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.

Calcareous Nannofossils and Molecular Fossils in Cobalt-rich Crusts and their Response to the P/E Global Event

A biostratigraphic study on calcareous nannofossils from the CM3D06 Co-rich ferromanganese crust from the Magellan seamounts in the northwestern Pacific enabled estimation of depositional age. The bio-imprinting of calcareous nannofossils and other fossil species suggests six age ranges for the nannofossils： late Cretaceous, late Paleocene, （early, middle, late） Eocene, middle Miocene, late Pliocene, and Pleistocene. Gas chromatography （GC） and gas chromatography-mass spectrometry （GC-MS） were used to test the Co-rich crusts, and a variety of molecular fossils were detected, such as chloroform bituminous ＂A＂ , n-alkane, isoprenoid and sterol. Peak carbon and molecular indices （such as C23-/C24＋, CPI, Pr/Ph, Pr/nC17, Ph/nCxs and j13C） indicate that the parent organic matter is dominated by marine phytoplankton and thallogen whereas there is little input of terrestrial organic matter. Researches on calcareous nannofossils, molecular fossils and molecular organic geochemistry data reveal that the Paleocene/Eocene （P/E） global event is recorded in the cobalt- rich crusts from the northwestern Pacific Ocean. A succession of biomes can be observed near the 85 mm boundary （about 55 Ma）, i.e., the disappearance of the late Cretaceous Watznaueria barnesae and Zigodicus spiralis, and Broisonia parka microbiotas above the P/E boundary, and the bloom of Coccolithus formosus, Discoaster multiradiatus, Discoaster mohleri and Discoaster sp. below the boundary. Typical parameters of molecular fossils, such as saturated hydrocarbon components and carbon-number maxima, Pr/Ph, Pr/C17, Ph/C18, distribution types of sterols, Ts/Tm ratios and bacterial hopane, also exhibit dramatic changes near the P/E boundary. These integrated results illustrate that the biome succession of calcareous nannofossils, relative content of molecular fossils and molecular indices in the cobalt-rich crusts near the 85 mm boundary faithfully record the P/E global event.

Biomineralization of organic matter in cobalt-rich crusts from the Marcus–Wake Seamounts of the western Pacific Ocean

Organic matter in cobalt-rich crust （CRC） from the Marcus-Wake Seamounts of the western Pacific Ocean, Sample CM1D03, has been analyzed to understand the source, geochemistry and mineralization of organic matter, and the mineralization environment. Biomarkers, includingn-alkanes, isoprenoids, terpanes and sterols, have been detected in various layers of the CRC sample, using gas chromatography （GC） and gas chromatography-mass spectrometry （GC-MS）. The content of organic carbon （OC） and its stable isotope （δ13C）, and the combined features of the biomarkers show that the mineralized organic matter in CM1D03 CRC was mainly derived from microorganisms and lower plankton （e.g., bacteria and algae, respectively） from marine surface water, with some terrestrial higher plant components. The ratio of chloroform bitu-men ＂A＂： OC was high in the CRC, between 10.51 and 20.66, showing significant migration characteristics of n-alkanes. Four mineralization categories of organic matter were recognized based on GC chromatograms ofn-alkane molecules： （1） primitive type （bacteria and algae）, which is characterized by moderately mature ofn-alkanes preserving the original characteristics of the organic matter from microorganisms and lower plankton; （2） microbial degradation type, which is characterized by low contents ofn-alkanes and rising baseline in the chromatogram, with the ＂bulge＂ being the products of organic matter by biodegradation; （3） organic matter migration type, which is characterized by low carbon number ofn-alkanes withnC18 as the main peak carbon, without odd even predominance, and low concentrations of isoprenoids and hydro-carbons with high carbon number; and （4） organic matter hydrothermal type, which is characterized by relatively low concentration of small molecular weightn-alkanes, pristane, and phytane, accompanied by higher concentration ofn-alkanes with carbon number greater thannC18. This study shows that biomarkers can record controlling factors of mineralization and their variation.

