南黄海表层沉积物中正构烷烃的组成特征、分布及其对沉积有机质来源的指示意义

黄海是1个重要的碳汇,其沉积物有机质来源复杂多样,而且在碳循环中的作用不同。边缘海有机质来源的定量估算是碳循环研究中的1个重要内容。正构烷烃是1种常用的指示有机质来源的生物标志物。本文对南黄海63个表层沉积物中正构烷烃的分布及其组成特征进行分析,并与其它生物标志物指标进行对比。结果显示,南黄海区域表层沉积物中正构烷烃多呈现双峰群分布,前峰群短链烷烃无明显奇偶碳数优势,主要来自海洋浮游藻类和细菌;后峰群长链烷烃具有奇碳数优势,主要来自于陆地高等植物,其中草本植物和木本植物来源所占比例相近。短链和长链正构烷烃在黄海中部都有高值分布,主要受中部细颗粒沉积物的吸附作用及较低的沉积速率影响。陆源海源烷烃含量比(∑T/∑M)和陆源海源优势烷烃含量比(TAR)对沉积有机质来源的指示是一致的,北部和近苏北沿岸处有高比值分布,指示有较高的陆源输入;低比值区分布于中南部,指示陆源输入较少。∑T/∑M(以及TAR)与生物标志物指标(∑T/1.5∑B)的分布趋势相似,只是北部高值区相对明显程度有所差别,可能与北部细菌作用较强、水深较大导致短链正构烷烃降解程度较大有关。     

冲绳海槽唐印和第四与那国热液区热液产物中烷烃组成和来源

通过气相色谱-质谱联用仪（GC-MS）和气相色谱-同位素质谱仪（GC-IRMS）,分别分析了冲绳海槽南部唐印和第四与那国热液区热液硫化物与热液沉积物中烷烃含量和正烷烃单体碳同位素组成特征。热液产物样品中正烷烃显示出明显的双峰分布,高分子正烷烃显示出明显的奇数碳优势,其丰度最大值位于C31处;低分子正烷烃显示出偶数碳优势,其丰度最大值位于C18处。正烷烃的分布特征以及正烷烃碳同位素组成表明,样品中正烷烃主要来源于热液微生物代谢活动和陆源高等植物的输入,其中,低分子的正烷烃主要来源于热液微生物代谢活动,而高分子的正烷烃主要来源于陆源高等植物。热液硫化物样品中低分子正烷烃含量和比重都高于热液沉积物,表明热液硫化物中热液微生物活动可能更加繁盛。热液硫化物中正烷烃单体的δ13C表现出随碳原子个数增加,同位素值减小的趋势,暗示该区非生物合成有机质的贡献可能不能忽略。     

化学键合玻璃毛细管气相色谱法测定海水中溶解态烷烃

前言海水中溶解态烷烃来源于海洋生物、陆源高等植物和海洋石油烃污染等。因此海水中的溶解态烷烃成分相当复杂,”其含有n-C_(14)至n-C_(35)的正构烷烃、异构烷烃、烯烃和环烷烃,常规的填充柱气相色谱缺乏足够的分辨能力,难于分离这样复杂的宽沸点烷烃组分,玻璃毛细管气相色谱法其有高分辨率和高灵敏度等特点,可用来测定海水中的烷烃。本法取表层海     

海洋沉积物中烃类化合物预处理条件优化及应用

运用分辨率高、稳定性好的ＨＰ６８９０ 毛细管气相色谱仪定性、定量测定海洋沉积物中的正构烷烃和多环芳烃。对沉积物样品的预处理中抽提、蒸发、柱层析、萃取等步骤条件进行优化。优化方法中,正构烷烃系列化合物回收率为６５ ％ ～７６ ％ ,多环芳烃系列化合物为８８ ％ ～９５％ ,标准偏差是２．７％ ～２０．２％ （ｎ＝ ３）     

