夏秋季东海陆架区二甲亚砜的分布特征及影响因素

于2013年10～11月和2014年5～6月调查测定了东海陆架区海水中二甲亚砜(DMSO)的浓度,探讨了溶解态二甲亚砜(DMSOd)和颗粒态二甲亚砜(DMSOp)的水平和垂直分布、季节变化及其影响因素;此外,对沉积物间隙水中DMSOd的浓度以及表层海水中不同粒径的DMSOp和叶绿素a(Chl a)进行了分析.结果显示,...     

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.     

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.     

Nonaqueous titration of functional groups in humic acid

Humic acid was titrated by sodium methoxide in dimethylsulfoxide using platinum-calomel electrode systems. Adding benzoic acid and phenol as internal standards to humic acid yielded two inflections. The titer at the first inflection point was equivalent to the carboxyl groups whose pK_a (H₂O) values were less than 7. The difference between the titers at the two inflection points was equivalent to the phenolic hydroxyl groups whose pK_a (H₂O) values were 7–10. Calculated results for the carboxyl and phenolic hydroxyl groups in humic acid obtained by the nonaqueous titration method agreed closely with those obtained by conventional methods.     

东海和黄海二甲基亚砜（DMSO）的季节和空间变化

Seasonal and spatial distributions of dissolved and particulate dimethylsulfoxide(DMSOd,DMSOp)were measured in the East China Sea and the Yellow Sea during March–April 2011 and October–November 2011.The concentrations of DMSOd and DMSOp in the surface water were 20.6(5.13–73.8)and 8.90(3.75–29.6)nmol/L in spring,and 13.4(4.17–42.7)and 8.18(3.44–22.6)nmol/L in autumn,respectively.Both DMSOd and DMSOp concentrations revealed similar seasonal changes with higher values occurring in spring,mainly because of the higher phytoplankton biomass observed in spring.Moreover,the ratios of DMSOp/chlorophyll a also exhibited an apparent seasonal change with higher values in autumn(35.7 mmol/g)and lower values in spring(23.4 mmol/g),thereby corresponding with the seasonal variation in the proportion of DMSO producers in the phytoplankton community between spring and autumn.In addition,DMSOd and DMSOp concentrations in the surface seawater revealed obvious diurnal variations with the maxima appearing in the afternoon.     

二甲基硫光化学氧化反应的动力学研究

实验研究水溶液中二甲基硫（ＤＭＳ）的光化学氧化反应的动力学。结果表明，在入射光频率与强度一定条件下，ＤＭＳ进行光化学氧化反应的速率会受到介质、ｐＨ、重金属离子的影响。Ｈｇ２＋能显著加快人工海水介质中ＤＭＳ的光氧化速率。ＤＭＳ进行光氧化的一级速率常数为４．４６×１０－５～３０．４×１０－５ｓ－１，其在光照下的人工海水介质中的半寿期为３．６ｈ。这说明光化学过程对于影响和控制ＤＭＳ在海洋中的浓度和分布起着十分重要的作用     

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.     

Study on the analysis and distribution of dimethylsulfoxide in the Jiaozhou Bay

A chemoreduction-purge-and-trap gas chromatographic method has been developed for the determination of trace dimethylsulfoxide (DMSO) in seawater. In the analysis procedure, DMSO was first reduced to dimethylsufide (DMS) by sodium borohydride and then the produced DMS was analyzed using the purge-and-trap technique coupled with gas chromatographic separation and flame photometric detection. Under the optimum conditions, 97% DMSO was reduced in the standard solution samples with a standard deviation of 5% (n=5). The detection limit of DMSO was 2.7 pmol of sulfur, corresponding to a concentration of 0.75 nmol/L for a 40 ml sample. This method was applied to determine the dissolved DMSO (DMSOd) and particulate DMSO (DMSOp) concentrations in the surface seawater of the Jiaozhou Bay, and the results showed that the DMSOd and DMSOp concentrations varied from 16.8 to 921.1 nmol/L (mean:165.2 nmol/L) and from 8.0 to 162.4 nmol/L (mean:57.7 nmol/L), respectively. The high concentrations of DMSOp were generally found in productive regions. Consequently, a significant correlation was found between the concentrations of DMSOp and chlorophyll a, suggesting that phytoplankton biomass might play an important role in controlling the distribution of DMSOp in the bay. Moreover, in the study area, the concentrations of DMSOd were significantly correlated with the levels of DMS, implying that the production of DMSOd is mainly via photochemical and biological oxidation of DMS.     

The atmospheric chemistry of dimethylsulfoxide (DMSO) kinetics and mechanism of the OH+DMSO reaction

We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with dimethylsulfoxide and its deuterated analogue. A rate coefficient of (1.0±0.3)×10^-10 cm³ molecule^-1 s^-1 was obtained ar room temperature. The rate coefficient was independent of pressure over the range 25–700 Torr, showed no dependence on the nature of the buffer gas and showed no kinetic isotope effect. A limited study of the temperature dependence indicated that the reaction displays a negative activation energy. The gas phase ultraviolet absorption spectrum was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross-section at 205 nm, the absorption peak, is (1.0±0.3)×10^-17 cm², where the large uncertainty results from experimental difficulties associated with the low vapor pressure and stickiness of DMSO.