Geochemistry of rare earth elements in cobalt-rich crusts from the Mid-Pacific M seamount

Rare earth elements（REEs） and major elements of 25 cobalt-rich crusts obtained from different depths of Mid-Pacific M seamount were analyzed using inductively coupled plasma-atomic emission spectrometer and gravimetric method.The results showed that they were hydrogenous crusts with average ∑REE content of 2084.69 μg/g and the light REE（LREE）/heavy REE（HREE） ratio of 4.84.The shale-normalized REE patterns showed positive Ce anomalies.The total content of strictly trivalent REEs increased with water depth.The Ce content and LREE/HREE ratios in Fe-Mn crusts above 2000 m were lower than those below 2000 m.The change in REE with water depth could be explained by two processes：adsorptive scavenging by setting matters and behaviors of REE in seawater.However, the Ce abundance took no obvious correlation with water depth reflects the constant Ce flux.The Ce in crusts existed mainly as Ce（IV）, implying that the oxidative-enriching process was controlled by kinetic factors.

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.

Resources calculation of cobalt-rich crusts with the grid subdivision and integral method

On the basis of three geological models and several orebody boundaries, a method of grid subdivision and integral has been proposed to calculate and evaluate the resources of cobalt-rich crusts on the seamounts in the central Pacific Ocean. The formulas of this method are deduced and the interface of program module is designed. The method is carried out in the software ＂Auto mapping system of submarine topography and geomorphology MBChart＂. This method and program will possibly become a potential tool to calculate the resources of seamounts and determine the target diggings for China＇ s next Five-year Plan.

An Effective Method to Determine the Distribution Boundary of Cobalt-Rich Fe-Mn Crusts on a Guyot: Synchronous Application of Sub-bottom Profiling and Deep-Sea Video Recording

Determining the upper boundary of the cobalt-rich crust distribution of a guyot is important for estimating the mineral resources available, however, it has also long been an unsolved question. Correlations between the sub-bottom structures, revealed by sub-bottom profiling, and crust distribution can be revealed for the first time by the synchronous application of sub-bottom profiling and deep-sea video recording. The lower boundary of the sediment corresponds with the upper boundary of the crust. By analysis of these two kinds of data, the lower boundary of the sediment can be determined; therefore, the upper boundary of the crust distribution can be deduced. According to this method of analysis, the upper boundary of water depth of crust distribution of a seamount in the western Pacific is about 1 560 m.

Distribution and Classification of Cobalt-Rich Crust

Based on the on the spot investigation and related data, cobalt rich crust is mainly distributed in the low latitude area near the equator, mostly within 20°S to 20°N, especially 5°-15°(S and N). The analysis of the microtopographic and microphysicognomy features shows that crusts are often present in the complicated topographic regions such as seamount slopes, convex parts of seamounts and joint faults, of which the ideal region is seamount slopes in water depth of 1 500-2 500 m. The authors analyze the relation of the crusts and their bedrock, bedrock type, crust thickness and occurrence, and then attempt to classify the crusts as different types.

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.

激光剥蚀-电感耦合等离子体质谱研究富钴结壳生长环带的元素分布

建立了以Ti为内标,富钴结壳标准物质GSMC-1为外标,193nmArF准分子激光剥蚀ICP-MS方法研究富钴结壳不同结壳层中元素组成及分布。所建立的定量方法用于GSMC-2和GSMC-3的测定,分析结果的相对标准偏差和相对误差均小于10%;各分析元素的检出限为3.2～191ng/g(除Si外),可以满足富钴结壳原位微区分析的要求。对取自西太平洋麦哲伦海山区富钴结壳样品MDD-42,从核心到最外结壳层以0.5mm的微间距剥蚀并采集140个样品点,不同生长环带的微区分析结果表明,成矿元素和伴生元素在不同结壳层中呈现不同的分布特性,直接反映了结壳形成时期的地质作用和古海洋沉积环境。

DTA-6000声学深拖系统在富钴结壳探测中的应用

富钴结壳作为一种潜在的海洋矿产资源逐渐引起人们的关注,研究发现海山微地形是影响富钴结壳分布的重要因素。DTA-6000声学深拖系统是我国具有自主知识产权的第一套深海拖曳观测系统,其最大工作深度6 000m,该设备上安装的高分辨率测深侧扫声纳和浅地层剖面仪能够分别获得高分辨率的海底地形地貌和浅地层剖面。它的测深覆盖范围600m,侧扫覆盖范围800m。声学深拖系统因其高效和价格优势,被列为富钴结壳资源调查的常规设备。大洋29航次中,DTA-6000声学深拖系统在采薇海山完成2条测线共约50km海山斜坡的探测,获得了高分辨率的地形地貌数据和浅地层剖面数据。介绍DTA-6000声学深拖系统及其在富钴结壳探测中的应用,并对探测结果进行了分析。

