Detection of methane plumes in the water column of Losatchev hydrothermal vent field, Mid-Atlantic Ridse

During DY105-17 cruise onboard the PJV ＂Da Yang Yi Hao＂ in 2005, methane concentrations in the water column above Logachev hydrothermal vent field were measured by applying stripping/trapping-gas chromatographic （GC） and the distinct methane plumes were detected. Results show that the background methane concentration within the Logachev area is from 1.05 nmol/L to 1.68 nmol/L, significantly higher than the background level of the Atlantic abyssal plain of 0.4-0.5 nmol/L, suggesting that hydrothermal venting is a major source of dissolved methane to the ocean. The highest anomalies of methane concentrations in the water column range from 7.14 nmol/L to 113.9 nmol/L and occur just at 180-500 m above the seafloor. The distribution of methane concentration and the structural characteristics of hydrothermal plumes are strongly influenced by the supply of underlying hydrothermal fluids, the mixing process of ocean bottom currents and the microbial oxidation. Furthermore, the differences in distribution of methane plume between the station MAR-CTD3 and the other stations indicate a probable unknown hydrothermal vent site nearby. There occurs high concentration of methane along with temperature and nephelometry anomalies, which strongly confirms that the subtle measurement of methane concentration in water column is one of the effective ways to locate active sites of hydrothermal venting.     

Water-driven structure transformation in nanoparticles at room temperature

The thermodynamic behaviour of small particles differs from that of the bulk material by the free energy term gammaA--the product of the surface (or interfacial) free energy and the surface (or interfacial) area. When the surfaces of polymorphs of the same material possess different interfacial free energies, a change in phase stability can occur with decreasing particle size. Here we describe a nanoparticle system that undergoes structural changes in response to changes in the surface environment rather than particle size. ZnS nanoparticles (average diameter 3 nm) were synthesized in methanol and found to exhibit a reversible structural transformation accompanying methanol desorption, indicating that the particles readily adopt minimum energy structural configurations. The binding of water to the as-formed particles at room temperature leads to a dramatic structural modification, significantly reducing distortions of the surface and interior to generate a structure close to that of sphalerite (tetrahedrally coordinated cubic ZnS). These findings suggest a route for post-synthesis control of nanoparticle structure and the potential use of the nanoparticle structural state as an environmental sensor. Furthermore, the results imply that the structure and reactivity of nanoparticles at planetary surfaces, in interplanetary dust and in the biosphere, will depend on both particle size and the nature of the surrounding molecules.     

电喷湿法制备二醋酸纤维素/硫化锌复合纳米粒子

二醋酸纤维素(CDA)/硫化铵((NH4)2S)复合溶液以丙酮为溶剂,在高压静电场力的作用下,喷射到对应的接收溶液ZnSO4中,通过水洗得到粒径分布比较均匀的CDA/ZnS复合纳米粒子.借助光学显微镜及扫描电镜(SEM)观察CDA/ZnS复合纳米粒子的微观形态,CDA质量分数大小较(NH4)2S质量分数对复合粒子粒径影响更大.利用透射电镜(TEM)观察发现ZnS被包覆在有机载体CDA小球中,尺寸大约为5～30nm.对试验产物进行X射线衍射(XRD)表征,证明产物同时含有CDA及ZnS.     

纳米ZnS的合成与表征

将通过直接沉淀法得到的纳米ZnS再经过水溶剂热处理,使其晶化.XRD及TEM结果显示ZnS是立方闪锌矿结构,为8-15nm的球状颗粒.水溶剂热晶化后,颗粒的大小、分散性、均匀度、晶化度均提高,表面活性剂的存在对颗粒的性质有影响.     

水热法制备ZnS:Mn纳米晶体及其发光特性

研究了水热法(200°C)制备的不同浓度Mn掺杂ZnS纳米晶体发光特性。所合成样品为10～16 nm的立方相纤锌矿结构,随着Mn掺杂浓度的增加,PL光谱峰值产生了红移。在摩尔比为10 ％ Mn掺杂时PL发光最强。讨论了样品的发光机理,计算了晶体场强度,同时观察到摩尔比为10 ％ Mn掺杂样品发出白光,说明其在白光LED及全色荧光粉中具有潜在的应用价值。     

