Authigenic sulfide minerals and their sulfur isotopes in sediments of the northern continental slope of the South China Sea and their implications for methane flux and gas hydrate formation

This is a report of the study of the authigenic sulfide minerals and their sulfur isotopes in a sediment core (NH-1) collected on the northern continental slope of the South China Sea, where other geophysical and geochemical evidence seems to suggest gas hydrate formation in the sediments. The study has led to the findings: (1) the pyrite content in sediments was relatively high and its grain size relatively large compared with that in normal pelagic or hemipelagic sediments; (2) the shallowest depth of the acid volatile sulfide (AVS) content maximum was at 437.5 cm (> 2 mu mol/g), which was deeper than that of the authigenic pyrite content maximum (at 141.5-380.5 cm); (3) delta S-34 of authigenic pyrite was positive (maximum: +15 parts per thousand) at depth interval of 250-380 cm; (4) the positive delta S-34 coincided with pyrite enrichment. Compared with the results obtained from the Black Sea sediments by Jorgensen and coworkers, these observations indicated that at the NH-1 site, the depth of the sulfate-methane interface (SMI) would be or once was at about 437.5-547.5 cm and the relatively shallow SMI depth suggested high upward methane fluxes. This was in good agreement with the results obtained from pore water sulfate gradients and core head-space methane concentrations in sediment cores collected in the area. All available evidence suggested that methane gas hydrate formation may exist or may have existed in the underlying sediments.

济阳坳陷高青—平南断裂带天然气地球化学及与火成岩的关系

济阳坳陷位于渤海湾盆地东南部，是中国东部重要的含油气坳陷之一，同时也是重要的天然气气藏富集区。坳陷中部高青－平南断裂从孔店组沉积时开始发育，至明化镇末期断裂停止活动。岩浆活动导致断裂带两侧天然气的分布较为复杂：既有纯烃类气藏，也有纯非烃类气藏，还有混合气藏。已有的工作主要是着重气藏形成的地质条件、成藏模式以及盆地演化过程中的构造-热事件中的岩浆活动对CO2气藏形成的总体影响。对烃类气藏成因研究不足，仅简单的归于油型气；同时天然气藏与火山活动之间的关系研究不够，本论文在天然气、火山岩地球化学基础上，探讨天然气的来源，综合分析了火山活动对天然气形成的影响。论文获得的主要认识如下： 1. 根据花沟地区天然气碳及稀有气体地球化学特征结合该地区火山岩流体包裹体组分，认为高青、花沟地区烃类气藏应该是有机与无机成因相结合的混合气体，其有机来源主要是来自油型气；无机来源主要是地幔脱气以及发生氧化还原反应生成的无机成因气；而平南、平方王地区烃类气主要为油型气。 2. CO2气藏主要是无机幔源成因。据CO2体积百分含量、CO2碳同位素（δ13CCO2）表明CO2是无机成因，氦同位素R/Ra、40Ar/ 36Ar表明区内CO2成因与无机幔源成因密切相关。不同地区幔源包裹体中的CO2含量不同，研究表明后期火山岩浆更富CO2。高青地区CO2气以幔源岩浆脱气成因为主；平方王和平南地区为幔源岩浆脱气和壳源岩石化学混合成因。 3. 稀有气体同位素组成说明该地区He、Ar为壳幔混合成因。40Ar/36Ar值317~3178之间，氦同位素R/Ra在1.44~5.96之间；在3He/4He-40Ar/36Ar以及3He/4He-4He/20Ne图中均处于壳源与幔源混合成因区域。 4. 岩浆活动对天然气成藏效应体现在对天然气形成与成藏的影响。 5. 高青－平南断裂带幔源流体活动方式和活动强度存在时间和空间上的差异是造成高青－平南断裂带天然气分布不同最主要的原因。CO2气藏更容易在两个断裂的交汇处形成，说明了断裂为天然气的运移提供通道。

Formation of Fe-oxyhydroxides from the East Pacific Rise near latitude 13 degrees N: Evidence from mineralogical and geochemical data

