顶空气相色谱法测定海水二甲基硫和浮游植物细胞二甲基硫丙酸的研究

建立了顶空ＧＣ／ＦＰＤ测定海水中二甲基硫（ＤＭＳ）和浮游植物细胞中二甲基硫丙酸（ＤＭＳＰ）的方法，并研究盐度、温度、气液相比ＤＭＳ诸因素对ＤＭＳ顶空灵敏度的影响。该法对ＤＭＳ测定的相对标准偏差均小于６％，平均回收率为１０６％，最低检出限为２０ｎｇ／Ｌ。细胞ＤＭＳＰ先经碱作用转化为ＤＭＳ，在５０℃下作用时间不少于６ｈ，峰高与浓度的双对数线性相关系数大于０．９９。对１９９４年冬、１９９５年夏采自胶州湾     

Effects of salinity downshock on dimethylsulfide production

During time-series observations in Sagami Bay, Japan, the concentration of dissolved dimethylsulfoniopropionate (DMSP_d), a precursor of dimethylsulfide (DMS), was negatively correlated with salinity. In the laboratory, low-salinity shock reduced DMS production rates of the natural bacterial community and induced rapid DMSP release from a dinophyte, Heterocapsa triquetra, suggesting that low-salinity shock reduced DMSP_d consumption but enhanced DMSP_d production, which agrees with the negative correlation between DMSP_d and salinity observed in Sagami bay. In addition, low-salinity shock did not affect DMSP lyase activity of H. triquetra. Low-salinity shock would increase the contribution from algae in DMS production, leading to an increase in potential DMS productivity in the environment.     

Simple determination of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) using solid-phase microextraction and gas chromatography-mass spectrometry

Solid-phase microextraction (SPME) is a simple, sensitive and less destructive method for the determination of dimethylsulfide (DMS) in seawater. Combined with detection by gas chromatography-mass spectrometry (GC-MS), the method had sufficient sensitivity (minimum detectable concentration of DMS was 0.05 nM), and practical levels of reproducibility (relative standard deviation ≤7%) and linearity (r ² > 0.995) over a wide concentration range (0.5 to 910 nM). The protocol developed was applied to a Sagami Bay water sample to determine concentrations of DMS and DMSP, and in situ DMSP-lyase activity.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

Seasonal variation of atmospheric dimethylsulfide at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric concentrations of dimethylsulfide (DMS) were carried out for two years in a marine site at remote area: the Amsterdam Island (37°50S–77°31E) located in the southern Indian Ocean. DMS concentrations were also measured in seawater. A seasonal variation is observed for both DMS in the atmosphere and in the sea-surface. The monthly averages of DMS concentrations in the surface coastal seawater and in the atmosphere ranged, respectively, from 0.3 to 2.0 nmol l^-1 and from 1.4 to 11.3 nmol m^-3 (34 to 274 pptv), with the highest values in summer. The monthly variation of sea-to-air flux of DMS from the southern Indian Ocean ranges from 0.7 to 4.4 mol m^-2 d^-1. A factor of 2.3 is observed between summer and winter with mean DMS fluxes of 3.0 and 1.3 mol m^-2 d^-1, respectively.     

2010年夏、秋季胶州湾浮游动物对表层海水中DMS分布的影响

于2010年7~11月对胶州湾夏、秋季浮游动物种类和丰度进行现场调查,并分析讨论了胶州湾夏、秋季浮游动物丰度的水平分布与环境因子(温度、盐度、水深、叶绿素a)和二甲基硫(DMS)、溶解态β-二甲基巯基丙酸内盐(DMSPd)、颗粒态β-二甲基巯基丙酸内盐(DMSPp)的相关性。结果表明,胶州湾浮游动物丰度分布不均匀,8月湾内西部沿岸海域C1站位出现调查期间的动物丰度最大值(656.1ind/m3),最小值(1.492ind/m3)出现在10月胶州湾东北部的A2站位。浮游动物丰度具有明显的季节变化,秋季浮游动物丰度低于夏季浮游动物丰度。浮游动物丰度与盐度、叶绿素a含量、细菌生物量的相关性不明显,2010年10月浮游动物丰度与DMS呈显著正相关(P0.05),11月的浮游动物丰度与DMSPp呈显著正相关(P0.05),其它月份(7、8、9月)的浮游动物丰度与DMS、DMSPd、DMSPp浓度的相关性均不明显。由于浮游动物摄食活动对DMS释放的影响受多种因素的制约,因此浮游动物与DMS的相互作用需要进一步研究。     

Biogeochemical Variation in Dimethylsulfide, Phytoplankton Pigments and Heterotrophic Bacterial Production in the Subarctic North Pacific during Summer

Dimethylsulfide (DMS), chlorophyll a (Chl-a), accessory pigments (fucoxanthin, peridinin and 19-hexanoyloxyfucoxanthin), and bacterial production (BP) were measured in the surface layer (0–100 m) of the subarctic North Pacific, including the Bering Sea, during summer (14 July–5 September, 1997). In surface sewater, the concentrations of DMS and Chl-a varied widely from 1.3 to 13.2 nM (5.1 ± 3.0 nM, mean ± S.D., n = 48) and from 0.1 to 2.4 µg L^–1 (0.6 ± 0.6 µg L^–1, n = 24), respectively. In the subarctic North Pacific, DMS to Chl-a ratios (DMS/Chl-a) were higher on the eastern side than the western side (p < 0.0001). Below the euphotic zone, DMS/Chl-a ratios were law and the correlation between DMS and Chl-a was relatively strong (r ² = 0.700, n = 27, p < 0.0001). In the euphotic zone, DMS/Chl-a ratios were higher and the correlation between DMS and Chl-a was weak (r ² = 0.128, n = 50, p = 0.01). The wide variation in DMS/Chl-a ratios would be at least partially explained by the geographic variation in the taxonomic composition of phytoplankton, because of the negative correlation between DMS/Chl-a and fucoxanthin-to-Chl-a ratios (Fuc/Chl-a) (r ² = 0.476, n = 26, p = 0.0001). Furthermore, there was a positive correlation between DMS and BP (r ² = 0.380, n = 19, p = 0.005). This suggests that BP did not represent DMS and dimethylsulfoniopropionate (DMSP) removal by bacterial consumption but rather DMSP degradation to DMS by bacterial enzyme.     

海水温度对衰亡期浒苔释放生源硫影响的模拟研究

为研究浒苔释放生源硫的特征,本文对采集于黄海绿潮中期和末期的浒苔进行了实验室模拟培养,探讨了不同温度对衰亡期浒苔释放生源硫化物的影响。实验结果表明,在10~25℃温度范围内,温度升高能够加速浒苔的衰亡。二甲基硫（DMS）的平均释放速率范围为2.79~150.70 nmol/（L·g·d）,二甲基硫基丙酸内盐（DMSP）的平均释放速率范围为2.16~113.26 nmol/（L·g·d）。温度升高能够使DMS和DMSP的释放速率加快,释放量增加,DMS最大平均释放速率在25℃条件下比10℃条件下升高了约60%,培养液中DMS浓度升高了2~3倍。采集于绿潮末期的浒苔培养液中的DMS和DMSP和采集于绿潮中期的浒苔相比,浓度有所增加,采集于浒苔绿潮末期浒苔培养液中DMS的最高平均浓度为418.41 nmol/L,约为中期的4倍;DMSP的最高平均浓度为316.14 nmol/L,是中期的3倍。浒苔绿潮的爆发会对水体中的硫体系循环产生影响,进而影响该海域生态环境。     

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.     

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.