Model Simulations on the Variability of Particulate MSA to Non-Sea-Salt Sulfate Ratio in the Marine Environment

A box model was constructed to investigate connections between the particulate MSA to non-sea-salt sulfate ratio, R, and DMS chemistry in a clean marine boundary layer. The simulations demonstrated that R varies widely with particle size, which must be taken into account when interpreting field measurements or comparing them with each other. In addition to DMS gas-phase chemistry, R in the submicron size range was shown to be sensitive to the factors dictating sulfate production via cloud processing, to the removal of SO₂ from the boundary layer by dry deposition and sea-salt oxidation, to the entrainment of SO₂ from the free troposphere, to the relative concentration of sub- and supermicron particles, and to meteorology. Three potential explanations for the increase of R toward high-latitudes during the summer were found: larger MSA yields from DMS oxidation at high latitudes, larger DMSO yields from DMS oxidation followed by the conversion of DMSO to MSA at high latitudes, or lower ambient H₂O₂ concentrations at high latitudes leading to less efficient sulfate production in clouds. Possible reasons for the large seasonal amplitude of R at mid and high latitudes include seasonal changes in the partitioning of DMS oxidation to the OH and NO₃ initiated pathways, seasonal changes in the concentration of species participating the DMS-OH reaction pathway, or the existence of a SO₂ source other than DMS oxidation in the marine boundary layer. Even small anthropogenic perturbations were shown to have a potential to alter the MSA to non-sea-salt sulfate ratio.     

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.     

一个SO2气相化学模式及其敏感性分析

气相化学过程是硫沉降过程中的重要过程。气相化学反应既是ＳＯ２气体的氧化去除过程,也为液相化学过程提供初值条件。首先建立了一个适合于研究硫沉降过程的气相化学数值模式,模式包括了５２个方程、３１个物种。然后利用这个气相化学模式探讨了ＳＯ２的气相氧化过程对大气温度、湿度、太阳光强等条件的敏感性并给出了ＳＯ２气相氧化率的日变化。     

Simulations of seasonal variations of sulfur compounds in the remote marine atmosphere

A photochemical box model is used to simulate seasonal variations in concentrations of sulfur compounds at latitude 40° S. It is assumed that the hydroxyl radical (OH) addition reaction to sulfur in the dimethyl sulfide (DMS) molecule is the predominant pathway for methanesulfonic acid (MSA) production, and that the rate constant increases as the air temperature decreases. Concentration of the nitrate radical (NO₃) is a function of the DMS flux, because the reaction of DMS with NO₃ is the most important loss mechanism of NO₃. While the diurnally averaged concentration of OH in winter is a factor of about 8 smaller than in summer, due to the weak photolysis process, the diurnally averaged concentration of NO₃ in winter is a factor of about 4–5 larger than in summer, due to the decrease of DMS flux. Therefore, at middle and high latitudes in winter, atmospheric DMS is mainly oxidized by the reaction with NO₃. The calculated ratio of the MSA to SO₂ production rates is smaller in winter than in summer, and the MSA to non-sea-salt sulfate (nssSO₄ ^2-) molar ratio varies seasonally. This result agrees with data on the seasonal variation of the MSA/nssSO₄ ^2- molar ratio obtained at middle and high latitudes. The calculations indicate that during winter the reaction of DMS with NO₃ is likely to be a more important sink of NO_x (NO+NO₂) than the reaction of NO₂ with OH, and to serve as a significant pathway of the HNO₃ production. If dimethyl sulfoxide (DMSO) is produced through the OH addition reaction and is heterogeneously oxidized in aqueous solutions, half of the nssSO₄ ^2- produced in summer may be through the oxidation process of DMSO. It is necessary to further investigate the oxidation products by the reaction of DMS with OH, and the possibility of the reaction of DMS with NO₃ during winter.     

