Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

Absolute rate constants for the reaction of ozone with dimethyl sulfide （DMS） were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range, the data could be fit to the simple Arrhenius expression as kDMS = （9.96 ± 3.61） × 10^-11 exp （-（7309.7 ± 1098.2）/T） cm^3/（molecule.s）. A compared investigation of the reaction between ozone and ethene had a kC2H4 value of （1.35 ± 0.11） × 10^-18 cm^3/（molecule.s） at room temperature.

STUDY ON THE ANALYSIS AND DISTRIBUTION OF DIMETHYL SULFIDE IN THE EAST CHINA SEA

A method is described for determining dimethylI sulfide （DMS） in seawater. DMS was first extractedfrom the seawater using organic reagent, then reverse-extracted by 5% HgCl2. In the laboratory DMS wasreleased by concentrated HCI and finally measured by GC-FPD. The limit of detection me O.05 ng ofS. Measurements of DMS along surface transects and on wtital profibe across the EaSt China Sca （Ers）continental sheif showed tha itS conodIations of S in the surface seawater ranged from 64-180 ng/L andthat itS vertical djstribuion was divided into 3 trpes. Model talculations of a stagnant film show a DMSflux of 10.6 umol/m2d the air-sea inteIha.

Using genetic algorithms to calibrate a dimethylsulfide production model in the Arctic Ocean

The global climate is intimately connected to changes in the polar oceans. The variability of sea ice coverage affects deep-water formations and large-scale thermohaline circulation patterns. The polar radiative budget is sensitive to sea-ice loss and consequent surface albedo changes. Aerosols and polar cloud microphysics are crucial players in the radioactive energy balance of the Arctic Ocean. The main biogenic source of sulfate aerosols to the atmosphere above remote seas is dimethylsulfide (DMS). Recent research suggests the flux of DMS to the Arctic atmosphere may change markedly under global warming. This paper describes climate data and DMS production (based on the five years from 1998 to 2002) in the region of the Barents Sea (30–35°E and 70–80°N). A DMS model is introduced together with an updated calibration method. A genetic algorithm is used to calibrate the chlorophyll-a (CHL) measurements (based on satellite SeaWiFS data) and DMS content (determined from cruise data collected in the Arctic). Significant interannual variation of the CHL amount leads to significant interannual variability in the observed and modeled production of DMS in the study region. Strong DMS production in 1998 could have been caused by a large amount of ice algae being released in the southern region. Forcings from a general circulation model (CSIRO Mk3) were applied to the calibrated DMS model to predict the zonal mean sea-to-air flux of DMS for contemporary and enhanced greenhouse conditions at 70–80°N. It was found that significantly decreasing ice coverage, increasing sea surface temperature and decreasing mixed-layer depth could lead to annual DMS flux increases of more than 100% by the time of equivalent CO2 tripling (the year 2080). This significant perturbation in the aerosol climate could have a large impact on the regional Arctic heat budget and consequences for global warming.

Flux of dimethylsulfide in the Jiaozhou Bay,China

Seasonal measurements of dimethylsulfide(DMS)in surface waters were carried out during 1993-1994 in the Jiaozhou Bay.A seasonal variation is observed for DMS concentrations in seawater,ranging from 0.6 to 8.97 nmol S/L with the highest values in spring.A factor of 4 was measured for DMS concentrations with mean concentrations of 5.85 nmol S/L or 6.58 nmol S/L in spring and 1.40nmol S/L in winter.A sea-to-air flux of DMS also showed a seasonal variation.