渤海-北黄海表层沉积物中正构烷烃的组合特征及其指示意义的探讨

正构烷烃的组合特征是古环境研究的有力工具,但在渤海-北黄海低碳数正构烷烃的来源及其指示意义的研究还较缺乏。本文主要对渤海-北黄海60个站位表层沉积物中的正构烷烃(C14~C38)的组成、分布、各指标间的相关性及其来源进行了研究。研究结果表明:(1)渤海-北黄海的正构烷烃组成呈单峰模式,C27、C29、C31正构烷烃含量较高,且具有明显奇碳优势。(2)各个站位中高碳数正构烷烃碳优势指数(CPIH)空间分布表明该研究海域陆源输入主要沉积在河口;烷烃指数(AI)表示该海域整体上陆源输入的草本植物与木本植物所占比例相似;低碳数正构烷烃碳优势指数(CPIL)的平均值为0.9,不具有奇偶碳优势,可能受到石油及其衍生物的影响。(3)主成分分析(PCA)发现渤海-北黄海表层沉积物中高低碳数正构烷烃分布不仅受水动力影响,来源也是其分布的重要影响因素。(4)将高碳数正构烷烃相对含量((C27+C29+C31)/TOC)和低碳数正构烷烃相对含量((C15+C17+C19)/TOC)分别与三种浮游植物生物标志物相对含量((B+D+A)/TOC)做相关性分析,进一步表明该研究海域高碳数正构烷烃来自陆源输入,C15、C17、C19正构烷烃不能作为海源生物标志物。此外,降解指数(C26正构醇/C29正构烷烃)与C15+C17+C19正构烷烃含量的对比表明降解不是该研究海域低碳数正构烷烃分布的主要控制因素。低碳数正构烷烃的来源和分布控制机制还有待进一步研究。     

黄河不同区段悬浮颗粒物中正构烷烃的组成及物源

研究黄河流域正构烷烃的迁移、转化。2003年10月在黄河兰州附近的新城至山东的利津设站,系统地研究了黄河悬浮颗粒物中正构烷烃的组成特征、来源和空间分布变化。结果表明:黄河悬浮颗粒物中正构烷烃的总浓度基本分布在1.29~7.56μg/L之间。碳数分布特征为:上游以单峰型为主;中、下游区域分布为双峰型。说明上游悬浮颗粒物中正构烷烃主要是受陆源影响,中游和下游正构烷烃除主要受陆源影响之外,具有明显的水生生物源的特征,水生生物源正构烷烃的变化规律与陆源明显不同。     

白令海北部陆坡全新世以来长链正构烷烃的古环境意义

本文对白令海北部陆坡B2-9站位沉积物岩芯开展了高分辨率的生物标志物分析,获得了研究区近一万年来陆源长链正构烷烃（简写为烷烃）的输入及其源区植被结构的变化等相关记录。结果表明,nC₂₇是烷烃中最高的主碳峰,对烷烃总量的贡献也最大,这可能与源区木本植物的丰度及其分布有关;nC₂₃的含量也较高,可能主要是来源于北半球沿海地区广泛分布的一类沉水植物。全新世期间,烷烃总量分别在7.8 ka B.P.,6.7 ka B.P.和5.4 ka B.P.经历了三次阶梯状的下降过程,呈现出四个相对稳定的阶段,可能主要受控于早全新世海平面上升以及源区气候环境和植被分布的变化。烷烃的分子组合特征各参数（如CPI、ACL以及nC₃₁/nC₂₇等）的变化则表明,烷烃主要来自陆生高等植物,且全新世期间植被结构较为稳定,木本植物占据优势。此外,在几个较短的时期内,烷烃总量及其分子组合特征等参数的变化具有同步性,表明在这些时期特殊的气候条件下,源区木本植物烷烃对烷烃总量的贡献率的增加可能低于草本植物烷烃和化石烷烃。     

长江口及邻近海域现代沉积物中正构烷烃分子组合特征及其对有机碳运移分布的指示

报道了长江口及邻近海域现代沉积物中正构烷烃的浓度及分布特征,通过因子分析法对正构烷烃来源进行了探讨.结果表明,调查站位正构烷烃主要可归纳为3种类型:陆源输入优势型(单峰群)、陆源和海洋内生混合类型(双峰群)和石油类污染类型(单峰型,不具奇偶优势).长江口邻近站位正构烷烃色谱指标的突变,是长江河口区2种不同水团造成沉积物差异的客观反映.除P4外,研究站位总正构烷烃含量(∑n-Alk)与有机碳总量(TOC)相关性良好,且长江口东南-浙江沿岸软泥区正构烷烃的陆源高等植物组分(TER-Alk)、海洋内生组分(PL-1)、奇偶碳优势指数(CPI)等指标与运移距离呈线形关系.在因子分析显示不同来源的4种正购烷烃中,以陆源烷烃输入比重最大(51.5%),在陆源烷烃中又以东海河流物质贡献最大(49.1%);根据因子负荷差异,推测东海北部沉积有机质可能多数来源于苏北沿岸及老黄河口水下三角洲,冲绳海槽区则可能大部分来源于长江及东海内陆架物质,并探讨了其运移机理.     

