1nm锰矿相的金属阳离子交换能力的研究

人工合成的1nm锰矿相和铜、钴、镍等二价金属阳离子的交换实验表明,1nm锰矿相具有强烈的金属阳离子交换能力.正是这种金属阳离子的交换能力,使得大洋多金属结核大量地富集了铜、钴、镍等有价金属元素.1nm锰矿相对几种金属阳离子的交换的优先顺序为:Cu>Co>Zn≥Ni>Ca>Mg.多金属结核中镍的含量往往高于铜、钴、锌等元素,但在交换顺序中它却低于铜、钴、锌等,这种不一致性说明结核成矿后期的金属离子交换并非是有价金属结合进结核的唯一途径.多金属结核富含铜、钴、镍等有价金属可能是结核初始成矿和成矿后期金属离子交换等多种因素共同作用的结果.     

有机质对S1nm锰矿相金属阳离子交换能力的影响

大洋多金属结核问题长期以来一直受到人们的关注[1～3].大量的研究结果表明,多金属结核中最有经济价值的铜、钴、镍等有价金属元素,主要赋存于仅占整个结核约15%锰矿相中.我们曾对人工合成1 nm锰矿相(synthetic 1nm manganate,以下简称S1nm锰矿相)金属阳离子交换能力作过初步探讨[4,5],研究表明,Cu2+,Co2+,Ni2+,Zn2+等与S1nm锰矿相具有强烈的阳离子交换能力,证明了多金属结核成矿后期的离子交换是铜、钴、镍、锌等有价金属元素进入多金属结核的重要途径之一.     

太平洋多金属结核中铁锰矿物分析及成因研究

铁锰矿物是大详多金属结核的重要组成,了解不同类型结核中主要铁锰矿物种类、形态、分布特点和结晶程度等,不仅有助于对锰矿物乃至多金属结核成因的研究,而且对选矿冶炼和资源的综合利用也具有现实意义.本文通过透射电子显微镜等多种手段综合分析与鉴定,指出多金属结核中主要铁锰矿物有钙锰矿、水羟锰矿、水钠锰矿、方锰矿、锰铁矿和针铁矿等.结晶程度普遍较差,钙锰矿结晶相对好于其他矿物,并在粗糙型结核中含量高,外层至核心含量稳定,变化小.水羟锰矿广为分布,但结晶差.铁矿物含量东区低于西区,结核外壳铁含量高于内核.锰矿物分布在叠层石柱体和纹层内,呈束状、纤维状和树枝状,与建造多金属结核的超微生物菌丝体形态一致.粗糙型结核是选冶的主要对象.     

南海多金属结壳(核)铁锰矿物/海水界面效应与成矿元素的富集

海底铁锰结壳和结核是重要的海底矿产资源,蕴含着丰富的金属元素并且具有巨大的经济价值。本文主要以南海多金属结壳（核）为研究对象,采用X射线粉晶衍射（XRD）、激光拉曼光谱、红外光谱分析（FTIR）以及X射线光电子能谱对铁锰矿物的矿物学和谱学特征进行了系统的分析和研究。粉晶衍射和拉曼光谱分析结果表明,南海多金属结壳的矿物组成为水羟锰矿、石英和长石,结核的矿物组成为钡镁锰矿、水羟锰矿、石英和长石,铁相矿物均为无定形铁氧化物/氢氧化物,并且锰相矿物和铁相矿物的结晶程度均较差。红外光谱分析结果显示多金属结核和结壳中的铁锰矿物具有大量表面羟基,这些含质子表面羟基官能团,可为海水中各成矿元素的络合提供丰富的活性位点。XPS分析表明多金属结核和结壳中铁锰矿物表面以Fe、Mn和O元素为主,其中Fe呈正三价态,Mn以正四、正三价为主,可能还含有少部分正二价态。对比南海多金属结壳（核）与太平海山结壳,南海多金属结壳（核）具有更为显著的表面羟基氧（-OH）含量,而太平洋海山结壳则以晶格氧（O^2-）为主,表明太平洋海山结壳铁锰矿物结晶程度较南海多金属结壳（核）高。综合研究表明,在海底铁锰结壳和结核中（氢）氧化锰/铁矿物与海水之间界面效应对金属离子的富集机理主要有：（1）金属离子与矿物表面羟基进行络合反应,形成以配位键相连的羟基络合物,或与表面的质子交换生成稳定的内层络合物;（2）矿物的带电表面与金属离子通过静电作用形成双电层,生成外层络合物;（3）金属离子与矿物结构中的Mn、Fe离子同晶置换而成为结构阳离子。     

