Paleoenvironments Recorded in a New-Type Ferromanganese Crust fromthe East Philippine Sea

We attempt to recover the paleocnvironments recorded in the accretion of a typical newtype hydrogenetic ferromanganese crust from the deep water areas of the East Philippine Sea. From detailed geochemical and U-series chronological studies, analysis of major and minor elements performed by X-ray fluorescence spectrometry （XRF） and inductively coupled plasma-mass spectrometer （ICPMS）, three major accretion periods and corresponding paleocnvironments can be ascertained. The first period is a faster accretion period in the terminal Late Miocene to the Early Pliocene with looser structure and higher volcanic detritus content, corresponding to the active Antarctic bottom waters and depressed temperature from the intermediate Middle Miocene to the Early Pliocene. The second period is a pulse of pelagic clay deposition at the Early to Middle Pliocene, reflecting the shrinkage of the Antarctic bottom waters and the global temperature elevation of this period. The third period is a slower accretion period from the Middle Pliocene, which indicates the more violent activity of Antarctic bottom waters once again and more depressed temperature than the first period, facilitating the accretion of a more compact and pure ferromanganese zone. The paleoceanographic histories of these studied areas had not been made clear in previous research.

Paleoenvironment evolution of the East Philippine Sea recorded in the new-type ferromanganese crust since the terminal Late Miocene

From systemic research of microstructure, geochemistry, uranium-series and 10Be isotope dating on a new-type deepwater ferromanganese crust from the East Philippine Sea, the paleoenvironment evolu-tion of the target area since the terminal Late Miocene was recovered. The vertical section changes of microstructure and chemical composition are consistent in the studied crust, which indicate three major accretion periods and corresponding paleoenvironment evolution of the crust. The bottom crust zone was formed in the terminal Late Miocene (5.6 Ma) with loose microstructure, high detritus content and high growth rate. Reductions of mineral element content, accretion rate and positive Ce-anomaly degree at 4.6 Ma indicate temporal warming, which went against the crust accretion and finally formed an accretion gap in the terminal Middle Pliocene (2.8―2.7 Ma). The more active Antarctic bottom sea-waters in the Late Pliocene (2.7 Ma) facilitated the fast transfer to the top pure crust zone. Hereafter, with the further apart of volcanic source and the keeping increase of eolian material (1.0 Ma), although surrounding conditions were still favorable, mineral element content still shows an obvious reducing trend. It thereby offers new carrier and data for the unclear paleoceanographic research of the target area since the terminal Late Miocene.

Distribution characteristics of seamount cobalt-rich ferromanganese crusts and the determination of the size of areas for exploration and exploitation

In 2001, the International Seabed Authority （ISBA） initiated the consideration relating to the Regulations for Prospecting and Exploration for Hydrothermal Polymetallic Sulphides and Cobalt-rich Ferromanganese Crusts in the Area at its 7th session. Since then, the consideration of the Regulations has been mainly focused on the size of areas to be allocated for exploration and exploitation of the crusts. This paper, based on the investigation data and the analysis of the distribution characteristics of the crusts, suggests a model for determining the size of areas for exploration and exploitation of the crusts, taking into account various factors such as production scale, crust thickness and grade, mineable area proportion, recovery efficiency, exploration venture, and so on. Through the modeling, the paper suggests that the exploration area （the area covered by each application for approval of a plan of work for exploration of cobalt-rich crusts） shall be 4 856 km2 and the exploitation area （the mine site area） shall be 1 214 km2, for 20 years of 1 million wet tonnes annual production.

Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

Noble gas isotopic compositions of various layers in three-layered （outer, porous and compact layers） cobalt-rich ferromanganese crusts and their basaltic and phosphorite substrates from the western Pacific Ocean were analyzed by using a high vacuum gas mass spectrum. The analytical results show that the noble gases in the Co-rich crusts have derived mainly from the ambient seawater, extraterrestrial grains such as interplanetary dust particles （IDPs） and wind-borne continental dust grains, and locally formation water in the submarine sediments, but different noble gases have different sources. He in the crusts derives predominantly from the extraterrestrial grains, with a negligible amount of radiogenic He from the eolian dust grains. Ar is sourced mainly from the dissolved air in the seawater and insignificantly from radiogenic Ar in the eolian continental dust grains or the formation water. Xe and Ne derive mainly from the seawater, with minor amounts of extraterrestrial Xe and Ne in the IDPs. Compared with the porous and outer layers, the compact layer has a relatively high 4He content and lower 3He/4He ratios, suggesting that marine phosphatization might have greatly modified the noble gas isotopic compositions of the crusts. Besides, the 3He/4He values of the basaltic substrates of the cobalt-rich crusts are very low and their R/R. ratios are mostly 〈0.1 R., which are similar to that of phosphorite substrates （0.087 R.）, but much lower than that of fresh submarine MORB （8.75±14 Ra） or seamount basalts （3-43 Ra）, implying that the basaltic substrates have suffered strong water/rock interaction and reacted with radiogenic ^4He and P-rich upwelling marine currents during phosphatization. The trace elements released in the basalt/seawater interaction might favor the growth of cobalt-rich crusts. The relatively low ^3He/^4He values in the seamount basalts may be used as an important exploration criterion for the cobalt-rich ferromanganese crusts.

The distribution of iodine and effects of phosphatization on it in the ferromanganese crusts from the Mid-Pacific Ocean

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 129I 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.

Material Properties of Marine Hydrogenous Ferromanganese Crust and Its Performance in Desulfurization

Marine hydrogenous ferromanganese crust, an important metal resource in the future, has significant potential in various applications as a type of natural nano-structured material. By employing scanning electronic microscopy, nitrogen adsorption-desorption isotherm measurement, Xray fluorescence spectrometer and X-ray diffraction methods, the micro-structure, surface properties and chemical composition of several plate-like ferromanganese crusts sampled from the northwestern Pacific were investigated comprehensively. Although obvious differences were observed from different layers, the crust is a typical porous material with high specific surface area, unique pore structure and abundant transition elements. Furthermore, the performance of natural crust in desulfurization process was preliminarily tested in laboratory experiments. The suffur capacities of the crust are 13.1% and 18.1% at room temperature and 350 ℃, respectively. The crust can be used not only as a metal resource, but also as an environmental material.

Ecological functions of uncultured microorganisms in the cobaltrich ferromanganese crust of a seamount in the central Pacific are elucidated by fosmid sequencing

Cobalt-rich ferromanganese is an important seafloor mineral and is abundantly present in the seamount crusts. Such crusts form potential hotspots for biogeochemical activity and microbial diversity, yet our understanding of their microbial communities is lacking. In this study, a cultivation-independent approach was used to recover genomic information and derive ecological functions of the microbes in a sediment sample collected from the cobalt-rich ferromanganese crust of a seamount region in the central Pacific. A total of 78 distinct clones were obtained by fosmid library screening with a 16S rRNA based PCR method. Proteobacteria and MGI Thaumarch-aeota dominated the bacterial and archaeal 16S rRNA gene sequence results in the microbial community. Nine fosmid clones were sequenced and annotated. Numerous genes encoding proteins involved in metabolic functions and heavy metal resistance were identified, suggesting alternative metabolic pathways and stress responses that are essential for microbial survival in the cobalt-rich ferromanganese crust. In addition, genes that participate in the synthesis of organic acids and exoploymers were discovered. Reconstruction of the metabolic pathways revealed that the nitrogen cycle is an important biogeochemical process in the cobalt-rich ferromanganese crust. In addition, horizontal gene transfer （HGT） events have been observed, and most of them came from bacteria, with some occurring in archaea and plants. Clone W4-93a, belonging to MGI Thaumarch-aeota, contained a region of gene synteny. Comparative analyses suggested that a high frequency of HGT events as well as genomic divergence play important roles in the microbial adaption to the deep-sea environment.

