气提—冷阱气相色谱测定海水中的二甲基硫

二甲基硫（ＤＭＳ）在大气化学和全球生物地球化学循环中起了重要作用,是影响气候变化的重要痕量气体。本文采用气提－冷阱捕集法处理海水样品,用带有火焰光度检测器的气相色谱仪分析。此方法的精密度为５．５％,回收率为８５％,最低检出限为５０ｐｇＳ（ＤＭＳ）。用此法实测了胶州湾及其附近海域表层海水的二甲基硫的含量     

6-DMAP诱导太平洋牡蛎三倍体——4.四倍体现象的研究

１９９６～１９９７年,在进行６－二甲基氨基嘌呤（６－ＤＭＡＰ）诱导太平洋牡蛎产生三倍体的实验过程中,发现一定数量的四倍体。解剖法获取精卵,人工授精。染色体倍性鉴别采用染色体计数法。（１）三因素四水平Ｌ１６（４５）正交设计。试验平行重复２次。最高四倍体诱导率为４０．０±０．０％。太平洋牡蛎四倍体各诱导因素的最优水平组合：当精卵混合２０ｍｉｎ时,将受精卵浸泡在含６－ＤＭＡＰ４５０μｍｏｌＬ－１的海水中１０ｍｉｎ;决定四倍体产生的三因素的主次顺序：６－ＤＭＡＰ浓度→诱导时机→诱导持续时间。（２）三因素三水平Ｌ９（３４）正交设计。试验平行重复３次。最高四倍体诱导率为９．６±４．９％。诱导太平洋牡蛎四倍体各因素的最优水平组合：当５０％受精卵出现第一极体时,将受精卵浸泡在含６－ＤＭＡＰ４５０μｍｏｌＬ－１的海水中１５ｍｉｎ;决定四倍体产生的三因素的主次顺序：诱导时机→６－ＤＭＡＰ浓度→诱导持续时间。     

水溶液中二甲基硫的化学氧化过程研究

实验研究水溶液中二甲基硫（ＤＭＳ）和Ｈ２Ｏ２进行氧化反应的动力学。结果表明ＤＭＳ被Ｈ２Ｏ２氧化的速率会受到介质、ｐＨ以及重金属离子的影响。其二级反应速率常数为２．２１×１０－２～４．９０×１０－２Ｌ·ｍｏｌ－１·Ｓ－１．Ｈｇ２＋的存在会加快反应速率，特别在人工海水条件下十分明显。ＤＭＳ易被Ｈ２Ｏ２氧化的事实说明，在海水中化学氧化过程会对ＤＭＳ的浓度和分布产生重要影响     

二甲基硫光化学氧化反应的动力学研究

实验研究水溶液中二甲基硫（ＤＭＳ）的光化学氧化反应的动力学。结果表明，在入射光频率与强度一定条件下，ＤＭＳ进行光化学氧化反应的速率会受到介质、ｐＨ、重金属离子的影响。Ｈｇ２＋能显著加快人工海水介质中ＤＭＳ的光氧化速率。ＤＭＳ进行光氧化的一级速率常数为４．４６×１０－５～３０．４×１０－５ｓ－１，其在光照下的人工海水介质中的半寿期为３．６ｈ。这说明光化学过程对于影响和控制ＤＭＳ在海洋中的浓度和分布起着十分重要的作用     

一种C_2对称二亚砜手性辅助试剂的应用——σ-对称十员氧杂环1,2-二醇的手性非对称化

顺－２－丁稀－１,４－二醇的１,４－二羟基被邻二苯甲基保护形成环烯２、然后氧化生成σ－对称十员氧杂环－１,２－二醇３,将３转化为单三甲基硅醚４后,在三氟甲磺酸三甲基硅酯（ＴＭＳＯＴｆ）的催化下,与Ｃ２－对称二亚砜手性辅助试剂１进行缩酮化反应得到光学活性缩酮５,随后的碱催化缩酮开裂反应非对映选择性大于９９％。最后,水解去掉手性辅助试剂,以良好的产率和９５％ｅｅ的光学纯度得到光学活性醇７。     

溴素的有机化学──I．2，4，6－三溴苯甲酸溴代和非溴代芳酯的合成

用ｍ－氨基苯甲酸作原料，经溴代、重氮化、还原脱氨、酰氯化和酯化反应等步骤，合成了六种新型的三溴苯甲酸的溴代和非溴代芳酯，即；双（２，４，６－三溴苯甲酸）－２＇，３＇，５＇，６＇－四溴－１＇，４＇－苯二酯，２，４，６－三溴苯甲酸－２＇，３＇，４＇，５＇，６＇－五溴苯酯，２，４，６－三溴苯甲酸－２＇，４＇，６＇－三溴苯酯，２，４，６－三溴苯甲酸－４＇－溴苯酯，２，４，６－三溴苯甲酸－４＇－甲基苯酯和２，４，６－三溴苯甲酸苯酯．通过对产物中碳、氢、溴元素的定量分析以及红外吸收光谱和氢核磁共振谱的研究，验证了合成产物的结构。     

