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.     

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%.     

A review of dimethylsulfoxide in aquatic environments

Abstract

Dimethylsulfoxide (DMSO) is an ubiquitous, albeit poorly understood, component of the marine sulfur cycle. Conventionally, the accepted formation pathways are the photochemical and microbial oxidation of dimethylsulfide (DMS). The principal loss mechanism is thought to be via microbial transformation, either consumption or reduction to DMS. The interactions between DMSO and DMS are likely to be important in controlling sea surface concentrations of DMS, and thus DMSO could influence the role played by DMS in global climate regulation. This review examines current knowledge of the distribution of DMSO in aquatic environments and the possible link between DMSO, DMS and global climate control. Mechanisms for the formation and loss of DMSO are also considered in addition to some of the factors influencing these processes. The review also considers that DMSO may be biosynthesized by phytoplankton, representing a non‐DMS source for DMSO, and that DMSO can undergo photochemical oxidation, a potential loss mechanism for DMSO in the marine environment.     

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.     

MEASUREMENT OF pH AND CHEMICAL ANALYSIS OF RAIN WATER IN RURAL AREA OF INDIA

Large number of rain water samples, at 7 rural locations in the semi-arid region of the DeccanPlateau were collected during 4 consecutive monsoon seasons (1979-1982).pH, conductivityand the major ionic components (C1~-, SO_4~= , NO_3~- , NH_4~+ , Na~+, K~+, Ca~(++), Mg~(++) of the abovesamples were determined. The pH of rain water was found to be highly alkaline and the valuesvaried from 6.4 to 7.8. Soil-oriented elements showed good correltioan (r~0.6) with pH valuesof rain water. The high concentration of soil-oriented elements, specially Ca~(++), is found to play animportant role in neutralizing the acidity of rain water and maintaining high alkaline pH. The studysuggested that the contribution of atmospheric aerosol of natural sources (sea and soil) to thechemical composition of rain water is more than that of anthropogenic origin.     

Relation between the concentrations of DMS in surface seawater and air in the temperate North Pacific region

The concentrations of DMS were simultaneously measured in both water and air at the sea surface on board a vessel during a trans-Pacific cruise around 40° N in August 1988. Those in the surface seawater varied widely with a mean of 162 ng S/1 and a standard deviation of 134 ng S/1 (n=37), but the variation was not a mere fluctuation and the high concentration (376 ng S/1) was found in the area between 145° W and 170° W. The atmospheric DMS concentration varied more widely with a mean value of 177 ng S/m³ and a standard deviation of 203 ng S/m³ (n=23). The diurnal variation of DMS was not significant in the air near the sea surface. However, the concentrations in the surface water was fairly well correlated with those in the surface air. The correlation coefficient (r ²=0.86) was larger than that between the atmospheric concentration and outflux of DMS (r ²=0.64). These findings mean that the turnover time of DMS in the atmosphere is not extremely short. Based on the linear relation between the atmospheric and seawater DMS, the turnover time of the atmospheric DMS has been calculated to be 0.9 days with an uncertainty of around 50%. The oxidation rate agrees fairly well with that expected from the OH radical concentration in the marine atmosphere.     

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.     

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.     

FT-IR Study of the Kinetics and Products of the Reactions of Dimethylsulphide, Dimethylsulphoxide and Dimethylsulphone with Br and BrO

Kinetics and products of the gas-phase reactions of dimethylsulphide (DMS), dimethylsulphoxide (DMSO) and dimethylsulphone (DMSO₂) with Br atoms and BrO radicals in air have beeninvestigated using on-line Fourier Transform Infrared Spectroscopy (FT-IR) as analytical technique at 740 ± 5 Torr total pressure and at 296 ± 3 K in a480 L reaction chamber. Using a relative rate method for determining the rate constants; the following values (expressed in cm³molecule^–1 s^–1) were found: k_DMS+Br = (4.9 ±1.0) ×10^–14, k_DMSO + Br < 6 × 10^–14,k_{DMSO 2} + Br 1 × 10^–15,k_DMSO + BrO = (1.0 ± 0.3) × 10^–14 andk_{DMSO 2} + BrO 3 × 10^–15 (allvalues are given with one on the experimental data). DMSO, SO₂, COS, CH₃SBr andCH₃SO₂Br were identified as the main sulphur containing products of the oxidation of DMS by Br atoms. From the reaction between DMSO and Br atoms, DMSO₂and CH₃SO₂Br were the only sulphur containing products thatwere identified. DMSO, DMSO₂ and SO₂ were identified as themain sulphur containing products of the reaction between DMS and BrO.DMSO₂ was found to be the only product of the reaction between DMSO and BrO. For the reactions of DMSO₂ with Br and BrO no products were identified because the reactions were too slow.The implications of these results for atmospheric chemistry are discussed.     

