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/m_2d the air-sea inteIha.     

On the Gas Phase Reactions Between Volatile Biogenic Mercury Species and the Nitrate Radical

Tropospheric mercury is dominated by gas phase species. In this paper, the gas phase reactions between the nitrate radical and volatile biogenic mercury species have been investigated. An upper limit for the gas phase rate coefficient for reaction between elemental mercury and NO₃-radicals was determined to 4 × 10^–15 cm³ molecule^–1 s^–1 by using the fast flow-discharge technique. The reaction between dimethyl mercury and NO₃, previously shown to be rapid, has also been studied in the laboratory with respect to product distribution using FT-IR. The result from the product study is consistent with a transformation of dimethyl mercury into inorganic, divalent mercury. All carbon delivered as dimethyl mercury was transformed into formaldehyde, methanol and methyl peroxynitrate. Hg was observed as a minor (2%) product. By exclusion, HgO is proposed as the mercury-containing product. Thus, the reaction between dimethyl mercury and the nitrate radical is excluded as a source of monomethyl mercury species in the atmosphere.     

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.     

Observations of the Nitrate Radical in the Marine Boundary Layer

A study of the nitrate radical (NO3) has been conducted through a series of campaigns held at the Weybourne Atmospheric Observatory, located on the coast of north Norfolk, England. The NO3 concentration was measured in the lower boundary layer by the technique of differential optical absorption spectroscopy (DOAS). Although the set of observations is limited, seasonal patterns are apparent. In winter, the NO3 concentration in semi-polluted continental air masses was found to be of the order of 10 ppt, with an average turnover lifetime of 2.4 minutes. During summer in clean northerly air flows, the concentration was about 6 ppt with a lifetime of 7.2 minutes. The major loss mechanisms for the radical were investigated in some detail by employing a chemical box model, constrained by a suite of ancillary measurements. The model indicates that during the semi-polluted conditions experienced in winter, the major loss of NO3 occurred indirectly through reactions of N2O5, either in the gas-phase with H2O, or through uptake on aerosols. The most important direct loss was via reactions of NO3 with a number of unsaturated nonmethane hydrocarbons. The cleaner air masses observed during the summer were of marine origin and contained elevated concentrations of dimethyl sulfide (DMS), which provided the major loss route for NO3. The box model was then used to investigate the conditions in the remote marine boundary layer under which DMS will be oxidised more rapidly at night (by NO3) than during the day (by OH). This should occur if the concentration of NO2 is more than about 60% that of DMS.     

Emissions of marine biogenic sulfur to the atmosphere of northern Europe

Measurements of DMS and other reduced sulfur compounds in surface waters have been carried out from a helicopter in the seas surrounding Scandinavia. Average summer time concentrations of DMS ranged from 70 to 150 ngS L^-1. Simultaneous measurements of biological and physical parameters revealed no correlation between DMS and phytoplankton species, species assemblages, total phytoplankton biomass, chlorophyll a, temperature, and salinity. The only exception was a correlation between DMS concentration, Chrysochromulina spp. belonging to the Prymnesiophyceae, and salinity over a narrow range of salinity in the Baltic Sea.The flux of reduced sulfur to the atmosphere in July in this region is estimated to be 120–170 gS m^-2 d^-1 from the Baltic, 240–810 in the Kattegat/Skagerrak, and 120–690 in the North Sea. Annual fluxes are roughly 100 times higher than these daily fluxes. On an annual basis, biogenic sulfur emissions from the coastal seas are negligible (<1%) compared to the anthropogenic emissions in northern Europe. However, during the summer months, the biogenic sulfur emissions from the seas surrounding the Scandinavian peninsula are estimated to be as high as 20–70% of the anthropogenic emissions in Scandinavia. This makes it of interest to incorporate the biogenic emissions in calculations of long-range transport and deposition of sulfur within the region.Other volatile sulfur species, mainly methyl mercaptan, contribute about 10% of the total flux of reduced sulfur. Estimated fluxes of CS₂ to the atmosphere ranged from 1 gS m^-2 d^-1 in the Baltic Sea to 6 gS m^-2 d^-1 in the North Sea. No emissions for H₂S or COS were detected.     

间苯二甲酸二甲酯的好氧微生物降解及其生化途径

从红树林污泥中通过富集培养分离到4株细菌,鉴定结果是多杀巴斯德菌(Pasteurella multocida Sa)、产酸克雷伯菌(Klebsiella oxytoca Sc)、少动鞘氨醇单胞菌(Sphingomonas paucimobilis Sy)和嗜中温甲基杆菌(Methylobacterium mesophilicum Sr).在纯培养降解间苯二甲酸二甲酯(DMI)时发现,单一纯菌株不能完全矿化间苯二甲酸二甲酯,而2种或3种纯菌株组成的混合菌可以将220mg·L-1的底物在12d内完全矿化.主要的中间产物有间苯二甲酸一甲酯(MMI)和间苯二甲酸(IA).根据鉴定出的中间产物,DMI的生化降解途径为:DMI→MMI→IA→CO2 H2O.研究结果表明,DMI的2个酯基的水解是决定DMI能否完全矿化的重要步骤,但 2个酯基的酶催化水解反应有差异,由不同的细菌分步来完成,说明是酯酶对不同底物的专性所致;第2个酯基的水解对整个降解过程有决定性作用.     

