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.     

胶州湾浮游动物的时空分布

根据2003年1—12月在胶州湾所获得的浮游动物样品,鉴定出浮游动物71种,幼虫、幼体34类。分析了该海域浮游动物的分布﹑时空变化及其与生态环境因子的关系,同相关历史资料进行了比较,结果表明,浮游动物的种类多样性符合中纬度海湾水域浮游动物分布的一般规律,生态属性以暖温带、近岸低盐种类为主。浮游动物生物量和丰度的分布具明显的季节性变化,生物量平均为84.28mg/m3,饵料生物丰度平均为531.76个/m3,非饵料生物为72.08个/m3。浮游动物生物量和饵料生物丰度的分布季节变化与海水平均温度的季节变化节律基本一致,相关回归分析亦证实与温度的关系更为密切。浮游动物生物量的时空分布﹑种类多样性的变化趋势,近20a来基本相同,高峰出现时间的差异,主要是受温度年季和季节变化差异因素的影响。     

挪威海和格陵兰海海水DMS分布特征及影响因素研究

于2012年7—9月现场测定了北极挪威海和格陵兰海区域海水二甲基硫(DMS)及其前体物质二甲巯基丙酸内盐(DMSP,分溶解态DMSPd和颗粒态DMSPp)的含量,研究了其空间分布格局及其影响因素,探讨了表层海水DMS的生物周转和去除途径。结果表明,表层海水DMS、DMSPd和DMSPp的平均浓度分别为5.36nmol/L、15.63nmol/L和96.73nmol/L,受挪威海流和北极深层水影响,表层海水二甲基硫化物浓度呈现出由低纬度向高纬度海域递减的趋势。DMSPd和DMSPp浓度与Chl a浓度均有显著的相关性,说明浮游植物生物量是影响挪威海和格陵兰海二甲基硫化物生产的重要因素。表层海水DMS生物生产和消费速率平均值分别为18.19nmol/(L·d)、15.67nmol/(L·d)。DMS微生物周转时间变化范围为0.03~1.80d,平均值为0.49d,DMS海-气周转时间是微生物消费时间的90倍,说明夏季挪威海和格陵兰海表层海水中DMS微生物消费过程是比海-气扩散更具优势的去除机制。     

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。     

胶州湾及青岛近海微表层与次表层中二甲基硫(DMS)与二甲巯基丙酸(DMSP)的浓度分布

以胶州湾及青岛近海为研究区域,利用吹扫-捕集气相色谱法研究了二甲基硫(DMS)和二甲巯基丙酸(DMSP,分为溶解态DMSPd和颗粒态DMSPp)在微表层与次表层中的浓度以及它们在微表层中的富集行为。结果表明,DMS、DMSPd和DMSPp在微表层中的浓度高于次表层,它们在微表层中的富集因子分别为1.17、1.84和1.51。研究发现,DMS及DMSPp浓度与叶绿素a(Chl-a)浓度有很好的相关性,但它们的周日变化与Chl-a并不完全同步。DMS/Chl-a和DMSPp/Chl-a的比值在次表层和微表层分别为4.35、13.47mmol/g和3.99、15.88mmol/g。胶州湾及青岛近海生态环境受人为活动干扰严重,使本海域DMS含量较高,从而贡献出较大的DMS海-气通量。     

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。     

海洋中DMSP的研究进展

DMSP(dimethylsulfoniopropionate，β-二甲基巯基丙酸内盐)作为DMS(dimethylsulfide,二甲基硫)的前体，是1种重要的生源硫化物。根据其在海洋生态系统和生物地球化学循环中所起着的重要作用，作者综述了国内外海洋科学工作者十几年来在EMSP研究方面的进展。     

