过渡金属元素Cu、Co、Ni在铁锰结核(壳)中富集的控制因素

在不同生成环境下生成的铁锰结核(壳)吸收不同的过渡金属元素。在成岩作用形成的铁锰结核中,Cu、Ni主要以锰相形式存在,而Co则以铁相的形式存在;在水成作用形成的铁锰结核(壳)中Cu、Co、Ni均以锰相的形式存在。这些过渡金属元素在成岩作用形成的结核中的存在与铁锰结核(壳)中锰矿物和铁的氧化物、氢氧化物的晶体化学特征密切相关,而在水成作用形成的铁锰结核(壳)中的富集与锰矿物和铁的氧化物、氢氧化物的晶体化。学特征关系不大。同时铁锰结核(壳)中锰矿物和铁的氧化物、氢氧化物又严格地受结核(壳)的生成环境的制约,因此,过渡金属元素Cu、Co、Ni在铁锰结核(壳)中的富集在一定程度上受结核(壳)生成环境的控制。     

Deep-Sea Nodules and Co-rich Mn Crusts

The mining of deep-sea manganese nodules has been a topic of interest since J.L. Mero undertook his preliminary studies in the 1960s to evaluate the prospects for mining deep-sea nodules. Despite the great deal of investment in deep-sea mining over more than 40 years, there has still been no successful attempt to mine the deep-sea nodules on a commercial scale. One of the major problems is that the nodules cannot be brought to the surface with the necessary amounts of recoverable nickel, cobalt and zinc to warrant the initial high investment necessary for this operation. It therefore appears that in the short term, deep-sea manganese and Co-rich Mn crusts will not be mined on a commercial scale in the foreseeable future. Nonetheless, investigations of deep-sea mineral deposits by a number of nations will continue and enable us to understand the deep-sea environment in increasing detail, which is necessary in view of the great extent of the deep oceans which cover an area of about 66% of the Earth's surface.     

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.     

Deep Seabed Mining: Past Failures and Future Prospects

The first attempt to exploit deep-sea manganese nodules ended in failure as a result of the collapse of world metal prices, the onerous provisions imposed by the U.N. Convention on the Law of the Sea (UNCLOS), and the overoptimistic assumptions about the viability of nodule mining. Attention then focused on Co-rich manganese crusts from seamounts. Since the mid-1980s, a number of new players have committed themselves to long-term programs to establish the viability of mining deep-sea manganese nodules. These programs require heavy subsidy by the host governments. Au-rich submarine hydrothermal deposits located at convergent plate margins are now emerging as a more promising prospect for mining than deep-sea manganese deposits.     

Deep Seabed Mining: Past Failures and Future Prospects

The first attempt to exploit deep-sea manganese nodules ended in failure as a result of the collapse of world metal prices, the onerous provisions imposed by the U.N. Convention on the Law of the Sea (UNCLOS), and the overoptimistic assumptions about the viability of nodule mining. Attention then focused on Co-rich manganese crusts from seamounts. Since the mid-1980s, a number of new players have committed themselves to long-term programs to establish the viability of mining deep-sea manganese nodules. These programs require heavy subsidy by the host governments. Au-rich submarine hydrothermal deposits located at convergent plate margins are now emerging as a more promising prospect for mining than deep-sea manganese deposits.     

Behavior of rare earth elements in coexisting manganese macronodules,micronodules, and sediments from the central Indian basin

Distribution characteristics of cobalt‐rich manganese deposits were evaluated from stereo photographs and video data on a seamount in the central Pacific Ocean by image analysis, photogrammetric technique, and visual observations. The results show that many locations have high crust coverages with highly undulating micro‐topography. High nodule coverages occur on relatively flat seafloor, and the nodule size distribution varies from uniform to inhomogeneous among different locations. Distribution of these deposits along detailed topographic sections show that the seafloor can be divided into nodule dominant zones between 0° and 3° slopes, with sediment patches up to 4° slopes; and crust dominant zones, which occur on slopes higher than 15°. The transition zone, between 4° and 15° slopes, has many locations, where nodules and crusts co‐occur in varying percentages. The observation of crust outcrops among sediments and nodules, as well as in the gravity core samples, indicates the presence of shallow buried crusts as well, which can substantially enhance resource evaluation of the deposits.     