Preparation of Low Cost Activated Carbon from Deactivated Resin Catalyst for Methyl Tert-Butyl Ether Synthesis and Its Application in Dimethyl Sulfide Adsorption with Transition Metal Impregnation

In this paper, a low-cost activated carbon(AC) was prepared from deactivated resin catalyst(DRC) for methyl tert-butyl ether(MTBE) synthesis through carbonization and subsequent steam activation treatment. The activated carbon was characterized in detail. After loading various transition metals, including Cu^(2+), Ag+, Co^(2+), Ni^(2+), Zn^(2+), and Fe^(3+) via the ultrasonic-assisted impregnation method, a series of metal-loaded adsorbents(xM-AC) were obtained and their dimethyl sulfide(DMS) adsorption performance was investigated in a batch system. Among these adsorbents, 15Cu-AC presented a superior DMS adsorption capacity equating to 58.986 mg/g due to the formation of S-M(σ) bonds between Cu^(2+) and sulfur atoms of DMS as confirmed by the Raman spectra and kinetic study.

Density Functional Investigation of Methanethiol and Dimethyl Sulfide Adsorption on Zeolite

The density functional theory and cluster model methods have been employed to investigate the interactions between methanethiol, dimethyl sulfide and zeolites. The molecular complexes formed by adsorption of methanethiol or dimethyl sulfide on silanol H3SiOSi（OH）2OSiH3 with five coordination forms or four coordination forms, and complexes formed by interactions of BrSnsted acid sites of bridging hydroxyl H3Si（OH）AI（OH）2OSiH3 with methanethiol or dimethyl sulfide have been investigated. Full optimization and frequency analysis of all cluster models have been carried out using the B3LYP hybrid method at 6-31＋G （d,p） basis set level for hydrogen, silicon, aluminum, oxygen, carbon, and sulfur atoms. The structures and energy changes of different coordination forms between methanethiol and H3Si（OH）Al（OH）2OSiH3, dimethyl sulfide and H3Si（OH）Al（OH）2OSiH3, methanethiol and H3SiOSi（OH）2OSiH3, dimethyl sulfide and H3SiOSi（OH）2OSiH3 complexes have been comparatively studied. The calculated results showed the nature of interactions that led to the formation of all complexes was van der Waals force confirmed by an insignificant change of geometric structures and properties. The conclusions that methanethiol and dimethyl sulfide molecules were adsorbed on bridging hydroxyl group prior to silanol group were obtained on the basis of adsorption heat, the most stable adsorption models of a 6 ring structure for interaction between bridging hydroxyl and methanethiol, and a 7 ring structure for interaction between bridging hydroxyl and dimethyl sulfide.

Dimethyl sulfide in the atmospheric surface layer of the Equatorial Pacific Ocean

This paper reports a case study of atmospheric stability effect on dimethyl sulfide(DMS) concentration in the air. Investigation includes model simulation and field measurements over the Pacific Ocean. DMS concentration in surface sea water and in the air were measured during a research cruise from Hawaii to Tahiti. The diurnal variation of air temperature over the sea surface differed from the diurnal cycle of sea surface temperature because of the high heat capacity of sea water. The diurnal cycle of average DMS concentration in the air was studied in relation to the atmospheric stability parameter and surface heat flux. All these parameters had minima at noon and maxima in the early morning. The correlation coefficient of the air DMS concentration with wind speed (at 15 m high) was 0. 64. The observed concentrations of DMS in the equatorial marine surface layer and their diurnal variability agree well with model simulations. The simulated results indicate that the amplitude of the cycle and the mean concentration of DMS are dependent on the atmospheric stratifications and wind speed.

Adsorptive Desulfurization of Propylmercaptan and Dimethyl Sulfide by CuBr_2 Modified Bentonite

Adsorptive desulfurization for removing propylmercaptan （PM） and dimethyl sulfide （DMS） over CuBr2 modi- fied bentonite was investigated under ambient conditions in this work. A saturated sulfur capacity as high as 196 mg of S per gram of adsorbent was demonstrated. The influence of loading amount of Cu （II） and calcination temperature on adsorptive desulfurization was investigated. Test results revealed that the optimum loading amount of Cu （II） was 15%, and the calcination temperature was 150 ℃. The pyridine-FTIR spectroscopy showed that a certain amount of Lewis acid could contribute to the increase of adsorption capacity. Spectral shifts of the v（C-S） and v（Cu-S） vibrations were detected from the Raman spectra of the Cu （II） complex which was a reaction product of CuBr2 with DMS. According to the hybrid orbital theory and the complex adsorption reaction, the desulfurization of PM and DMS over the CuBr2 modified bentonite is ascribed to the formation of S-M （σ） bonds.

