黄、渤海二甲基硫化物的浓度分布与迁移转化速率研究

于2015年8-9月对黄、渤海海域进行现场调查，研究了海水中二甲基硫（DMS）、β-二甲巯基丙酸内盐（DMSP）、二甲亚砜（DMSO）的浓度分布、相互关系及影响因素，测定了DMS的生物生产与消耗、光化学氧化和海-气扩散速率，对DMS的迁移转化速率进行综合评价。结果表明:表层海水中DMS、溶解态DMSP（DMSPd）、颗粒态DMSP（DMSPp）、溶解态DMSO（DMSOd）和颗粒态DMSO（DMSOp）浓度的平均值分别为（6.12±3.01）nmol/L、（6.03±3.45）nmol/L、（19.47±9.15）nmol/L、（16.85±8.34）nmol/L和（14.37±7.47）nmol/L，整体呈现近岸高远海低，表层高底层低的趋势。DMS、DMSPd和DMSOp浓度与叶绿素（Chl a）浓度存在显著的相关性。表层海水中DMS光氧化速率顺序为:k_UVA > k_UVB > k_可见，其中UVA波段占光氧化的70.8%。夏季黄、渤海微生物消耗、光氧化及海-气扩散对DMS去除的贡献率分别为32.4%、34.5%和33.1%，表明3种去除途径作用相当。黄、渤海DMS海-气通量变化范围为0.79~48.45 μmol/（m2·d），平均值为（11.87±11.35）μmol/（m2·d）。     

海水中二甲基硫的光化学氧化研究

二甲基硫(DMS)是海洋中最重要的挥发性生源硫化物,其在大气中的氧化产物会对全球气候变化和酸雨的形成产生重要影响。海水中DMS的光化学氧化,作为一个重要的去除途径,是控制海水中DMS浓度的重要因素。这个复杂的动态过程会受到光照、深度、海水中的溶解无机和有机物这些物理、化学因素的影响。根据光化学降解在DMS的全球生物地球化学循环中的重要作用,作者综述了国际海洋科学工作者近20年来在海水中DMS光化学研究方面的最新进展。     

海水中无机氮

海水中无机氮主要包括NO_3-N、NO_2-N及NH_4-N。它是浮游植物所必须的营养盐之一。浮游植物大量繁殖时,海水中的无机氮下降,其中NO_3-N可被消耗殆尽;浮游植物又是浮游动物的饵料,其排泄物或残骸分解释放的有机氮经细菌作用转化成无机氮而使海水中无机氮得以再生无机氮在不同环境下经细菌或酶进行硝化或反硝化而互相转化。海水的垂直对流作用,使底部再生的无机氮补充到上层。此     

冷泉渗漏区海底微生物作用及生物标志化合物

在有冷泉活动和水合物产出的海底环境中,甲烷氧化古细菌和硫酸盐还原细菌十分发育,它们主导着海底天然气(主要是甲烷)的缺氧氧化作用,并在海底碳循环和生物种群繁衍中发挥着重要作用。海底天然气渗漏活动区的甲烷氧化古细菌使渗漏CH4缺氧氧化为HCO3-,硫酸盐还原细菌使SO42-转化为HS-,从而使细菌微生物获得生命所需的能量,生物种群得以发育和繁衍。甲烷氧化古细菌有ANME-1、ANME-2、ANME-3三个种群,形成相应的醚类异戊二烯类和类异戊二烯烃类生物标志物。硫酸盐还原细菌有Desulfosarcina和Desulfococcus两个主要的细菌群落,形成二烃基甘油二醚和脂肪酸生物标志化合物。这种天然气渗漏区内微生物活动产生的生物标志化合物都具有特别负的碳同位素组成,δ13C值为-41.1‰~-95.6‰,说明微生物群落在生命代谢过程中摄取了来自甲烷的碳,同时也反映了天然气渗漏系统缺氧带存在的古细菌和硫酸盐还原细菌活动。     

第六节 海水中无机氮

海水中无机氮主要包括NO3-N、NO2-N及NH4-N。它是浮游植物所必须的营养盐之一。浮游植物大量繁殖时，海水中的无机氮下降，其中NO3-N可被消耗殆尽，浮游植物又是浮游动物的饵料，其排泄物或残骸分解释放的有机氮经细菌作用转化成无机氮而使海水中无机氮得以再生无机氮在不同环境下经细菌或酶进行硝化或反硝化而互相转化。     