海洋微生物对石油烃降解研究：Ⅱ.石油烃降解细菌对正烷烃的降解作用

报导使用气相色谱法测定石油烃降解细菌对柴油的正烷烃的降解作用。结果表明 ,石油烃降解细菌对正烷烃有明显的降解作用 ,混合菌株的降解率明显高于单菌株的降解率 ;在2 0℃的条件下 ,经过 2 1 d后 ,绝大部分的正烷烃被降解 ,总的降解率为 94.93% ,其中细菌的降解率为 75.67% ,理化降解率为 1 9.2 6% ;温度对正烷烃的降解率有明显的影响 ,温度在 1 0℃时 ,正烷烃降解速度较慢 ,在 2 0℃正烷烃的降解比 1 0℃快 ,在 35℃的条件下 ,正烷烃的降解速度最快。     

渤海微生物自然混合菌群降解20号重柴油中正烷烃的研究

本文运用气相色谱法,对渤海微生物自然混合菌群降解20号重柴油中的烷烃的能力进行了实验室研究。 实验测定了在5,50,500ppm三个油浓度下微生物自然混合菌群对正烷烃的降解能力。20天内,微生物对正烷烃(C_(11)—C_(22))的生物降解率分别为56.63％,61.45％和72.36％;物理化学降解率分别为34.18％,38.18％和19.85％。正烷烃的总降解率分别为90.81％,99.63％和92.21％。在本实验条件下,经过20天的降解,20号重柴油中的C_(11)—C_(22)烷烃绝大部分被降解。     

海洋真菌Neosartorya fischeri 1008F1的次级代谢产物抑菌及抗肿瘤活性的研究

通过抑菌及抗肿瘤活性实验,明确海洋真菌Neosartorya fischeri 1008F1次级代谢产物中的活性有效组分。应用对峙培养法和生长速率法,对菌株的抑菌活性进行测定。应用MTT法,对菌株的抗肿瘤活性进行测定。应用凝胶(Sephadex LH-20)柱层析的方法,对菌株发酵产物的提取物进行分离。结果发现,海洋真菌Neosartorya fischeri 1008F1的水溶性提取物对番茄早疫菌(Alternaria solani)具有一定的抑制活性。菌株的粗提物浸膏经Sephadex LH-20柱梯度洗脱后,得到的组分B、C、D、E和F。在0.5 g/L的供试浓度下,组分B、C和D对胃癌细胞SGC-7901的抑制率均高于80%,而组分B、C、D、E和F对肝癌细胞BEL-7404的抑制率均高于70%。     

Chemical and GC-MS characterization of marine particulate lipids

The lipid fraction of particulate organic matter in seawater was analyzed by gravimetry, liquid chromatography, gas chromatography (GS), and gas chromatography—mass spectrometry (GS—MS). Gravimetric concentrations in the Gulf of Mexico were in the range of 12–70 μg 1^?1 for near-surface samples and 9–52 μg 1^?1 for near-bottom samples. The lipids accounted for ～20% of the particulate organic carbon. Particulate lipids were found to be a much more complex mixture of organic compounds than the dissolved lipids and their composition was much more variable. The majority of the extracted weight was recovered in the polar liquid chromatography fraction (49–85%). The major components of the analyzable particulate lipids were similar to those of the dissolved lipids, namely, n-alkanes, pristane, phytane, and methyl, ethyl and propyl fatty acid esters. Often olefins, alkylated benzenes, quinones, and the unresolved GC area contribute a substantial part to the total particulate lipids. Minor components included ketones, phenols, indanes, acids, benzoates, aromatics and possibly derivatives of inositol, dioxane, and pyran. The low concentrations observed confirm that the area is relatively pristine though some evidence for chronic low-level oil pollution was present. Seasonal, diurnal, vertical and areal variations were observed in the particulate lipids. Lipid concentrations not only decreased with depth but they were also a decreased percentage of the organic carbon present. This may indicate the loss of labile carbon with depth due to reworking in the euphotic zone. Anoxic conditions appeared to promote the preservation of lipid materials in the particulate phase, n-Alkanes and fatty acid esters were common to both the particulate and dissolved phases and had similar distributions.     

