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.     

1nm锰矿相结构稳定性的研究

对在潮湿状态和经室温干燥后的人工合成Slnm锰矿相进行X衍射测定结果显示:1nm锰矿相与0.7nm锰矿相之间存在某种相变关系,那些结构不稳定的S1nm锰矿相,由于干燥等原因而失去层间-OH-H₂O层,而使原先的1nm相“崩塌”成为0.7nm锰矿相.1nm锰矿相结构稳定性主要是由被结合进层间的Cu、Co、Ni等二价金属阳离子的特性与数量所决定的,其所含的金属阳离子的数量与其锰矿相的结构稳定性呈正相关,而不同的金属阳离子在稳定1nm锰矿相的结构的能力的大小可排列为:Ni>Cu>Co>Zn>Ca≥Mg>Na.     

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.     

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。     

地形坡度对多金属结核分布的控制作用

选取我国东太平洋多金属结核开辟区内的一个区域作为研究区,利用人工神经网络中应用最为广泛的BP网络,建立控制多金属结核分布的地质因素与多金属结核分布之间的映射关系,探讨地形坡度对多金属结核分布的控制作用.结果表明,在经度、纬度、水深、坡度四个因素中,坡度对结核分布影响程度最大;多金属结核主要分布于坡度小于5°的地方;当坡度小于5°时,丰度与地形坡度呈正相关,品位与地形坡度呈负相关,丰度与品位呈负相关;品位与坡度似呈指数关系,坡度增大,品位降低.     

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。     

深海多金属结核物理特性及其对采输过程的影响概述

文章旨在确定深海多金属结核的物理特性,并分析其对采输过程的影响,以指导工程应用。总结了深海多金属结核开采的最新研究进展,通过对数据进行统计整理、回归分析,确定了结核形成机理及主要成分、在海底的分布特性、结核形态及构造、结核尺寸与重量关系、含水量、密度、孔隙特性及结核强度等关键物理特性。研究表明：结核形状多样,质松多孔隙,含水率高,近似均匀分布在海床上或浅泥层中。颗粒质量和尺寸联合概率分布具有长右尾特性,需使用更广义的联合概率密度函数copula才能准确建模。结核抗拉强度随结核直径增大按对数函数递减。此外,深海高压环境下结核的开采需更多能耗,且结核表现出更高的延性。结合固液两相流分析和颗粒沉降理论,分析了结核形状、尺寸、密度等主要参数对水力举升过程的影响,确定了颗粒破碎的主要方式和规律,总结了不同粒径级配输运造成堵塞的可能原因。     

西太平洋多金属结核及其表层沉积物地球化学特征：沉积环境对结核生长的影响

西太平洋深海盆地同时发育多金属结核和富稀土沉积物,但针对多金属结核及其表层沉积物之间关系的研究较少。通过多金属结核-表层沉积物地球化学分析,揭示关键金属元素在结核、沉积物中的富集和分馏过程,探讨沉积过程与环境对多金属结核生长的影响。研究区多金属结核具有相对高的Co、REY含量,低的Mn/Fe比值,显示为典型的水成成因。主成分分析及相关性分析结果指示结核的成矿过程是在水成作用、成岩作用以及陆地碎屑、生物碎屑输入的作用下,Fe-Mn氧化物对海水及孔隙水中各类金属元素的选择性富集。研究区表层沉积物主要为深海黏土,相较于多金属结核富集大部分金属元素,深海黏土更为富集Si、Al、Na、K等元素。沉积物中Co、Ni、Cu等金属元素的富集与Fe-Mn微结核的含量相关,而REY与磷酸盐组分更为密切。Fe-Mn氧化物组分对海水中金属元素选择性吸附形成多元素的富集及显著的Ce正异常、Y负异常,而磷酸盐组分主要继承海水的稀土特征,它们的含量决定了沉积物中金属元素及稀土元素的含量和模式。结核及沉积物在关键元素富集的过程中有相似的过程,Fe-Mn氧化物组分是二者元素富集过程的载体。研究区的低生物生产力和低沉积速...     

温州围垦工程对河口水交换能力的影响

在建立温州近海及河口二维潮流数值计算模式的基础上,建立了该区域的水交换数学模型,并以2002年为基准水平年,利用该模型对温州市在建和拟建的围垦工程对瓯江、飞云江和鳌江河口水交换能力的影响进行了模拟,探讨了各个河口对应于不同阶段围垦工程的水交换半更换期的变化,指出随着时间的增加,河口内污染物总量受涨、落潮流的影响呈波动状态,涨潮时增大,落潮时减小,总体呈逐渐减少的趋势,其中,瓯江口现状情况下半更换期为12 d左右,近期工程和中期工程后,半更换期为13 d左右,远期工程后,半更换期接近14 d;而飞云江口和鳌江口不同时期围垦方案的半更换期变化不大,其中飞云江口的半更换期约为7～9 d,鳌江口的半更换期约为1.5 d.     