全球三大洋海山钴结壳资源量估算

钴结壳具有Co、Ni、Cu和Mn及其他金属的潜在矿产资源和储存在结壳层中古环境信息的双重意义。与深海多金属结核和热液硫化物矿床相比,具有较高Co、Ni和Pt含量的海山钴结壳有可能成为商业勘探的潜在目标。为合理地估算出全球三大洋海山钴结壳资源量,基于我国西太平洋海山钴结壳拖网采样调查资料和对太平洋海山钴结壳资源分布规律和钴结壳矿区圈定参数指标的深入研究,按海山不同高度、不同洋壳年龄赋予不同结壳厚度,进而计算出全球三大洋海山钴结壳分布面积为3 039 452.14km2和干结壳资源量为(1 081.166 1~2 162.332 2)×108 t。太平洋海山钴结壳分布面积为2 123 087.12km2和干结壳资源量为(513.244~1 026.488)×108 t,大西洋海山钴结壳分布面积为512 509.74km2和干结壳资源量为(116.503 2~233.006 4)×108 t,印度洋海山钴结壳分布面积为403 855.28km2和干结壳资源量为(81.484 9~162.969 8)×108 t。三大洋海山钴结壳的Mn、Co、Ni和Cu金属量分别为(138.848 0~277.696 0)×108 t,(3.967 6~7.935 2)×108 t、(2.793 6~5.587 2)×108 t和(0.825 1~1.650 2)×108 t。根据钴结壳的Co含量、Co通量和厚度相关分析,所赋予的钴结壳厚度占理论推测厚度的6.10%~12.20%,这与Ku等得出"钴结壳生长时间约占其整个生命史4%"的认识非常相近。三大洋海山钴结壳实测厚度与赋值厚度对比分析表明,太平洋海山钴结壳赋值厚度平均值为1.87cm,实测厚度平均值为1.77cm,相对误差为5.35%,大西洋和印度洋相对误差分别为18.18%和23.23%。研究数据表明按海山高度和洋壳年龄所赋的钴结壳厚度基本合理,估算出的钴结壳资源量基本可靠。本文首次估算出三大洋海山钴结壳资源量,为整个海盆和三大洋海山钴结壳资源量估算提供了新方法。     

Variations in the elemental composition of ferromanganese structures from Lake Baikal

The elemental composition of ferromanganese sedimentary structures from the bottom of Lake Baikal represented by nodules and crusts, as well as the enclosing sediments, have been studied by the atomic absorption, chemical, and ICP-MS methods. It is established that the contents of the rock-forming and accompanying elements in them are highly variable. In this connection, the examined samples are divided in two groups differing by their Mn/Fe values. In most of the samples, they range from 0.01 to 0.1, although some of the ferromanganese structures or their parts are substantially enriched in manganese. The contents of most of the rare and dispersed elements in the ferromanganese structures are usually at the background level, although the samples maximally enriched in iron or manganese are characterized by relatively high copper, nickel, cobalt, vanadium, zinc, and molybdenum concentrations.     

Production policy for the deep sea mineral resources

The fundamental principles governing the exploitation of deep sea mineral resources stipulate that these resources shall be developed as a common heritage for the benefit of mankind as a whole.1 The mineral resources that concern us at present are the metalliferous nodules containing nickel, copper, cobalt and manganese which are found over parts of the ocean floor. Included in the task set for the UNCLOS III was the responsibility to devise a legal and administrative framework which would give practical effect to these principles of exploitation and to enable the mining of the manganese nodules to become a reality.     

Morphological Features of Co-Rich Manganese Deposits and Their Relation to Seabed Slopes

The morphological features associated with Co-rich manganese deposits, the size variations of nodules, and the occurrence of different substrates have been analyzed, to evaluate the influence of various seabed slope angles on the distribution of these features. The coverage and size of the crusts depend on their surface morphology and seabed topography, resulting in cobble-type, lineated, or step-like outcrops. Small nodules (1 - 4 cm in diameter) dominate all seabed slopes, with a few locations having nodules ranging from 1 to 8 or 1 to 10 cm. Sediments invariably occur as substrates for nodules and as cover for crusts, their coverage being inversely proportional to that of the nodules and crust outcrops. Steeper seafloor areas have large crust outcrops exposed with no or few nodules and sediments associated with them. The intermediate slopes have a combination of nodules, sediments, and crusts in various proportions, depending on topography and gradient. Large-scale nodule occurrences, followed by sediment fields and crust outcrops on seabed slopes of greater than 3 degrees, 3 - 7 degreees, and less than 15 degrees, respectively, represent typical morphological distribution zones of the Co-rich manganese deposits on a seamount in the central Pacific Ocean. A transition zone between nodule-dominated fields and large crust outcrops occurs for slopes from 7 degrees to 15 degrees. This detailed study on distribution of Co-rich deposits gives a better understanding for purposes of their exploitation.     