南海西北部一次海上海雾的微物理及化学特性分析

利用2017年3月MICAPS资料、欧洲气象中心再分析ERA-Interim数据及在南海西北部海上的海雾观测数据,分析了南海西北部一次海上海雾的微物理特征和雾水化学特性,并将海上海雾与南海岸边海雾进行对比分析。结果表明:此次海雾为南海偏南暖气流移至冷海面发生冷却并达到饱和而形成。海雾过程中气压与气温变化趋势相反,相对湿度不断增加,雾滴数浓度、液态含水量和平均直径的平均值分别为198 cm-3、0.116 g/cm3和5.6 μm。相比广东湛江东海岛和广东茂名博贺地区岸边海雾个例,本次海上海雾水汽充足,雾滴偏大。本次海雾属于酸性海雾,pH值变化范围为2.51~3.50,海雾后的雨水样本pH值则为4.05。海雾发生初期电导率比其它阶段高很多,说明海雾发生的初始阶段雾水溶解了大量的气溶胶。海上雾水中Na+和Cl-浓度最高,浓度分别为32 535 μmol/L和53 466 μmol/L,K+浓度远高于Mg2+和Ca2+,而东海岛岸边海雾相反。      

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.     

庐山云雾水化学组分的某些特征

在庐山电视台采集的云雾水与同时段、同一地点采集的雨水相比,除Cl~-外各种离子浓度前者明显高些,pH值也较高。云雾水和地面同时段雨水相比较,云雾水中NO~-_3,SO~-_4,NH~+_4,Ca~(++),F~-及Mg~(++)等离子浓度也较高,但云雾水和雨水二者比值较小,云雾水的pH值也较高。云雾水中离子浓度和上风向污染源关系密切,其主要通过气溶胶的输送从而影响云雾水成份。有雨情况下云雾水中的离子浓度随时间推移而逐渐减少。     

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.     

Grab sampling for the determination of sulfur dioxide and dimethyl sulfide in air by isotope dilution gas chromatography/mass spectrometry

Developments allowing the direct determination of sulfur dioxide and dimethyl sulfide in grab samples by gas chromatography/mass spectrometry with isotopically labeled standards (GC/MS/ILS) are reported. Isotopomers of DMS and SO₂ are used as internal standards. Spiked air samples are dried to a dew point of <–60 °C and trapped cryogenically in loops of Teflon tubing. Sealed samples are transported to the laboratory under liquid nitrogen and later subjected to GC/MS analysis. Holding times of up to one month do not result in significant sample loss. For samples collected in a clean marine environment, concentrations of SO₂ and DMS greater than 5 and 8 pptv, respectively, are significantly different from blanks at the 95% confidence level. Average measurement precision derived from a propagation of errors are 9% for SO₂ and 42% for DMS at concentrations from 5–15 pptv.Improvements are outlined which should provide sensitivity and precision comparable to that of on-site GC/MS. The technique will allow increased flexibility for the determination of trace sulfur species in the field under conditions where deployment of a mass spectrometer is not possible.     

Short-Term Variability of Atmospheric DMS and Its Oxidation Products at Amsterdam Island during Summer Time

A one-month experiment was performed at Amsterdam Island in January 1998, to investigate the factors controlling the short-term variations of atmospheric dimethylsulfide (DMS) and its oxidation products in the mid-latitudes remote marine atmosphere. High mixing ratios of DMS, sulfur dioxide (SO₂) and dimethylsulfoxide (DMSO) have been observed during this experiment, with mean concentrations of 395 parts per trillion by volume (pptv) (standard deviation, = 285, n = 500), 114 pptv ( = 125, n = 12) and 3 pptv ( = 1.2, n = 167), respectively. Wind speed and direction were identified as the major factors controlling atmospheric DMS levels. Changes in air temperature/air masses origin were found to strongly influence the dimethylsulfoxide (DMSO)/DMS and SO₂/DMS molar ratios, in line with recent laboratory data. Methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^2–) mean concentrations in aerosols during this experiment were 12.2± 6.5 pptv (1, n=47) and 59 ± 33 pptv (1, n=47), respectively. Evidence of vertical entrainment was reported following frontal passages, with injection of moisture-poor, ozone-rich air. High MSA/ nss-SO₄ ^2– molar ratios (mean 0.44) were calculated during these events. Finally following frontal passages, few spots in condensation nuclei (CN) concentration were also observed.     

