The coupling of carbon and sulfur in sediments in the early diagenesis of methane hydrate potential area of northern South China Sea

天然气水合物作为21世纪理想的替代能源，成为了全球科学界的研究热点。天然气水合物在地层中能否稳定存在主要受温度、压力、自身结构以及成份组成的影响。海平面升降、底层水温变化、沉积速率的改变等自然环境的变化及海底滑坡、地震和火山爆发等地质灾害的发生都会引起天然气水合物的突发性分解释放。我国南海北部作为天然气水合物的潜在赋存区，在地质历史中也曾多次发生天然气水合物的分解释放。天然气水合物所分解释放的甲烷向上逸散，与沉积物中的硫酸盐发生氧化还原反应，甲烷厌氧氧化-硫酸盐还原反应（AOM-SR）是沉积物早期成岩过程中最重要的反应之一，其反应过程不仅受到沉积物中的有机质和向上逸散的甲烷等碳源的影响，沉积物...As an ideal alternative energy in the 21st century, gas hydrate has become a research focus in the global science field. The existing of gas hydrate is mainly under the influence of temperature, pressure and composition. Not only the variations of sea level, deposition rate and the sea water temperature at the bottom, but also sundry geological hazards, such as underwater landslides and earthquake...学位：理学硕士院系专业：海洋与地球学院_海洋地质学号：2242011115140

Electrochemical Behavior of Vinyl Ethylene Sulfite as an Electrolyte Film-forming Additive in Lithium Ion Batteries

研究了具有不饱和双键和亚硫酸酯双官能团的乙烯基亚硫酸乙烯酯(VES)作为锂离子电池电解液成膜添加剂对中间相碳微球(CMS)和lIfEPO4电极电化学性能的影响.结果表明:在1MOl/llIClO4/PC电解液体系中,少量的VES(5%)能够在电化学过程中先于PC在CMS表面还原,形成稳定的SEI膜,明显抑制PC和溶剂化锂离子共嵌入石墨层间,改善了电池的循环性能.此外,电解液1MOl/llIClO4/PC+5%VES(V∶V)在lIfEPO4电极中展现出良好的电化学稳定性.A film-forming additive, vinyl ethylene sulfite (VES) with both vinylene group and sulfite group, affects the electrochemical performance of carbonaceous mesophase spherules (CMS) and LiFePO4 electrode.The results indicated that a small amount of VES (5%) could be reduced prior to the propylene carbonate (PC) solvent on the surface of CMS electrode in PC-based electrolyte to form a stable solid electrolyte interphase (SEI) layer, so co-intercalation of PC and solvated lithium ions to graphite could be suppressed.Furthermore, the electrolyte of 1 mol/L LiClO4/PC+5%VES (V∶V) exhibited excellent electrochemical stability in the LiFePO4 electrode.国家自然科学基金(Nos.20473068;29985310);国家“973”计划(No.2007CB209702)资助项

南海北部天然气水合物的形成分解与微生物的偶联关系

微生物在天然气水合物的形成和分解中扮演了重要的角色.南海北部是我国天然气水合物未来开发的战略选区之一,目前已多次在该海域采集到天然气水合物样品,证实了南海北部蕴藏着丰富的天然气水合物资源.通过分析天然气水合物形成与分解同微生物的偶联关系,综述了与天然气水合物形成分解有关的微生物类型及其标志化合物,结合我国南海北部天然气水合物赋存或潜在赋存区的微生物相关研究工作进展,提出未来使用微生物地球化学方法勘探天然气水合物的技术指标和相关的研究方向.国家自然科学基金(41773078,41276046);;厦门大学校长基金(0050-ZK1104

Electrochemical Behavior of Vinyl Ethylene Sulfite as an Electrolyte Film-forming Additive in Lithium Ion Batteries

A film-forming additive, vinyl ethylene sulfite (VES) with both vinylene group and sulfite group, affects the electrochemical performance of carbonaceous mesophase spherules (CMS) and LiFePO4 electrode. The results indicated that a small amount of VES (5%) could be reduced prior to the propylene carbonate (PC) solvent on the surface of CMS electrode in PC-based electrolyte to form a stable solid electrolyte interphase (SEI) layer, so co-intercalation of PC and solvated lithium ions to graphite could be suppressed. Furthermore, the electrolyte of 1 mol/L LiClO4/PC+5%VES (V:V) exhibited excellent electrochemical stability in the LiFePO4 electrode