Field study of dimethylsulfide oxibation in the boundary layer: Variations of dimethylsulfide,methanesulfonic acid,sulfur dioxide,non-sea-salt sulfate and aitken nuclei at a coastal site

Measurements of atmospheric dimethylsulfide (DMS) and its oxidation products, sulfur dioxide (SO₂), methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^2-) were monitored during the period June 9–26, 1989 at a coastal site in Brittany. As indicated by the radon (Rn-222) activities and the high concentrations of NOx the air masses, for most of the experiment, were continental in origin. The observed concentrations range from 1.9 to 65 nmol/m³ for DMS (n=157), 0.6 to 94.2 nmol/m³ for SO₂ (n=50), 0.6 to 11.6 nmol/m³ for MSA (n=44) and 42 to 350 nmol/m³ for nss-SO₄ ^2- (n=44). Aitken nuclei reached values as high as 4.5 × 10⁵ particles/m³. When continental conditions predominated, the measured SO₂ concentrations were lower than those expected from a consideration of the observed DMS concentrations and the existence of SO₂ background of the continental air masses. Similarly, compared to the MSA/DMS ratio in the marine atmosphere, higher concentrations of MSA were observed than those expected from the measured levels of DMS. The presence of enhanced levels of MSA was also endorsed by the observation that the measured mean MSA/nss-SO₄ ^2- ratio of 6±3% was similar to the mean value of 6.9% observed in the marine atmosphere. These above observations are in line with recent laboratory findings by Barnes et al. (1988), which show an increase of the MSA/DMS yield with a simultaneous decrease of the SO₂/DMS yield in the presence of NOx.     

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%.     

积云对二氧化硫和硫酸盐气溶胶作用的研究

利用一个冰雹云模式与云化学模式耦合而成的二维积云化学模式,研究对流云的输送、微物理转化、云内化学过程、湿清除对SO2及硫酸盐气溶胶的作用。云化学模式的结果表明,由于SO2在向上输送的过程中可溶解于云水和雨水中,从而阻止了SO2向上部的转移,因此对气相SO2来说,云的输送是一个相当无效的过程,而液相清除起主要作用。硫酸盐气溶胶的收支分析表明,降水清除了1.67 mol的SO2-4,占气溶胶总量的64%,其中液态降水清除了0.72 mol,固态降水清除了0.95 mol,说明了冰相过程在硫沉降中的重要性。     

欧拉型区域硫沉降模式研究

建立了一个三维硫沉降欧拉模式，模式中比较全面地考虑了硫沉降过程中的物理、化学机制。包括平流、扩散、干湿沉降和积云的垂直输送作用等物理过程，气相化学、液相化学和气溶胶表面的非均相化学等化学过程。其中非均相化学和积云的垂直输送参数化在国内外同类模式中尚不多见。模式结果与实测及其他模式结果的对比表明，该模式能够较好地模拟出SO2的水平和垂直分布及SO2-4在降水中的浓度。     

Spatial and temporal variations of methanesulfonic acid and non sea salt sulfate in Antarctic ice

A simultaneous glaciochemical study of methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^-) has been conducted on the Antarctic plateau (South Pole, Vostok) and in more coastal regions. The objective was to investigate marine sulfur emissions in very remote areas. Firstly, our data suggest that MSA and nss-SO₄ present in antarctic ice are mainly marine in origin and that DMS emissions have been significantly modulated by short term (eg. El Nino Southern Oscillation events) as well as long term climatic changes in the past. Secondly, our study of spatial variations of these two sulfur species seems to indicate that the atmosphere of coastal antarctic regions are mainly supplied by local DMS emissions whereas the atmosphere of the high plateau is also influenced by DMS emissions from more temperate marine latitudes. Thirdly, our study of the partitioning between MSA and nss-SO₄ suggest that the temperature could have been an important parameter controlling the final composition of the high southern latitude atmosphere over the last climatic cycle; colder temperature favoring the formation of MSA. However, our data also support a possible role played by changes in the transport pattern of marine air to the high antarctic plateau.     

