中、西太平洋多金属结壳生长速率变化与制约因素

多金属结壳在不同生长区域、层位存在生长速率的差异,这在一定程度上反映了其生长条件的优劣,说明其受到了诸多海洋要素的制约。本研究在总结生长速率变化与结壳生长区域、年代和结构构造的关系的同时,分析生长间断发生与生长速率变化的关系,并尝试对多金属结壳生长环境条件的转变进行探讨。多金属结壳的生长速率随采样海山区位置由东向西(莱恩海山区—麦哲伦等海山区)、结构构造由致密到疏松再到较致密和生长期由老到新由高至低变化。最低含氧带之下合适的深度、较强的氧化性、较丰富的陆源物质供给和海洋中较高的碳酸钙溶解率有利于结壳的生长,使其具有较大的生长速率。多金属结壳生长间断的发生对应3种生长速率变化情形:①在生长速率由低升高前,主要对应65～60 Ma的间断期,此时水动力条件不佳,结壳因生长环境过差而间断,由差转好时复生长;②生长速率由高转低时,主要对应51～42 Ma和40～35 Ma的两次间断期,此时气候回暖同时陆源风尘供应水平较低,结壳在生长环境变差时间断,稍好时复生长;③生长速率持续偏低时,对应28～18 Ma的间断期,此时大洋CaCO_3溶解率持续偏低,结壳在长时间较差的生长环境中断续生长。     

80 Ma以来海水Os同位素组成曲线的精细特征:中、西太平洋多金属结壳的记录

80 Ma以来的海水Os同位素标准曲线具有K/T（白垩纪/第三纪）界线低值、E/O（始新世/渐新世）界线低值和中新世“挠曲”3个特征形态，这可以解释为陨击事件或超基性岩风化事件造成的陆、幔源物质供给关系的变化。将海水Os同位素标准曲线与多金属结壳Os同位素组成曲线进行对比，根据形态和取值的贴合程度可以为结壳进行年代厘定。由于取样精度的限制和生长间断的广泛存在，仅以此3个特征比对曲线存在不确定性。本研究综合对比中、西太平洋6块结壳的Os同位素组成曲线，总结出了4种记录在结壳中的海水Os同位素曲线的特征规律：K/T界线之前的“早期异常（波动）”；E/O界线之后曲线上升过程中的“小停顿”；E/O界线之后曲线上升过程末尾的“异常偏高点”；“中新世‘挠曲’错后”至10 Ma左右。这些新的特征形态可作为年代控制点，使得结壳年代框架的厘定可以更准确可靠。这4种特征形态可以初步解释为地质历史时期海洋中、幔源物质的供应关系变化或是看作随着数据的积累而对标准曲线的细化和校正。     

铁锰结壳年代学方法及其应用

铁锰结壳记录了丰富的古海洋和古气候信息,要分析这些信息,必须先确定各壳层的生长年龄。目前主要使用的定年方法有:Be同位素定年、U系同位素定年、Os同位素定年、经验公式法、古地磁地层学方法和古生物地层学方法等。每种定年方法均各有利弊,其中10Be是年龄小于10 Ma结壳的最佳定年方法; U系同位素定年精度高,但定年范围小于0.5 Ma; Os同位素定年时间尺度长,且可以判断沉积间断,但需要有区域的海水Os同位素演化曲线; Co经验公式因为简单易行,是结壳估算年龄最为常用的方法,但该法无法判断沉积间断,在使用时需特别谨慎,应确保经验公式适用于所研究的样品;如果结壳厚度大、生长速率较快且不存在沉积间断,古地磁地层学方法可以快速地进行定年;此外,如果结壳中古生物化石较多,可考虑采用古生物地层学方法。在分析铁锰结壳年代学方法利弊基础上,本文利用U系定年法、古地磁地层学法和经验公式计算法分别对南海铁锰结壳进行定年,通过比较,认为目前铁锰结壳较优的定年方法为古地磁地层学方法。     

磷酸盐化对莱恩海山链MP2海山结壳Co富集的影响

利用电子探针对中太平洋莱恩海山链MP2海山典型富钴结壳样品的剖面分别进行壳层、碎屑矿物和自生矿物主元素原位分析.通过对壳层(主要的成矿金属元素、脉石元素)、碎屑矿物和自生矿物中的Si,Al,Ca和P等元素质量分数的研究,探讨磷酸盐化作用对MP2海山富钴结壳中Co元素富集的影响.发现结壳第Ⅱ层未磷酸盐化壳层存在贫钴壳层,...     