胶州湾浮游动物生物完整性指数的建立

为补充中国海湾环境质量状况评估方法,作者通过整理和综合胶州湾常规监测项目中6年(2003~2008)的监测数据,经数据整理与综合、生境区域划分、评价因子选择、因子阈值确定、指数建立、指数验证与应用6个过程,初步建立了胶州湾浮游动物生物完整性指数(指数存在季节性差异,本实验以夏秋季节为例)。指数建立过程中将生境区域通过溶解性无机氮(DIN)、磷酸盐(PO_4)及透明度3项指标划分为参照区和受损区,低营养盐、高透明度海域划为参照区,相反则划为受损区。通过检验11项浮游动物因子参照区与受损区的差异性,最终确定7项为指数建立的评价因子。对7项评价因子得分加权平均即得胶州湾浮游动物生物完整性指数得分。将指数得分划分为5个等级,分别表征不同的浮游动物要素质量状况。胶州湾浮游动物生物完整性指数的建立为从浮游动物角度评估胶州湾环境质量提供了新的方法,是对胶州湾生态环境质量综合评价的良好补充,能够更全面地反映海区浮游动物的质量状况,同时为发展和完善海湾生态系统质量综合评价体系奠定良好基础。     

胶州湾表层沉积物中甲藻孢囊的分布

为了解胶州湾表层沉积物中甲藻孢囊的分布特征,于2015年7月采集胶州湾12个站位的表层沉积物进行甲藻孢囊分析,共鉴定甲藻孢囊37种(分属5个类群)和2种未定种,包括自养型20种和异养型17种,优势种为膝沟藻。其Shannon-Wiener多样性指数[H′(log2)]介于2.84—3.91,平均值为3.42;均匀度指数介于0.75—0.98,平均值为0.88,总体值较高。胶州湾海域各站位的甲藻孢囊丰度介于96—969cyst/g DW(干重),平均丰度为401cyst/g DW,呈现出临近湾口处丰度较高,而湾内较低的空间分布差异特征。尤其值得注意的是,有两种产虾夷扇贝毒素(Yessotoxin,YTX)甲藻[具刺膝沟藻(Gonyaulax spinifera)和多边舌甲藻(Lingulodinium polyedrum)]的孢囊和3种产麻痹性贝类毒素(PSP)甲藻[塔玛/链状亚历山大藻(Alexandrium catenella/tamarense)、微小/相似亚历山大藻(A.minutum/affine)和链状裸甲藻(Gymnodinium catenatum)]的孢囊在胶州湾海域大多数站位均有分布,尽管其数量不高,但其广泛的分布范围仍需引起我们的重视。     

Seasonal variations of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) in the sea-surface microlayer and subsurface water of Jiaozhou Bay and its adjacent area

The distributions of DMS and its precursor dimethylsulfoniopropionate, in both dissolved (DMSP_d) and particulate fractions (DMSP_p) were determined in the seasurface microlayer and corresponding subsurface water of the Jiaozhou Bay, China and its adjacent area in May and August 2006. The concentrations of all these components showed a clear seasonal variation, with higher concentrations occurring in summer. This can be mainly attributed to the higher phytoplankton biomass observed in summer. Simultaneously, the enrichment extents of DMSP_d and DMSP_p in the microlayer also exhibited seasonal changes, with higher values in spring and lower ones in summer. Higher water temperature and stronger radiant intensity in summer can enhance their solubility and photochemical reaction in the microlayer water, reducing their enrichment factors (the ratio of concentration in the microlayer to that in the corresponding subsurface water). A statistically significant relationship was found between the microlayer and subsurface water concentrations of DMS, DMSP and chlorophyll a, demonstrating that the biogenic materials in the microlayer come primarily from the underlying water. Moreover, our data show that the concentrations of DMSP_p and DMS were significantly correlated with the levels of chlorophyll a, indicating that phytoplankton biomass might play an important role in controlling the distributions of biogenic sulfurs in the study area. The ratios of DMS/chlorophyll a and DMSP_p/chlorophyll a varied little from spring to summer, suggesting that there was no obvious change in the proportion of DMSP producers in the phytoplankton community. The mean sea-to-air flux of DMS from the study area was estimated to be 5.70 μmol/(m²·d), which highlights the effects of human impacts on DMS emission.     