中太平洋C海山富钴结壳铁锰矿物的组成、成分特征及其成因意义

采用X射线衍射和微区电子探针法,对2006年"大洋一号"考察船在中太平洋C海山取得的典型富钴结壳样品进行了铁锰矿物的组成和成分特征分析,结果显示:(1)结壳的老壳层中铁锰矿物具有水羟锰矿、钡镁锰矿和钠水锰矿的特征组合,其相对含量分别为45.5%、30.1%和24.4%;中间壳层和年轻壳层中铁锰矿物为水羟锰矿,表明结壳各层生长的环境条件不同.(2)铁锰矿物集合体中Mn/Fe值从老壳层到年轻壳层具有明显降低的趋势,老壳层Mn/Fe值大于20,最高达90;中间壳层Mn/Fe值在2～5之间,年轻壳层Mn/Fe值在1～2之间.铁锰矿物集合体探针测得的结壳老壳层元素的总百分含量稳定在75%左右,中间壳层和年轻壳层为50%～80%.Si、Ti元素含量从老壳层到年轻壳层有增加的趋势,在中间疏松层中百分含量均达到最高值,分别为3.17%和1.53%,表明自老壳层到年轻壳层,碎屑物质或有机质等对结壳的影响程度有增大的趋势.由此可见,研究区富钴结壳主要为水成成因,主要发育了水羟锰矿;老壳层生长期间受到局部海水氧化还原条件变化的影响,铁锰相矿物发生重结晶或重组而形成了水羟锰矿、钡镁锰矿和钠水锰矿特征组合,这种特征铁锰矿物组合的研究对于全面理解海水环境条件变化与结壳成因的关系具有重要的意义.     

东太平洋多金属结核富钡镁锰矿细脉蛋白石层的成因机制

为探讨东太平洋CC区多金属结核中富钡镁锰矿细脉蛋白石层的成因机制,利用矿相显微镜、电子探针和ICP-OES,对蛋白石层及其周围铁锰氧化物进行了显微结构特征和化学成分特征的研究。结果表明:高反射率矿物结晶程度较好,主要由MnO组成,具有高Mn低Fe的特征,为成岩成因的钡镁锰矿。中反射率矿物结晶程度较差,主要由MnO和FeO组成,为水成成因的水羟锰矿。低反射率矿物为一种半透明矿物,主要由SiO₂组成,为生物成因的蛋白石。根据钡镁锰矿、水羟锰矿和蛋白石的成因机制,为蛋白石层及其内部钡镁锰矿细脉的形成过程建立了一个模型,共分为5个生长阶段:第1阶段,结核呈半埋藏状态在氧化环境中形成水羟锰矿;第2阶段,结核呈半埋藏状态接受SiO₂胶体的沉淀作用形成蛋白石层;第3阶段,结核呈半埋藏状态在氧化环境中形成水羟锰矿的同时,其成岩作用和蛋白石的脱水作用使蛋白石层中产生大量的裂缝;第4阶段,结核呈埋藏状态在弱氧化-还原环境中发生交代作用和重结晶作用形成钡镁锰矿;第5阶段,结核呈半埋藏状态形成水羟锰矿。     

Cu、Co、Ni、Ti和Mg在成岩型铁锰结核中的地球化学特征

选择了东太平洋赤道附近的系列成岩型铁锰结核(壳)样品,根据其中的矿物相的种类,利用化学上的相分析手段——选择性提取实验,借助晶体化学和矿物学手段对过渡金属元素Cu、Co、Ni、Ti和碱土金属元素Mg在成岩型铁锰结核中的地球化学特征进行了研究。结果显示,元素Cu、Co、Ni、Ti和Mg等元素在成岩型铁锰结核中的富集受这些元素在海水中的存在状态和结核中组成矿物这两方面因素的制约。成岩型结核中10-水锰矿结构的稳定性并不完全是由于其充分吸收了Cu、Co、Ni等过渡金属元素,碱土金属Mg对于10-水锰矿结构的稳定性起到了重要作用。     