Measurement of ^(129)I in ferromanganese crust with AMS

In the present study, the analytical method for ^129iodine （^129I） in ferromanganese crusts is developed and ^129iodine/^127iodine （^129I/^127I） ratio in ferromanganese crusts is measured by the accelerator mass spectrometry （AMS）. The developed method is applied to analyze ^129I/^127I ratio in two ferromanganese crusts MP5D44 and CXD08-1 collected from the Mid-Pacific Ocean. The results show that ^129I/^127I ratio in MP5D44 and CXD08-1 crusts varies from 7×10^-14 to 1.27×10^-12, with the lowest value falling on the detection limit level of AMS reported by previous literatures. For the depth distribution of ^129I/^127I, it is found that both MP5D44 and CXD08-1 crusts have two growth generations, and the ^129I/^127I profiles in two generations all displayed an approximate exponential decay. According to the ^129I/^127I ratio, the generate age of bottom layer of MP5D44 and CXD08-1 was estimated to be 54.77 and 69.69 Ma, respectively.

Composition and Origin of Ferromanganese Crusts from Equatorial Western Pacific Seamounts

In the equatorial western Pacific, iron-manganese oxyhydroxide crusts(Fe-Mn crusts) and nodules form on basaltic seamounts and on the top of drowned carbonate platform guyots that have been swept free of pelagic sediments. To date, the Fe-Mn crusts have been considered to be almost exclusively of abiotic origin. However, it has recently been suggested that these crusts may be a result of biomineralization. Although the Fe-Mn crust textures in the equatorial western Pacific are similar to those constructed by bacteria and algae, and biomarkers also document the existence of bacteria and algae dispersed within the Fe-Mn crusts, the precipitation, accumulation and distribution of elements, such as Fe, Mn, Ni and Co in Fe-Mn crusts are not controlled by microbial activity. Bacteria and algae are only physically incorporated into the crusts when dead plankton settle on the ocean floor and are trapped on the crust surface. Geochemical evidence suggests a hydrogenous origin of Fe-Mn crusts in the equatorial western Pacific, thus verifying a process for Fe-Mn crusts that involves the precipitation of colloidal phases from seawater followed by extensive scavenging of dissolved trace metals into the mineral phase during crust formation.

Assessment of acoustic backscatter intensity surveying on deep-sea ferromanganese crust: Constraints from Weijia Guyot, western Pacific Ocean

Near-bottom observation data from the manned deep submersible Jiaolong with high-precision underwater positioning data from Weijia Guyot,Magellan Seamounts in the Western Pacific Ocean are reported.Three substrate types were identified:Sediment,ferromanganese crust,and ferromanganese crust with a thin cover of sediment.The ferromanganese crusts show clear zoning and their continuity is usually disturbed by sediments on areas of the mountainside with relatively gentle slope gradients.The identified substrate spatial distributions correspond to acoustic backscatter intensity data,with regions of high intensity always including crust development and regions of low intensity always having sediment.Therefore,acoustic backscatter intensity surveying appears useful in the delineation and evaluation of crust resources,although further more work is needed to develop a practicable methodology.

Factors Controlling the Distribution of Transitional Metal Elements in Marine Hydrogenic Ferromanganese Crusts

A series of selective dissolution experiments were conducted on the hydrogenic ferromanganese crusts collected near Line Island to study the geochemistry of Mn, Fe, Cu, Co, Ni and Ti. Despite of the fact that the very close intergrowth between amorphous ferric oxyhydroxides and δ-MnO2 exists in the hydrogenic ferromanganese crusts, there is no isomorphous substitution between iron and manganese. This is because the two elements in oxides have different crystal chemistry and geochemistry, such assertion being in agreement with the results of selective dissolution experiments. Transitional metal elements such as Cu, Co, Ni and Ti are enriched in different phases, i.e. Ni and Co are incorporated into δ-MnO2 while Cu and Ti are incorporated into ferric oxyhydroxides. The distributions of the elements in amorphous ferric oxyhydroxides and δ-MnO2 are controlled by the existing states of the elements in the seawater and the crystal chemistry and geochemistry of these elements/ions in oxides.