Y型聚乙二醇干扰素琢-2b注射液治疗HCV基因2/3型慢性丙型肝炎患者疗效和安全性的多中心随机对照试验研究

目的以标准剂量的聚乙二醇干扰素(Peg IFN)α-2a联合利巴韦林作为阳性对照,评价新型试验药物Y型Peg IFNα-2b注射液联合利巴韦林治疗2型/3型慢性丙型肝炎(CHC)患者的疗效和安全性。方法采用多中心、随机开放、阳性药对照的Ⅲ期临床试验,筛选符合要求的2型/3型CHC患者,按照2:1的比例随机分配到Y型Peg IFNα-2b组和Peg IFNα-2a组,同时口服利巴韦林,疗程24 w,停药随访24 w。采用Abbott Real Time HCV Genotype II检测HCV基因型,采用Cobas Taq Man实时定量PCR法检测血清HCV RNA水平。详细记录不良事件。主要疗效指标为持续病毒学应答(SVR),并进行非劣效检验。结果本试验实际入组2型/3型CHC患者255例,实际治疗241例。全分析集(FAS)数据显示,158例试验组和83例对照组患者SVR分别为85.4%(95%CI 79.94%~90.94%)和79.5%(95%CI 70.84%~88.20%,P=0.2402);对符合方案分析集(PPS)人群分析显示,试验组和对照组患者SVR分别为87.9%(95%CI 82.45%~93.27%)和85.9%(95%CI 77.82%~94.01%,P=0.7060),率差的95%可置信区间均符合非劣效标准;对PPS人群分析显示,85.8%受试者获得了早期病毒学应答(RVR),RVR的阳性预测值为90.1%;试验组和对照组不良事件发生率相似,分别为95.6%和95.2%,严重不良事件发生率分别为3.8%和3.6%。结论应用Peg IFNα联合利巴韦林治疗2型/3型CHC患者,新型试验药物Y型Peg IFNα-2b具有与对照药物Peg IFNα-2a相似的疗效和安全性。国家科技部“十二五”重大专项(编号:2012ZX10002-003)；“重大新药创制”十二五科技重大专项(编号:2012ZX09303019)

Vertical Microbial Community Structure Characteristics of Sediment in Gas Hydrate Potential Area of Northern South China Sea Jiulong Methane Reef