东南太平洋秘鲁海盆DEA区浅层埋藏型铁锰结核的矿物学和地球化学特征及成因类型

本文通过对秘鲁海盆DEA区浅层埋藏型铁锰结核开展地球化学和矿物学研究,探讨了埋藏型大洋锰结核的有用组分的富集、清扫机制及成因类型。该区铁锰结核致密层和疏松层互层具有明显的多孔树状微结构,结核主要由10?锰矿相、7?锰矿相(水钠锰矿)和δ-MnO₂(水羟锰矿)等锰相矿物组成,成分上具有高Mn、低Fe和中等Ni+Cu、Mo(分别为44.79%、0.55%、0.46%、0.05%)的亚氧化成岩型特征和低的Co、Ti、Zn和REY元素(REY_SN均小于1)含量。铁锰结核中低含量的Mo和大部分的Ni与Mn氧化物清扫有关,其中Mo与Mn相关系数R=0.65,高Mn/Fe(>300)中Ni含量同样很高(0.34%),其他元素如Cu、Ti和REY均与Fe的羟基氧化物及铝硅酸盐相关性较高(R>0.8)。铁锰结核Fe、Ni+Cu、Mo、REY元素含量和Mn/Fe比值在分层上呈现规律性变化,致密层的Ce_SN负异常和疏松层的Ce_SN正异常进一步表明,铁锰结核的生长过程经历亚氧化-氧化成岩作用的环境条件变化,该变...     

LED光谱对许氏平鲉视网膜形态的影响

光作为一个复杂的环境因子,对鱼类的存活、摄食、生长及视觉均产重要影响。为了探究LED光谱对许氏平鲉(Sebastods schlegelii)视网膜结构和视网膜各层细胞数目与厚度的影响,本文选取1 000尾许氏平鲉幼鱼(体质量为38.80±0.43 g、体长为10.20±0.17 cm)分别养殖在5种光谱下(蓝光(λ450 nm)、绿光(λ525 nm)、黄光(λ590 nm)、白光(λ460 nm)、红光(λ630 nm)),其中白光组为对照组,其余4组为处理组。经过为期60 d的处理后,分别对各组的视网膜进行取样观察。结果表明:不同的LED光谱对许氏平鲉的视网膜结构未产生影响,但各个光谱下视网膜细胞数目略有差别,在5种不同光谱条件下,在单位面积(100μm×100μm)内,蓝光组内网层细胞数量(24.33±2.08)显著低于白光组(P<0.05);红光组外核层细胞数量(33.33±3.51)显著低于除白光组外的其他各组(P<0.05),通过对比各个光谱下视网膜各层细胞数量可得,蓝光组与红光组数量最少,其他各层差异不大。综上所述,饲养于不同光谱处理组的许氏平鲉幼鱼的视网膜...     

低层大气季节变化及与黄海雾季的关系

根据2005～2006年青岛气象台逐日L波段探空雷达资料和地面观测资料,计算、分析了低层大气湍流混合高度、湍流混合强度和温度层结的季节变化,并分析了其与黄海海雾季节变化的关系.结果表明:温度层结、湍流强度和高度均有明显的季节变化,这些变化与海雾的季节变化密切关联.春、夏季节湍流强度较强,湍流混合高度相对较低,有利于近海面的凝结水汽在低空聚集而形成雾.雾季典型的层结结构是"上稳下湍",即:近地(海)面至150 m左右为条件性不稳定,其上方为大约400 m厚的稳定层.盛雾期稳定层的稳定性减弱,湍流强度加强.另外,黄海雾季由7月最盛到8月突然结束,与东海雾季逐渐结束明显不同.8月黄海终雾期迅速的原因与风向的突然转变有关.偏东风为整个黄海带来较冷的空气,使条件性不稳定发展,雾季终止.风向的突然转变与区域性海陆热性质差异和大尺度背景环流的调整有关.     

Study on mineral structural stability of marine 1nm manganate

I~D~IONThe numerous research results on the deep-sea manganese nodules show that the most valuable metal elements such as Cu, Ni are mainly concentrated in the manganese minerals, which only take about 15% Of the weight in the total manganese nodules, therefore, many marine scien.tists pay more attention in their research on the manganese minerals rather than the other mineralsin the deep-sea maganeses nodules.There are more than tens of different kinds of manganese mineral phases in the nod…     

Study on the cation substitution capacity of synthetic 1nm manganate

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Porous Structure of Tailings of Marine Manganese Nodules and Crusts as Deduced from the Adsorption of Nitrogen

Tailings of marine manganese nodules and crusts have many useful properties. One property in particular which could be of great significance is their high gas adsorption capacity. This capacity has a direct relationship with the pore structure of the tailings. The present investigation deals with the size, volume, surface area, and distribution of pores in the tailings via nitrogen adsorption-desorption techniques. The results show that the pore diameter of these tailings varies between 1.203 and 243.6 nm. The most frequent diameter of pores is 2 to 50 nm. These are classified as mesopores. The Barrett-Joyner-Halenda adsorption pore diameter is 1.203 to 14.078 nm. The small pores give the largest contribution to pore surface area. The large pores give the biggest contribution to pore volume. The pores could be derived from several sources. These include: (a) the amorphous fraction of the tailings which has been calcined, (b) the accumulative clearances between nanometer grains or crystals, and (c) the original porosity of the marine minerals.     