富钴结壳定年简介

富钴结壳生长通常十分缓慢,其速率一般为几mm/Ma。因此这些结壳提供了成矿环境(海水、沉积物等)的长期历史记录。然而,富钴结壳完整、精细定年的可靠性仍然是一个问题。为此,国外学者采用了多种方法对结壳进行定年,井得到其生长速率。以下分别介绍这些方法的原理、应用及其优、缺     

西太平洋Lamont海山中新世以来富钴结壳成矿环境的演化

分析了西太平洋Lamont海山12个站位33个富钴结壳样品的主元素和稀土元素,结果表明,该海山富钴结壳成因类型属于水成成因,并且在形成过程中基本未受到磷酸盐化作用的影响。Lamont海山的一个富钴结壳样品剖面的电子探针数据显示,该海山富钴结壳的成矿环境在新第三纪以来至少存在2个演化阶段:第1阶段,23~15 Ma,富钴结壳中Mn相对富集,成矿环境以富氧贫硅为特征;第2阶段,15~0 Ma,富钴结壳中Fe相对富集,成矿环境以贫氧富硅为特征。成矿环境的氧化能力总体上呈现下降的趋势。联系新生代世界大洋,尤其是西太平洋的地质演化背景,认为引起成矿环境演变的原因主要是西太平洋大洋板块的WNW向漂移和新第三纪以来全球水道开合,造成了Lamont海山所处海区最低含氧带逐渐减薄。     

西太平洋麦哲伦海山富钴结壳成分特征及古环境记录

针对取自西太平洋麦哲伦海山的富钴结壳,运用EPMA技术研究了其微区成分特征,估算并讨论了结壳的生长速率和生长年龄,并结合前人研究成果讨论了结壳的古环境记录。研究发现:结壳Mn、Fe、Co、Ni、Cu、Ca、P和Al的元素平均含量分别是29.04%、17.40%、0.73%、0.33%、0.15%、1.72%、0.35%和0.45%,与中、西北太平洋、印度洋及大西洋结壳相比具有高Mn、富Co和贫Ni的特征;结壳初始生长年龄为19.26 Ma,在8.05~11.3 Ma之间出现了约3 Ma的生长间断;进一步研究表明,结壳的Al/(Fe+Mn)、Co/(Ni+Cu)和Fe/Mn微区记录能分别较好地反映亚洲季风气候演变、海水氧化性演变和冰室期-变暖期的古气候演变及其相互之间的联系。     

西太平洋铁锰结壳中两类不同成因磷酸盐的元素特征、形成机制及指示意义

太平洋铁锰结壳在中新世以前大多经历了磷酸盐化,一般认为其形成代表了高生产力时期富磷组分对先期已形成结壳的交代作用,即磷酸盐化事件的产物.然而,前人对铁锰结壳磷酸盐化的机制研究多基于点-线分析元素或同位素,对铁锰结壳生长结构及二维元素分布特征研究较少.本研究以西太平洋水成铁锰结壳MDD53为研究对象,利用电子探针(EPM...     

中太平洋海山铁锰结壳生物地层学研究

用生物地层学方法对位于中太平洋同一座海山上的2块铁锰结壳样品进行了生物地层学详细研究,发现2块样品的生长层位对应,生物组合也相同.经鉴定,2块结壳的主要生长期都是晚古新世、中始新世至晚始新世、中中新世至上新世、上新世至更新世,2个主要的结壳生长间断分别在渐新世和早始新世.     