Dimethyl sulfide,a metabolite of the marine microorganism,protects SH-SY5Y cells against 6-hydroxydopamine and MPP~＋-induced apoptosis

Dimethyl sulfide(DMS)has been historically recognized as a metabolite of the marine microorganism or a disgusting component for the smell of halitosis patients.In our recent study,DMS has been identified as a cytoprotectant that protects against oxidative-stress induced cell death and aging.We found that at near-physiological concentrations,DMS reduced reactive oxygen species(ROS)in cultured PC12 cells and alleviated oxidative stress.The radical-scavenging capacity of DMS at near-physiological concentration was equivalent to endogenous methionine(Met)-centered antioxidant defense.Methionine sulfoxidereductase A(MsrA),the key antioxidant enzyme in Met-centered defense,bound to DMS and promoted its antioxidant capacity via facilitating the reaction of DMS with ROS through a sulfonium intermediate at residues Cys72,Tyr103,Glu115,followed by the release of dimethyl sulfoxide(DMSO).MTT assay and trypan blue test indicated that supplement of DMS exhibited cytoprotection against 6-hydroxydopamine and MPP+induced cell apoptosis.Furthermore,Msr A knockdown abolished the cytoprotective effect of DMS at near-physiological concentrations.The present study reveals new insight into the potential therapeutic value of DMS in Parkinson disease.

Sea to Air Flux of Dimethyl Sulfide and Its Effect on the Environment

Reviews on the current studies on the sea to air flux of dimethyl sulfide (DMS) have been made at home and abroad, pointing out that the flux of DMS is influenced by many factors. There is great difference between the results coming from different models. Besides, this paper focuses on the oxidation mechanisms of DMS by OH and NO3 radicals after it enters the atmosphere, the oxidation products’ contribution to acid rain and fog and the relationships among the DMS, CCN and climate system.

The concentration and distribution of dimethyl sulfide in the marine atmospheric boundary layer near the equator

A one-dimensional photochemical model with parameterized vertical eddy diffusion is used to simulate the dimethyl sulfide (DMS) in the marine atmospheric boundary layer near the equator. The boundary condition of theDMS flux over sea surface is assigned from gas exchange models that deped on sea surface wind speed and DMS concentration in surface water. Photolysis rates at various altitudes are calculated as a function of Solar zenith angle, andthe radiation calculation includes ozone absorption,surface reflection and molecular scattering.The simulated results of the DMS diurnal cycle are in good agreement with the observations. Sensitivity tests ofthe model indicate that the concentration of the DMS in the marine surface layer appears to be affected by a combination of chemical processes and meteorological conditions. In addition, photochemical processes are rather important.The reaction of the DMS with OH radical, the heterogeneous conversion of SO2 and the deposition of NSS-SO andthe methanesulfonic acid (MSA) are critical factors of controlling the DMS, SO2, NSS-SO and the MSA concentrations and distributions in the atmosphere.The DMS concentration in air is directly proportional to surface windspeed, but it is inversely proportional to boundary layer height in the convective boundary layer. The distributions ofthe DMS concentrations in air are strongly influenced by atmospheric stratification in stable conditions.