黄海绿潮浒苔提取物的化感效应及化感物质的分离鉴定

化感作用是浒苔绿潮暴发的重要原因之一,目前,对于浒苔产生化感物质的结构、种类以及产量的研究鲜有报道。本文针对黄海浒苔绿潮致灾藻种,利用毒性鉴别程序（TIE）对其体内的化感物质进行分离提取及结构鉴定,明确了浒苔产生化感物质的主要成分。首先用石油醚、乙酸乙酯和甲醇3种有机溶剂分别对新鲜浒苔进行提取,得到3种不同溶剂粗提物,其中乙酸乙酯粗提物的抑藻活性最强,对测试物种中肋骨条藻的半数有效浓度（96h-EC₅₀）值为22.25 mg/L;其次对乙酸乙酯粗提物进行萃取分离得到初步提纯物,其对中肋骨条藻的96h-EC₅₀值为21.12 mg/L;然后用硅胶层析柱对上述初步提纯物进行分离,共得到6种组分,其中抑藻活性最强的组分对中肋骨条藻的96h-EC₅₀值为10.57 mg/L;最后,对新鲜浒苔提取物用红外光谱和气相色谱-质谱联用仪进行检测,实验结果表明主要化感物质为:4,7,10,13,16,19-二十二碳六烯酸、2-十六碳烯酸、棕榈酸、5,8,11,14,17-二十碳五烯酸、9,12-十八碳二烯酸、9,12,15-十六碳三烯酸、花生四烯酸、13-二十二碳烯酸等8种脂肪酸。研究结果对于系统阐释浒苔绿潮暴发机制具有重要意义。     

Determination of volatile fatty acid turnover rates in organic-rich marine sediments

Volatile fatty acid (VFA) apparent turnover rates in organic-rich marine sediments were determined by measuring whole sediment VFA concentration and the corresponding first-order reaction rate constants. In order to measure VFA concentrations, bulk wet sediment samples were basified, freeze-dried, extracted with methanol, derivatized to form methyl esters of the VFAs, and analyzed by packed-column gas chromatography using hexanoic acid as an internal standard. The detection limits for acetate, propionate, iso-butyrate and butyrate were 1.0, 0.4, 0.2 and 0.2 μmol l^?1_s, respectively, for 600 ml samples. Rate constants for acetate and propionate were determined by anaerobically incubating samples at in-situ temperatures with tracer levels of ¹⁴C-labelled VFAs. Metabolized label was recovered as CO₂, CH₄, cellular material, water-soluble material, and VFA (ether-soluble) fractions. Apparent turnover rates measured during summer and winter in anoxic Cape Lookout Bight, North Carolina (U.S.A.) sediments were in the range of 19–330 μmol l^?1_s h^?1 for acetate and 0.7–7.0 μmol l^?1_s h^?1 for propionate.     

Dynamics of fatty acids in newly biosynthesized phytoplankton cells and seston during a spring bloom off the west coast of Hokkaido Island, Japan

¹³C uptake experiments were carried out at a station off the west coast of Hokkaido Island, Japan, during the period between late winter and spring bloom in 1997. The composition of newly biosynthesized particulate fatty acids was determined using a ¹³C tracer and gas chromatography/mass spectrometry (¹³C GC/MS), and compared with that of particulate matter (seston). Two fatty acid compositional ratios revealed that diatoms biomass (16:1(n−7)/16:0, ∑C₁₆/∑C₁₈) were strikingly high in new cells compared with seston on 17 April, coinciding with the dominance of fucoxanthin. In this study, the Polyunsaturation Index (a measure of the percentage of C₁₆ fatty acids that are polyunsaturated) in new cells is generally close to that in seston, while there was a notable discrepancy between new cells and seston in surface (10 m) waters on 17 April. This large difference between new cells and seston is ascribed to: (1) an increase of newly synthesized storage lipids (mainly 16:0 and 16:1) induced by nitrogen limitation in the top 10 m of the water column; (2) an addition of earlier synthesized phytoplankton cells (high Polyunsaturation Index at logarithmic growth stage) and non-phytoplankton components (detritus and bacteria and zooplankton) into seston. The highest Polyunsaturation Index of C₁₆ fatty acids in seston (33%) occurred at 100 m water depth. This may be caused by “settling planktonic aggregates” or “diatom resting spores”. In the present study, it is reasonable to suggest that the Polyunsaturation Index of C₁₆ fatty acids can be a useful indicator for the ecophysiological state of marine diatom populations.     