九州-帕劳海脊13°20′N海山铁锰结壳生长过程中Si、Al、Ca的含量变化及对碎屑物质供给的指示

作为深海铁锰结壳的重要组成部分,碎屑物质类型多样,不仅影响关键金属富集成矿,而且还可以指示结壳形成过程中的古海洋环境和重大地质历史事件。本文对九州-帕劳海脊13°20′N海山铁锰结壳样品进行了扫描电镜和激光剥蚀微区分析,并结合前期研究工作,发现大颗粒的碎屑物质主要由亚洲大陆风尘来源的石英、长石或两者的聚集体,以及主要分布在结壳外层的有孔虫壳体所组成,而细颗粒的碎屑物质包括陆源风尘沉降和周边岛弧物质风化搬运共同带入的黏土矿物,以及各种形态的生物体及其残片。结壳形成的早期其碎屑物质的供给量处于高峰阶段,晚期则降低到谷底,该趋势与Si、Al在结壳各层位中的含量分布特征一致,且可能有相当数量的细颗粒生物硅进入了铁锰氧化物纹层。结壳内早期被动增生的钙质生物体在中后期会遭受破碎和溶解,但其中的Ca并没有完全从结壳内迁移出去,而是大量被铁锰氧化物所吸附。结壳中的Ca主要赋存在细颗粒碎屑物质中,使得Ca在各层位全样样品和铁锰氧化物微区纹层中的含量极为相近,这与Si、Al的特征完全不同。研究区结壳样品属于典型开阔大洋海山型结壳,但因为受亚洲大陆风尘物质和硅藻供给的影响,其内部关键金属的富集在一定程度上受...     

中太平洋铁锰结壳碘分布及磷酸盐化对其影响

In the present paper, iodine(I), iron(Fe), manganese(Mn), cobalt(Co), phosphorus(P) and calcium(Ca)contents in three ferromanganese crusts from the Pacific Ocean are measured by spectrophotometric method and inductively coupled plasma atomic emission spectrometers(ICP-AES) to investigate the contents and distribution of iodine in ferromanganese crusts. The results show that iodine contents in three crusts vary between 27.1 and 836 mg/kg, with an average of 172 mg/kg, and the profile of iodine in the three crusts all exhibits a two-stage distribution zone: a young non-phosphatized zone and an old phosphatized zone that is rich in I, P and Ca. The iodine content ratios of old to young zone in MP5D44, CXD62–1 and CXD08–1 are 2.3, 3.4 and 13.7, respectively.The boundary depths of two-stage zone in MP5D44, CXD62–1 and CXD08–1 locate at 4.0 cm, 2.5 cm and 3.75 cm,respectively, and the time of iodine mutation in three crusts ranges from 17–37 Ma derived from 129 I dating and Co empirical formula, which is consistent with the times of Cenozoic phosphatization events. The present study shows that the intensity of phosphatization is the main responsible for the distribution pattern of iodine in the crusts on the basis of the correlation analysis. Consequently, iodine is a sensitive indicator for phosphatization.     

Influence of substrate rocks on Fe–Mn crust composition

Principal Component and other statistical analyses of chemical and mineralogical data of Fe–Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.     

西北太平洋多金属结核铂族元素地球化学特征

Polymetallic nodules and cobalt (Co)-rich crusts are enriched in platinum-group elements (PGEs),especially platinum (Pt) and may be important sinks of PGEs.At present,little information is available on PGEs in polymetallic nodules,and their geochemical characteristics and the causes of PGEs enrichment are unclear.Here PGEs of polymetallic nodules from abyssal basin in the Marcus-Wake Seamount area of the Northwest Pacific Ocean are reported and compared with the published PGEs data of polymetallic nodules and Co-rich crusts in the Pacific.The total PGEs (ΣPGE) content of polymetallic nodules in study area is 258×10~(–9) in average,markedly higher than that of Clarion-Clipperton Zone (CCZ) nodules (ΣPGE=127×10~(–9)) and lower than that of Co-rich crusts in the Marcus-Wake Seamount (ΣPGE=653×10~(–9)),similar to that of Co-rich crusts in the South China Sea(ΣPGE=252×10~(–9)).The CI chondrite-normalized PGEs patterns in different regions of polymetallic nodules and cobalt-rich crusts are highly consistent,with all being characterized by positive Pt and negative Pd anomalies These results,together with those of previous studies,indicate that PGEs in polymetallic nodules and Co-rich crusts are mainly derived directly from seawater.Pt contents of polymetallic nodules from the study area are negatively correlated with water depth,and Pt/ΣPGE ratios in nodules there are also lower than those of the Corich crusts in the adjacent area,indicating that sedimentary water depth and oxygen fugacity of ambient seawater are the possible important controlling factors for Pt accumulation in crusts and nodules.     

