黄东海及朝鲜海峡冰后期陆架沉积物的环境磁学研究

There are four chapters in this dissertation. The first chapter briefly synthesizes the basic theories, methods and present-day applying situation of environmental magnetism. The second chapter probes into the magnetic mineral diagenesis in the post-glacial muddy sediments from the southeastern South Yellow Sea and its response to marine environmental changes, using the muddy sediment of Core YSDP103 formed in the shelf since about 13 ka BP. The third chapter illustrates the high-resolution early diagenetic processes by investigating the rapidly deposited muddy sediments during the last 6 ka in Cores SSDP-102 and SSDP-103 from the near-shore shelf of Korea Strait. The fourth chapter presents the results of detailed rock magnetic investigation of the surface sediments from the fine-grained depositional area on the outer shelf of the East China Sea in an attempt to provide environmental magnetic evidence for the provenance of the fine-grained deposit. Core YSDP103 was retrieved in the muddy deposit under the cold eddy of the southeastern South Yellow Sea, and the uppermost 29.79 m core represents the muddy sediments formed in the shelf since about 13 ka BP. The lower part from 29.79 to 13.35 m, called Unit A2, was deposited during the period from the post-glacial transgression to the middle Holocene (at about 6 ~(14)C ka BP) when the rising sea level reached its maximum, while the upper part above 13.35 m (called Unit Al) was deposited in a cold eddy associated with the formation of the Yellow Sea Warm Current just after the peak of post-glacial sea level rise. For the the uppermost 29.79 m core, detailed investigation of rock-magnetic properties and analyses of grain sizes and geochemistry were made. The experimental results indicate that the magnetic mineralogy of the core is dominated by magnetite, maghemite and hematite and that, except for the uppermost 2.35 m, the magnetic minerals were subject to reductive diagenesis leading to significant decline of magnetic mineral content and the proportion of low-coercivity component. More importantly, ferrimagnetic iron sulphide (greigite) is found in Unit A2 but absent in Unit Al, suggesting the control of marine environmental conditions on the magnetic mineral diagenesis. Magnetic parameters show abrupt changes across the boundary between the Unit Al and A2, which reflects a co-effect of environmental conditions and primary magnetic components of the sediments on the diagenesis. Alternating zones of high and low magnetic parameters are observed in Unit A2 of Core YSDP103, which is presumably due to periodic changes of the concentration and/or grain size of magnetic minerals carried into the study area. Cores SSDP-102 and SSDP-103, two studied sediment cores from the Korea Strait contain mud sequences (14 m and 32.62 m in thickness) that were deposited during the last 6,000 years. Analyses of grain sizes and geochemistry of the cores have demonstrated that the sediments have uniform lithology and geochemical properties, however, marked down-core changes in magnetic properties suggest that diagenesis has significantly impacted the magnetic properties. An expanded view of early diagenetic reactions that affect magnetic mineral assemblages is evident in these rapidly deposited continental shelf sediments compared to deep-sea sediments. The studied sediments can be divided into four descending intervals, based on magnetic property variations. Interval 1 is least affected by diagenesis and has the highest concentrations of detrital magnetite and hematite, and the lowest solid-phase sulfur contents. Interval 2 is characterized by the presence of paramagnetic pyrite and sharply decreasing magnetite and hematite concentrations, which suggest active reductive dissolution of detrital magnetic minerals, the absolute minimum abundance of magnetite is reached at the end of this interval. Interval 3 is marked by a progressive loss of hematite with depth, and at the base of this interval, 82% to 88% of the hematite component was depleted and the bulk magnetic mineral concentration was reduced to the lowest value in the entire studied mud section. Interval 4 has an increasing down-core enhancement of authigenic greigite, which is interpreted to have formed due to arrested pyritization resulting from consumption of pore water sulfate with depth. This is the first clear demonstration from an active depositional environment for a delay of thousands of years for acquisition of a magnetization carried by greigite. This detailed view of diagenetic processes in continental shelf sediments suggests that studies of geomagnetic field behavior from such sediments should be conducted with care. Paleoceanographic and paleoclimatic studies based on the magnetic properties of shelf sediments with high sedimentation rates like those in the Korea Strait are also unlikely to provide a meaningful signature associated with syn-depositional environmental processes. The rock magnetic properties of the surface sediments from the fine-grained depositional area on the outer shelf of the East China Sea, an area surrounded by sands, are investigated with a view to providing information on the sediment provenance. Multiple magnetic parameters such as magnetic susceptibility (%), anhysteretic remanent magnetization (ARM), saturation rernanent magnetization (SIRM), coercivities of SIRM (Her), and S ratios (relative abundance of low-coercivity magnetic minerals) are measured for all 179 surface samples, and partial representative samples are examined for their magnetic hysteresis parameters, temperature-dependence of magnetic susceptibility and x-ray diffraction spectra. Our research indicates that the magnetic mineralogy is dominated by magnetite with a small amount of hematite and is primarily of pseudo-single domain (PSD) to multidomain (MD) nature with a detrital origin. In the surface sediments, the granulometry of magnetic fractions is basically independent of grain sizes of the sediment containing the magnetic grains, and the composition of magnetic minerals remains almost homogeneous, that is, with a relatively constant ratio of low to high coercivity fraction throughout the area. The magnetic concentration in the study area generally decreases to the east or southeast accompanied by magnetic-particle fining to the east or to the northeast. The geographic pattern of magnetic properties is most reasonably explained by a major source of sediment jointly from the erosion of the old Huanghe River deposit and the discharge of the Changjiang River. The rock magnetic data facilitate understanding of the transport mechanism of fine-grained sediments in the outer shelf of the East China Sea.