Transformation of suspended particulate matter into sediment in the Kara Sea in September of 2011

The biogeochemical processes participating in the transformation of the particulate matter into sediment along the Yenisei River-St. Anna Trough (Kara Sea) meridional profile were studied using hydrochemical, geochemical, microbiological, radioisotope, and isotope methods. The water-sediment contact zone consists of three subzones: the suprabottom water, the fluffy layer, and the surface sediment. The total number, biomass, and integral activity of the microorganisms (dark ¹⁴CO₂ assimilation) in the fluffy layer are usually higher than in the suprabottom water and sediment. The fluffy layer shows a decrease in the oxygen content and the growth of the dissolved biogenic elements. It was provided by the particulate organic matter supporting the vital activity of the heterotrophs from the overlying water column and by the flux of reduced compounds (NH₄, H₂S, CH₄, Fe²⁺, Mn²⁺, and others) from the underlying sediments. The C_org isotopic composition of the fluffy layer and the sediments is 2–4 ‰ heavier than that of the particulate matter and sediment due to the presence of the isotopically heavy biomass of microorganisms. A change in the isotopic composition of the C_org in the fluffy layer and surface sediment as compared to the C_org of the particulate matter is a widespread phenomenon in the Arctic shelf seas and proves the leading role of microorganisms in the transformation of the particulate matter into sediment.     

Cycling of dissolved and particulate nitrogen and carbon in the Framvaren Fjord, Norway: stable isotopic variations

The reaction pathways of nitrogen and carbon in the Framvaren Fjord (Norway) were studied through stable isotope analysis (δ¹⁵N and δ¹³C) of dissolved inorganic and particulate organic matter (POM). The variations in the isotopic compositions of the various C and N pools within the water column were use to evaluate the historical deposition of material to the sediments. The high δ¹⁵N-NH₄⁺ at the O₂/H₂S interface, as a consequence of microbial uptake between 19 and 25 m, results in extremely depleted δ¹⁵N-particulate nitrogen (PN) of approximately 1‰ within the particulate maximum at approximately 19 m. The carbon isotopic distribution of dissolved inorganic carbon (DIC) and particulate organic carbon (POC) within the interface suggests that the distinct microbial flora (Chromatium sp. and Chlorobium sp.) fractionate inorganic carbon to different degrees. The extremely light δ¹³C-POC within the interface (−31‰) appears to be a result of carbon uptake by Chromatium sp. while δ¹³C-POC of −12‰ is more indicative of Chlorobium sp. Nitrogen isotopic mass balance calculations suggested that approximately 75% of the material sinking to the sediments was derived from the dense particulate maximum between 19 and 25 m. The sediment distribution of nitrogen isotopes varied from 2‰ at the surface to approximately 6‰ at 30 cm. The nitrogen isotopic variations with depth may be an indicator of the depth or position of the O₂/H₂S interface in the fjord. Low sediment δ¹⁵N indicated that the interface was within the photic zone of the water column, while more enriched values suggested that the interface was lower in the water column potentially allowing for less fractionation during biological incorporation of dissolved inorganic nitrogen. Results indicate that the dense layers of photo-autotrophic bacteria in the upper water column impart unique carbon and nitrogen isotopic signals that help follow processes within the water column and deposition to the sediments.     