The feasibility of assessing the diets of minke whale (<Emphasis Type="Italic">Balaenoptera acutorostrata</Emphasis>) in the East Sea through fatty acid composition in blubber and stable isotopic ratio of skin

To track the diet of minke whale (Balaenoptera acutorostrata) in the East Sea (Japan Sea), a conjoint analysis of fatty acids and C and N stable isotopes was performed on blubber and skin from the whale and its potential prey. The total lipid content in the blubber of minke whales ranged from 37.9% to 82.7% of wet mass (mean ± SD, 63.1 ± 17.2%), with triacylglycerols being the dominant lipids (96.9%–99.2% of total lipids). The lipid and fatty acid (FA) contents were systematically stratified throughout the depth of the blubber layers; contents of the dominant monounsaturated FAs (MUFAs), including 18:1ω9 and 16:1ω7, increased from the innermost layer to the outermost layer, whereas contents of saturated FAs (SFAs) and polyunsaturated FAs (PUFAs) were higher in the innermost layer than in the outermost layer. This stratification is related to the different physiological roles of the blubber layers; e.g., thermoregulation, streaming, and buoyancy. A comparison of the FA compositions of the innermost layer of minke whales with those of potential prey indicates that FA compositions in the whales are similar to those of Pacific herring. In addition, stable isotope ratios (δ¹³C and δ¹⁵N) suggest that minke whale and Pacific herring have the same or similar diets. Therefore, the diets of minke whale from the East Sea (Japan Sea) could be inferred from information on the diet of the Pacific herring, although FA compositions and stable isotope ratios for Pacific herring would not exactly reflect the whale’s diet. Although the very limited number of samples was used in this study, our preliminary findings are very promising to help understand the feeding ecology of minke whales in the East Sea (Japan Sea).     

南海东北部夏季叶绿素a浓度垂向变化特征及其对水动力过程的响应*

叶绿素a浓度是估算海洋初级生产力的一个重要参数, 在海洋中垂向分布极不均匀, 其分布特征及影响机制是海洋生态学研究的重要基础问题。利用海洋光学观测的高垂向分辨率剖面数据, 系统地研究叶绿素a浓度垂向剖面的时空分布特征及其与海洋动力环境要素的关系, 可为揭示南海典型动力过程的生态环境效应提供重要基础。文章基于2015年夏季黑潮调查航次实测生物光学剖面, 利用676nm处吸收基线高度(a_LH(676))与叶绿素a浓度(Chla)之间的关系, 建立了具有较高反演精度的叶绿素a浓度反演算法(Chla=49.96×(a_LH(676))^0.9339, 决定系数R²=0.87和均方根误差RMSE=0.16mg·m^-3); 进一步结合观测期间物理过程, 揭示了叶绿素垂向分布对不同水动力过程的响应特征。研究结果表明, 近岸区域表层叶绿素a浓度变化范围为0.42~1.57mg·m^-3, 随着水深增加, 叶绿素a浓度逐渐降低, 在沿岸上升流影响区域, 叶绿素a浓度明显增高, 垂向上相对趋于均一分布; 次表层叶绿素极大值(Subsurface Chlorophyll Maximum, SCM)现象在外海显著存在, 受中尺度过程影响明显, SCM深度在34m到100m之间变化, 在吕宋岛以西海域, 黑潮入侵加速了上层水体的混合, SCM所在水层被显著抬升至34m左右; 在冷涡影响区域, 次表层叶绿素极大值层被抬升, 涡旋中心比涡旋边缘抬升更为显著, 同时SCM的厚度增大。     

Aggregation of riverine colloidal iron in estuaries: A new kinetic study using stopped-flow mixing