湖泊生态系统铁同位素与硫同位素地球化学研究--以红枫湖、阿哈湖为例

湖泊生态系统是陆地水体生态系统的重要组成部分。随着社会经济的不断发展，各种人为因素对湖泊生态系统的影响日益突出，打破了其自然演变规律，诸如 “二次污染”、水体富营养化、重金属污染等环境问题接踵而来。而铁是水生生态系统初级生产力所必需的重要微量营养元素之一，在一定的条件下可以控制和影响浮游藻类的生长速度和种类；而且，铁的氧化还原敏感性很强，其价态的改变往往会影响其它相关重金属的迁移和转化。因此，湖泊生态系统中铁的生物地球化学循环研究具有非常重要的意义。近年来的研究显示，铁同位素分析技术可以用于各种生物作用和非生物作用过程的研究，在海洋和河流生态系统中已有广泛的应用，而对湖泊生态系统的研究则鲜见报导。乌江流域中等富营养化的湖泊――红枫湖和贵阳西南郊矿化程度较高的湖泊――阿哈湖是研究湖泊生态系统中铁生物地球化学循环的理想场所。本文选取这两个性质不同的湖泊为研究对象，运用硫同位素、铁同位素及重金属和营养盐等地球化学方法手段，对两湖流域内硫酸盐的来源、硫同位素的季节和剖面变化特征、铁的来源及铁同位素组成的季节和剖面变化特征及其控制和影响因素等进行了研究和探讨，进一步完善了铁同位素分馏机理，为深化理解和研究湖泊生态系统中铁和硫的生物地球化学循环提供一定的科学依据。论文所获的主要认识总结如下： 两湖流域内湖水与河水的硫酸盐硫同位素地球化学 （1）阿哈湖流域和红枫湖流域水体的硫酸盐浓度和δ34S值均有较宽的分布范围。各入湖支流中，受煤矿废水或煤矸石淋溶液污染的河水的δ34S值相对较低（-8.10‰～-14.92‰），而受生活污水影响严重的河水则具有相对较高的δ34S值（-5.68‰～+0.88‰）。相比而言，阿哈湖流域水体纳入了大量的煤矿废水和煤矸石淋溶液，硫污染程度较红枫湖流域更为严重。因此，阿哈湖湖水具有相对较高的硫酸根浓度（平均为2.30 mmol.L-1）和相对较低的δ34S值（平均为-8.10‰），而红枫湖则具有相对较低的硫酸根浓度（平均为0.96 mmol.L-1）和相对较高的δ34S值（平均为-6.80‰）。 （2）阿哈湖湖水中的硫酸盐主要受煤矿废水、煤矸石淋溶液以及雨水等的控制；红枫湖湖水的硫酸盐主要来源于煤中黄铁矿的氧化和雨水输入，土壤硫化物的氧化和蒸发岩的溶解对湖水硫酸盐硫同位素组成的贡献较小。相比之下，雨水对红枫湖湖水硫同位素的影响更为明显。 （3）红枫湖和阿哈湖湖水的硫酸盐的δ34S值均具有明显的剖面变化特征，而且两湖的变化趋势相似，总体表现为，夏秋季节表层湖水和底层湖水的δ34S值相对较高，而冬春季节湖水剖面上下几乎没有变化。湖水硫酸盐浓度也呈现类似的变化特征，这主要与季节性厌氧湖泊夏季分层冬季混和的典型特点有关。夏季湖水分层期间，大量降雨在湖泊表层的滞留使得δ34S值升高而硫酸盐浓度降低，湖泊底部水层中硫酸盐细菌的还原作用使得底层湖水的硫酸盐浓度降低，而δ34S值升高。 两湖流域内铁同位素地球化学 （1）阿哈湖流域各类样品的δ56Fe值分布在-2.03‰～+0.12‰之间，分布范围较宽。其中湖水悬浮颗粒物的δ56Fe值在-1.36‰～-0.03‰之间，整体相对偏负。湖周各支流河水悬浮颗粒物的δ56Fe值在-0.88‰～+0.07‰之间，也相对富集轻的铁同位素；湖底沉积物和孔隙水的δ56Fe值的分布范围分别为-1.75‰～-0.59‰和-2.03‰～+0.12‰；大气颗粒物和浮游藻类的δ56Fe值分别为+0.06±0.02‰和+0.08‰。与阿哈湖相比，红枫湖流域各类样品的δ56Fe值的分布范围相对较窄，在-0.92‰～+0.36‰之间。湖水悬浮颗粒物的δ56Fe值在-0.85‰～+0.14‰之间，河水悬浮颗粒物的铁同位素组成变化范围为-0.89‰～+0.10‰，二者的变化范围相似。