海洋底栖动物的环境修复作用

底栖动物的生物沉降作用能够促进悬浮颗粒物的沉降过程以及海水-沉积物界面间的营养盐交换,因此可以净化水体中的悬浮物、溶解性有机碳和营养盐等;底栖动物的生物扰动作用可以改变沉积物的物理化学性质,影响水层-沉积层的物质交换和能量传递,因此通过影响沉积物的氧化还原条件、菌群结构以及污染物的降解特性来促进污染物的降解转化过程;同时,底栖动物的摄食及消化过程可以提高污染物的生物可利用性以及外源酶的生物转化,从而对海洋环境修复产生促进作用。     

胶州湾海水中DMS和DMSP的分布及其影响因素

为了解人为活动对二甲基硫(DMS)和二甲巯基丙酸(DMSP)生物生产的干扰,分别于2005年8月、11月对胶州湾海域进行采样。测定结果表明:胶州湾海水中8月DMS、DMSPd和DMSPp在次表层的平均含量分别为4.89,17.9和23.93nmol·L-1,在微表层中的平均含量分别为4.58,19.98和21.49nmol·L-1,11月DMS、DMSPd和DMSPp在次表层的平均含量分别为2.07,12.99和16.74nmol·L-1,在微表层中的平均含量分别为1.44,16.13和19.62nmol·L-1。DMS和DMSP的水平分布由于受到陆源输入的影响,呈现出自湾内向湾外递降的趋势。DMS和DMSP的含量夏季高于秋季。DMS和Chl-a在每个季节具有一定的相关性。DMS浓度的增加导致DMS通量增加。对海水微表层和次表层的研究表明,DMS和DMSPp并未在微表层中富集,而DMSPd有一定程度的富集。DMS,DMSP,Chl-a在海水微表层和次表层之间浓度分布的相关性体现了2层水体之间存在强烈的交换作用。     

海水中痕量DMS和DMSP分析方法的研究

二甲基硫（DMS）是海洋排放的占优势地位的生源硫气体,其在大气中的氧化产物能够影响到环境酸化和世界的气候变化.因此, 测定海水中的DMS对于准确地评价其在全球硫循环所起的重要作用具有重要意义.本文中作者研究了海水中DMS的痕量分析技术.海水中的DMS首先采用气提-冷阱捕集技术进行预浓缩, 然后用带有火焰光度检测器的气相色谱（GC-FPD）进行分析.该方法的精确度在5%以内, 平均回收率为85.6% （82.8%-90.5%）, 最小检出限为0.15 ng S.β-二甲基巯基丙酸内盐（DMSP）的分析是通过将其在碱性溶液中分解成DMS来进行.作者采用此方法实测了黄海中DMS和DMSP的含量, 获得了理想的结果.     

海洋浮游细菌生长率和被摄食的研究综述

海洋浮游细菌利用海水中的溶解有机碳合成自身物质,是海洋浮游生态系统的二次生产者。微型浮游动物是细菌的主要摄食者,也是细菌生产向较高营养级传递的中介。研究海洋浮游细菌的生长率和被(微型浮游动物的)摄食率对理解海洋浮游生态系统的功能具有重要作用。本文综述了利用改变海水中生物类群组成(或功能)的培养方法研究海洋浮游细菌生长率和被摄食率的历程和现状,为我国的同类研究提供借鉴。改变海水中生物类群组成(或功能)进行培养的方法有海水分粒级培养、海水稀释培养和添加选择性抑制剂培养。这些方法各有其局限性,应用并不广泛。细菌及其主要摄食者异养鞭毛虫群落在自然海区和实验室内都有生长周期,鞭毛虫的生长周期落后于细菌,因此细菌的生长率有时会小于被摄食率,有时会大于被摄食率。我国这方面的研究相对落后,应值得引起重视,建议从海水稀释培养法入手开展相关研究。     

锰细菌对锰、铁金属离子的转移作用

本文报道了锰细菌对锰的氧化和铁的氧化还原作用的实验结果.在好氧的条件下锰细菌能使可溶性的Mn2+氧化为Mn4+.在锰细菌的生长繁殖过程中其环境的pH不断升高,更有利于锰的氧化;环境的温度升高可加快细菌对锰的氧化速度.锰细菌在含低价铁的培养液中可以较快地把Fe2+氧化为Fe3+,它的氧化速度要比锰的氧化速度快;在厌氧的培养条件下,锰细菌可将溶液中的高价铁还原为低价铁,而且使其环境的pH明显下降.     