锍镍试金富集-等离子体质谱法测定西太平洋富钴结壳中的铂族元素

根据西太平洋麦哲伦海山富钴板状结壳样品的成分特征,对常规的锍镍试金配方作了改进;酌情减少捕集剂羰基镍的加入量,可显著降低铂族元素的空白值。富集后的样品,采用电感耦合等离子体质谱测定铂族元素(PGE)。其中,Ru、Rh、Pd、Ir和Pt用常规外标法测定, ^(175)Lu作内标;Os用同位素稀释法测定。用国家一级标准物质GBW 07290和GBW 07291作监控分析质量的参考样,结果满足要求。

基于声学深拖调查的海山微地形地貌研究--以马尔库斯-威克海岭一带的海山为例

利用"大洋一号"科学考察船DY115-21航次第1航段采集于西太平洋马尔库斯-威克海岭一带海山的声学深拖数据资料,借助GeoDas和PDS 2000等软件,对获取的侧扫声呐、浅剖以及多波束数据资料进行了后处理,获得了该海区高分辨率的地形地貌特征,并结合深海摄像资料,探讨了其海底特征地貌的成因。结果表明:根据水深及其所处海山的位置,可将研究区划分为斜坡和山顶2个区段,其中斜坡段前半部分的地形基本无起伏,后半部分的地形变化相对较大,并发育了2个近圆形的平底坑;山顶段的地形相对平缓,在高差变化相对较大的地方,发育了台状凸起和小尺度陡坎2种地貌类型。斜坡段发育的圆形平底坑可能是残存的古火山口;山顶段台状凸起和小尺度陡坎则可能是由侵蚀和沉降作用共同影响的结果,各平坦区段间的海底声强反射信号差别较大,表明其底质类型较复杂,结合海底摄像和浅钻资料分析可知,底质中发育有表层沉积物、富钴结壳和基岩等。

阴离子树脂-活性炭分离富集等离子体发射光谱法测定富钴锰结壳中的痕量金银铂钯

采用717阴离子树脂活性炭联合交换分离富集技术,电感耦合等离子体发射光谱法同时测定富钴锰结壳中痕量金、银、铂、钯.方法检出限四元素分别为:Au 1.3、Ag 0.4、Pd 0.6、Pt 4.8 ng/g.样品加标回收率在89.0%～110.3%,相对标准偏差3.5%～7.8%(n=4).方法已用于富钴锰结壳中痕量金银铂钯的测定.

大洋富钴结壳的基本框架--超微生物建构的锰质叠层石柱体

大洋富钴结壳和锰结核一样是潜在的海底矿产资源,对其成因的研究将有助于指导找矿和资源评价。通过大型反光显微镜、透射电子显微镜和其他测试手段,系统研究了结壳的结构构造、物质组成以及叠层石纹层与超微生物的关系。发现结壳与光滑型锰结核的叠层石类型及超微生物种极其相似,它们都以微小叠层石和中华微放线菌为主要特征,具有相同的生物成因机制。认为超微生物建构的锰质叠层石柱体是大洋富钴结壳的基本框架,从而对结壳矿体的形成提出了新的见解。

MC-ICP MS测定富钴结壳中的铜锌同位素的化学分离方法研究

建立了富钴结壳中Cu和Zn同位素的化学分离方法。采用新型阴离子交换树脂AG MP-1M,分别以8.2 mol/L HCl+0.01%HF+0.001%H_2O_2,2 mol/L HCl+0.001%H_2O_2和0.5 mol/L HNO_3作为淋洗液,能有效分离富钴结壳中的Cu,Co,Fe和Zn,且Cu和Zn的回收率均接近100%。同位素标准溶液在离子交换分离前后同位素组成一致,表明分离前后Cu和Zn没有分馏。全流程空白小于5 ng。此方法可作为多接收器电感耦合等离子体质谱仪高精度测定富钴结壳Cu和Zn同位素的方法。

