Synthesis, characterization and fabrication on a glassy carbon electrode of a tetra-iron substituted sandwich-type pentadecatungstodiarsenate heteropolyanion

A novel sandwich-type compound, Na-12[Fe-4(H2O)(2)(As2W15O56)2].41H(2)O, has been synthesized. The compound was well-characterized by means of IR, UV-vis, W-183 NMR and elemental analyses. The compound crystallizes in the triclinic, P (1) over bar symmetry group. The structure of the compound is similar to that of Na-16[M-4(H2O)(2)(As2W15O56)(2)].nH(2)O (M = Cu, Zn, Co, Ni, Mn, Cd), and consists of an oxo-aqua tetranuclear iron core, [(Fe4O14)-O-III(H2O)(2)], sandwiched by two trivacant alpha-Wells-Dawson structural moieties, alpha-[As2W15O56]. Redoxelectrochemistry of the compound has been studied in buffer solutions at pH = 4.7 using polarography and cyclic voltammetry ( CV). The compound exhibited four one-electron couples associated with the Fe(III) center followed by three four-electron redox processes attributed to the tungsten-oxo framework. The compound-containing monolayer and multilayer films have been fabricated on a 4-aminobenzoic acid modified glassy carbon electrode surface by alternating deposition with a quaternized poly(4-vinylpyridine) partially complexed with [Os(bpy)(2)Cl](2+/-). CV, X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy and atomic force microscopy (AFM) have been used to characterize the multilayer films.

聚(苯乙烯-4-乙烯基吡啶)钕配合物的研究

含氮聚合物是一类很有意义的配位体,它在某些反应的催化过程中起载体作用。在含氮聚合物中,聚(苯乙烯-4-乙烯基吡啶)(PS4VPY)也是一种很重要的配体,因其杂环氮原子有一定的反应能力和配位能力。聚(4VPY)过渡金属(如Co、Ni、Cu和Zn)配合物已有报道。但PS4VPY的稀土配合物未见报道。本文报道NdCl_3·PS4VPY的合成和表征,及催化活性。

电感耦合等离子体发射光谱法测定大气降水中多种元素

本文研究了长白山自然保护区大气降水（雨水或雪水）中的多元素分析。采用ICP-AES法测定水中的K、Na、Ca、Mg、Mn、Fe、Sr、Ba、Cu、Zn、Ni和V等元素，用干扰系数法对光谱干扰进行修正。为该地区天气环境背景值和大气污染现状提供了富贵资料。

Characterization of degQ(Vh), a serine protease and a protective immunogen from a pathogenic Vibrio harveyi strain

Vibrio harveyi is an important marine pathogen that can infect a number of aquaculture species. V. harveyi degQ (degQ(Vh)), the gene encoding a DegQ homologue, was cloned from T4, a pathogenic V. harveyi strain isolated from diseased fish. DegQ(Vh) was closely related to the HtrA family members identified in other Vibrio species and could complement the temperature-sensitive phenotype of an Escherichia coli strain defective in degP. Expression of degQVh in T4 was modulated by temperature, possibly through the sigma(E)-like factor. Enzymatic analyses demonstrated that the recombinant DegQVh protein expressed in and purified from E. coli was an active serine protease whose activity required the integrity of the catalytic site and the PDZ domains. The optimal temperature and pH of the recombinant DegQVh protein were 50 C and pH 8.0. A vaccination study indicated that the purified recombinant DegQVh was a protective immunogen that could confer protection upon fish against infection by V. harveyi. In order to improve the efficiency of DegQVh as a vaccine, a genetic construct in the form of the plasmid pAQ1 was built, in which the DNA encoding the processed DegQVh protein was fused with the DNA encoding the secretion region of AgaV, an extracellular beta-agarase. The E.coli strain harboring pAQ1 could express and secrete the chimeric DegQVh protein into the culture supernatant. Vaccination of fish with viable E. coli expressing chimeric degQ(Vh) significantly (P < 0.001) enhanced the survival of fish against V. harveyi challenge, which was possibly due to the relatively prolonged exposure of the immune system to the recombinant antigen produced constitutively, albeit at a gradually decreasing level, by the carrier strain.