西太平洋多金属结核区表层沉积物细菌群落结构及其对沉积扰动的响应

本文基于大洋第48航次在西太平洋马尔库斯 威克海山多金属结核区采集的6个表层沉积物样品的高通量测序结果,开展底栖细菌群落结构调查,共获得253012条序列,分属于41个门、85个纲、189个目、261个科和322个属。其中,变形菌纲(Proteobacteria)为优势类群,分为γ 、α 和δ 三个亚群,分别占总序列条数的24.76%、20.21%和6.48%。绿弯菌门(Chloroflexi)、酸杆菌门(Acidobacteria)、芽单胞菌门(Gemmatimonadetes)、浮霉菌门(Planctomycetes)、放线菌门(Actinobacteria)、拟杆菌门(Bacteroidetes)及硝化螺旋菌门(Nitrospirae)等类群的序列数和属种较丰富。对序列条数大于1%的OTU(operational taxonomic units)分析,共获得优势菌群23个目,包含6个优势科,10个优势属,其中,铁锰功能细菌占10.20%,主要来自交替单胞菌属(Alteromonas)(6.90%)、假交替单胞菌属(Pseudoalteromonas)(1.80%)和希瓦氏菌属(Shewanella)(1.00%)等,另外还存在参与氮和硫元素循环的种属。PICRUSt功能预测分析显示结核区细菌主要涉及信号转导、蛋白转运、原核生物固碳、群体感应、能量转换、氨基酸和嘧啶代谢等功能。BC1826站位与其他站位相比,细菌多样性较低。结合沉积柱粒度分析结果,推测BC1826站位微生物群落结构的差异与沉积扰动有关,两者具有一定的响应关系。与已有研究成果汇总对比发现,西太平洋结核区与东太平洋结核区的细菌群落组成结构有较大差异。     

Study on the cation substitution capacity of synthetic 1nm manganate

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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…     

海洋有机质的光谱分析方法评述

海洋有机质的光谱分析已成为海洋碳循环的研究热点之一。本文从天然有机质吸收光谱和荧光光谱分析的基本原理入手,系统梳理了有机质光谱分析中容易被忽视的基本概念,讨论了过滤与保存方式、p H值、荧光内滤效应等对有机质光谱分析的影响。结合色氨酸、酪氨酸、腐殖酸及大量现场样品的实验结果,对吸收光谱和三维荧光光谱的不同解析方法进行了系统的分析与对比。基于在南海、西菲律宾海获取的现场调查数据,对于文献中常用的荧光指数(FI)、腐殖化指数(HIX)、自生源指数(BIX)等光谱参数的内在含义及其在海洋环境中的适用性进行了评述。此外,还归纳和总结了胶体有机质和颗粒有机质荧光分析的最新进展,并对今后在光谱分析与观测领域有待完善和突破的一些关键领域进行了展望。     

溶解有机物的光降解及其对浮游细菌和浮游植物的影响

作为海洋中最大的动态有机碳储库,溶解有机物的光降解(主要是紫外波段)对生源要素的生物地球化学循环以及海洋生态系统的结构和功能具有重要的影响。本文探讨了影响溶解有机物光降解的环境因素、其光化学过程和产物,并重点阐述了溶解有机物的光降解对浮游细菌和浮游植物的影响。溶解有机物的来源和成分复杂,其光降解在不同海区有不同的生态效应,为了能更准确地把握其生态效应,需要更全面和深入的研究。     

Experimental evidence for an effect of early-diagenetic interaction between labile and refractory marine sedimentary organic matter on nitrogen dynamics

In most natural sedimentary systems labile and refractory organic material (OM) occur concomitantly. Little, however, is known on how different kinds of OM interact and how such interactions affect early diagenesis in sediments. In a simple sediment experiment, we investigated how interactions of OM substrates of different degradability affect benthic nitrogen (N) dynamics. Temporal evolution of a set of selected biogeochemical parameters was monitored in sandy sediment over 116 days in three experimental set-ups spiked with labile OM (tissue of Mytilus edulis), refractory OM (mostly aged Zostera marina and macroalgae), and a 1:1 mixture of labile and refractory OM. The initial amounts of particulate organic carbon (POC) were identical in the three set-ups. To check for non-linear interactions between labile and refractory OM, the evolution of the mixture system was compared with the evolution of the simple sum of the labile and refractory systems, divided by two. The sum system is the experimental control where labile and refractory OM are virtually combined but not allowed to interact. During the first 30 days there was evidence for net dissolved-inorganic-nitrogen (DIN) production followed by net DIN consumption. (Here ‘DIN’ is the sum of ammonium, nitrite and nitrate.) After  30 days a quasi steady state was reached. Non-linear interactions between the two types of OM were reflected by three main differences between the early-diagenetic evolutions of nitrogen dynamics of the mixture and sum (control) systems: (1) In the mixture system the phases of net DIN production and consumption commenced more rapidly and were more intense. (2) The mixture system was shifted towards a more oxidised state of DIN products [as indicated by increased (nitrite + nitrate)/(ammonium) ratios]. (3) There was some evidence that more OM, POC and particulate nitrogen were preserved in the mixture system. That is, in the mixture system more particulate OM was preserved while a higher proportion of the decomposed particulate N was converted into inorganic N. It can be concluded that during the first days and weeks of early diagenesis the magnitude and composition of the flux of decompositional dissolved N-compounds from sediments into the overlying water was influenced by non-linear interactions of OM substrates of different degradability. Given these experimental results it is likely that the relative spatial distributions of OM of differing degradability in sediments control the magnitude and composition of the return flux of dissolved N-bearing compounds from sediments into the overlying water column.     