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     

海带雌配子体对无机碳的利用

采用ｐＨ漂移技术（ｐＨ－ｄｒｉｆｔ ｔｅｃｈｎｉｑｕｅ）,对海带雌配子体克隆的碳素营养进行了研究。结果表明,海带雌配子体对无机碳的利用能力较弱,其ｐＨ补偿点为８．８５,ＣＯ２补偿点为１．６３５μｍｏｌ／Ｌ。与ＨＣＯ＾－３利用有关的抑制剂：Ａｃｅｔａｚｏｌａｍｉｄｅ（Ａｚ）,４’４’－ｄｉｉｓｏｔｈｉｏｃｙａｎａｔｏｓｉｌｂｅｎｅ－２,２－ｄｉｓｕｌｆｏｎｉｃ ａｃｉｄ（ＤＩＤＳ）,４－ａｃｅｔａｍ     

南海沉积物中烷基环己烷、烷基苯、胡萝卜烷和萜烷等化合物

本文研究了南海中部柱状样中烷基环己烷、烷基苯、胡萝卜烷和萜烷的分布特征，它们来自藻类和喜盐细菌。４－甲基甾烷的先驱物４－甲基甾醇存在于钙质超微化石颗石藻中，它为南海沉积物中含有４－甲基甾烷提供了依据。沉积物中保存有生物构型的ββ藿烷，如Ｃ２９１７β（Ｈ），２１β（Ｈ）－３０－降藿烷、Ｃ３０１７β（Ｈ），２１β（Ｈ）－藿烷、Ｃ３１１７β（Ｈ），２１β（Ｈ）－升藿烷和Ｃ３２１７β（Ｈ），２１β（Ｈ）－３０－二升藿烷，表明沉积有机质成熟度低。     

栉孔扇贝胚胎超低温液氮保存

选用两种低温保护剂配方，Ａ：１０％甘油＋４％葡萄糖；Ｂ：１５％ＤＭＳＯ（二甲基亚铜）＋４％葡萄糖＋２％柠檬酸盐，利用微机控制生物降温仪，对栉孔扇贝胚胎进行液氮低温保存。似１℃／ｍｉｎ由室温降温至－２０℃，接着以２０℃／ｍｉｎ降温至－８０℃，然后样品直接入液氮保存（－１９６℃），１周后，经４５℃水浴解冻，栉孔扇贝胚胎（发育６ｄ）的存活率达６５．１％（Ａ配方）和５６．５％（Ｂ配方）；而采用６℃／ｍｉｎ     

对虾养殖生态系中有机碳的初步研究本研究由

对于围隔养殖对虾生态系中有机碳的变动进行了研究 ,结果表明 :溶解有机碳 (DOC)含量波动在 5 .2 99～ 13.39mg/ L之间 ,平均为 8.5 3mg/ L± 2 .2 5 mg/ L;颗粒有机碳 (POC)含量波动在0 .6 5～ 6 .6 3mg/ L之间 ,平均为 3.2 5 mg/ L± 1.76 mg/ L;总有机碳 (TOC)含量波动在 6 .92～ 2 0 .0 2mg/ L之间 ,平均为 11.78mg/ L± 3.82 mg/ L ;其中 DOC∶ POC∶ TOC为 0 .72∶ 0 .2 8∶ 1。各种有机碳组分的含量明显高于自然海水中各种有机碳的含量 ;各种有机碳组分的含量在养殖期间总体上呈上升的趋势 ;其变化与 DCOD的变化呈显著线性正相关的关系。     

海水中溶解有机碳（DOC）的测定

本文论述了海水中溶解有机碳(DOC)的测定方法,对DOC的测定原理及氧化方法进行了讨论,并提出了妨碍海水中DOC测定准确度提高的因素,这对于建立高准确度和精密度的新分析方法具有重要的意义。     

厦门西港和九龙江口颗粒有机碳的研究

研究了九龙江河口及相邻海区颗粒有机碳 ( POC)的分布变化特征及 POC与浮游植物生物量的关系。结果表明 ,九龙江河口区和厦门西港 POC的平均含量分别为 762和 793μg C/L。春季 ,河口区的 POC含量高于西港 ,而秋季则相反。春季 ,河口区和西港的 POC含量与ATP(三磷酸腺苷 )含量都呈正相关关系 ,其中 ,浮游植物有机碳 ( POCB)分别占 POC的 4 4 %和 2 2 %。     