The chemical changes of DOM from black waters to coastal marine waters by HPLC combined with ultrahigh resolution mass spectrometry

How dissolved organic matter (DOM) undergoes chemical changes during its transit from river to ocean remains a challenge due to its complex structure. In this study, DOM along a river transect from black waters to marine waters is characterized using an offline combination of reversed-phase high performance liquid chromatography (RP-HPLC) coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS), as well as tandem ESI-FTICR-MS. In addition, a water extract from degraded wood that mainly consists of lignins is used for comparison to the DOM from this transect. The HPLC chromatograms of all DOM samples and the wood extract show two major well-separated components; one is hydrophilic and the other is hydrophobic, based on their elution order from the C₁₈ column. From the FTICR-MS analysis of the HPLC fractions, the hydrophilic components mainly contain low molecular weight compounds (less than 400 Da), while the hydrophobic fractions contain the vast majority of compounds of the bulk C₁₈ extracted DOM. The wood extract and the DOM samples from the transect of black waters to coastal marine waters show strikingly similar HPLC chromatograms, and the FTICR-MS analysis further indicates that a large fraction of molecular formulas from these samples are the same, existing as lignin-like compounds. Tandem mass spectrometry experiments show that several representative molecules from the lignin-like compounds have similar functional group losses and fragmentation patterns, consistent with modified lignin structural entities in the wood extract and these DOM samples. Taken together, these data suggest that lignin-derived compounds may survive the transit from the river to the coastal ocean and can accumulate there because of their refractory nature.     

Distribution and partitioning of trace metals (Cd,Cu, Ni,Pb, Zn) in Galveston Bay waters

The distribution of several trace metals has been studied in the surface waters of Galveston Bay, Texas, in order to assess the impact of complexation with organic and reduced sulfur species on the partitioning of trace metals between particulate and aqueous species. The distribution of trace metals in the filter-passing fraction (<0.45 μm) showed two apparent trends: (1) the carrier phase metals (i.e., Fe and Mn) were largely removed in the Anahuac Channel region, which was dominated by direct Trinity River inputs; (2) the other metals (Cd, Cu, Ni, Pb, and Zn) showed non-conservative mixing behaviour, with mid-salinity maxima, within the estuarine regions of Galveston Bay. The average percentage of metal in the filter-passing fraction, as compared to the total metal load, decreased in that region from 95% to 9% in the order Ni>Cu>Cd>Zn>Pb>Mn>Fe, while an increasing trend was found in the same sequence for the acid-leachable fractions. The average values of K_d1, the particle-water partition coefficient, expressed as the ratio of weak acid-leachable particulate fractions to the filter-passing fractions, increased in the order Ni<Cu<Cd<Zn<Mn<Pb<Fe. This sequence is consistent with the relative importance of particulate transport of these trace metals from estuaries to coastal oceans. The observed decrease of K_d1 of Cu with increasing concentrations of suspended particulate matter (SPM), also called the “particle concentration effect” (PCE), can be eliminated when the free ionic, rather than the total concentration of Cu in the filter-passing fraction is used for calculating this ratio. A particle concentration effect would be expected if the binding of these trace metals by particles is mediated by solution (i.e., filter-passing) phase ligands. Complexation of Cd, Cu, Ni, Pb, and Zn with reduced sulfur species could be one of the causes for the observed linear correlations between metals and reduced sulfur species in both the filter-passing and filter-retained fractions. Significant correlations between Cu in the weak acid-leachable fraction and chlorophyll a (Chl a) concentrations suggest biological mediation of Cu uptake into the particulate fraction.     

Estuarine nitrification: A naturally occurring fluidized bed reaction?

The rates of nitrification in the water column of the Tamar river estuary, southwest England have been measured using the incorporation of H¹⁴CO₃ in samples with and without the inhibitor of nitrification, 2-chloro-6-(trichloromethyl) pyridine (N-Serve). N-Serve proved successful in totally inhibiting NH₄-oxidizing bacteria but the activity of NO₂-oxidizing bacteria was inhibited by only 30%; other organisms were only slightly affected. Measurements of the nitrification rate made over the entire salinity range of the estuary (0–30‰) showed that maximum nitrification always coincided with the turbidity maximum. The field data suggest that the organisms responsible for nitrification were associated with periodically resuspended particulate material and that the turbidity maximum acts in a manner similar to a fluidized bed reactor. A dispersion model has been used to demonstrate that nitrification in the water column can account for 100% of the NO₂ maximum which is apparent down estuary from the turbidity maximum.