Characterization of degQ(Vh), a serine protease and a protective immunogen from a pathogenic Vibrio harveyi strain

Vibrio harveyi is an important marine pathogen that can infect a number of aquaculture species. V. harveyi degQ (degQ(Vh)), the gene encoding a DegQ homologue, was cloned from T4, a pathogenic V. harveyi strain isolated from diseased fish. DegQ(Vh) was closely related to the HtrA family members identified in other Vibrio species and could complement the temperature-sensitive phenotype of an Escherichia coli strain defective in degP. Expression of degQVh in T4 was modulated by temperature, possibly through the sigma(E)-like factor. Enzymatic analyses demonstrated that the recombinant DegQVh protein expressed in and purified from E. coli was an active serine protease whose activity required the integrity of the catalytic site and the PDZ domains. The optimal temperature and pH of the recombinant DegQVh protein were 50 C and pH 8.0. A vaccination study indicated that the purified recombinant DegQVh was a protective immunogen that could confer protection upon fish against infection by V. harveyi. In order to improve the efficiency of DegQVh as a vaccine, a genetic construct in the form of the plasmid pAQ1 was built, in which the DNA encoding the processed DegQVh protein was fused with the DNA encoding the secretion region of AgaV, an extracellular beta-agarase. The E.coli strain harboring pAQ1 could express and secrete the chimeric DegQVh protein into the culture supernatant. Vaccination of fish with viable E. coli expressing chimeric degQ(Vh) significantly (P < 0.001) enhanced the survival of fish against V. harveyi challenge, which was possibly due to the relatively prolonged exposure of the immune system to the recombinant antigen produced constitutively, albeit at a gradually decreasing level, by the carrier strain.

Physiological and immune responses of zhikong scallop Chlamys farreri to the acute viral necrobiotic virus infection

The Zhikong Scallop, Chlamys farreri, is one of the most Important bivalve mollusks cultured in northern China However, mass mortality of the cultured C farreri has posed a serious threat to the maricultural Industry in recent years. Acute Viral Necrobiotic Virus (AVNV) is believed as an important etiological agent causing the scallop mass mortalities To understand the mechanism behind the AVNV associated scallop disease and mortality, we assessed the physiological and immune responses of C farreri to the virus infection using oxygen consumption rate, ammonium-nitrogen excretion rate, hemocyte copper, zinc superoxide dismutase gene expression, and plasma superoxide dismutase activity and alkaline phosphatase activity as indicators Scallops challenged by AVNV at 25 C developed typical disease signs 2 days after virus injection Before the disease manifested, scallop oxygen consumption and NH4+-N excretion rates rose and then fell back. Real-time PCR revealed that the hemocyte cytosol Cu, Zn SOD gene expression was upregulated followed by recovery The plasma SOD activity, however, augmented consistently following virus injection Moreover, plasma AKP activity first lowered and then elevated gradually to the highest level at 24 h post virus injection Scallops challenged by AVNV at 17 degrees C neither developed notable disease nor showed obvious responses that could be associated with the virus infection. While the results suggested a correlation between the elevated seawater temperature and the AVNV infection associated C farreri mortalities, they also indicated that the viral infection provoked multiple physiological and immune responses in the host scallops (C) 2010 Elsevier Ltd All rights reserved

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.

Distribution and mobility of metals in agricultural soils near a copper smelter in South China

The distribution and mobility of heavy metals in the paddy soils surrounding a copper smelting plant in south China was investigated. We assessed the degree of metal contamination using an index of geoaccumulation. The metals were divided into two groups: (1) Cu, Zn, Pb and Cd, whose concentrations were heavily affected by anthropogenic inputs, and (2) Ni, Co and Cr, which were mainly of geochemical origin. Concentrations of Cu, Cd, Zn, and Pb in the polluted soils were higher than the Chinese soil quality criteria. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the residual and NH2OH HCl extractable fractions. In contrast, Cd was predominantly associated with the MgCl2 extractable fraction. A large proportion of Cu was bound to the acidic H2O2 extractable fractions, while Zn was predominantly found in the residual phase. The fraction of mobile species, which potentially is the most harmful to the environment, was found to be elevated compared to unpolluted soils in which heavy metals are more strongly bound to the matrix. The mobility of the metals was studied by water extraction using a modification of Tessier's procedure, and the order of mobility was Zn > Cd > Cu > Ce > Pb.