长江口盐度梯度下不同形态碳的分布、来源与混合行为

河口碳的生物地球化学过程是全球碳循环的重要组成。通过测定溶解无机碳（DIC）及其稳定同位素丰度（δ13C_DIC）,溶解有机碳（DOC）,有色溶解有机物（CDOM）,颗粒有机碳（POC）及其稳定同位素丰度（δ13C_POC）与元素比值（N/C）及相关指标,研究了2014年7月长江口盐度梯度下不同形态碳的分布、来源和混合行为。结果表明,DIC浓度、DOC浓度、POC含量分别为1 583.2~1 739.6 μmol/L,128.4~369.4 μmol/L和51.2~530.8 μmol/L,这些不同形态碳及CDOM的荧光组分的分布模式相似,均是从口内到口外,整体呈现先增大后减小的趋势,并与盐度呈现非保守混合行为。添加作用主要发生在在口门处最大浑浊带附近。与含量相反,从口内到口外,δ13C_DIC和δ13C_POC均呈现逐渐减小再增大的趋势,在口门附近达到最低值,分别为-9.7‰和-26.7‰。在口门附近不同形态碳含量上升及δ13C_DIC、δ13C_POC的降低可能主要与沉积物再悬浮及微生物作用有关。基于蒙特卡洛模拟的三端元混合模型的结果显示,河口内外POC来源变化明显,口内POC以陆源有机碳贡献为主,平均为62.3%,口外海源贡献逐渐增加。CDOM相关参数结果表明长江口CDOM主要来自陆源输入,海源及人类活动等也对其产生影响。     

Final dissolved organic carbon broad community intercalibration and preliminary use of DOC reference materials

A broad community intercalibration exercise for accurate measurement of dissolved organic carbon (DOC) in seawater has been carried out over a period of 5 years. A set of 10 natural samples with DOC content from 40 to 200 μM C were accompanied by two glucose standards and a “zero C” blank; all sealed in glass ampoules. Samples were sent to all interested analysts for “blind” analysis; 62 laboratories in 17 countries participated. A total of 59 separate analyses were determined to be acceptable by screening criteria based on standards and blank; another nine sets of analyses did not pass the screening. The majority of the analyses, both those passing and those that did not, were performed with high temperature combustion (HTC) methods, six sets of analyses were done using wet chemical oxidation methods.From the 53 sets of acceptable HTC analyses, the coefficient of variation (%CV) for analytical comparability of the samples was 10% (“community precision”). It is estimated that the individual replicate injection precision for most instruments was approximately 2% and that no additional variability was caused by differences within the ampoules of individual samples. The additional variability over 2% was likely a result of both random and systematic differences in analytical capabilities from instrument to instrument and from day to day for individual instruments. With an arbitrary selection after the fact, smaller subsets of analysts can show comparability better than 10% and duplicate or triplicate runs on different days of the full sets of samples in several laboratories showed comparability in the 2–6.5% range. Experienced oceanic analysts, with internal or shared reference materials, can now show reproducibility and comparability at a level closer to 2%.Preliminary use of DOC reference materials by 14 participants showed day-to-day reproducibilities for their laboratories in the 2–6% range in most cases; several with poorer reproducibility do not normally perform DOC analyses on samples with concentrations as low as the deep ocean reference used here. Use of these reference materials can also give a demonstration of comparability between laboratories. For credibility of DOC analyses, it is necessary for analysts to use community reference materials and report results of their analytical performance with these references.This paper does not identify individual data nor should it be considered an evaluation of individual laboratories or analysts. The purpose is to show the summary picture of the international community of DOC analysts as it existed in the mid- to late 1990s.     

Chemical properties of colored dissolved organic matter in the sea-surface microlayer and subsurface water of Jiaozhou Bay, China in autumn and winter

The distribution and chemical properties of chromophoric dissolved organic matter (CDOM) in the Jiaozhou Bay, China were examined during four cruises in 2010-2011. The influence of freshwater and industrial and municipal sewage along the eastern coast of the bay was clearly evident as CDOM levels (defined as a 305 ), and dissolved organic carbon (DOC) concentrations were well correlated with salinity during all the cruises. Moreover, DOC concentrations were significantly correlated with chlorophyll a concentrations in the surface microlayer as well as in the subsurface water. The concentrations of DOC and CDOM displayed a gradually decreasing trend from the northwestern and eastern coast to the central bay, and the values and gradients of their concentrations on the eastern coast were generally higher than those on the western coast. In addition, CDOM and DOC levels were generally higher in the surface microlayer than in the subsurface water. In comparison with DOC, CDOM exhibited a greater extent of enrichment in the microlayer in each cruise, with average enrichment factor (E F ) values of 1.38 and 1.84, respectively. Four fluorescent components were identified from the surface microlayer and subsurface water samples and could be distinguished as peak A, peak T, peak B and peak M. For all the cruises, peak A levels were higher in the surface microlayer than in the subsurface water. This pattern of variation might be attributed to the terrestrial input.     