Seasonal Variation of Dimethylsulfoxide in Rainwater at Amsterdam Island in the Southern Indian Ocean: Implications on the Biogenic Sulfur Cycle

A continuous record of dimethylsulfoxide (DMSO) in rainwater was performed at Amsterdam island (37°S 77°E) from December 1995 to February 1997. Eighty one rainwater samples were collected. DMSO, methanesulfonic acid (MSA), the major anions, and cations were analyzed. DMSO concentrations ranged from 7.0 to 369 nM, with a distinct seasonal variation. The mean concentrations during the summer and the winter periods were 90 nM and 25.6 nM respectively. The observed DMSO seasonal cycle is in line with the observations of DMS in the atmosphere and MSA in rainwater, measured simultaneously during the reported period. However, the summer to winter ratio of DMSO is significantly lower than that observed for DMS and MSA. The DMSO to MSA ratio and its observed seasonal variability are also presented. The implications on the biogenic sulfur cycle are discussed.     

A Study of DMS Oxidation in the Tropics: Comparison of Christmas Island Field Observations of DMS, SO2, and DMSO with Model Simulations

This study reports comparisonsbetween model simulations, based on current sulfurmechanisms, with the DMS, SO₂ and DMSOobservational data reported by Bandy et al.(1996) in their 1994 Christmas Island field study. For both DMS and SO₂, the model results werefound to be in excellent agreement with theobservations when the observations were filtered so asto establish a common meteorological environment. Thisfiltered DMS and SO₂ data encompassedapproximately half of the total sampled days. Basedon these composite profiles, it was shown thatoxidation of DMS via OH was the dominant pathway withno more than 5 to 15% proceeding through Cl atoms andless than 3% through NO₃. This analysis wasbased on an estimated DMS sea-to-air flux of 3.4 ×10⁹ molecs cm^-2 s^-1. The dominant sourceof BL SO₂ was oxidation of DMS, the overallconversion efficiency being evaluated at 0.65 ± 0.15. The major loss of SO₂ was deposition to theocean's surface and scavenging by aerosol. Theresulting combined first order k value was estimated at 1.6 × 10^-5 s^-1. In contrast to the DMSand SO₂ simulations, the model under-predictedthe observed DMSO levels by nearly a factor of 50. Although DMSO instrument measurement problems can notbe totally ruled out, the possibility of DMSO sourcesother than gas phase oxidation of DMS must beseriously considered and should be explored in futurestudies.     

Summertime Seawater Concentrations of Dimethylsulfide in the Western Indian Ocean: Reconciliation of Fluxes and Spatial Variability with Long-Term Atmospheric Observations

Dimethylsulfide (DMS) measurements in the seawater of the subtropical and the temperate western Indian Ocean were conducted for the first time from 3 December to 20 December 1997. In total, 443 surface seawater DMS determinations were performed between 24°–49° S and 50° E–77° E with a frequency of 1 sample every 10 km. An important spatial variability was observed in seawater DMS concentrations with values ranging from 0.9 to 35.8 nM. DMS maxima coincided in most cases with thermal fronts and were in reasonable agreement with mean pigment figures obtained from satellite observations. The deduced DMS fluxes are consistent with long-term observations of atmospheric DMS and rainwater concentrations of nss- SO4= and MSA measured at Amsterdam island (37° S, 77° E); then account for the differences observed in atmospheric DMS concentrations between Amsterdam island and Cape Grim, Indian Ocean monitoring stations.     