Ferromanganese Crusts near Johnston Island: Geochemistry,Stratigraphy and Economic Potential

The 200-mi exclusive economic zone (EEZ) around Johnston Island, 700 mi west of Hawaii, contains economically attractive concentrations of cobalt, nickel, platinum, and rare earth elements contained in manganese crusts on the surface of seafloor plateau areas. Detailed mineralogy and geochemistry reveal these deposits to be largely hydrogenous in origin although also containing elemental additions due to biological, weathering, hydrothermal, detrital, and diagenetic processes. The major mineralogical phase is vernadite (delta manganese dioxide) laid down in strataform crustal deposits. The most valuable metal, cobalt, shows concentrations highest in the upper layers of the crusts and decreasing with stratigraphic depth. Upcoming submersible dives will fully document the significance of this deposit.     

电磁方法在海底多金属硫化物探测中的应用

海底硫化物矿体的三维展布是当前大洋调查急需解决的关键问题,在陆地上电磁方法一直是解决矿产资源三维问题的重要手段之一。2011年我国自主研发了调查海底多金属硫化物的瞬变电磁设备,并于2011年6月在中国大洋第22航次第5航段中的大西洋中脊“贝利珠”热液区( 13.2°S、14.4°W)进行了试验,取得了我国首批海底热液区的瞬变电磁资料。本文对这批资料进行初步分析,阐述一种新的海底硫化物探测方法及其试用结果,得到的视电阻率断面与热液区的实际有很好的对应关系,从2条测线的实测结果来看,设备的探测深度达到海底面以下50~100 m。在本次试用过程中,较好验证了自主研发的深海瞬变电磁设备、获得的数据以及探测深度的可靠性。     

Morphological Features of Co-Rich Manganese Deposits and Their Relation to Seabed Slopes

Abstract

The morphological features associated with Co-rich manganese deposits, the size variations of nodules, and the occurrence of different substrates have been analyzed, to evaluate the influence of various seabed slope angles on the distribution of these features. The coverage and size of the crusts depend on their surface morphology and seabed topography, resulting in cobble-type, lineated, or step-like outcrops. Small nodules (1–4 cm in diameter) dominate all seabed slopes, with a few locations having nodules ranging from 1 to 8 or 1 to 10 cm. Sediments invariably occur as substrates for nodules and as cover for crusts, their coverage being inversely proportional to that of the nodules and crust outcrops.

Steeper seafloor areas have large crust outcrops exposed with no or few nodules and sediments associated with them. The intermediate slopes have a combination of nodules, sediments, and crusts in various proportions, depending on topography and gradient. Large-scale nodule occurrences, followed by sediment fields and crust outcrops on seabed slopes of < 3°, 3–7°, and > 15°, respectively, represent typical morphological distribution zones of the Co-rich manganese deposits on a seamount in the central Pacific Ocean. A transition zone between nodule-dominated fields and large crust outcrops occurs for slopes from 7° to 15°. This detailed study on distribution of Co-rich deposits gives a better understanding for purposes of their exploitation.     

浅论富钴结壳柱状构造的成因机制

柱状构造为富钴结壳中多种微观构造类型之一。为探讨富钴结壳柱状构造的形成机制,利用高分辨率电子探针技术分析了位于中太平洋某海山的富钴结壳中柱状构造的微观形态和微区元素化学特征,结果表明,柱状构造是由围绕核心的微层呈弓形外延辐射生长逐渐分枝而成。壳层由亮色、暗色微层交替叠置而成,其中亮色微层富锰、钴、镍和氧,而暗色微层富铁和硅;同一微层各部分的生长速率不同,介于0.27~0.92 mm/Ma。柱状构造壳层亮色、暗色微层交替变化以及相应成分的不同是微观氧化还原环境变化的结果,而柱状构造的分枝和同一微层生长速率的差异则与富钴结壳生长界面有界面双电层有关。     

The incorporation of minor transition metals into marine manganese nodules

The mechanisms of incorporation of minor transition metals into marine manganese nodules are discussed on the basis of differential chemical leaching.A small portion of iron and manganese in deep-sea nodules was dissolved in dilute acetic acid. Hydrogenous cobalt and nickel in nodules were also slightly leached with the acid solution, while 50–60 % of hydrogenous copper and zinc were leached. This difference suggests that the greater parts of hydrogenous cobalt and nickel are present in the lattices of manganese oxide phases, while the major parts of hydrogenous copper and zinc are present in the sorption sites of manganese oxide phases.The enrichment of minor transition metals in manganese nodules may be controlled by their substitution for manganese atoms in manganese oxide lattices after their sorption on manganese oxide phases.     