Determination of multiple trace elements in seawater using chelation ion chromatography and ICP-MS

An off-line chelation system combined with ICP-MS technique was developed for the quantitative determination of trace elements in seawater, namely V, Co, Ni, Cu, Zn, Mo, Cd, Pb, U and rare earth elements(REEs). The system was built based on an ion chromatography equipped with MetPac((R)) CC-I chelation columns which had a strong selective chelation to these target elements within a pH range 5.2-5.6. Acidified seawater samples and NH4Ac(2 mol/L) were blended to meet suitable pH before being injected into the chelation column, thus target elements were retained while alkali and alkaline metals were excluded. Then chelated elements were eluted by HNO3 (1 mol/L) and samples were collected for ICP-MS analysis. Varying the ratio of input( gen. 200 mL) to output( gen. 5 mL), the target elements which were concentrated as 40 times as their concentrations were far beyond instrumental quantification limits. At last, a certificated seawater CASS-4 was introduced and our detected values were in good agreement with those certified values.

冲绳海槽西南端中全新世以来的沉积特征及其物源与环境意义

作为大陆向大洋的过渡带，由于享有得天独厚的沉积环境，具有独特的构造特征以及与黑潮主流之间的密切关系，一直以来，冲绳海槽都是中外学者研究的重点靶区。2005年5月，由我国与法国联合主持的IMAGES 航次在台湾东北海域获取MD05-2908柱状岩芯（24º48.04′N,122 º29.35′E,水深为1275米），该柱状岩芯为一34.17米长高质量的连续沉积记录，岩性以深灰色粘土质粉砂为主，含水量较高，粘性、可塑性强，含有数层厚度不等的夹层。岩芯年龄模式依据17个AMS 14C定年数据建立，岩芯底部年代约6.8ka，为中全新世以来的沉积。在实验室对样品按照2cm的间隔进行分割后分别进行了粒度分析、粘土矿物提取与测试、碎屑矿物提取与鉴定、常微量元素和稀土元素分析等实验。 粒度分析结果显示，MD05-2908岩芯沉积物粒度垂向上总体比较均一，以细颗粒的粘土与粉砂质为主，但不同层位也稍有差别，表现为底部层位粒度较粗，含砂量较高，说明底部沉积环境比较复杂。粘土粒级（<2µm）矿物主要由四种粘土矿物和少量石英、长石碎屑组成。其中，粘土矿物相对含量变化中，伊利石（～68％）与绿泥石（～17%）构成主要成分，含有蒙皂石（～10％）和高岭石（～5％）。结合台湾东北外海表层沉积物的研究，利用粘土矿物伊利石/蒙皂石和绿泥石/高岭石比值得出岩芯粘土矿物主要为陆源碎屑粘土矿物，其源岩主要为台湾中央山脉的变质岩与台湾东部的沉积岩。重矿物分析共选取了41个层位，对63~250μm粒级的样品在实体镜和偏光显微镜下进行鉴定，结果显示，岩芯重矿物主要由绿泥石（29%）、普通角闪石（22%）、白云石（10%）、黑云母（8%）、绿帘石（7%）、白云母（7%）、褐铁矿（5%）等组成。稳定矿物少，矿物成熟度低。碎屑矿物风化程度低，磨蚀不明显，分选较差，表明沉积物来自于近源，后期改造作用不明显。常量元素分析结果表明，SiO2 、Al2O3和Fe2O3是岩芯沉积物中的最主要组分，这三种组分占沉积物总量的82%左右。 整个岩芯自下而上各常量组分变化不大，其平均值与东海陆架沉积物基本接近。微量元素变化比较明显， Ba、Cr、Cu、Zn元素的含量比东海陆架沉积物中的含量要高，而Sr的含量明显低于东海陆架。对常微量元素的R型因子分析表明，常量元素SiO2、Al2O3、Fe2O3、MgO和K2O，微量元素Cr、Cu、Ni、Zn、Pb、Rb和Mn可代表陆源物质；常量元素CaO和微量元素Sr、Ba可代表生物源物质。岩芯沉积物以陆源物质为主，生源物质的贡献起次要作用。岩芯沉积物中稀土元素总量平均为169.87×10-6，并且轻稀土含量均高于重稀土，LREE/HREE平均值为10.14，表明了轻稀土对稀土总量的贡献远高于重稀土，沉积物富集轻稀土，反映了沉积物的陆源特征。 岩芯MD05-2908中全新世以来平均5m/ka的高沉积速率主要源于丰富的物质供应和适宜的沉积环境。岩芯细粒级沉积物中，地球化学特征表明沉积物主要来源于陆源碎屑物质，粘土矿物特征与台湾东部陆源物质相同；粗粒级沉积物中，重矿物含量及矿物特征也表明岩芯沉积物粗颗粒组分主要来自于近源沉积。台湾宜兰境内的兰阳溪每年携带约一千万吨冲积物入海成为研究区重要的物质来源。由于受到黑潮的强烈影响，逆时针涡流及底层反向流的存在是岩芯高沉积速率重要控制因素。因此，利用动力分选的粉砂组分可以用来示踪古洋流强度，结果显示，6.8ka以来黑潮的强弱波动频繁，并表现出一定的旋回性变化，频谱分析表明，其具有的千年尺度周期（1500a）、百年尺度周期（604a、242a、192a、153a、133a）与十年尺度周期（22a）的周期性变化均与太阳辐射量变化有密切关系，因此，黑潮的强弱变化在大背景上是由太阳活动所控制的。 根据测年资料可以识别出岩芯存在5期快速堆积事件，这与区域性降水增加有关，降雨量增加导致陆源物质输入的增加。另外，岩芯位于大陆斜坡区，附近存在有三支海底峡谷，并且地震活动频繁，沉积在宜兰陆架及东海陆架处的浅海沉积物由于受到地震、风暴等活动的影响而受扰动崩塌、因重力作用而向低处输送，产生二次侵蚀并经由海底峡谷搬运到冲绳海槽南段堆积,使得沉积环境更为复杂，但同时也为冲绳海槽提供了丰富的物质供应。