X-射线荧光光谱法定量分析海山富钴结壳中MnO_2与MnO的含量之比值

通过普通X-射线荧光光谱仪,结合PeakFit谱峰处理软件,对不同比例的MnO和MnO2的混合样品的Kβ谱峰参数进行了研究,用数学方法将实测的谱峰分解为各个单一的谱峰参数(峰位、峰高、半高宽、子峰面积),找出了各个谱峰参数与不同价态锰的含量之间的关系,并据此确定了中太平洋海山区大量富钴结壳样品中不同价态锰的相对含量.分析结果显示,富钴结壳中+4价锰从核心向外有增高的趋势,可以认为这与该区第三纪以来南极底流活动的增强有关.

九州-帕劳海脊南段共生多金属结核与富钴结壳地球化学特征及其资源意义

深海多金属结核与富钴结壳富含Mn、Co、Ni、Cu及稀土等元素,极具资源潜力,因而广受关注。选择采集自九州-帕劳海脊南段水深约3000 m的6个多金属结核和2个富钴结壳样品进行地球化学特征研究。结果显示本区样品Mn/Fe比值为0.88~1.07,Co及稀土元素含量高,与库克群岛多金属结核元素特征相似,表现出典型的水成成因特征。与其他地区水成结核、结壳相比,样品具有较高的Ca含量,可能和其所在位置海脊部位水深较浅、位于碳酸盐补偿深度(CCD)以上有关。样品表现出Y负异常、Nd含量高等水成结核的特点,但微弱的Ce正异常特征与其他地区水成多金属结核/壳的强烈Ce正异常特征不同,这表明其生长于弱氧化环境。本区结核分布在CCD以上,最小溶氧层(OMZ)以下,是一种水成成因、贫氧生长的新型多金属结核,其物质来源、成矿模式将为揭示多金属结核的形成分布规律提供一条全新的认识途径。同时研究区结核、结壳Co及稀土元素含量较高,且分布位置较浅,易于开采,具有一定的资源潜力。

Nanometer properties of oceanic polymetallic nodules and cobalt-rich crusts

An ammonia leaching process was utilized to extract Co, Ni and Cu from oceanic polymetallic nodules, whereas an acid leaching process was utilized to extract Co, Ni, Cu, Zn and Mn from cobalt-rich crusts. Both processes produced nanometer materials-ammonia leaching residue and acid leaching residue. A systematic study was conducted on the phase, composition and physicochemistry properties of these residues. The result shows that both residues contain a large amount of nanometer minerals. Ammonia leaching residue mainly consists of rhodochrosite, with the average grain diameter of 17.9 nm; whereas the acid leaching residue mainly consists of well-developed bassanite, with the average grain deameter of 9.5 nm. The bassanite also has a microporous structure, the volume of the pore space is 1.23×10-2 mL/g. Both the ammonia and acid leaching residues have a large specific surface area, and they display a strong adsorption capacity to saturate sodium chloride vapour, N2 and SO2. Both residues have high

深海沉积矿产成矿机制研究:进展与展望

深海沉积矿产主要包括富钴结壳、多金属结核、富稀土沉积物等,其中前二者富含钴、镍、铜、稀土等关键金属元素,后者富含中重稀土元素,是可供未来开发的战略性矿产。结壳、结核、深海稀土分别赋存于海山、海盆表面和海底沉积物中,三者的成矿过程存在关联,海水在成矿过程中发挥了重要作用。钴、镍、铜、稀土等关键金属元素基本未形成独立矿物。以往工作多集中对三种矿产展开单独研究,限制了深海成矿过程的整体认识。本文通过梳理国内外学者对结壳、结核和深海稀土三种深海沉积矿产的空间分布、元素赋存状态、富集机制及控矿条件等方面的进展和存在问题,提出以地球系统科学思想为指导,聚焦成矿元素,开展多圈层相互作用下成矿元素的源-运-聚过程和山-盆体系下“结壳-结核-深海稀土”三者时空耦合机制研究,为深海成矿预测提供理论指导。