ZnS纳米陶瓷微球的制备

以ZnCl2和Na2 S2 O3为前驱物在二氯苯/水溶液界面上,在超重力为1000/g的条件下水热合成了高密度的ZnS 纳米陶瓷微球,研究了前驱物浓度、温度和超重力大小对ZnS 纳米陶瓷微球性能的影响。采用FE-SEM,TEM, XRD,FT-IR, UV-Vis和BET对样品的形貌、微结构、物相和性能进行表征。结果发现,ZnS纳米陶瓷微球是由尺寸为2-20 nm的ZnS晶粒组成的直径为300-500 nm的微球,其密度与施加的超重力大小有关。随着超重力的增大,晶粒粒度减小,制得的ZnS纳米陶瓷微球的密度就增大。在120℃,1000/g超重力的条件下,在二氯苯/水溶液界面上反应30 min制备得到的ZnS纳米陶瓷微球具有高分散性和较高的密度。     

ZnS/PbS核壳结构微球的制备和表征

用简单两步法制备ZnS/PbS核壳结构复合微球,采用SEM、EDS、TEM、XRD、FT-IR和固体紫外等测试手段对核壳结构复合微球样品进行性能表征,发现所得复合微球由ZnS核和PbS壳构成,其平均粒径约为8μm;而且具有中空结构的ZnS微球表面被很多细小的PbS颗粒包覆形成核壳结构。UV-vis表明ZnS/PbS核壳结构复合微球在紫外-可见光区都有良好的吸收,说明其在光电器件领域中将会有很好的发展前景。另外,还探讨了复合微球形成的机理。     

量子点ZnS的制备及其光催化降解有毒有机污染物

分别以硫化钠(Na2S)和硫脲(CH3CSCH3)为硫源与醋酸锌(Zn(CH3COO)2.2 H2O)通过水热法反应制备了ZnS量子点,通过透射电子显微镜(TEM)及X-射线衍射(XRD)对ZnS进行了初步表征,结果表明:两类硫源制备的ZnS量子点均为颗粒状立方闪锌矿结构,量子尺寸分别为19.6 nm,25.1nm.在紫外光(λ≤387)照射下以有机染料罗丹明B(Rhodamine B,RhB)及无色小分子2,4-二氯苯酚(2,4-Dichlorophenol,DCP)的光催化降解为探针反应,研究了介质pH条件和光催化剂ZnS用量对光催化反应的影响,表明pH=10、光催化剂用量为50 mg条件下以Na2S为硫源制得的ZnS活性较好,能使RhB在70 min内褪色完全,呈现出ZnS量子点的量子尺寸效应.同时,此实验条件下11 h对2,4-二氯苯酚(2,4-Dichlorophenol,DCP)的深度氧化矿化率为90%.用酶催化分光光度法和苯甲酸荧光光度法分别跟踪测定了催化反应过程中产生的H2O2和.OH,表明量子点ZnS对有毒有机物的光催化氧化过程涉及H2O2和.OH的氧化历程.     

An off-axis hydrothermal vent field near the Mid-Atlantic Ridge at 30 degrees N.

Evidence is growing that hydrothermal venting occurs not only along mid-ocean ridges but also on old regions of the oceanic crust away from spreading centres. Here we report the discovery of an extensive hydrothermal field at 30 degrees N near the eastern intersection of the Mid-Atlantic Ridge and the Atlantis fracture zone. The vent field--named 'Lost City'--is distinctly different from all other known sea-floor hydrothermal fields in that it is located on 1.5-Myr-old crust, nearly 15 km from the spreading axis, and may be driven by the heat of exothermic serpentinization reactions between sea water and mantle rocks. It is located on a dome-like massif and is dominated by steep-sided carbonate chimneys, rather than the sulphide structures typical of 'black smoker' hydrothermal fields. We found that vent fluids are relatively cool (40-75 degrees C) and alkaline (pH 9.0-9.8), supporting dense microbial communities that include anaerobic thermophiles. Because the geological characteristics of the Atlantis massif are similar to numerous areas of old crust along the Mid-Atlantic, Indian and Arctic ridges, these results indicate that a much larger portion of the oceanic crust may support hydrothermal activity and microbial life than previously thought.     

水热法制备ZnS:Mn纳米发光粉

采用水热法,以十六烷三甲基溴化氨(C16TAB)作为表面活性剂,在填充度为75%和温度180℃的条件下,制备了ZnS:Mn的纳米发光粉体.利用激发光谱、发射光谱和透射电子显微镜对其光学特性和形貌进行了研究.实验发现,与未进行表面修饰的ZnS:Mn纳米粒子相比,ZnS:Mn纳米颗粒发光亮度增加数倍,而且随着表面活性剂浓度的增加,ZnS:Mn发光强度显著增强.当质量比m(C16TAB):m(Zn)=1:5时,发光强度达到最大,粒径分布均匀,呈球形,平均粒度为50 nm.     