Rate Constants for Reaction Between Hydroxyl Radical and Dimethyl Sulfide Under Real Atmospheric Condition

The rate constants of the reaction between hydroxyl radical （OH-） and dimethyl sulfide （DMS） were investigated by using the relative methods in air, N2, and 02. Strong influences of ground state oxygen O（3p） on DMS consumption were found by the photolysis of HONO and CH3ONO as OH. sources, and the rate constants obtained in these systems varied significantly. The rate constants of the reaction between DMS and OH- （generated by photolysis of H2 O2） at room temperature were 8.56 × 10^-12, 11.31× 10^-12, and 4.50× 10^-12 cm3/（molecule.s）, in air, O2, and N2, respectively. The temperature dependence of the rate constants for OH- with DMS over the temperature range of 287-338 K was also investigated in nitrogen and air, and the Arrhenius expression was obtained as follows： kaire=（7.24±0.28）× 10^-13exp[（770.7±E97.2）/T], kN2 =（3.40±0.15） × 10^-11 exp[-- （590.3±165.9）/T].

Ab Initio Investigation of Methanthiol and Dimethyl Sulfide Adsorption on Zeolite

The Hartree-Fock and cluster model methods have been employed to investigate interactions of methanthiol or dimethyl sulfide on zeolites. Molecular complexes formed by adsorption of methanthiol on silanol H3SiOSi（OH）2OSiH3 with five coordination forms and dimethyl sulfide on silanol H3SiOSi（OH）2OSiH3 with four coordination forms, and Bronsted acid sites of bridging hydroxyl H3Si（OH）Al（OH）2OSiH3 entering into interactions with methanthiol or dimethyl sulfide have been investigated. Full optimization and frequency analysis of all cluster models have been carded out using the Hartree-Fock method at 6-31＋G＊＊ basis set level for hydrogen, silicon, aluminum, oxygen, carbon, and sulfur atoms. The structures and energy changes of different coordination forms derived from methanthiol and H3Si（OH）Al（OH）2OSiH3, dimethyl sulfide and H3Si（OH）Al（OH）2OSiH3, methanthiol and H3SiOSi（OH）2OSiH3, dimethyl sulfide and H3SiOSi（OH）2OSiH3 complexes have been comparatively studied. The calculated results showed that the nature of interactions leading to the formation of the bridging hydroxyl-methanthiol, silanol-methanthiol, bridging hydroxyl-dimethyl sulfide, silanol-dimethyl sulfide complexes was governed by the Van der Waals force as confirmed by a small change in geometric structures and properties. Methanthiol and dimethyl sulfide molecules were adsorbed on bridging hydroxyl group prior to silanol group as evidenced by the heat of adsorption, and the protonization of methanthiol adsorption on bridging hydroxyl model, which was supposed in the literature, was not found.

苏北盐沼DMS、CS_2和CH_4排放通量沿高程梯度的变化

在中国东部海岸带盐沼沿环境梯度采用静态箱技术原位测定CH4、DMS和CS2气体的通量。结果表明,苏北海岸带盐沼整体上表现为CH4、DMS和CS2气体的源,其中,互花米草带(Spartina alterniflora)排放率最高。CH4、DMS和CS2排放率之间的正相关关系支持DMS是甲烷生产底物的推断。高等植物地上部分是CH4、DMS和CS2气体的重要源,但植物排放这些气体的机制还不清楚。盐沼CH4、DMS和CS2气体的净排放可能与盐沼丰富的有机质含量有关,有机质为土壤微生物提供充足的碳源和能量。

秋季COS和DMS在草坪与大气间的交换

利用静态箱法研究了羰基硫 (COS)和二甲基硫 (DMS)在绿化草坪与大气之间的交换 .在秋季 ,草坪对COS的吸收通量为 0 75— 1 4 5 μg·m- 2 ·h- 1 ,对DMS的排放通量为0 0 5— 0 35 μg·m- 2 ·h- 1 .COS和DMS的交换通量与环境温度、光照及初始浓度等因素有关 ,其中 ,周围大气COS的浓度对草坪吸收COS的影响最为明显 .草坪对COS的吸收通量与DMS的排放通量呈正相关 ,相关系数 (R2 )大于 0 7.此外 。