The mineralogical and geochemical characteristics of Fe-oxyhydroxide samples from one dredge station (long. 103 degrees 54.48'W, lat. 12 degrees 42.30'N, water depth 2655 m) on the East Pacific Rise near lat 13 degrees N were analyzed by XRD, ICP-AES, and ICP-MS. Most Fe-oxyhydroxides are amorphous, with a few sphalerite microlites. In comparison with Fe-oxyhydroxides from other fields, the variable ranges in the chemical composition of Fe-oxyhydroxide samples are very narrow; their Fe, Si, and Mn contents were 39.90%, 8.92%, and 1.59%, respectively; they have high Cu (0.88%-1.85%) and Co (65x10(-6)-704x10(-6)) contents, and contain Co+Cu+Zn+Ni > 1.01%. The trace-element (As, Co, Ni, Cu, Zn, Ba, Sr) and major-element (Fe, Ca, Al, Mg) contents of these samples are in the range of hydrothermal sulfide from the East Pacific Rise near 13 degrees N, reflecting that this type of Fe-oxyhydroxide constitutes a secondary oxidation product of hydrothermal sulfide. The Fe-oxyhydroxide samples from one dredge station on the East Pacific Rise near 13 degrees N are lower in Sigma REE (5.44x10(-6)-17.01x10(-6)), with a distinct negative Ce anomaly (0.12-0.28). The Fe-oxyhydroxide samples have similar chondrite-normalized rare-earth-element (REE) patterns to that of seawater, and they are very different from the REE composition characteristics of hydrothermal plume particles and hydrothermal fluids, showing that the REEs of Fe-oxyhydroxide are a major constituent of seawater and that the Fe-oxyhydroxides can become a sink of REE from seawater. The quick settling of hydrothermal plume particles resulted in the lower REE content and higher Mn content of these Fe-oxyhydroxides, which are captured in part of the V and P from seawater by adsorption. The Fe-oxyhydroxides from one dredge station on the East Pacific Rise near 13 degrees N were formed by secondary oxidation in a low temperature, oxygenated environment. In comparison with the elemental (Zn, Cd, Pb, Fe, Co, Cu) average content of hydrothermal sulfide samples from the East Pacific Rise near 13 degrees N, the Zn, Cd, and Pb contents of the Fe-oxyhydroxides are lower, and their Fe, Co, and Cu contents are higher.

Experimental Evidence of Critical Sensitivity in Catastrophe

The paper presents an experimental study on critical sensitivity in rocks. Critical sensitivity means that the response of a system to external controlling variable may become significantly sensitive as the system approaches its catastrophic rupture point. It is found that the sensitivities measured by responses on three scales (sample scale, locally macroscopic scales and mesoscopic scale) display increase prior to catastrophic transition point. These experimental results do support the concept that critical sensitivity might be a common precursory feature of catastrophe. Furthermore, our previous theoretical model is extended to explore the fluctuations in critical sensitivity in the rock tests.

Electrochemical, spectroscopic and SPM evidence for the controlled formation of self-assembled monolayers and organised multilayers of ferrocenyl alkyl thiols on Au(111)

Organised multilayers were formed from the controlled self-assembly of ferrocene alkyl thiols on Au(111) surfaces. The control was accomplished by increasing the concentration of the thiol solutions used for the assembly. Cyclic voltammetry, ellipsometry, scanning probe microscopy (STM and AFM) and in situ FTIR spectroscopy were used to probe the differences between mono- and multilayers of the same compounds. Electrochemical desorption studies confirmed that the multilayer structure is attached to the surface via one monolayer. The electrochemical behaviour of the multilayers indicated the presence of more than one controlling factor during the oxidation step, whereas the reduction was kinetically controlled which contrasts with the behaviour of monolayers, which exhibit kinetic control for the oxidation and reduction steps. Conventional and imaging ellipsometry confirmed that multilayers with well-defined increments in thickness could be produced. However, STM indicated that at the monolayer stage, the thiols used promote the mobility of Au atoms on the surface. It is very likely that the multilayer structure is held together through hydrogen bonding. To the best of out knowledge, this is the first example of a controlled one-step growth of multilayers of ferrocenyl alkyl thiols using self-assembly techniques.

Experimental Evidence of Critical Sensitivity in Catastrophe

The paper presents an experimental study on critical sensitivity in rocks. Critical sensitivity means that the response of a system to external controlling variable may become significantly sensitive as the system approaches its catastrophic rupture point. It is found that the sensitivities measured by responses on three scales (sample scale, locally macroscopic scales and mesoscopic scale) display increase prior to catastrophic transition point. These experimental results do support the concept that critical sensitivity might be a common precursory feature of catastrophe. Furthermore, our previous theoretical model is extended to explore the fluctuations in critical sensitivity in the rock tests.