Seasonal variations of dimethylsul.de (DMS) and dimethylsulfoniopropionate (DMSP) in the sea-surface microlayer and subsurface water of Jiaozhou Bay and its adjacent area

The distributions of DMS and its precursor dimethylsulfoniopropionate, in both dissolved (DMSPd) and particulate fractions (DMSPp) were determined in the sea-surface microlayer and corresponding subsurface water of the Jiaozhou Bay, China and its adjacent area in May and August 2006. The concentrations of all these components showed a clear seasonal variation, with higher concentrations occurring in summer. This can be mainly attributed to the higher phytoplankton biomass observed in summer. Simultaneously, the enrichment extents of DMSPd and DMSPp in the microlayer also exhibited seasonal changes, with higher values in spring and lower ones in summer. Higher water temperature and stronger radiant intensity in summer can enhance their solubility and photochemical reaction in the microlayer water, reducing their enrichment factors (the ratio of concentration in the microlayer to that in the corresponding subsurface water). A statistically signi.cant relationship was found between the microlayer and subsurface water concentrations of DMS, DMSP and chlorophyll a, demonstrating that the biogenic materials in the microlayer come primarily from the underlying water. Moreover, our data show that the concentrations of DMSPp and DMS were signi.cantly correlated with the levels of chlorophyll a, indicating that phytoplankton biomass might play an important role in controlling the distributions of biogenic sulfurs in the study area. The ratios of DMS/chlorophyll a and DMSPp/chlorophyll a varied little from spring to summer, suggesting that there was no obvious change in the proportion of DMSP producers in the phytoplankton community. The mean sea-to-air .ux of DMS from the study area was estimated to be 5.70 μmol/(m2 ·d), which highlights the e.ects of human impacts on DMS emission.     

胶州湾北部浮游动物的生物量和生产力

结合海洋生态系统动力学研究,以碳为基本 单位研究了胶州湾北部浮游动物的生物量和生产力的季节变化和平面分布及其周转率等。浮 游动物生物量的变化范围为8.73 ～ 24.05 mgC/m3;生产力的变化范围为0.26 ～ 1.09 mgC /m3.d。二者具有显著的季节变化。 其平面分布表现为不均匀性。海水中Chl a的含量、 初级生产力及盐度等是影响浮游动物生物量和生产力的主要因素。该水域浮游动物的周转率 平均为0.047(0.019 ～ 0.13),其变化与水温呈显著正相关,与浮游动物平均个体干重呈负 相关。     

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.     

胶州湾浮游病毒的分布研究

运用荧光显微镜技术,对2007年6～8月胶州湾14个站点的浮游病毒丰度进行了检测,分析了病毒在不同月份的水平与垂直分布变化,发现胶州湾浮游病毒的丰度在0.48×107～22.78×107个/mL之间,平均值为(5.72±4.72)×107个/mL,7月份病毒丰度明显高于其他两个月(P0.01)。病毒呈现从湾内至湾口至湾外递减的趋势,病毒垂直分布变化不明显。病毒-细菌比率(VBR)范围为3.90～150.72,平均值42.05±28.55,处于较高水平。利用多元相关性分析发现,病毒丰度与异养细菌丰度、聚球藻蓝细菌丰度和叶绿素a含量相关,其相关系数r分别为0.605(P0.01),0.265(P0.01)和0.604(P0.05),确定系数R2分析表明,异养细菌和叶绿素a对浮游病毒丰度的影响基本相当。病毒丰度与温度、盐度无明显相关性。对VBR的分析表明,调查区域藻类病毒占总浮游病毒的比例较高;通过VBR与异养细菌丰度的负相关性分析,认为胶州湾噬菌体的宿主菌种群较单一。     

青岛沿岸海区海藻体中DMSP含量测定

实验研究海藻体中二甲基硫基丙酸酯（Ｄｉｍｅｔｈｙｌｓｕｌｆｏｎｉｕｍｐｒｏｐｉｏｎａｔｅ,ＤＭＳＰ）的简单测定方法。改进顶空进样方法灵敏度低的缺点,采用碱解和萃取吸收同时进行气相色谱火焰光度检测法测定不同种类的底栖藻中所含的ＤＭＳＰ。并以此测定不同季节胶州湾部分地区近岸表层水体浮游藻所含的ＤＭＳＰ,同时还测定水体中的磷酸盐浓度。结果表明在底栖藻中ＤＭＳＰ含量随季节呈现一定的规律性变化,不同藻体内ＤＭＳＰ含量相差可达两个数量级,而单位水体微藻中的ＤＭ－ＳＰ亦随季节呈现一定的规律性变化     

Experimental studies on dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) production by four marine microalgae