海洋污染对毛蚶超氧化物歧化酶影响的研究

采用体内、体外染毒实验,研究了海洋中常见污染物0＃柴油、二甲苯以及重金属镉离子(Cd2+)对毛蚶(Scapharca subcrenata)肌肉超氧化物歧化酶(SOD)活性的影响.结果表明,在实验剂量范围内,3种污染物对毛蚶肌肉中SOD均表现出不同程度诱导作用;0＃柴油和二甲苯体内、体外染毒对毛蚶SOD活性影响规律基本一致,这两种污染物对毛蚶SOD活性变化的剂量-效应曲线均为抛物线型;Cd2+在体内、体外染毒对毛蚶肌肉SOD活性诱导曲线均不呈抛物线型,低浓度Cd2+对毛蚶SOD活性表现为显著诱导,随后曲线迅速下降,表明毛蚶对Cd2+污染反应十分敏感,也表明Cd2+对毛蚶毒性作用较强,3种毒物对毛蚶的毒性强弱次序为,Cd2+,0＃柴油、二甲苯.     

DMS and SO2 Measurements in the Tropical Marine Boundary Layer

Dimethyl sulfide (DMS) and sulfur dioxide (SO₂) mixing ratios were measured in the boundary layer on Oahu, Hawaii in April and May 2000. Average DMS and SO₂ levels were 22 ± 7 (n = 488) pmol/mol and 23 ± 7 (n = 471) pmol/mol respectively. Anti-correlated DMS and SO₂ diurnal cycles, consistent with DMS + OH oxidation were observed on most days. Photochemical box model simulations suggest that the yield of SO₂ and total SO₂ sink are ∼85% and ∼2 × 10⁴ molec cm^{− 3} s^{− 1} respectively. On several days the rate of decrease in DMS and increase in SO₂ levels in the early morning were larger that predicted by the model. Dynamical and chemical causes for the anomalous early morning data are explored.     

Atmospheric Loss Processes of Dimethyl and Diethyl Carbonate

A combined study of the OH gas phase reaction and uptake on aqueous surfacesof two carbonates, dimethyl and diethyl carbonate has been carried out todetermine the atmospheric lifetimes of these compounds. Rate coefficients havebeen measured for gas phase reactions of OH radicals with dimethyl and diethylcarbonate. The experiments were carried out using pulsed laser photolysis– laser induced fluorescence over the temperature range 263–372K and the kinetic data were used to derive the following Arrhenius expressions(in units of cm³ molecule^–1 s^–1):for dimethyl carbonate, k₁ = (0.83±0.27)×10^–12 exp [–(247± 98)/T] and fordiethyl carbonate, k₂ = (0.46±0.15)×10^–12 exp [(503± 203)/T]. At 298 K, therate coefficients obtained (in units of 10^–12 cm³molecule^–1 s^–1) are: k₁ =(0.35± 0.04) and k₂ = (2.31± 0.29). The results arediscussed in terms of structure-activity relationships.The uptake coefficients of both carbonates on aqueous surfaces were measuredas a function of temperature and composition of the liquid phase, using thedroplet train technique coupled to a mass spectrometric detection. Dimethyland diethyl carbonate show very similar results. For both carbonates, themeasured uptake kinetics were found to be independent of the aqueous phasecomposition (pure water, NaOH solutions) but dependent on gas-liquid contacttime which characterises a surface saturation effect. The uptake coefficientvalues show a slight negative temperature dependence for both carbonates.These values vary from 1.4×10^–2 to0.6×10^–2 in the temperature range of 265–279 Kfor dimethyl carbonate, from 2.4×10^–2 to0.9×10^–2 in the temperature range of 270–279 Kfor diethyl carbonate. From the kinetic data, the following Henry's lawconstants were derived between 279 and 265 K: dimethyl carbonate,H₁ = 20–106 M atm^–1; and diethyl carbonate,H₂ = 30–98 M atm^–1. The reported data showthat the OH reaction is the major atmospheric loss process of these twocarbonates with lifetimes of 33 and 5 days, respectively, while the wetdeposition is a negligible process.     

Measurements of various sulphur gases in a coastal marine environment

Measurements of several sulphur gases have been made in coastal seawaters (including microlayers) and marine air off Great Yarmouth, U.K., and in a freshwater lake. The results show dimethyl sulphide to be the dominant sulphur gas in all the waters examined, with lesser amounts of carbonyl sulphide and carbon disulphide. For the marine air and water samples carbonyl sulphide showed no significant seasonal variation in concentration. The seawater was always supersaturated with respect to the carbonyl sulphide concentration in the air; the mean saturation value being 4.6. Likewise the seawater was always supersaturated with dimethyl sulphide, but for this gas the concentrations in the water showed substantial seasonal variation (× 40), with a maximum value of about 500 ng(S) l^-1 in late June, approximately contemporaneous with the second plankton bloom in the region.Sea surface microlayers harvested cryogenically showed a mean enrichment of 2.4 relative to subsurface water for carbonyl sulphide. Some part of the observed microlayer enrichment for this gas may be due to freezing-on of atmospheric carbonyl sulphide onto the frozen microlayer sample. In general, microlayer samples did not exhibit a significant enrichment for dimethyl sulphide. However, under conditions of high biological production, enrichments of several-fold were found, but may be attributable, at least in part, to biological production of dimethyl sulphide in the microlayer water in the period between collection and analysis.