中国地区硫酸盐气溶胶的分布特征

建立了一个三维欧拉型排放/输送/转化/沉降模式,其主要特点是采用独立的气相化学子模式计算各种不同条件下SO2的转化速率,建立转化率的数据库,直接为欧拉模式调用,并对液相化学和湿清除过程进行了参数化处理。这样使模式既考虑了大气化学过程的非线性,又具有较高的计算效率,能够方便地计算年（季）尺度的硫酸盐气溶胶SO2-4的浓度分布。利用中尺度气象模式MM4和欧拉输送模式模拟了中国地区硫酸盐气溶胶的时空分布,其结果可以方便地应用到考虑硫酸盐气溶胶气候效应的气候模式中去。     

Airborne measurements of dimethylsulfide,sulfur dioxide,and aerosol ions over the Southern Ocean South of Australia

Vertical distributions of dimethylsulfide (DMS), sulfur dioxide (SO₂), aerosol methane-sulfonate (MSA), non-sea-salt sulfate (nss-SO₄ ^2-), and other aerosol ions were measured in maritime air west of Tasmania (Australia) during December 1986. A few cloudwater and rainwater samples were also collected and analyzed for major anions and cations. DMS concentrations in the mixed layer (ML) were typically between 15–60 ppt (parts per trillion, 10^–12; 24 ppt=1 nmol m^–3 (20°C, 1013 hPa)) and decreased in the free troposphere (FT) to about <1–2.4 ppt at 3 km. One profile study showed elevated DMS concentrations at cloud level consistent with turbulent transport (cloud pumping) of air below convective cloud cells. In another case, a diel variation of DMS was observed in the ML. Our data suggest that meteorological rather than photochemical processes were responsible for this behavior. Based on model calculations we estimate a DMS lifetime in the ML of 0.9 days and a DMS sea-to-air flux of 2–3 mol m^–2 d^–1. These estimates pertain to early austral summer conditions and southern mid-ocean latitudes. Typical MSA concentrations were 11 ppt in the ML and 4.7–6.8 ppt in the FT. Sulfur-dioxide values were almost constant in the ML and the lower FT within a range of 4–22 ppt between individual flight days. A strong increase of the SO₂ concentration in the middle FT (5.3 km) was observed. We estimate the residence time of SO₂ in the ML to be about 1 day. Aqueous-phase oxidation in clouds is probably the major removal process for SO₂. The corresponding removal rate is estimated to be a factor of 3 larger than the rate of homogeneous oxidation of SO₂ by OH. Model calculations suggest that roughly two-thirds of DMS in the ML are converted to SO₂ and one-third to MSA. On the other hand, MSA/nss-SO₄ ^2- mole ratios were significantly higher compared to values previously reported for other ocean areas suggesting a relatively higher production of MSA from DMS oxidation over the Southern Ocean. Nss-SO₄ ^2- profiles were mostly parallel to those of MSA, except when air was advected partially from continental areas (Africa, Australia). In contrast to SO₂, nss-SO₄ ^2- values decreased significantly in the middle FT. NH₄ ⁺/nss-SO₄ ^2- mole ratios indicate that most non-sea-salt sulfate particles in the ML were neutralized by ammonium.     

Modelling the formation of H2SO4–H2O particles in rural, urban and marine conditions

The factors which affect the formation of new sulphuric acid particles in different atmospheric conditions are investigated. An atmospheric chemistry gas phase box model coupled to a three mode integral aerosol dynamics model is used. The simulations show the dependence of the concentration of nucleation mode particles on initial pre-existing particles, the intensity of UV radiation, the emissions of dimethylsulphide (DMS) and the ratio of emissions of hydrocarbons (HC) and NO_x present in the atmosphere. Eight different basic cases are simulated in urban, rural and marine conditions. The effects of pre-existing particles as a sink of sulphuric acid are clearly seen. The increased UV radiation is also seen to enhance particle formation via sulphuric acid route significantly.     