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。     

中国多金属结核西示范区的结核小尺度分布特征

利用在中国多金属结核西示范区加密调查中获取的海底视像资料,通过水下定位数据处理和结核覆盖率计算,并结合多波束地形测量数据,从结核覆盖率分布角度对多金属结核的小尺度分布特征进行研究。研究结果表明:多金属结核分布与地形有一定的对应关系,在地形平缓区域,结核覆盖率变化较平缓,而在某些地形陡峭区域,由于块状结壳的形成,结核/结壳覆盖率出现明显的跃升;西示范区为结核高覆盖率分布区,结核覆盖率沿东西方向变化不大,由北向南呈增高趋势;地形坡度对结核分布有明显的影响,在区内0°~3.6°的坡度范围内,坡度越大,结核覆盖率越高。     

Precautionary management of deep-sea mining

Interest in deep-sea mining developed in the early 1970s, with a focus on manganese nodules in international waters. Mining may actually occur first, however, on rich polymetallic sulfide deposits associated with hydrothermal vents within exclusive economic zones. Even though mining for polymetallic sulfides may not take place for several years, precautionary performance standards, environmental regulations, and the establishment of Marine Protected Areas may help guide the marine mining industry toward a goal of minimizing environmental impacts. Once substantial investments in prospecting and exploring a potential mining site are made, implementation of environmental regulations may prove to be much more difficult.     

News from the seabed – Geological characteristics and resource potential of deep-sea mineral resources

Marine minerals such as manganese nodules, Co-rich ferromanganese crusts, and seafloor massive sulfides are commonly seen as possible future resources that could potentially add to the global raw materials supply. At present, a proper assessment of these resources is not possible due to a severe lack of information regarding their size, distribution, and composition. It is clear, however, that manganese nodules and Co-rich ferromanganese crusts are a vast resource and mining them could have a profound impact on global metal markets, whereas the global resource potential of seafloor massive sulfides appears to be small. These deep-sea mineral commodities are formed by very different geological processes resulting in deposits with distinctly different characteristics. The geological boundary conditions also determine the size of any future mining operations and the area that will be affected by mining. Similarly, the sizes of the most favorable areas that need to be explored for a global resource assessment are also dependent on the geological environment. Size reaches 38 million km² for manganese nodules, while those for Co-rich crusts (1.7 million km²) and massive sulfides (3.2 million km²) are much smaller. Moreover, different commodities are more abundant in some jurisdictions than in others. While only 19% of the favorable area for manganese nodules lies within the Exclusive Economic Zone of coastal states or is covered by proposals for the extension of the continental shelf, 42% of the favorable areas for massive sulfides and 54% for Co-rich crusts are located in EEZs.     

Minor and rare elements in manganese crusts and nodules and sediments from the Manihiki plateau and adjacent areas: Results of HMNZS Tui cruises

Six manganese crusts, 13 manganese nodules, and 16 sediments were analyzed by instrumental neutron activation analysis. Data were generated on selected major and minor elements but geochemical evaluations are based only on Fe, Sc, U, Th, and the rare earth elements (REE). Manganese crusts and manganese nodules have comparable trivalent REE contents and show a shale‐like distribution pattern. Both crusts and nodules are characterized by a positive Ce anomaly but the anomaly is higher in nodules. REE contents in manganese nodules show a linear dependence on the Fe content, and it is concluded that these elements are incorporated in the Fe‐rich (δ‐MnO₂) phase. In the crusts, the REE correlate with Sc and are therefore assumed to be associated with the clay minerals. Uranium contents are significantly higher in the crusts than in nodules whereas Th is slightly higher in the nodules. There is a clear positive correlation between U and Th in nodules but there are too few data to make a similar conclusion for crusts. Compositional data suggest a division of the sediments into two groups. The carbonate sediments have much lower REE contents and a more pronounced negative Ce anomaly than the clays, while both show a lithogenous component as indicated by a slight negative Eu anomaly.