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.     

Distribution of biogenic sulphur compounds during and just after the southwest monsoon in the Arabian Sea

The Arabian Sea is characterised by strong seasonal oscillations of biological productivity generated by its monsoonal climate. The southwest monsoon causes reversal in the surface circulation of the Arabian Sea, which generates a seasonal upwelling of nutrient-rich waters along the coast of Oman. Concentrations of biogenic sulphur compounds were measured on a transect from the eutrophic waters off the coast of Oman to the oligotrophic waters of the open Arabian Sea, during the UK NERC Arabesque cruise 27 August–4 October 1994. The concentrations of dimethylsulphide (DMS), dimethylsulphoxide (DMSO) and dimethylsulphoniopropionate (DMSP) were found to be elevated in the eutrophic area due to enhanced biological production. However, this increase in DMS, DMSO and DMSP concentration was not observed until after the southwest monsoon had relaxed, and appeared to correspond to increased concentrations of hexanoyloxyfucoxanthin, an indicator of prymnesiophytes. DMSO concentrations were correlated with those of DMS and DMSP in the near surface waters of the Arabian Sea. Additionally, DMSO appeared to be ubiquitous throughout the water column, being easily detectable in deep waters, which suggests that DMSO may act as a sink for DMS in the world’s oceans.     

海洋中二甲基硫的生物生产与消费过程

DMS是海洋中最主要的挥发性有机硫化物,对全球气候变化和环境酸化产生重要影响。DMS的生物生产与消耗主要发生在海洋真光层。生物的生产与消耗被认为是海洋中DMS的主要来源和去除途径。海洋中DMS的生物生产和消耗是密切相关的,两者的速率基本保持平衡。目前,有关DMS生物生产与消费速率的测定方法有放射性同位素示踪和加抑制剂2种,后者颇受青睐,不过有关抑制机理还需进一步的研究。     

Spatial distributions of dimethylsulfide in the South China Sea

The concentration of dimethylsulfide (DMS) and supporting parameters were determined in surface seawater and vertical profiles at 26 stations in the South China Sea. The concentrations of DMS in surface seawater ranged from 61 to 148 ng S/l, with a mean of 82 ng S/l. High concentrations of DMS were found in the productive regions. The vertical profiles of DMS were characterized by a maximum at depths typically between 20 and 75 m. The concentrations of DMS were correlated with the levels of chlorophyll a both in the surface seawater and in the vertical distribution. The concentrations of DMS were higher than expected for this chlorophyll-poor tropical sea, as indicated by markedly high DMS (ng S/l)/chlorophyll a (μg/l) ratios ranging from 315 to 3524 with a mean of 1768 for all the surface seawater samples. DMS concentration was significantly correlated with seawater temperature and dissolved oxygen, but it showed an inverse relationship to nutrients (including nitrate, phosphate and silicate). On the basis of sea surface concentrations of DMS and gas exchange calculations, the mean flux of DMS from the South China Sea to the atmosphere was estimated to be 5.5 μmol m⁻² d⁻¹.     

