.018±0.002 parts per million by volume (ppmv) during the period from January 1978 to December 1983. The concentrations in the north temperate zone are always greater than those in the south temperate zone by 7±1% because the major methane sources are all predominantly located in the northern hemisphere. The average world-wide tropospheric concentration of methane in dry air was 1.625 ppmv at the end of 1983, measured against an NBS standard certified as 0.97 ppmv (but with an accuracy of only ±1%). The world-wide concentration increases are described by a linear equation with a standard deviation of 0.003 ppmv for ten different collection periods during 1978–1983. The precision of measurement of the methane concentration in the atmospheric samples and in the standard was measured to be ±0.4% for each. Repetitive measurements of an air sample collected in November 1977 have shown the same concentration for six years with a standard deviation for these data of ±0.003 ppmv.The causes for the steady increase in methane concentration in the troposphere cannot be fixed with certainty from present data. Contributing causes can include increases in the source strengths from cattle and rice fields. The atmospheric concentrations of CO, CH₄ and HO are all closely coupled with one another, and increased concentrations of CO and/or CH₄ should cause reduced concentrations of HO, which in turn should lengthen the atmospheric lifetimes of CO and CH₄.Among other physical and chemical effects, a increase of 0.18 ppmv per decade should contribute a greenhouse warming of about 0.04°C per decade. Other secondary contributions to the greenhouse effect from increases in CH₄ may arise from methane-induced increases in stratospheric H₂O, in tropospheric O₃, and in numerous other trace species whose concentration is controlled by reaction with HO radicals.An increased CH₄ source strength may result from the effect of increasing atmospheric temperatures on the known aqueous biological CH₄ sources, such as swamps, and may be an added consequence of the greenhouse effect.