四角蛤蜊Mactra veneriformis对镉和汞污染胁迫的生理响应

本论文基于对我国沿海重金属污染加剧以及滩涂贝类资源衰退现象的关注，围绕典型滩涂贝类四角蛤蜊生物化学、细胞生物学和免疫学特征开展研究，调查了渤海湾天津近岸海域四角蛤蜊体内重金属含量和分布规律，以及四角蛤蜊对沉积物重金属的富集能力。室内模拟研究了四角蛤蜊对重金属镉和汞的富集能力及同化机制（assimilation mechanism）差异性，四角蛤蜊各组织对镉和汞的解毒机理和负载能力，以及重金属胁迫对四角蛤蜊血细胞结构和功能的损伤效应。研究结果可望为探讨四角蛤蜊受重金属胁迫细胞水平上的响应机制，揭示重金属污染和贝类资源衰退的关系，建立快速可靠的重金属污染生物标志物指标体系，开展生态健康评估和生境修复等提供科学依据。主要研究结果如下： 1．查明了渤海湾天津近岸四角蛤蜊体内和表层沉积物中Cd、Pb、Cu、Zn、Mn、Cr和Ni七种重金属的含量和周年时空分布特征；表层沉积物中Cd具有较强的污染程度和潜在生态风险，四角蛤蜊对重金属元素Cd和Pb具有较高的富集能力，对环境重金属污染具有很好的指示作用。 2．查明了Cd对四角蛤蜊在24h，48h和96h的半致死浓度（LC50）分别为15.96mg/L、5.15mg/L和2.38mg/L，汞的24h，48h和96h LC50分别为3.71mg/L，0.61mg/L和0.21mg/L。镉和汞对四角蛤蜊的安全质量浓度分别为0.0238mg/L和0.0021mg/L。 3．四角蛤蜊软体部对Cd和Hg的富集能力有显著差异。暴露过程中，四角蛤蜊软体部Cd和Hg的增加量分别为0.12-7.7µg/g和0.002-0.024µg/g，富集率分别为0.3-6.2%和0.11-0.68%，吸收率常数分别为0.07-1.10和0.001-0.005。 4．四角蛤蜊受Cd和Hg胁迫后，外套膜、鳃和肝胰腺的金属硫蛋白（MT）含量均在暴露浓度和胁迫时间上都有极显著变化。组织内MT含量的大小关系为：肝胰腺＞鳃＞外套膜。肝胰腺可以作为双壳贝类MT重金属污染指示研究的目标组织。四角蛤蜊对Cd和Hg不同的解毒机制，导致组织中MT的表达含量和Cd胁迫显著相关，而与Hg胁迫无显著相关性。 5．四角蛤蜊肝胰腺和鳃中抗氧化系统酶、脂质过氧化产物、酸性磷酸酶（ACP）和碱性磷酸酶（ALP）在不同Cd胁迫浓度和暴露时间下有显著差异。与对照组相比，超氧化物歧化酶（SOD）、过氧化氢酶（CAT）、谷胱甘肽过氧化物酶（GPx）的活力和丙二醛（MDA）含量均随着暴露时间的增加而增加，达到一个峰值，然后减低。而ACP和ALP活力则表现出先被抑制，然后升高的变化趋势。肝胰腺中CAT和GPx活力高于鳃，鳃中SOD和MDA含量高于肝胰腺，这种差异与两种组织不同的解毒机理有关。 6．重金属胁迫能够造成四角蛤蜊血细胞超微结构的损伤、溶酶体膜稳定性改变、微核和总畸形核生成，各种损伤均表现出明显的浓度依赖效应。2μg/L Hg暴露14天后，血细胞溶酶体膜中性红保持时间（NRR）、微核生成率（MN）和总畸形核生成率（TNA）与对照组相比没有显著差异。相同暴露时间下，25 μg/L Hg处理组血细胞NRR值低于25 μg/L Cd处理组，而MN和TNA值则相反，说明Hg胁迫对四角蛤蜊血细胞溶酶体膜具有较强的损伤作用。研究发现，NRR、MN和TNA三种指标对于衡量重金属污染对四角蛤蜊血细胞的毒性效应有很好的协同检测作用，可望作为有效的生物标志物在环境监测技术中得以应用。