The production of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) by marine microalgae was investigated to elucidate more on the role of marine phytoplankton in ocean-atmosphere interactions in the global biogeochemical sulfur cycle.Axenic laboratory cultures of four marine microalgae–Isochrysis galbana 8701,Pavlova viridis,Platymonas sp.and Chlorella were tested for DMSP production and conversion into DMS.Among these four microalgae,Isochrysis galbana 8701 and Pavlova viridis are two species of Haptophyta,while Chlorella and Platymonas sp.belong to Chlorophyta.The results demonstrate that the four algae can produce various amounts of DMS(P),and their DMS(P) production was species specific.With similar cell size,more DMS was released by Haptophyta than that by Chlorophyta.DMS and dissolved DMSP (DMSPd) concentrations in algal cultures varied significantly during their life cycles.The highest release of DMS appeared in the senescent period for all the four algae.Variations in DMSP concentrations were in strong compliance with variations in algal cell densities during the growing period.A highly significant correlation was observed between the DMS and DMSPd concentrations in algal cultures,and there was a time lag for the variation trend of the DMS concentrations as compared with that of the DMSPd.The consistency of variation patterns of DMS and DMSPd implies that the DMSPd produced by phytoplankton cells has a marked effect on the production of DMS.In the present study,the authors’ results specify the significant contribution of the marine phytoplankton to DMS(P) production and the importance of biological control of DMS concentrations in oceanic water.     

海洋中β-二甲基巯基丙酸内盐降解过程的研究进展

二甲基硫(DMS)是海水中一种最重要的、含量最丰富的还原态挥发性生源有机硫化物,前体β-二甲基巯基丙酸内盐(DMSP)的降解过程受各种因素影响。其中主要包括温度、DMSP的浓度、氧气、盐度、酸度、颗粒粒度、藻类生长期、季节变化、氧化压力、抑制剂等。它们均与DMSP降解速率呈一定的函数关系,并对DMSP的降解产物产生影响。藻类是DMSP的主要来源,因此着重讨论了温度、盐度、酸度等对不同浮游植物细胞内DMSP与DMS生物生产和转化过程的影响。结合海洋硫循环的研究现状和海洋化学发展的趋势,探究了用颗粒态DMSP与Chla的比率来量化碳和硫通量的方法及DMSP裂解酶活性的检验技术。大气中CO2压力持续增加导致的海洋酸化对藻类中DMSP降解过程的影响也是进一步研究的重点。     

秋季胶州湾有色溶解有机物荧光特性研究及其来源分析

利用三维荧光光谱(EEMs)-平行因子分析(PARAFAC)技术研究了秋季胶州湾有色溶解有机物(CDOM)的荧光成分组成、分布特征及来源。PARAFAC模型解析出胶州湾CDOM由2类5个荧光组分组成,即类腐殖质成分C1(355nm/430nm)、C2(320nm/390nm)、C3(380nm/465nm)、C4(420(330)nm/505nm)及类蛋白质成分C5(280/325nm)。类腐殖质成分C1、C2、C3和C4的平面分布模式基本一致,呈现由近岸海域向湾中心海域逐渐减小的趋势,而类蛋白质成分C5则是由湾东北部近岸海域向西南部海域呈逐渐减小的趋势。分析表明,秋季胶州湾CDOM类腐殖质成分C1、C2、C3和C4的主要来源为陆源输入,而类蛋白质成分C5主要受城市排污的影响。系统聚类分析表明,以团岛南端和红岛西侧连线为界,所有采样站位被分为两类,分界线西部区域站位CDOM各荧光成分相对含量分别为C1:31.8%~35.5%,C2:30.3%~33.7%,C3:17.1%~20.2%,C4:4.5%~5.2%,C5:9.6%~12.5%;分界线东部区域站位CDOM各荧光成分相对含量分别为C1:30.6%~34.6%,C2:28.8%~32.7%,C3:17.0%~19.1%,C4:3.3%~4.8%,C5:12.1%~18.2%。西部区域CDOM具有较高的C4含量和较低的C5含量,大沽河等河流的陆源输入特征明显,而东部区域CDOM则具有较高的C5含量和较低的C4含量,反映该区域受城市排污影响显著。另外,秋季胶州湾CDOM的HIX范围为1.8~3.2之间,较小的腐殖化因子值反映了秋季胶州湾CDOM的腐殖化程度高较低,在环境中存在时间较短。