红枫湖沉积物的δ56Fe值在-0.18‰～+0.08‰之间，明显比阿哈湖沉积物的铁同位素组成偏正；而对应孔隙水的铁同位素组成的变化范围为-0.59‰～-0.24‰，均要比对应沉积物的铁同位素值要低。藻类和鲫鱼鱼肉的δ56Fe值分别为+0.36‰和-0.92‰。 （2）通过对两湖研究区湖水悬浮颗粒物与各输入端员环境样品的铁同位素值的研究表明，湖水悬浮颗粒物的δ56Fe值不仅受各输入端员的控制和影响，湖泊内部相关的生物地球化学过程也对湖水悬浮颗粒物的铁同位素组成变化产生了重要影响。两湖研究区内湖水悬浮颗粒物的铁同位素组成均存在季节变化特征，但受湖泊自身特点的影响，主要控制因素方面存在一定差异。夏季阿哈湖湖水悬浮颗粒物的铁同位素值变幅较大，其变化主要表现在表层和底层。表层因受陆源输入的有机结合态铁的影响而具有较负的δ56Fe值，而大气沉降颗粒物和湖泊表层的浮游藻类的影响并不显著。夏季湖水分层期间，“Ferrous Wheel”铁循环对于界面附近铁同位素的重分配起到了主要的控制和影响作用，湖水悬浮颗粒物的铁同位素值在氧化－还原界面附近达到了极负值。水－沉积物界面附近滞水层中亚铁类硫化物的生成可能也是水－沉积物界面附近水层内颗粒物的δ56Fe值偏负的原因之一。而冬季湖水混和时期，阿哈湖湖水剖面悬浮颗粒物的δ56Fe值的变幅明显减小。与阿哈湖不同，藻类的吸附作用可能在夏季红枫湖上层水体中占有主导地位，其湖水悬浮颗粒物的铁同位素组成随叶绿素水平的降低而逐渐降低。下层湖水悬浮颗粒物的铁同位素组成变化也受“Ferrous Wheel”铁循环的影响，在红枫湖后五剖面 20m 处达到-0.18‰，大坝剖面底层约为-0.46‰，其变幅没有阿哈湖悬浮颗粒物的δ56Fe值大，可能是受到了湖水中大量有机物质的影响。冬季红枫湖后五剖面的变化趋势与夏季相似，上层和下层水体悬浮颗粒物分别受不同影响因素的控制。上层水体悬浮颗粒物的铁同位素变化不明显，与Fe、Al、Mn、Zn、Co等元素的含量呈现良好的正相关关系；而底层水体悬浮颗粒物的δ56Fe值变幅比夏季要大，HW采样点20m处可达-0.85‰，与Fe、Al、Zn、Co等呈现良好的负相关关系，具体影响因素还有待于进一步研究。

In situ study of carbon nanotube formation by C2H2 decomposition on an iron-based catalyst

The properties and formation of nanotubes have been extensively studied, but very few deal with the catalytic production mechanism of nanotubes. Two different techniques, thermogravimetric analysis and UV-Raman, have been applied to analyse the carbon deposition by catalysed decomposition of acetylene over an iron-based catalyst. The nature of the produced carbon materials depends on reaction temperature. Also, TEM allows identification of carbon nanotubes, encapsulated particles, and other nanostructures, while UV-Raman confirms its graphitic and graphite-like nature. (C) 2000 Elsevier Science Ltd. All rights reserved.