皱纹盘鲍血细胞内活性氧抗病机制及几种环境污染物及其影响的研究

本研究首次揭示了皱纹盘鲍(Haliotis discus hannai) 血细胞内存在着利用活性氧（Reactive oxygen species, ROS）的抗病机制。为今后我国研究贝类的活性氧抗病机制和筛选免疫药物提供了理论基础。本研究主要结果如下：1. 利用鲁米诺（Luminol, 3-氨基邻苯二甲酰肼）为依赖的化学发光法在体外条件下用不同刺激物（酵母细胞和酵母聚糖）对皱纹盘鲍血细胞进行刺激，测定血细胞吞噬活动中历经呼吸爆发产生活性氧的化学发光反应。结果表明皱纹盘鲍血细胞在体外条件下，经刺激物诱导吞噬活动中有明显的呼吸爆现象和很强的活性氧产生。不同有刺激物诱导血细胞产生的化学发光强度不同；同一刺激物的不同处理和不同浓度对血细胞产生活性氧的化学发光强度的影响不同。刺激物经皱纹盘鲍自体血清调理和未经调理对血细胞刺激所产生的化学发光强度不同。SOD和NaN_3对皱纹盘鲍血细胞吞噬过程中活性氧产生的化学发光有抑制作用。上述结果证明了皱纹盘鲍血细胞内存在有象高等动物血细胞内一样的MPO-H_2O-卤素系统的氧化性抗病机制，即在血细胞吞噬异物过程中能够释放活性氧（ROS）对异物进行杀灭的功能。2. 利用活性氧清除剂（过氧化氢酶、SOD、苯甲酸钠、2，5-二甲基呋喃、NBT和EDTA等）对皱纹盘鲍血细胞释放的活性氧进行分类测试，结果表明活性氧清除剂对皱纹盘鲍血细胞吞噬的化学发光都有明显的抑制作用，从而证明皱纹盘鲍血细胞能够释放的活性氧的种类有：超氧阴离子（O_2~-），过氧化氢（H_2O_2），羟自由基（OH~·）和单线态氧（~1O_2）。3. 在体外条件下利用化学发光法定量地研究了不同种类和不同浓度的农药：对硫磷（Parathion）、敌敌畏（Dichlorovos)、乐果（Dimethoate)、2，4-D 丁酯(2,4-D butylester)和甲胺磷（Methamidophos）对皱纹盘鲍血细胞氧化性抗病机制的影响。结果显示不同农药对皱纹鲍血细胞产生ROS的影响程度不同，及同一种农药的不同浓度的浸泡1h或浸泡12h处理皱纹盘鲍血细胞都能够抑制血细胞吞噬时的化学发光，表明农药能够抑制皱纹敌国鲍血细胞吞噬活动中的活性氧（ROS）的产生，而且这种抑制作用随着农药浓度的增加而加强。几种农药抑制皱纹盘鲍血细胞产生活性氧（ROS）的强度不同：2，4D-丁酯，敌敌畏和乐果的抑制作用强于对硫磷和甲胺磷。同时测定了不同浓度的农药浸泡12h后的皱纹盘鲍因细胞吞噬酵母细胞的吞噬百分率和吞噬指数，结果显示多数农药在低浓度时能够提高皱纹盘鲍血细胞的吞噬百分率和吞噬指数，而在高浓度时则能抑制血细胞吞噬酵母细胞的活力而降低血细胞的吞噬百分率的吞噬指数。4. 