Geochemical characteristics and geological implication of ferromanganese crust from CM6 Seamount of the Caroline Ridge in the Western Pacific

Ferromanganese crusts(Fe-Mn crusts)grow very slow and can be treated as condensed stratigraphic sections recording paleo-oceanographic environmental information and local key geological events during the mineralization process.Geochronology,textures,mineralogy,and geochemistry of a Fe-Mn crust sample from the CM6 Seamount of the Caroline Ridge in the Western Pacific Ocean were analyzed by means of electron probe microanalysis and X-ray diffraction.The Fe-Mn crust shows three layers in textural characteristics from bottom to top.The lower,middle,and upper layers presence mottled,botryoidal,and columnar textures,respectively.Ferruginous vernadite,Fe hydroxide,amorphous silicate minerals,calcite,quartz,and feldspar are the main minerals of the Fe-Mn crust.Using cobalt chronometry method,the cumulative growth time of the Fe-Mn crust was determined to be 11 Ma or 25 Ma,of which25 Ma is inconsistent with other lines of age constraint brought by dating of the substrate.The co-existence of abundant silicate minerals and bioclasts in the middle and lower layers of the Fe-Mn crust diluted the ferromanganese oxide deposits,thus affected the texture,minerals,and geochemical characteristics of the Fe-Mn crust.Variations in Mn Co,Ni,and other elements content and the burial of opal-A recorded the expansion of oxygen minimum zone(OMZ)in the upper layer of the Fe-Mn crust.In addition,the highreflectivity Fe-rich laminae might indicate the surrounding volcanic activity.The Fe-Mn crust sample was determined to be hydrogenic by electron probe micro-analyzer(EPM A).The findings help us understand the geochemical characteristics of the Fe-Mn crust in the Caroline Ridge Seamount in the Western Pacific and the variations of paleo-oceanographic environment clues borne by the Fe-Mn crusts.

Copper and zinc isotope variations in ferromanganese crusts and their isotopic fractionation mechanism

Ferromanganese(Fe-Mn)crusts are potential archives of the Cu and Zn isotope compositions of seawater through time.In this study,the Cu and Zn isotopes of the top surface of 28 Fe-Mn crusts and 2 Fe-Mn nodules were analysed by MC-ICP-MS using combined sample-standard bracketing for mass bias correction.The Zn isotope compositions of the top surface of Fe-Mn crusts are in the range of 0.71‰to 1.08‰,with a mean δ^(66)Zn value of 0.94‰±0.21‰(2 SD,n=28).The δ^(65)Cu values of the top surface of Fe-Mn crusts range from 0.33‰to0.73‰,with a mean value of 0.58‰±0.20‰(2 SD,n=28).The Cu isotope compositions of Fe-Mn crusts are isotopically lighter than that of dissolved Cu in deep seawater(0.58‰vs.0.9‰).In contrast,the δ^(66)Zn values of Fe-Mn crusts appear to be isotopically heavy compared to deep seawater(0.94‰±0.21‰vs.0.51‰±0.14‰).The isotope fractionation between Fe-Mn crusts and seawater is attributed to equilibrium partitioning between the sorption to crusts and the organic-ligand-bound Cu and Zn in seawater.The Cu and Zn isotopes in the top surface of Fe-Mn crusts are not a direct reflection of the Cu and Zn isotopes,but a function of Cu and Zn isotopes in modern seawater.This study proposes that Fe-Mn crusts have the potential to be archives for paleoceanography through Cu and Zn isotope analysis.

机器学习:海底矿产资源智能勘探的新途径

海底蕴藏着丰富的关键矿产资源,是当前研究的热点,也是未来产业新领域。随着海洋探测技术的不断进步,海底矿产勘探的数据量和数据维数急剧增加,给数据处理与解释带来了巨大困难和挑战。面对海量数据,传统的数据解释与分析方法暴露出许多问题。机器学习以其强大的自学能力,为无法解决或难以解决的问题提供了一系列智能分析决策方案,提高了数据分析的效率,是海底矿产资源智能勘探的新途径。近年来,机器学习在地球科学领域获得了广泛的关注和研究。为此,围绕机器学习技术应用于海底资源勘探技术,本文首先简要介绍了机器学习中经典的模型算法,然后详细阐述了机器学习在海底能源矿产和金属矿产两个方面的应用现状,最后总结了机器学习在海底矿产智能勘探领域的应用前景,指出了现有研究中存在的问题,提出了解决方案和未来的发展方向。

西太平洋维嘉海山埋藏型富钴结壳生长速率初步研究

富钴结壳是一种水成成因,生长在海底岩石或岩屑表面的皮壳状铁锰氧化物和氢氧化物,主要分布于CCD以上、最低含氧层(OMZ)中或以下800~2500 m水深之间的类叠层石结构,具典型的层状结构,奇特的韵律性生长剖面蕴含着其生长过程中所保留下来的比较完整的古海洋演化和古环境信息(任江波等,2013;王彦美等,2017)。