本研究应用微生物16S rrnA-dggE和T-rflP技术,结合环境参数,对我国天然气水合物潜在区南海九龙甲烷礁附近973-4柱状样沉积物中3个层位12个不同深度(表层20 CM至382 CM,中层552 CM至796 CM,深层862CM至1 196 CM)细菌群落结构及其分布进行了对比研究。其中T-rflP实验表明,细菌丰度、香农指数和均匀度变化趋势相同,由深层到716 CM处先降后升,中层716 CM深度范围处微生物群落丰度、均匀度、香农指数相对较高,716CM至表层先降后升。dggE图谱和T-rflP色谱峰聚类分析表明:表层20 CM至192 CM相似性较高,表层236 CM至382 CM与深层1 082 CM、1 196 CM群落结构相似性较高,但中层沉积物中微生物群落结构与表层及深层均有较大差异。环境参数表明中层甲烷含量较高,推测甲烷是影响微生物群落结构差异的主要因素之一。T-rflP色谱峰与微生物数据库比对及dggE条带测序也表明了:本区变形杆菌(PrOTEObACTErIA)为优势菌群,其中α-、γ-、δ-变形杆菌(PrOTEObACTErIA)为主要的细菌亚群,其他细菌包括放线菌(ACTInObACTErIA)、厚壁菌门(fIrMICuTES)、绿弯菌门(CHlOrOflEXI)为次优势菌群。甲烷含量较高的中层,甲烷氧化菌(METHAnOTrOPHS),硫还原菌(SulfATE-rEduCIng bACTErIA)等与甲烷密切相关的细菌均有被检测到,表明该区域存在与天然气水合物的分解释放相关的微生物群落。Although the marine sediments bacteria play an important role in marine environment,a comprehensive view of community characteristics is still lacking,to understand the characteristics of microbial community structure in gas hydrate potential region and to evaluate how bacterial community structure response to gas hydrate,we used PCRbased technology: terminal restriction fragment length polymorphism( T-RFLP) and denaturing gradient gel electrophoresis( DGGE),combine environment parameters such as sediment grain size,total organic carbon( TOC),deposition rate and sediment age to research the diversity of bacterial communities and structure in sediments from the adjacent region of Jiulong Methane Reef 973-4 in the northern South China Sea,and we divided the 973-4 core into three parts in the base of environmental parameters: surface layer,contain 20 cm,192 cm,236 cm,326 cm,382cm; middle layer,contain 552 cm,592 cm,716 cm,796 cm; and deep layer,contain 862 cm,1 082 cm,1 196 cm.The environment parameters show that the total organic carbon content decrease from surface to deep,and the content was between 0.20% to 1.83%,mostly greater than 0.5%,it can provide source for the formation of gas hydrate; the average sediment grain is between 6 μm to 8 μm; the age of the bottom of 973-4 core is 43 431 a,reveal to oxygen isotopic Ⅲ period,and the average deposition rate of this core was 34.6 cm·ka-1,meet the deposition rate of natural gas hydrate formation conditions.The result of T-RFLP show that there were much higher values of richness,Shannon-wiener index and evenness index in surface layer sediments and deep layer than the middle layer,but 716 cm was higher than other depths sediments in middle layer by the analysis of terminal restriction fragment( T-RFs).The Shannon-wiener index in some depth was lower than 2.0,show the low diversity of microbial.The three parameters have the same trend.Three parameters increased initially then reduced from deep layer to 716 cm,and the trend from 716 cm to surface layer was decrease and then increase.Though clustering result on the terminal restriction fragments( T-RFs) areas and denaturing gradient gel electrophoresis patterns shows that: the surface sediments 20 cm to 192 cm have higher similarity,the value is 52%,236 cm were similar to 1 196,the similarity is 76%,382 cm to 1 082 cm similarity is 38%,besides have similarity with 326 cm,552 cm,796 cm; the different depths in middle layer have similarity,simultaneously 716 cm and 862 cm were higher similar,this is connection with the methane level in middle layer,and methane can affect the community composition of microbial.Middle layer located in oxygen isotopicⅡ period,the template is cool,it led to the sea levels drop and made the change of the methane,and the change of methane concentration lead to great difference of microbial community structure in middle with surface and deep layers.The deep sediments microbial community has higher similarity with the surface layer because of the methane concentration was lower than middle layer and the similar total organic carbon content.Through clustering analysis and sediment environment parameters indicated that the vertical distribution of bacterial was coincided with the sediment total organic carbon content,grain size and methane concentration.And the difference of microbial community structure related to the geologic conditions for example depth,the change of sediment properties,methane concentration.Through compare T-RFLP chromatogram to Mica3 database and sequencing the DGGE bands to analysis the diversity of the sediments and the result showed that: Proteobacteria were the dominant phylum,and α-,γ-,δ-Proteobac-teria were the main class within Proteobacteria,other bacteria include Actionmycetes,Firmicutes and Chloroflexi.The dominate bacteria in surface layer is δ-Proteobacteria,most of microbial were related to the hydrothermal vent of deep sea sediments,and δ-Proteobacteria have related with sulfur cycle,indicated that sulfide metabolism especially the sulfate reduction was important process; in middle layer α-Proteobacteria,δ-Proteobacteria were the dominant bacteria and almost related to the deep-sea methane seep and pacific deep-sea sediment,suggest that sulfate reduction and methane oxidation were the main process in middle layer; α-Proteobacteria was dominated in deep layer,we conclude that methane oxidation was the main process,indicating that our deep-sea sampling might be influence by the gas hydrate.In addition,methane oxidizing bacteria such as Methanotrophs and Sulfate-reducing bacteria occur in middle layer where has higher methane concentration areas,and the bacterial were related to the bacterial retrieved from sulfide chimneys,hydrothermal vent environment and areas where has confirm existing gas hydrate,indicated that the microbial community structure in core 973-4 have relation with gas hydrate decomposition and release,suggest that this zone maybe exist gas hydrate.Our data suggest that other bacteria are also involved in methane oxidation in these environments,and combine with the environment parameters we conclude that this zone exist gas hydrate,and conclusion the sulfate reduction methane oxidation transform zone located in the depths of 500 cm to 900 cm.国家自然科学基金(批准号:40976035;41276046); 国家“973”计划子课题(编号:2009CB21951)联合资

南海北部陆坡沉积物中P-S-Fe的相互作用及其对划分硫酸盐-甲烷转换带的指示意义

对南海北部陆坡台西南海域973-4岩心沉积物中自生磷灰石磷(PCAF)和铁氧化物结合态磷(PFe)及4种活性Fe组分进行了分步提取测定。结果显示:沉积物自生磷灰石磷(PCFA)含量为0.34%3.24%,是该站沉积物P的主要成分,其含量自海底向下反复波动;铁氧化物结合磷(PFe)含量为0%1.38%,总体上出现多次升降。Fepy含量为0.05%0.72%,平均含量为0.27%,Fecarb含量为0.14%0.64%,平均含量为0.33%,在硫酸盐-甲烷转换带（SMTZ）上部Fepy和Fecarb均出现上升现象,在SMTZ下部Fepy迅速下降而Fecarb含量缓慢上升。Feox含量为0.32%0.73%,平均含量为0.46%;Femag含量为0.18%0.34%,平均含量为0.25%。Feox和Femag含量变化趋势基本一致。结合沉积物总硫（TS）、酸可挥发性硫（AVS）及孔隙水中硫酸根(SO42-)等指标分析可得出:973-4柱中两种SO42-还原模式产生的CO32-均会抑制磷灰石晶体的凝聚成核作用;可以利用Fepy和Fecarb含量的反向变化及Feox和Femag的迅速升高对SMTZ上下部进行判定划分;PCAF和PFe含量在SMI界面以下的往复波动的现象为研究水合物不稳定分解影响的环境范围及古SMI界面提供了新的思路。国家自然科学基金项目(41276046,41773078);;国家重点基础研究发展计划“973”项目子课题(2009CB21951