在体外条件下利用化学发光法定量地研究了不同种类和不同浓度的重金属：铭（Cr）、镉（Cd）、汞（Hg）、铅（Pb）、铜（Cu）和锌（Zn）对皱纹盘鲍血细胞氧化性抗病机制的影响。结果显示不同种类和不同浓度的重金属浸泡1hr.处理皱纹盘鲍血细胞都不同程度地抑制了血细胞吞噬时的化学发光，表明重金属能够抑制皱纹盘鲍血细胞吞噬活动中的活性氧（ROS）的产生，而且这种抑制作用随着重金属浓度的增加而加强。不同的重金属抑制强度不同，从强到弱依次为Hg > Cd > Cu > Pb > Cr > Zn. 研究表明六种重金属中，Hg对皱纹盘鲍血细胞的免疫毒性最大。

中国河口、近岸海洋沉积物酸提取相中元素相关性及其背景值的研究

本文详细研究了黄河口（五、八月）、长江口、龙口湾、日照近海以及冀东唐海近岸海域表层沉积物中元素Zn、Pb、Ni、Cu、Co、Fe、K、Corg、Cr、Mn、P的总量和元素Zn、Cu、Pb、Co、Cr、Li、Ni、Mn、Fe、K 、Al、P的可提取量。在此基础上，着重研究了沉积物中元素总量间的相关性、元素可提取量间的相关性、元素的含量与粒度组成之间的关系、元素的总量与可提取量的关系以及可提取部分背景值等几个方面的内容。通过对不同地区不同类型的大量沉积物的研究结果表明：沉积物中元素Cu、Zn、Ni、Fe、Corg、Cr的总量在不同河口、不同类型的沉积物中与其它元素存在着显著的正相关关系。考虑到参比元素的限制条件，可以利用Ni、Fe、Corg、Cr作为参比元素，这些参比元素在不同地区、不同类型的沉积物中具有普遍性。元素Cu、Zn、Pb、Ni、Fe、K、Cr、Corg、Mn的总量与粘土含量呈显著的正相关关系。用1N HCl或0.5N HCl+H_2O_2提取沉积物，元素Cu、Zn、Pb、Co、Li、Ni、Fe、K、Al的提取量之间以及与其它元素的可提取量存在显著的正相关关系。Li、Ni、Fe、Al、Co同样可以作为参比元素，这比用总量来评价环境质量具有更方便的特点。元素Zn、Cu、Pb、Co、Li、Ni、Fe、K的可提取量与粘土含量成显著的正相关关系。与1N HC1、0.5N HCl+H_2O_2两种提取方法相比较，25%(V/V) CH_3COOH只提取了部分结合松散的金属，元素的可提取量之间以及与粘土含量之间的相关关系较差。采用不同的提取方法，元素的提取率的大小顺序与提取方法是一致的，与沉积物的区域及类型关系不明显。元素的提取率与粘土之间相关性差，说明虽然随着颗粒变细，各元素含量的绝对值增加，但相对比例变化不明显。在以上内容研究的基础上，提出了沉积物中元素可提取部分背景值的概念，这个概念具有一定的普遍性，对今后环境质量的正确评价，特别是评价对生物体影响方面，更具有重要的意义。Li、Al、K三种元素在采用提取量进行环境质量评价时，可以作为参比元素。这在以前的文献中尚没有报道，是在前人工作的基础上的又一发展。初步发现了沉积物中部分元素可提取相的元素粒度控制规律。