银氧化锡触点材料的水热制备及组织分析

利用水热法制备AgSnO2粉体,压制烧结后制得AgSnO2块体样品. 对AgSnO2粉体样品进行X射线衍射、扫描电镜和能谱分析,结果表明:通过在溶液体系中实现银和二氧化锡的共沉积,水热法能制得颗粒细小均匀的球形AgSnO2复合粉体. 块体样品X射线衍射谱表明,水热法制备的AgSnO2粉体由于改变了Ag和SnO2的结合状态,烧结时二氧化锡晶体在(110)晶面上表现出一定的择优取向. 对块体样品的显微组织分析表明,AgSnO2块体样品能够克服氧化物的聚集,二氧化锡颗粒在银基体中均匀弥散分布.     

Evolutionary mechanism of b-oriented TS-1 film on porous α-Al2O3 supported chitosan surface in hydrothermal reactions

The acid-base titration, atomic force microscopy (AFM), contact angle technique, energy dispersive X-ray (EDX) and electron probe microanalysis (EPMA) were performed to check the existence of the gel-layer on the chitosan surface after it was dipped in aqueous TPAOH solution as well as in TS-1 synthesis solution. The evolution of TS-1 monolayer and multi-layered film on the chitosan surface was studied using SEM imaging at different stages during hydrothermal reactions. Experimental evidence for the formation mechanism of supported zeolite films and membranes revealed that a gel-layer enriched with TPA cations and TS-1 precursors was first formed on the chitosan surface, followed by the nucleation within the gel-layer especially on the chitosan surface. The nuclei formed on the chitosan surface were further transformed into crystalline particles and TS-1 crystal grains. The nuclei beyond the chitosan surface subsequently grew up, leading to the formation of multi-layered TS-1 film with preferential b-orientation. The result is significant for engineering the microstructure of supported zeolite films and membranes in hydrothermal reactions.     

花垣铅锌矿床流体包体中的子矿物

湖南西部花垣铅锌矿床，是近年来发现的产于下寒武统清虚洞组上部藻礁灰岩中的大型ＭＶＴ矿床。矿床的矿石矿物中普遍有流体包裹体存在，其中有子矿物发现。采用ＳＥＭ和ＥＤＸ对它们进行研究后，在４种主矿物中发现有７种子矿物：闪锌矿、石膏、方解石、重晶石、石盐、黄铁矿和沥青。硫酸盐类矿物在包体中的发现，证明成矿流体中，ＳＯ２－４的含量较高，而且可能是与金属离子共同迁移。     

Hydrothermal plume anomalies along the Central Indian Ridge

Water column turbidity and temperature were investigated along the Central Indian Ridge （CIR） from 25°19＇S to 23°48＇S during a December 2005 cruise on board Chinese PJV DayangYihao. Measurements were made using NOAA＇s MAPR （Miniature Autonomous Plume Recorder） sensors during CTD casts, TV grabber operations, and tow-yo profiles, yielding the following results on hydrothermal plume anomalies： （1） Strong hydrothermal turbidity and temperature anomalies were recorded over the previously discovered Kairei （25°19.2＇S, 70°02.4＇E） and Edmond （23°52.7＇S, 69°35.8＇E） vent fields, with the plume anomalies concentrated at depths of 2150--2300 m and 2700--2900 m, respectively. The maximum height of the turbidity anomalies near the Kairei vent field recorded in December 2005 was slightly below 2100 m, which is consistent with the plume depth measured in June 2001, indicating that the Kairei plume may have maintained its buoyancy flux in the intervening 4.5 years. （2） The water column beneath the Kairei plume has background anomalies of about 0.005ANTU, whereas no such background turbidity anomalies were observed below the Edmond hydrothermal plume. （3） No visible turbidity anomalies were detected from 24°42＇S to 24°12＇S including the Knorr Seamount. Thus 24°12＇S marks the southern end of the hydrothermal plume. （4） Significant turbidity anomalies were observed at four individual sections from 24°12＇S to 23°56＇S at the depth of 2500--3000 m along the eastern rift valley wall. Whether the individual sections of anomalies are connected is still unknown due to the absence of data at the intervening gaps. If the four sections are connected with each other and are linked to the Edmond vent field farther to the north, the total along-axis length of the plume anomaly would be more than 37 km, implying a plume incidence value Ph of 0.38, greater than the predicted Ph of 0.21 --0.25 based on the spreading rate of the Central Indian Ridge.     