Nitrosyl and Nitryl Chloride Formation in H2SO4/HNO3/H2O/HCl Solutions at 200 K

Infrared spectroscopy has been used to measure the vapor pressure of chlorine containing species generated from H2SO4/HNO3/H2O/HCl solutions at 200 K. The vapor pressure was observed to be a function of solution composition. Two solution compositions were investigated. One solution remained a liquid whereas the second solution was a mixed liquid and solid phase (an ice slurry). The liquid solution had a composition of 64.6 wt.% H2SO4/4.8 wt.% HNO3/30.1 wt.% H2O/0.5 wt.% HCl and produced only vapor phase HCl. The ice slurry solution had a composition of 76.6 wt.% H2SO4/3.0 wt.% HNO3/20.1 wt.% H2O/0.3 wt.% HCl and produced HCl, ClNO, and ClNO2 vapor phase components. The sulfuric acid, nitric acid, and water content of these solutions are representative of those present in polar stratospheric clouds (PSCs), however the HCl concentrations are much higher than present within these clouds. The partitioning of chlorine between vapor phase HCl (50%) and ClNO/ClNO2 (50%) for the ice slurry solution suggests a possible mechanism of halogen activation within PSCs. A reaction mechanism to model the observed chemistry is proposed.     

Influence of Transport over a Mountain Ridge on the Chemical Composition of Marine Aerosols during the ACE-2 Hillcloud Experiment

Aerosol chemical composition and trace gas measurements were made at twolocations on the northeastern peninsula of Tenerife during the ACE-2HILLCLOUD experiment, between 28 June and 23 July 1997. Measurementswere made of coarse (#gt;2.5 m aerodynamic diameter) and fine (#lt; 2.5m) aerosol Cl^–, NO₃ ^–,SO₄ ^2–, non-sea saltSO₄ ^2– (NSSS),CH₃SO₃ ^– (MSA) andNH₄ ⁺, and gas phase dimethylsulphide (DMS), HCl,HNO₃, SO₂, CH₃COOH, HCOOH andNH₃. Size distributions were measured using a cascadeimpactor. Results show that in marine air masses NSSS and MSA wereformed via DMS oxidation, with additional NSSS present in air massescontaining a continental component. Using a Eulerian box model approachfor aerosols transported between upwind and downwind sites, a mean NSSSproduction rate of 4.36 × 10^–4 gm^–3 s^–1 was calculated for daytimeclear sky periods (highest insolation), with values for cloudy periodsduring daytime and nighttime of 3.55 × 10^–4 and2.40 × 10^–4 g m^–3s^–1, respectively. The corresponding rates for MSA were6.23 × 10^–6, 8.49 × 10^–6and 6.95 × 10^–6 g m^–3s^–1, respectively. Molar concentration ratios forMSA/NSSS were 8.7% (1.8–18.2%) and 1.9%(1.3–3.5%) in clean and polluted air masses, respectively.Reactions occurring within clouds appeared to have a greater influenceon rates of MSA production, than of NSSS, while conversely daytime gasphase reactions were more important for NSSS. For MSA, nighttimein-cloud oxidation rates exceeded rates of daytime gas phase productionvia OH oxidation of DMS. NSSS, MSA and ammonium had trimodal sizedistributions, with modes at 0.3, 4.0 and >10.0 m (NSSS andNH₄ ⁺), and 0.3, 1.5 and 4.0 m (MSA). Nosignificant production of other aerosol species was observed, with theexception of ammonium, which was formed at variable rates dependent onneutralisation of the aerosol with ammonia released from spatiallynon-uniform surface sources. Seasalt components were mainly present incoarse particles, although sub-micrometre chloride was also measured.Losses by deposition exceeded calculated expectations for all species,and were highest for the seasalt fraction and nitrate.     

污染源、干沉降和气相化学影响硫沉降的数值研究

利用欧拉型区域硫沉降模式对污染源、干沉降和气相化学等物理化学过程在酸沉降中的作用进行了数值分析。结果表明:排放源的强度和高度影响着污染物的分布和输送,其影响是非线性的。在区域酸沉降模式中,干沉降速度和气相化学转化率简单地取为常数对SO#-[2]及SO#+[2-]#-[4]浓度分布引起的误差是不可忽视的。     

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.