Photochemical oxidation of dimethylsulfide in seawater

Dimethylsulfide(DMS) is generally thought to be lost from the surface oceans by evasion into the atmosphere as well as consumption by microbe.However,photochemical process might be important in the removal of DMS in the oceanic photic zone.A kinetic investigation into the photochemical oxidation of DMS in seawater was performed.The photo-oxidation rates of DMS were influenced by various factors including the medium,dissolved oxygen,photosensitizers,and heavy metal ions.The photo-oxidation rates of DMS were higher in seawater than in distilled water,presumably due to the effect of salinity existing in seawater.Three usual photosensitizers(humic acid,fulvic acid and anthroquinone),especially in the presence of oxygen,were able to enhance the photo-oxidation rate of DMS,with the fastest rate observed with anthroquinone.Photo-oxidation of DMS followed first order reaction kinetics with the rate constant ranging from 2.5×10-5 to 34.3×10-5 s-1.Quantitative analysis showed that approximately 32% of the photochemically removed DMS was converted to dimethylsulfoxide.One of the important findings was that the presence of Hg2 could markedly accelerate the photo-oxidation rate of DMS in seawater.The mechanism of mercuric catalysis for DMS photolysis was suggested according to the way of CTTM(charge transfer to metal) of DMS-Hg2 complex.     

Complexation of dimethylsulfide with mercuric ion in aqueous solutions

The tendency of dimethylsulfide (DMS) to form complexes with heavy metal ions in aqueous solutions and the factors that influence it have been investigated. Among five heavy metal ions examined (Cu²⁺, Cd²⁺, Zn²⁺, Pb²⁺ and Hg²⁺), only Hg²⁺ bound significantly with DMS in aqueous solutions in which Hg²⁺ concentration was increased to much higher levels than that of natural seawater. The complexation capacity of Hg²⁺ for DMS was influenced by pH and media. The affinity of Hg²⁺ for DMS was generally lower at high than at low pH, presumably due to the competition of hydroxide ion to form hydroxomercury species. In different solutions, the affinity of Hg²⁺ for DMS followed the following sequence: ultra-purified water > 35‰ NaCl solution > seawater. It seems apparent that chloride had a negative impact on the complexation of DMS by Hg²⁺, owing to the competition of chloride with DMS for complexing Hg²⁺. In addition, the affinity of Hg²⁺ for DMS in the bulk seawater appeared to be higher than that in the surface microlayer seawater. The tendency of Hg²⁺ to form complexes with DMS in aqueous solution can be reduced by the presence of 2 mM amino-acid such as glycine, alanine, serine and cysteine, as these ligands give stable mercury complexes. However, the presence of 2 mM acetate in experimental solutions had no significant effect on the complexation of Hg²⁺ with DMS, even though this ligand has a relatively strong complexing capacity for Hg²⁺. Although mercury ions appeared to have a strong affinity for DMS, the concentration of mercury in seawater is too low to produce a great effect on the distribution of DMS in oceans.     

Factors determining the vertical profile of dimethylsulfide in the Sargasso Sea during summer

The major source of reduced sulfur in the remote marine atmosphere is the biogenic compound dimethylsulfide (DMS), which is ubiquitous in the world's oceans and released through food web interactions. Relevant fluxes and concentrations of DMS, its phytoplankton-produced precursor, dimethylsulfoniopropionate (DMSP) and related parameters were measured during an intensive Lagrangian field study in two mesoscale eddies in the Sargasso Sea during July–August 2004, a period characterized by high mixed-layer DMS and low chlorophyll—the so-called ‘DMS summer paradox’. We used a 1-D vertically variable DMS production model forced with output from a 1-D vertical mixing model to evaluate the extent to which the simulated vertical structure in DMS and DMSP was consistent with changes expected from field-determined rate measurements of individual processes, such as photolysis, microbial DMS and dissolved DMSP turnover, and air–sea gas exchange. Model numerical experiments and related parametric sensitivity analyses suggested that the vertical structure of the DMS profile in the upper 60 m was determined mainly by the interplay of the two depth-variable processes—vertical mixing and photolysis—and less by biological consumption of DMS. A key finding from the model calibration was the need to increase the DMS(P) algal exudation rate constant, which includes the effects of cell rupture due to grazing and cell lysis, to significantly higher values than previously used in other regions. This was consistent with the small algal cell size and therefore high surface area-to-volume ratio of the dominant DMSP-producing group—the picoeukaryotes.     