硫代甜菜碱(DMSP)对大气环境的影响及其对水产动物营养的促进作用

一种二甲基硫化合物硫代甜菜碱(DMSP)成为环境科学和水产科学共同关注的热点之一。研究表明,DMSP是海洋植物产生的渗透调节物质,大量存在于海藻和盐生高等植物体内。含有DMSP的生物体死亡之后,DMSP被海洋细菌的二甲硫醚生成酶降解,生成二甲硫醚(DMS)和丙烯酸。DMS从海洋水面逾出,进入大气形成酸雨;由于DMS能形成云,所以有降低温室效应的作用。DMSP本身则对哺乳动物、禽类及水产动物(鱼和虾)的营养代谢有促进作用。酶学研究表明,动物肝脏中的两种硫甲基转移酶能把DMSP分子中硫原子上的甲基转移出来,提供给机体代谢所需。作为海洋植物渗透调节物质的主要成分,DMSP来源于植物体内的蛋氨酸。研究DMSP的生成变化规律,对进一步了解海洋气候和开发使用新的水产动物饲料添加剂有重要价值。

Cd对前沟藻(Amphidinium hoefleri)生产二甲基硫(DMS)影响的实验研究

为了探讨Ｃｄ污染对海藻ＤＭＳ生产的可能影响，以模拟实验方式，为期３周进行Ｃｄ对海洋甲藻类的前沟藻（Ａｍｐｈｉｄｉｎｉ－ｕｍｈｏｅｆｌｅｒｉ）生产ＤＭＳ的实验室研究．结果表明，Ｃｄ可以抑制前沟藻种群数量的增长，对照组藻细胞最大数量是高浓度组（１０ｍｇ／Ｌ）的２５倍；Ｃｄ可以促进前沟藻细胞生产ＤＭＳ，其中高浓度组细胞ＤＭＳ产率大约是对照组的１０倍；Ｃｄ对藻数量的抑制作用和对藻生产ＤＭＳ的促进作用共同作用的结果，导致低浓度组（Ｃｄ浓度０．２５ｍｇ／Ｌ）ＤＭＳ浓度高于对照组，而高浓度组（Ｃｄ浓度≥２ｍｇ／Ｌ）ＤＭＳ浓度低于对照组．

顶空-气相色谱-质谱法测定富马酸二甲酯(DMF)胶囊中硫酸二甲酯(DMS)的定性、定量分析方法

采用气相色谱-质谱法对富马酸二甲酯(DMF)胶囊中残留硫酸二甲酯(DMS)进行测定。并采用顶空富集方法,与溶剂萃取富集法比较,此文中提出的顶空分离法具有不需用大量萃取溶剂,简化了操作步骤,加快了分析速度等优点。质谱中选择EI离子源-选择离子检测模式。方法简单、快速、选择性好,硫酸二甲酯(DMS)的质量浓度在一定范围内与其峰面积呈线性关系。同时考察了方法的最低检测浓度和重复性。

分光光度测溴法定量分析二甲基硫(DMS)的含量

使用苯作为生物排放含硫化合物二甲基硫的吸收液,吸收后以溴水氧化.通过间接测定溴的质量分数,从而确定DMS的质量浓度.该方法测定DMS的波长为460nm,线性范围为0.08～25mg/L,表观摩尔吸光系数为4.5×105,相关系数为0.9963.同时,对DMS和Br2的反应机理进行讨论.

分光光度测溴法定量分析二甲基硫(DMS)的含量

使用苯作为生物排放含硫化合物二甲基硫的吸收液 ,吸收后以溴水氧化。通过间接测定溴的浓度 ,从而确定DMS的浓度。该方法测定DMS的测定波长为 4 6 0nm ,线性范围为 0 0 8～ 2 5mg/L ,表观摩尔吸光系数为 4 5× 10 5,相关系数为 0 996 3。同时 ,还对DMS和Br2 的反应机理进行了讨论。