The role of organic matter in the sorption capacity of marine sediments

Past studies have suggested that desiccation enhances hydrophobicity of salt marsh sediment, and that drying and rewetting sediment can be used to investigate sorption mechanisms of amino acids and other organic compounds [Liu, Z., Lee, C., 2006. Drying effects on sorption capacity of coastal sediment: The importance of architecture and polarity of organic matter. Geochim. Cosmochim. Acta 70, 3313–3324]. Here we further develop this technique to study sorption of hydrophobic and hydrophilic organic compounds in a wide range of marine sediments. Our results show that hydrophilic compounds sorb strongly to wet coastal sediments; in dried sediments, sorption of hydrophilic compounds decreases, while sorption of hydrophobic compounds is greatly enhanced. Small compounds with aromatic rings sorb more in dried than wet coastal sediments, suggesting that aromatic groups have a stronger effect on sorption than polar groups like amino and carboxyl moieties. Sorption of lysine, glutamic acid and putrescine decreases greatly when sediment is pretreated with KCl, indicating the importance of cation ion exchange. However, α-amino acids sorb much more than corresponding β- or γ-amino acids, and l-alanine sorbs more than d-alanine, suggesting that amino group location and chiral selectivity play an important role in sorption. Comparison of lysine and tyrosine sorption in different sediments indicates that source and diagenetic state of organic matter are important factors determining sorption capacity. Lysine sorbs much more to organic detritus from salt marsh sediment than to fresh Spartina root materials, marine particles, lignin or humic acids, indicating the importance of structural integrity in sorption. Desorption hysteresis of glutamic acid, putrescine and lysine (in dried sediment) suggests the presence of enzyme-type sorption sites of high sorption energy or multiple binding mechanisms. Taken together, these findings suggest that organic matter plays the major role in amino acid sorption in organic-rich sediments.     

The effect of Ruppia cirrhosa features on macroalgae and suspended matter in a Mediterranean shallow system

Relationships among chemical–physical features, total gross suspended organic matter, coverage of the seagrass Ruppia cirrhosa and its associated algal community in eight ponds of a saltworks system of western Sicily (Mediterranean Sea) were investigated in spring and summer 2004. All biological features varied both at different levels of seagrass coverage and between seasons. A low algal diversity (46 taxa, 14.75 ± 1.41 on average) was highlighted; algal coverage and species richness showed to be negatively correlated. Ruppia cirrhosa coverage was negatively correlated with algal coverage, but positively correlated with species richness. Moreover, a significant correlation among R. cirrhosa coverage, the availability of suspended matter in the water column and the chlorophyll a concentration was detected.     

Impact of halides on the photobleaching of dissolved organic matter

Understanding absorbance photobleaching of marine dissolved organic matter (DOM) is important because DOM chromophores impact oceanic primary productivity by affecting the depth of the photic zone, absorb UV radiation and affect ocean color used in remote sensing. However, the fundamental mechanisms which account for this bleaching are largely unknown. Controlled laboratory studies demonstrated that the presence of seawater concentrations of chloride and bromide ions enhanced absorbance photobleaching reaction rates by ~ 40%, regardless of DOM source or the presence or absence of carbonate ions. In contrast, halide ions generally did not affect fluorescence bleaching rates. Variations in ionic strength did not alter the enhancement in absorbance photobleaching by halide ions. Accordingly, the enhancement in absorbance photobleaching was specific to halide ions, rather than a generalized salinity effect. We confirmed the formation of hydroxyl radical (HO^•) in illuminated samples, and its significant scavenging in the presence of halide salts. Gamma-radiolysis experiments and associated modeling indicated that a small component (~ 12%) of the photobleaching enhancement by halides was consistent with the hypothesis that halide scavenging of HO^• will form reactive halogen radicals that target electron-rich chromophores within DOM more selectively than HO^•. The mechanism responsible for the major component of absorbance photobleaching rate enhancement by halides remains unresolved.     

有机质对海底沉积物中粘土矿物X射线衍射分析结果的影响

X射线衍射法广泛应用于分析粘土矿物的含量和结晶特征,由于粘土矿物易与有机质结合形成有机-粘土复合体,是否去除有机质对分析结果有很大影响,实验结果表明影响最大的是伊-蒙混层矿物(含蒙脱石)和伊利石的含量,为得到可靠实验数据,必须重视对样品的前处理工作,对不同批次样品应该保持一致的处理程序。