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

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Determination of part-per-trillion levels of atmospheric dimethyl sulfide by isotope dilution gas chromatography/mass spectrometry

Stable isotopic dilution was applied to the determination of dimethyl sulfide (DMS) in ambient air at the low part-per-trillion by volume (pptrv) levels. Perdeuterated DMS was used as an internal standard in the gas chromatography/mass spectrometry determination. The isotopically labelled internal standard provided insensitivity to possible losses of DMS in sampling and analysis. The lower limit of detection (LLD) was 1 pptrv with a sample acquisition time of 2 min.     

水声学方法对黄河口水下底坡失稳现象研究

对黄河三角洲东北部地区的高分辨率水声学资料进行了综合研究。根据所记录的破坏土体变形程度、运动产生的平面形状和地貌特征形态,对土体失稳过程进行分类：浅表土体变形、塌陷凹坑、滑坡和沉积物重力流。结果表明：（１）浅表土体形变的变形程度最低,出现在研究区斜坡上部平滑海底,主要为绳网状泄水构造和表层拉张裂隙。（２）塌陷凹坑在研究区内广泛出现,是局部土体液化后发生了垂直沉降的结果。（３）滑坡多发生在水下斜坡的中上部,由弧形塌陷区、狭窄的冲沟通道和负地形沉积物堆积区组成。滑坡陡坎后缘发现拉张裂隙。（４）沉积物重力流是土体发生变形程度最大,搬运距离最长的土体破坏变形形式。局部区域多次受到沉积物重力流切割和充填作用。     

Grazing suppression of dimethylsulphoniopropionate (DMSP) accumulation in iron-fertilised, sub-Antarctic waters

The impact of in situ iron fertilisation on the production of particulate dimethylsulphoniopropionate (DMSPp) and its breakdown product dimethyl sulphide (DMS) was monitored during the SOLAS air-sea gas exchange experiment (SAGE). The experiment was conducted in the high nitrate, low chlorophyll (HNLC) waters of the sub-Antarctic Southern Ocean (46.7°S 172.5°E) to the south-east of New Zealand, during March-April, 2004. In addition to monitoring net changes in the standing stocks of DMSPp and DMS, a series of dilution experiments were used to determine the DMSPp production and consumption rates in relation to increased iron availability. In contrast to previous experiments in the Southern Ocean, DMS concentrations decreased over the course of the 15-d iron-fertilisation experiment, from an integrated volume-specific concentration in the mixed layer on day 0 of 0.78 nM (measured values 0.65-0.91 nM) to 0.46 nM (measured values 0.42-0.47 nM) by day 15, in parallel with the surrounding waters. DMSPp, chlorophyll a and the abundance of photosynthetic picoeukaryotes exhibited indiscernible or only moderate increases in response to the raised iron availability, despite an obvious physiological response by the phytoplankton. High specific growth rates of DMSPp, equivalent to 0.8-1.2 doublings d⁻¹, occurred at the simulated 60% light level of the dilution experiments. Despite the high production rates, DMSPp accumulation was suppressed in part by microzooplankton grazers who consumed between 61% d⁻¹ and 126% d⁻¹ of the DMSPp production. Temporal trends in the rates of production and consumption illustrated a close coupling between the DMSP-producing phytoplankton and their microzooplankton grazers. Similar grazing and production rates were observed for the eukaryotic picophytoplankton that dominated the phytoplankton biomass, partial evidence that picoeukaryotes contributed a substantial proportion of the DMSP synthesis. These rates for DMSPp and picoeukaryotes were considerably higher than for chlorophyll a, indicating higher cycling rates of the DMSP-producing taxa than for the bulk phytoplankton community. When compared to the total phytoplankton community, there was no evidence of selection against the DMSP-containing phytoplankton by the microzooplankton grazers; the opposite appeared to be the case. SAGE demonstrated that increased iron availability in the HNLC waters of the Southern Ocean does not invariably lead to enhanced DMS sea-air flux. The potential suppression of DMSPp accumulation by grazers needs to be taken into account in future attempts to elevate DMS emission through in situ iron fertilisation and in understanding the hypothesised link between levels of Aeolian iron deposition in the Southern Ocean, DMS emission and global albedo.     