ZnS和C60纳米线阵列的构筑和表征

以多孔氧化铝为模板,通过水热反应制备出ZnS 和 C₆₀纳米线阵列,分别用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)、拉曼光谱以及选区电子衍射图谱(SAED)等,对纳米线阵列形貌和化学成分进行表征.结果表明,ZnS 和C₆₀纳米线均为有序阵列.ZnS纳米线为多晶结构,在波长332 nm紫外光激发下, 发射519 nm特征荧光.同时介绍了水热条件下,在多孔氧化铝模板中填充目的产物,以及制备纳米线有序阵列的相关过程.该方法具有一定的普适性.     

化学浴沉积法制备ZnS薄膜的研究

基于化学浴沉积法,采用硫酸锌、硫脲、水合肼和氨水混合溶液于适当温度下在玻璃衬底上沉积得到表面均匀的ZnS薄膜.对在不同沉积时间以及退火时间下得到的ZnS薄膜运用X射线衍射法观测其晶型结构,发现较长的沉积时间(5 h)和退火时间(3 h)制得的薄膜结晶度好,且检测出为闪锌矿晶型.并对其透光性能做了检测,发现pH值对透光度有显著影响.     

Discovery of abundant hydrothermal venting on the ultraslow-spreading Gakkel ridge in the Arctic Ocean

Submarine hydrothermal venting along mid-ocean ridges is an important contributor to ridge thermal structure, and the global distribution of such vents has implications for heat and mass fluxes from the Earth's crust and mantle and for the biogeography of vent-endemic organisms. Previous studies have predicted that the incidence of hydrothermal venting would be extremely low on ultraslow-spreading ridges (ridges with full spreading rates <2 cm x yr(-1)-which make up 25 per cent of the global ridge length), and that such vent systems would be hosted in ultramafic in addition to volcanic rocks. Here we present evidence for active hydrothermal venting on the Gakkel ridge, which is the slowest spreading (0.6-1.3 cm x yr(-1)) and least explored mid-ocean ridge. On the basis of water column profiles of light scattering, temperature and manganese concentration along 1,100 km of the rift valley, we identify hydrothermal plumes dispersing from at least nine to twelve discrete vent sites. Our discovery of such abundant venting, and its apparent localization near volcanic centres, requires a reassessment of the geologic conditions that control hydrothermal circulation on ultraslow-spreading ridges.     

La掺杂对化学沉积ZnS薄膜影响的电化学研究

采用化学沉积法在导电玻璃上制备了ZnS及其La掺杂薄膜.用扫描电子显微镜(SEM)对其形貌进行表征,并用CHI660B电化学综合分析测试仪对ZnS和La掺杂ZnS薄膜的沉积过程进行分析.结果表明,化学沉积法制备了致密的、由球状颗粒组成的ZnS薄膜,掺杂La后,由于电负性较低的La在电极表面的吸附,电位负移,沉积速率下降,薄膜颗粒尺寸增大.电化学方法为研究ZnS的化学沉积提供了有效的分析技术.     

济南市春季大气中PM2.5、PM10颗粒物分布状态及元素分析

采用扫描电镜和能谱仪对济南市区春季大气中PM_(2.5)、PM_(10)颗粒物的显微形貌、粒径分布和化学元素进行连续30 d全天候研究,对大气颗粒物的粒径与数量进行统计回归分析,绘制相应粒径变化柱状图。依据检出的元素来推断大气颗粒物化学组成和来源,提出控制大气颗粒物PM2.5、PM10污染的有效对策。实验结果显示,大气颗粒物显微形态有球状、片状、棒状等不同形状且主要集中于0～1.0μm和1.0～2.5μm粒径范围,检出C、O、Cl、Si、Ca、K、Na、Mg、Al、Fe、S等多种化学元素,大多以矿物质氧化物、硫酸盐、硅铝酸盐等形式存在,主要来源于土壤尘、风沙尘、燃煤飞灰等。该方法简单、快速、科学,值得进一步推广应用。     

反应温度对水热合成二氧化钛微粒的影响

采用水热合成工艺,以钛酸丁酯(Ti(OC4H9)4)为前驱体,通过改变水热合成反应的温度,合成了不同晶型和形貌的二氧化钛(TiO2)微粒。使用扫描电子显微镜和X射线衍射仪对产物进行表征。结果表明:水热反应的温度对TiO2微粒的晶型、晶粒尺寸和形貌有较大影响。随着水热反应温度的增加,二氧化钛微粒的晶粒粒径越来越大,结晶程度越来越完整,形貌也越来越规则。当水热反应温度较低时(80℃),晶型以锐钛矿为主,衍射峰峰宽较宽,峰强也较弱,晶粒刚开始发育;随着反应温度增加,开始出现金红石晶型,衍射峰锐化,峰的强度增强,晶粒粒径增大,晶粒逐渐发育完全;当反应温度达到160℃时,以金红石晶型为主,晶粒发育完全,结晶完善。