New and important roles for DMSP in marine microbial communities

The algal osmolyte dimethylsulfoniopropionate (DMSP) is recognised as the major precursor of marine dimethylsulfide (DMS), a volatile sulfur compound that affects atmospheric chemistry and global climate. Recent studies, using ³⁵S-DMSP tracer techniques, suggest that DMSP may play additional very important roles in the microbial ecology and biogeochemistry of the surface ocean. DMSP may serve as an intracellular osmolyte in bacteria that take up phytoplankton-derived DMSP from seawater. In addition, DMSP appears to support from 1 to 13% of the bacterial carbon demand in surface waters, making it one of the most significant single substrates for bacterioplankton so far identified. Furthermore, the sulfur from DMSP is efficiently incorporated into bacterial proteins (mostly into methionine) and DMSP appears to be a major source of sulfur for marine bacterioplankton. Assimilatory metabolism of DMSP is via methanethiol (MeSH) that is produced by a demethylation/demethiolation pathway which dominates DMSP degradation in situ. Based on the linkage between assimilatory metabolism of DMSP and bacterial growth, we offer a hypothesis whereby DMSP availability to bacteria controls the production of DMS by the competing DMSP lyase pathway. Also linked with the assimilatory metabolism of DMSP is the production of excess MeSH which, if not assimilated into protein, reacts to form dissolved non-volatile compounds. These include sulfate and DOM–metal–MeSH complexes, both of which represent major short-term end-products of DMSP degradation. Because production rates of MeSH in seawater are high (3–90 nM d⁻¹), reaction of MeSH with trace metals could affect metal availability and chemistry in seawater. Overall, results of recent studies provide evidence that DMSP plays important roles in the carbon, sulfur and perhaps metal and DOM cycles in marine microbial communities. These findings, coupled with the fact that the small fraction of DMSP converted to DMS may influence atmospheric chemistry and climate dynamics, draws attention to DMSP as a molecule of central importance to marine biogeochemical and ecological processes.     

二甲基硫的海洋化学研究

二甲基硫（ＤＭＳ） 是海洋排放到大气中的最主要的生源硫化物。作者综述了ＤＭＳ在海洋中的分布特征、影响ＤＭＳ转化的因素、ＤＭＳ的海空扩散及其对环境的影响等。ＤＭＳ在海洋中存在很大程度的时空变化,这一变化不仅与海洋初级生产力水平有关,而且还与浮游植物的种类组成密切相关。微生物的降解、光化学的氧化以及海空扩散是ＤＭＳ在海洋中迁移变化的三个最重要的途径。ＤＭＳ的海－ 空扩散也存在较大的时空变化。ＤＭＳ的释放会对全球的气候变化和酸雨的形成产生重要的影响。本文同时就国内外的研究现状和今后的研究方向进行了分析和总结。     

Depth-dependent fate of biologically-consumed dimethylsulfide in the Sargasso Sea

Biological consumption is a major sink for dimethylsulfide (DMS) in the surface ocean, but the fate of DMS is poorly known. We determined the fate of sulfur from biologically consumed DMS in samples from the upper 60 m of the Sargasso Sea during July 2004. Using tracer levels of ³⁵S-DMS in dark incubations we found that DMS was transformed into three identifiable non-volatile, sulfur-containing product pools: dimethylsulfoxide (DMSO), sulfate, and particle-associated macromolecules. Together, DMSO and sulfate accounted for most (81–93%) of the non-volatile sulfur products. Only a small fraction (∼ 2%) of the consumed DMS-sulfur was recovered in cellular macromolecules, leaving 5–17% of the metabolic products of DMS consumption unidentified. The relative importance of the two major products varied with depth. DMSO was the main sulfur product (∼ 72%) from DMS metabolism in the surface mixed layer, whereas sulfate was the most important product (∼ 74%) below the mixed layer. Changes in temperature and photosynthetically-active radiation (PAR) did not cause shifts in DMS fate in short term incubations (7–12 h), however these or other factors (e.g., exposure to ultraviolet radiation), operating over longer time scales, could potentially influence the observed pattern of DMS fate with depth. Biological DMSO production rates ranged from 0.07 to 0.33 nM day^− 1, with the highest rate found at 30 m, just below the surface mixed layer. With DMSO concentrations ranging from 4.0 to 8.6 nM, turnover times for DMSO were long (15–61 days) when only the biological production from DMS was considered. Identification of the main sulfur containing products from DMS metabolism improves understanding of this important process in the marine sulfur cycling. Detection and quantification of DMSO production from biological DMS consumption also provides a more complete picture of DMSO biogeochemistry in the ocean.