Dimethylsulfide production in Sargasso Sea eddies

Lagrangian time series of dimethylsulfide (DMS) concentrations from a cyclonic and an anticyclonic eddy in the Sargasso Sea were used in conjunction with measured DMS loss rates and a model of vertical mixing to estimate gross DMS production in the upper 60 m during summer 2004. Loss terms included biological consumption, photolysis, and ventilation to the atmosphere. The time- and depth (0–60 m)-averaged gross DMS production was estimated to be 0.73±0.09 nM d⁻¹ in the cyclonic eddy and 0.90±0.15 nM d⁻¹ in the anticyclonic eddy, with respective DMS replacement times of 5±1 and 6±1 d. The higher estimated rate of gross production and lower measured loss rate constants in the anticyclonic eddy were equally responsible for this eddy's 50% higher DMS inventory (0–60 m). When normalized to chlorophyll and total dimethylsulfoniopropionate (DMSP), estimated gross production in the anticyclonic eddy was about twice that in the cyclonic eddy, consistent with the greater fraction of phytoplankton that were DMSP producers in the anticyclonic eddy. Higher rates of gross production were estimated below the mixed layer, contributing to the subsurface DMS maximum found in both eddies. In both eddies, gas exchange, microbial consumption, and photolysis were roughly equal DMS loss terms in the surface mixed layer (0.2–0.4 nM d⁻¹). Vertical mixing was a substantial source of DMS to the surface mixed layer in both eddies (0.2–0.3 nM d⁻¹) owing to the relatively high DMS concentrations below the mixed layer. Estimated net biological DMS production rates (gross production minus microbial consumption) in the mixed layer were substantially lower (by almost a factor of 3) than those estimated in a previous study of the Sargasso Sea, which may explain the relatively low mixed-layer DMS concentrations found here during July 2004 (3 nM) compared to previous summers (4–6 nM).     

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.     

Controls of dimethyl sulphide in the Bay of Bengal during BOBMEX-Pilot cruise 1998

The air-sea exchange is one of the main mechanisms maintaining the abundances of trace gases in the atmosphere. Some of these, such as carbon dioxide and dimethyl sulphide (DMS), will have a bearing on the atmospheric heat budget. While the former facilitates the trapping of radiation (greenhouse effect) the latter works in the opposite direction through reflectance of radiation back into space by sulphate aerosols that form from oxidation of DMS in atmosphere. Here we report on the first measurements made on DMS in the Bay of Bengal and the factors regulating its abundance in seawater. Phytoplankton alone does not seem to control the extent of DMS concentrations. We find that changes in salinity could effectively regulate the extent of DMSP production by marine phytoplankton. In addition, we provide the first ever evidence to the occurrence of DMS precursor, DMSP, in marine aerosols collected in the boundary layer. This suggests that the marine aerosol transport of DMSP will supplement DMS gaseous evasion in maintaining the atmospheric non-sea salt sulphur budget.     

DMS oxidation and turbulent transport in the marine boundary layer: A numerical study

DMS oxidation in the marine boundary layer has been simulated with a mesoscale meteorological model including detailed physical parameterizations. The impact of vertical turbulent transport on the DMS and SO₂ diurnal cycles with and without in-cloud SO₂ oxidation has been studied in a one-dimensional version of the model and compared to results obtained with a zero-dimensional box model. Initialisation has been done using balanced values issued from the imposed sea-air fluxes, dry deposition fluxes and chemical source/sink terms. Particular emphasis has been put on the important role played by evolving vertical mixing in the marine boundary layer.     

固载杂多酸催化合成富马酸二甲酯

以富马酸与甲醇为原料，固载杂多酸PW12／C为催化剂合成了富马酸二甲酯。详细探讨了影响酯化反应的各种因素，得出了富马酸与甲醇反应的最佳条件，即m（催化剂）∶m（富马酸）8∶100，n（富马酸）∶n（甲醇）＝1∶8，回流搅拌反应3h。在该条件下，酯化产率为91.6%。结果表明，此法催化剂用量少，催化活性高，反应时间短，酯收率高，反应工艺简单。     

Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development

Detailed theoretical (Part I, this article) and experimental (Part II) investigations are presented for the mechanism of the atmospheric photooxidation of dimethyl sulfide (CH₃SCH₃) and dimethyl disulfide (CH₃SSCH₃). In this paper, comprehensive mechanisms for the atmospheric chemistry of CH₃SCH₃ and CH₃SSCH₃ are developed based on fundamental considerations of all available kinetic and mechanistic information.