Relevance of peat draining rivers in central Sumatra for the riverine input of dissolved organic carbon into the ocean

Sources and discharges of dissolved organic carbon (DOC) from the central Sumatran river Siak were studied. DOC concentrations in the Siak ranged between 560 and 2594 μmol l⁻¹ and peak out after its confluence with the river Mandau. The Mandau drains part of the central Sumatran peatlands and can be characterized as a typical blackwater river due to its high DOC concentration, its dark brown-coloured, acidic water (pH 4.4–4.7) and its low concentration of total suspended matter (12–41 mg l⁻¹). The Mandau supplies about half of the DOC that enters the Siak Estuary where it mixes conservatively with ocean water. The DOC input from the Siak into the ocean was estimated to be 0.3 Tg C yr⁻¹. Extrapolated to entire Indonesia the data suggest a total Indonesian DOC export of 21 Tg yr⁻¹ representing 10% of the global riverine DOC input into the ocean.     

Dissolved Organic Matter in Oceanic Waters

The amount of information on oceanic dissolved organic matter (DOM) has increased dramatically in the last decade thanks to the advances in chemical characterization. This information has supported the development of some novel and important ideas for DOM dynamics in the ocean. Consequently, we have a better understanding of the importance of DOM in oceanic biogeochemical cycles. Here we review studies published mainly during 1995–2001, synthesize them and discuss unsolved problems and future challenges. The measurement, distribution and turnover of dissolved organic carbon (DOC) are presented as the bulk dynamics of the oceanic DOM. The size spectrum, elemental composition, and chemical compositions at molecular and functional group levels are described. The mechanisms proposed for the survival of biomolecules in DOM are discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dissolved organic matter cycling in the confluence of the Atlantic and Indian oceans south of Africa

The boundary between the Atlantic and Indian sectors of the Southern Ocean is a key spot of the thermohaline circulation, where the following water masses mix up: Indian Central water (ICW), South Atlantic Central Water (SACW), Antarctic Intermediate Water (AAIW), Circumpolar Deep Water (CDW), North Atlantic Deep Water (NADW), Weddell Sea Deep Water (WSDW) and Antarctic Winter Water (WW). An optimum multiparameter analysis based on the distributions of potential temperature, salinity, NO (=O₂+9.3×NO₃) and silicate during the GoodHope 2004 (GH04) cruise allowed us to (i) define the realms of these water masses; (ii) obtain the water mass proportion weighted-average (archetypal) apparent oxygen utilization (AOU) and dissolved organic carbon (DOC) concentrations of each water mass; and (iii) estimate the contribution of DOC to the oxygen demand of the study area. WW represented only 5.2% of the water volume sampled during GH04, followed by WSDW with 10.8%, NADW with 12.7%, SACW with 15.3%, AAIW with 23.1% and CDW with 32.8%. The distributions of DOC and AOU were mainly explained by the mixing of archetypal concentrations of these variables, 75±5% and 65±3% respectively, which retained the variability due to the basin-scale mineralization from the formation area to the barycentre of each water mass along the GH04 line. DOC accounted for 26±2% and 12±5% of the oxygen demand of the meso- and bathypelagic ocean, respectively. Conversely, local mineralization processes, retained by the residuals of the archetypal concentrations of DOC and AOU, did not contribute to improve significantly the mixing model of DOC.     

南黄海溶解有机碳的生物地球化学特征分析

依据1997-2003年每年1次的南黄海调查得到的溶解有机碳(DOC)数据,重点分析了2002年秋末冬初季节南黄海DOC的分布特征及其生物地球化学控制机制。结果表明,2002年秋末冬初南黄海表层海水DOC质量浓度为1.62~2.42 mg/L,平均值为2.02 mg/L,高于大洋的平均值,具有典型近海特征;南黄海DOC分布呈现北部高,南部低,在量值上,A断面>B断面>C断面,且有显著近岸高、远离海岸中部海区低的特点。近岸高值区主要受陆源输入影响,包括径流输入和人类活动两个方面,陆源输入相对生物生产过程更为重要;中部低值区主要受控于来自东海低DOC海流的冲淡作用。垂直方向上DOC质量浓度变化不大,这明显与南黄海海水混合较好有关。7 a中南黄海DOC质量浓度总体上呈略微下降趋势,北部海域表现尤为明显,南黄海生物生产量的下降及近年来南黄海整体环境质量的提高是引起DOC下降的主要原因。