南黄海重金属的演变特征及控制因素

本文以南黄海1997～2006年10年表层海水和沉积物中重金属为主要研究对象，同时结合对生态环境信息的综合分析，系统探讨了海水和沉积物中重金属的生物地球化学特征、影响控制因素、演变趋势，并对海域生态风险进行了评估，获得了以下一系列新的结果和认识： 1．系统获得了南黄海海水和沉积物中重金属的地球化学分布模式，揭示了影响和控制其生物地球化学特征的因素 南黄海表层海水中重金属As、Cd、Cu、Hg、Pb、Zn的平均浓度分别为2.33、0.078、1.41、0.0036、0.37、6.21 μg/L，低于其它中国近海海水，而高于水交换较好的深海；表层海水重金属的分布模式（除Pb外）表现为在离岸较远的南黄海中部地区其含量较低，而近岸海区则普遍含量较高，区域分布呈现“高Cd-Cu-Hg-Zn区”，“高Pb-Cu-Zn区”以及“高Pb区”三个地球化学分区。 南黄海表层沉积物中重金属比邻近海域沉积物中的浓度低，南黄海重金属主要受沉积物粒度控制，即在细粒度高的南黄海中部区域重金属（除As外）的含量较高，粗粒度的近岸区则较低，区域分布呈现“高Cd-Cu-Pb-Zn区”，“高Hg低As-Cu-Zn区”以及“高As低Cd-Hg-Zn区”三个地球化学分区。 人类活动已经显著影响了南黄海海水中重金属的含量水平，重金属分布是径流、大气沉降、pH、盐度和重金属自身性质等各种影响因子耦合的结果。沉积物重金属的富集因子Pb>As>Hg>Cd>Zn>Cr>Cu，其中Pb和As主要来自人为污染排放，污染状况相对较重，Cr和Cu几乎没有受到人为污染的影响。沉积物的粒度是控制表层沉积物重金属分布的最主要因素，次要的因素包括沉积物有机质的含量、沉积速率以及重金属存在形态等。 2．首次获得了南黄海海水和沉积物中重金属的演变趋势 近10年来南黄海表层海水中，Zn呈上升趋势，As、Cd、Cu、Pb基本稳定变化不大，而Hg则呈略下降趋势。Zn的线性上升趋势明显，在近岸水域和中央水域中其浓度和公元年的统计关系分别为y=0.9524x+0.0034（R=0.97）和y=0.8622x+0.0299（R=0.95）（其中y为Zn的浓度，x为年度，取1997～2004）。近10年沉积物中重金属年际变化较小，浓度变化在多年均值的±（10%～30%）之间变动。As、Cd、Cu、Hg、Pb、Zn的均值变化范围分别为7.17±1.70、0.108±0.024、17.61±1.65、0.024±0.008、18.44±4.26、70.53±5.73 mg/kg，除了Hg随公元年呈较好的线性增加（y=0.0033x-6.50，R=0.75）外，其它重金属未显现出有明显的演变趋势。 近百年来，南黄海重金属的变化可分为3个阶段，20世纪60年代以前，20世纪60年代至90年代，及20世纪90年代至今。第一个阶段的60年可以看作是南黄海未明显受人类活动影响的一个时期，该段时期内明显的特征是重金属含量的变化受径流输入不均等多种因素影响，变化规律性不强；第二阶段是南黄海近岸工农业迅猛发展的阶段，由近岸传输到这一海域的重金属量增加，南黄海沉积物重金属浓度增加，沉积物质量有下降的趋势，这一阶段是人类活动影响南黄海最为明显的一个阶段；第三个阶段是20世纪90年代至今，南黄海沉积物重金属浓度呈降低趋势，与中韩两国减排及治污措施有关。近几年，南黄海沉积物的环境质量较20世纪末期有了较明显的改善。 3. 初步阐明了南黄海重金属的环境污染危害和潜在生态风险 采用潜在生态危害指数法和地积累指数等方法对南黄海沉积环境进行分析，结果表明，中等重金属污染程度海区占研究海区面积的38.7%，中等生态风险的区域则占了研究海区面积77.8%，但均未发现沉积物中的重金属与生物量的分布有明显的关系，总体表明，南黄海沉积物中的重金的污染状况及生态风险较低，南黄海沉积物质量良好。