The initial exploration for ^(26)Al chronology in deep-sea ferromanganese crust

Background The deep-sea ferromanganese crust(DSFC)is a natural archive for recording the history of the Earth’s evolution,as one of the most common authigenic assemblages in marine sediments.Although the depositional age dating using meteoric ^(10)Be has been successfully used in the study on the chronology of DSFC,the research on ^(26)Al has not seen relevant reports in this aspect due to the influence of factors such as measurement sensitivity and ^(26)Al in situ production.Method The first exploration for ^(26)Al chronology in DSFC was carried out by using accelerator mass spectrometry(AMS)measurements of ^(10)Be and ^(26)Al,and the comparison of relationship between isotopic ratios and concentrations of Al and Be.Results The growth rates of G.R=(1.44±0.09)mm/Ma,(3.58±0.29)mm/Ma,(1.52±0.10)mm/Ma and(2.93±0.14)mm/Ma are derived using ^(10)Be/^(9)Be,^(26)Al/^(27)Al ratios,^(10)Be and ^(26)Al concentrations,respectively.Conclusion The ^(26)Al chronological methods have been explored based on a DSFC sample and encouraging results were obtained.The results are preliminary and insufficient;some information is still needed to explain the difference between ^(26)Al and ^(10)Be chronology.

九州-帕劳海脊南段铁锰结壳物质组成特征及成因机制

铁锰结壳(又称富钴结壳、多金属结壳)富含Co、Cu、Mn、Ni、Ti、V、REE、Y和Zn等人类日常生活和高新技术产业亟需的关键金属,是一种重要的战略性矿产资源。本文对九州-帕劳海脊南段水深1 900~2 600 m处获得的9个站位铁锰结壳样品进行了矿物学和地球化学研究,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,研究区铁锰结壳的矿物组成以水羟锰矿为主,同时含有大量非晶态铁氧/氢氧化物;Mn、Fe、Co、Ni、Cu平均含量分别为16.15%、15.38%、0.32%、0.33%、0.10%;CaO/P_(2)O_(5)均值为5.93,表明九州-帕劳海脊南段铁锰结壳样品均未发生磷酸盐化作用;铁锰结壳明显富集稀土元素(含Y,REYs),平均含量为1 194μg/g,轻稀土显著富集,稀土元素经后太古代澳大利亚页岩(PAAS)标准化后配分模式整体相对平坦,呈现Ce正异常而Eu无异常,与海水呈现镜像关系,说明铁锰结壳稀土元素主要来源于海水。铁锰结壳的矿物组成和元素判别图均表明九州-帕劳海脊南段铁锰结壳属于水成型,未受明显的成岩作用影响。

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到了制约。

大洋富钴结壳研究进展及展望

富钴结壳是一种重要的海底矿产资源,具有独特的经济价值和科学意义,其不仅富含Mn、Co、Ni、Cu、PGE和REY等金属,而且在反演新生代以来古海洋环境记录等方面扮演着独特的角色。锰氧化物(MnO_(2)·xH_(2)O)和铁羟基氧化物(FeOOH)是构成富钴结壳的主要矿物,矿物颗粒十分微小(纳米级)。水羟锰矿和水钠锰矿具有层状结构且层电荷为负,通过吸附阳离子来补偿。前人通过连续浸出实验、元素相关性统计分析、吸附实验和拓展X射线吸收精细结构(EXAFS)光谱广泛研究了微量元素在矿物中的赋存状态,确定了微量元素在锰氧化物矿物中主要存在三种类型络合物:共六边(edge-sharing)、共双角(double-corner sharing)和共三角(triple-corner sharing)。综合研究表明,在最低含氧带之下铁锰氧化物(氢氧化物)从海水沉淀到周围海山坚硬基岩上形成富钴结壳的机制主要是无机胶体化学反应和矿物表面反应。最后针对已有的相关研究现状以及富钴结壳研究面临的挑战,富钴结壳的成矿物质来源及演化、微量元素富集机制、蕴含的古海洋信息等问题仍需要进一步深入探讨。