DMS and SO2 at Baring Head, New Zealand: Implications for the Yield of SO2 from DMS

Atmospheric dimethyl sulfide (DMS) and sulfur dioxide (SO₂) concentrations were measured at Baring Head, New Zealandduring February and March 2000. Anti-correlated DMS and SO₂ diurnalcycles, consistent with the photochemical production of SO₂ from DMS, were observed in clean southerly air off the ocean. The data is used to infer a yield of SO₂ from DMS oxidation. The estimated yields are highly dependent on assumptions about the DMS oxidation rate. Fitting the measured data in a photochemical box model using model-generated OH levels and the Hynes et al. (1986) DMS + OH rate constant suggests that theSO₂ yield is 50–100%, similar to current estimates for the tropical Pacific.However, the observed amplitude of the DMS diurnal cycle suggests that the oxidation rate is higher than that used by the model, and therefore, that theSO₂ yield is lower in the range of 20–40%.     

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.     

Sulfur dioxide and dimethyl sulfide in the central Pacific troposphere

Boundary-layer and free-troposphere measurements of sulfur dioxide, dimethyl sulfide, and carbon disulfide were made during transits of the central and southern Pacific Ocean between Hawaii and Australia. Sulfur dioxide was generally less than 100 pptv and highly variable with no correlation with respect to geographic location or altitude. Dimethyl sulfide in the boundary layer had a concentration range of <10 to 200 pptv. Highest concentrations of DMS were in the equatorial region of the southern hemisphere although the concentrations were dependent on location and meteorological regime. In the region of the Fiji Islands several boundary layer samples had SO₂, DMS, and CS₂. In 1989, additional SO₂ measurements were made between Hawaii and the equator and to the west of Hawaii downwind of the Kilauea volcano plumes.Paper submitted to the 7th International Symposium of the Commission for Atmospheric Chemistry and Global Pollution on the Chemistry of the Global Atmosphere held in Chamrousse, France, from 5 to 11 September 1990.     

Emission and flux of DMS from the Australian Antarctic and Subantarctic Oceans during the 1988/89 summer

DMS emissions and fluxes from the Australasian sector of the Antarctic and Subantarctic Oceans, bound by 46–68° S and 65.5–142.6° E, were determined from a limited number of samples (n=32) collected during three summer resupply voyages to Australian Antarctic continental research bases between November 1988 and January 1989 (a 92 day period). The maximum DMS emission from this sector of the Antarctic Ocean was in an area near the Antarctic Divergence (60–63° S) and the minimum DMS emission was from the Antarctic coastal and offshelf waters. The greatest emission of DMS from this sector of the Southern Ocean was from the Subantarctic waters. DMS flux from the Australasian Antarctic Ocean was 64.3×10⁶ (±115) mol d^–1 or 5.9 (±10.6)×10⁹ mol based on an emission of 10.9 (±19.5) µmol m^–2 d^–1 (n=26). The flux of DMS from the Australasian sector of the Subantarctic Ocean was probably twice the flux of DMS from the adjacent Antarctic Ocean.     

A sensitive method for measuring atmospheric concentrations of sulfur dioxide

A new sensitive method for measuring atmospheric concentrations of sulfur dioxide is presented. Samples are obtained using the mist chamber, which collects highly water-soluble gases with high efficiency, and concentrates them in a small volume of water. Particles are removed from the sampled air stream with a teflon filter, before it enters the mist chamber. After collection, the pH of the water is raised above pH 10 using sodium carbonate, then hydrogen peroxide (H₂O₂) is added to oxidize sulfur that may be present in the sulfur (IV) oxidation state, to sulfate. After a reaction time of at least 16 hours, the sulfate concentration is measured by ion chromatography. From the sulfate concentration, the water volume used in the mist chamber, and the volume of air sampled, the atmospheric concentration of SO₂ is computed. The method is not sensitive to other atmospheric sulfur gases such as DMS, SC₂, H₂S, COS, or MSH. The estimated overall precision of the method is 10%. The detection limit at the present stage of technique development is approximately 20 ppt (parts per trillion, or 10^-12 mol · mol^-1) for a 45 minute sampling time, with lower concentrations being detectable with lower precision.