冲绳海槽晚第四纪沉积特征及其物源和环境意义

本文通过对冲绳海槽北端和南部两个海区沉积物样品的粒度、矿物和元素组成与分布特征的研究，探讨了冲绳海槽沉积物的来源，给出了一定元素组合的物源意义。通过对冲绳海槽两个柱状沉积物的粒度、矿物、元素在地层中的分布特征的研究，结合浮游有孔虫氧同位素地层划分，探讨了冲绳海槽晚第四纪沉积记录的古环境意义。 冲绳海槽陆架和陆坡沉积物明显具有陆架残留沉积的特征，沉积物主要由陆源碎屑矿物、生物碎屑、粘土矿物和少量自生矿物组成。在冲绳海槽北端，陆架和陆坡砂质区沉积物的主要来源是冰期低海面时古黄河的残留沉积，在现代沉积环境下受到海洋生物和自生沉积作用的改造；济州岛南部的细粒沉积区的物源主要是周围陆架残留沉积，在黄海暖流和黄海沿岸流的综合作用下，残留沉积中的细粒组分再沉积形成的。冲绳海槽北端海槽区沉积物主要是火山活动的产物，火山玻璃和火山型的辉石、紫苏辉石和磁铁矿明显富集。冲绳海槽南部沉积物的主要物源是长江沉积物，此外还有大量的海相生物沉积和自生沉积。对元素分布特征的研究表明，冲绳海槽陆架区富含陆源粗碎屑组分SiO_2和生源碎屑组分CaO和Sr，生物沉积对陆源沉积明显具有稀释作用。陆坡区由于受黑潮暖流的影响，往往富集Fe_2O_3和P_2O_5。在海槽区，陆源细粒组分以及与细粒组分相关的元素A1_2O_3、K_2O、Cu、Zn、Co、Ni和Cr等明显富集。利用R型因子分析的方法确定了两个研究区元素组合，结合沉积物的矿物组成给出不同元素组合的物源意义。对冲绳海槽北部(Y127孔)和南部(E017孔)两个柱状沉积物的浮游由孔虫的δ~(18)O进行了分析，将其与本区具有高分辨率的柱状样氧同位素曲线对比进行，结果表明，δ~(18)O值较敏感地记录了冲绳海槽晚第四纪以来的古环境变化。δ~(18)O的高值往往与冷期相对应，δ~(18)O的低值与暖期相对应。冲绳海槽在12ka BP左右开始了逐渐转暖的过程，在10ka BP左右(YD事件)发生了短暂的降温过程，但降温幅度很小。根据沉积物化学组成在地层中的变化规律，大部分元素较敏感地记录了全新世气候转暖事件，但是对于千年尺度的YD事件，多数元素对此没有明显的响应。冲绳海槽火山活动对沉积物的组成和沉积环境的塑造起到了至关重要的作用。根据氧同位素地层划分，在冲绳海槽北部12ka BP曾有火山活动的纪录，距今约8ka BP以来，冲绳海槽有两次较大规模火山活动的记录。火山活动往往会在短期引起气候的变冷，从而造成海区生态环境的破坏，生物沉积作用减弱。但从长期变化来看，可能是气候变暖的因素之一。火山层的主要特征为沉积物主要由粉砂组成，平均粒径明显高于周围层位，在矿物组成上表现为蒙皂石、火山玻璃和火山型的辉石、紫苏辉石和磁铁矿的含量较高，在化学组成上表现为Na_2O与Zr的同高于周围层位，而陆源性较强的元素TFe_2O_3和K_2O，以及生源组分CaCO_3和Sr的含量普遍低于周围非火山层。