Fine-scale compositional variations in a Co-rich Mn crust from the Marcus-Wake Seamount cluster in the western Pacific based on electron microprobe analysis (EMPA)

The internal structure and composition of a 37-mm-thick Co-rich Mn crust from the Lamont Guyot in the Marcus-Wake Seamount cluster have been studied in detail by means of electron-probe microanalysis (EPMA). 184 point analyses for 16 elements were carried out at an average spacing of 0.20 mm and each point was dated using the Co-geochronometer method. Two types of variation in composition were observed in the crust: long-term trends and short-term erratic variations. The long-term trends were identified using the fifth order polynomial. Mn and Ni were shown to increase in concentration from 23.3 Ma to a maximum at about 20 Ma and then decline steadily to the Present, whereas Fe, P and Si showed the opposite trend. By contrast, Co displayed a double humped pattern with maxima at about 19 Ma and 3.5 Ma and minima at 23.3 Ma, about 11 Ma and at Present. The long-term trends in element concentrations in the crust lead us to suggest that much of the Fe in western Pacific Ocean ferromanganese crusts is aeolian in origin and derived from the deserts of central Asia. Cooling of the Asian mainland at about 20 Ma led to an increase in the flux of Fe to the oceans. This was supplemented by an additional input of Fe into the crusts as a consequence of the dissolution of biogenic CaCO₃ tests at 4.5−10.5 Ma. For the short-term erratic variations, three periods of 0.61, 0.96 and 1.65 m.y. were identified by spectral analysis. The second harmonics of these periods are 1.22, 1.92 and 3.30 m.y., which may correspond to the highest-order periods for eccentricity of 1.31, 2.04 and 3.47 m.y. This suggests the possibility that the high-frequency oscillations of the time series data are linked to climatic changes controlled by the highest-order periods of the Milankovitch cycles.     

西太平洋卡罗琳洋脊CM4海山铁锰结壳矿物学和地球化学特征

2017年8月中国科学院海洋研究所在西太平洋低纬度海区的卡罗琳洋脊CM4海山开展了多学科综合调查,发现该海山山体表面分布着大量的铁锰结壳。本文对该海山的5个铁锰结壳样品进行了矿物学和地球化学研究,利用X射线衍射(XRD)、电感耦合等离子光谱及质谱(ICP-OES、ICP-MS)等测试技术分析了铁锰结壳的矿物组成、主微量元素和稀土元素含量,并进一步探讨了铁锰结壳的成因类型。结果表明,该海山铁锰结壳的矿物组成以水羟锰矿为主,含有少量钡镁锰矿、水钠锰矿、针铁矿、纤铁矿、石英和方解石。该海山铁锰结壳的Mn、Fe、Co、Ni、Cu元素平均含量分别为24.24%、15.14%、0.16%、0.34%、0.01%。与全球各大洋海山区铁锰结壳相比,该海山样品的Cu含量很低。该海山铁锰结壳的稀土元素(REY)含量相对偏低,总体为轻稀土(LREE)富集;稀土(REY)配分模式显示相对平坦的特征,呈明显的Ce正异常,轻微的Y负异常和Ho正异常。样品的矿物组成、元素比值、元素组合等都表明该海山铁锰结壳属于水成成因,未受明显的成岩作用影响。     

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。     

麦哲伦海山群富钴结壳元素地球化学特征及赋存状态

为探究大洋富钴结壳的元素地球化学特征和赋存状态,以西太平洋麦哲伦海山群5个富钴结壳样品为研究对象,通过X射线衍射法、等离子体发射光谱法、等离子体质谱法及相态分析手段,分析了富钴结壳的矿物组成、主量元素和稀土元素含量。结果表明,富钴结壳样品主要结晶矿物为水羟锰矿,次要矿物包括石英、斜长石和钾长石,同时含有大量非晶态铁氧/氢氧化物。富钴结壳样品中Mn和Fe含量最高, Mn为16.87%～26.55%, Fe为14.34%～18.08%。富钴结壳明显富集稀土元素,其稀土总量为1 287～2 000μg/g,Ce含量为632～946μg/g,约占稀土总量的50%;轻稀土含量为1 037～1 604μg/g,重稀土含量为249～395μg/g,轻稀土元素明显高于重稀土元素。稀土元素配分模式呈现Ce正异常而Eu无异常,具有Ce富集特征。麦哲伦海山群富钴结壳是水成沉积成因,基本没有受到海底热液活动和成岩作用的影响。元素赋存状态与其矿物相密切相关, Na、K、Ca、Mg和Sr主要赋存于碳酸盐相, Mn、Ba、Co和Ni主要赋存于锰氧化物相, Fe、Al、P、Ti、Cu、Pb、V、Zn、Zr和REE主要...