The kinetics of aggregation of riverine colloidal iron have been examined using a stopped-flow technique which probes the first few seconds of mixing between river and sea water end members. A significant fraction, up to 80%, of the colloidal iron is aggregated during the first 1–2 s of mixing, indicating that the aggregation process is much faster than previously thought. Most of the aggregation induced by seawater results from the divalent cations Mg²⁺ and Ca²⁺, with the overall ionic strength having little influence. At equal concentrations of 27 mM, the rate of aggregation by alkaline earth cations increased with ionic size Mg²⁺ < Ca²⁺ < Sr²⁺ < Ba²⁺. The aggregation rates were indifferent to the anion (Cl⁻ or SO₄²⁻) present. Very high aggregation rates were also induced by the common water treatment coagulant Al₂(SO₄)₃ at concentrations in the range 20–30 µM Al(III), several orders of magnitude lower that those used for the seawater cations. Our results support the view that specific chemical interactions between the cations and the colloid particle surface, rather than simple electrical effects, control the colloid stability.     

Etropus crossotus, an annual flatfish species; age and growth of the fringed flounder in South Carolina

Fringed flounder, Etropus crossotus, a small flatfish common along the southeastern coast of the US, were collected along the South Carolina coast in the fall of 1992, and in the North Inlet estuary from August 1992 until July 1994. Standard length was 82% of total length and the relationship between standard length and wet weight showed near-isometric growth with no significant differences between males and females. Dry weight was 21% of wet weight and ash-free dry weight 14% of wet weight with no significant differences between sexes. Daily increments in the sagittal otoliths were used for age determination. No annual structures could be identified. The maximum age was about 14.5 months. Age-at-length was not different between the sexes. The relationship between age and length was exponential, with age (in days) equalling an e power of 4.242 + 0.135 × standard length (in cm). Back-calculated hatch dates and catches of early juveniles indicated a spawning season that lasted from March to October. Females started to be sexually mature at 7 to 7.5 cm standard length, but 50% maturity was reached at 8 to 8.5 cm. Females could grow to that size within one spawning season. Individuals hatched early in the spawning season could produce eggs in the latter portion of that season's spawning period.     

Elemental mercury concentrations and formation rates in the Scheldt estuary and the North Sea

Concentrations of Hg⁰ in surface waters and atmosphere of the Scheldt estuary and the North Sea are presented and their relationship with biological processes is discussed. Hg⁰ concentrations in the Scheldt estuary range from 0.1 to 0.38 pmol·l⁻¹ in the winter and from 0.24 to 0.65 pmol·l⁻¹ in the summer and show a positive relationship with phytoplankton pigments. In the North Sea Hg⁰ concentrations range from 0.06 to 0.8 pmol·l⁻¹ and are higher in coastal stations. Transfer velocities across the air–sea interface were calculated using a classical shear turbulence model. Volatilization fluxes of Hg⁰ were calculated for the Scheldt estuary and the North Sea. For the Scheldt estuary the fluxes range from 226–284 pmol·m⁻²·d⁻¹ in winter and 500–701 pmol·m⁻²·d⁻¹ in summer and for the North Sea the fluxes range from 59–1110 pmol·m⁻²·d⁻¹ for an average windspeed of 8.1 m·s⁻¹. These fluxes are comparable to the wet and dry depositional fluxes to the North Sea. Hg⁰ formation rates necessary to balance the volatilization fluxes vary from 0.2 to 4% d⁻¹.     

渤海复杂断块油藏精细挖潜的实践与认识

位于渤海的渤西复杂断块油田群由4个储量均为约1 000×10^4m^3的复杂断块油田组成。油田群内部断层发育,含油层系多,油气水关系复杂。经过长期衰竭开发,地层能量下降快、各层采出不均衡、剩余油分布复杂,开发效果逐渐变差。为了解决开发过程中出现的诸多突出矛盾,通过动静结合、精细地质研究寻找剩余油;通过晚期加强注水、细分开发层系缓解层间矛盾;通过老井上返、滚动勘探开发等方法实现产量接替。这些方法的研究与应用,延长了海上老油田的开发寿命,提高油田采收率5%～12%,对于海上复杂断块油田的精细挖潜和高产稳产具有重要的指导作用。     

丁二酸柱撑水滑石的制备及表征

以镍铝水滑石为前体（主体），以蒸馏水为分散介质，用离子交换法组装丁二酸根（客体）插层水滑石，同时用一步合成法合成丁二酸根插层水滑石，并用XRD，IR，TG-DTA和元素分析等手段对样品进行了表征。结果表明，离子交换法制得的产品中丁二酸根阴离子取代了镍铝水滑石前体层间的碳酸根离子，组装得到晶体结构良好的丁二酸根插层水滑石，层间距为1．23nm。