Mineralogical and geochemical constraints on the origin of ferromanganese crusts from the Rivera Plate (western margin of Mexico)

Marine hydrogenetically precipitated ferromanganese crusts are widespread in the Pacific Ocean. They occur as pavements coating volcanic or sedimentary hard-rock substrates, mainly on the slopes of seamounts, plateaus and hills in ocean basins and continental margins. We studied three ferromanganese crusts from one dredge haul from the Rivera Plate (western margin of Mexico), which are up to 15 mm thick and grow directly on a substrate of pillow basalt fragments. They consist of laminated, botryoidal, porous aggregates mostly of Fe and Mn oxyhydroxides and up to 10% silicates. XRD analysis showed the predominance of poorly crystallized mineral phases in the crusts that include Mn-feroxyhyte and vernadite, and an authigenic smectite-like clay. Detrital minerals probably derive from granodiorites of the eastern wall of the neighboring Middle America Trench. Scattered barite grains occur on the crust surface and suggest plume fall-out derived from hydrothermal vents, although a possible pelagic source cannot be dismissed. Ratios between major (Fe, Mn, Si) and trace (Co, Ni, Cu) elements reveal that such crusts are predominantly hydrogenetic in origin, although they show a hydrothermal influence that increases in the outer layers. Iron contents range from 16.2 to 25.2 wt.%, and manganese from 3.4 to 14.5 wt.%. The Fe/Mn ratio ranges from 1.6 to 7.0. The SiO₂/Al₂O₃ ratio ranges from 4.3 to 6.6, indicating the presence of biogenic silica (radiolarians). The concentrations of copper (up to 383 ppm) and cobalt (up to 534 ppm) are significantly below those of the typical hydrogenetic crusts, whereas Ni (up to 1320 ppm) is about the same or slightly lower. REE normalized profiles and ΣREE values (486 to 732 ppm) match those reported for hydrogenetic crusts, but suggest a hydrothermal contribution for the later crust layers. The inferred crust growth rates using the Co-chronometer (44 and 229 mm/Myr) are higher than those reported for pure hydrogenetic crusts (mostly 1 to 6 mm/Myr), thus indicating an increasing hydrothermal influence. The highest growth rate (229 mm/Myr, corresponding to the outer crust layers) suggests a regional hydrothermal input of iron and manganese to seawater. The intensification of regional submarine hydrothermal activity began about 13,000 yr ago, and may be related to the tectonic activity in the complex junction of the Rivera, Cocos, Pacific and North America plates.     

Comparative mineralogy and geochemistry of hydrothermal iron‐rich crusts from the Pitcairn,Teahitia‐mehetia,and Macdonald hot spot areas of the S. W. pacific

Abstract

Hydrothermal iron‐rich crusts have been recovered from a number of hot spot volcanos including Crough Seamount, Pitcairn Volcanos 2 and 1, Cyana Seamount, Teahitia, Moua Pihaa, and Macdonald Seamount in the S. W. Pacific. Mineralogically, the crusts consists of ferrihydrite with traces of the weathering products of volcanic ash (feldspar, nontronite, pyroxene, and serpentinite). The iron oxyhydroxide phase has a mean particle size of 3–4 nm indicating rapid deposition. Electron microprobe studies have revealed the presence of filamentous iron‐silica deposits within the crusts reflecting the possible bacterial oxidation of iron from the hydrothermal fluids. The crusts display wide variability in composition both between individual sampling stations and between seamounts. Endmember analysis shows that the compositional data can be resolved into three endmembers: a Fe‐rich endmember, a light and heavy rare earth element endmember, and a Ba (barite)‐rich endmember. The Fe‐rich endmember appears to contain very low concentrations of most trace elements. For bulk samples, the composition of the iron‐rich crusts reflects dilution of the iron oxyhydroxide phase by volcanic ash and, to a lesser extent, a hydrogenous component. This is illustrated by the wide variability in SiO₂ (11.1–71.3%) and Mn (0.01–1.21%) contents of the crusts. For iron‐rich crusts containing greater than 40% Fe, the Pitcairn crusts display lower contents of Pb, Ba, Mo, U, Th, As, and rare earth elements (REE) and lower cerium anomalies than those from Teahitia. REE profiles of crusts from each of the hot spot volcanoes are characterized by small negative cerium anomalies but pronounced positive europium anomalies. The low average La/Fe ratios of the crusts from the various seamounts (47–572 X 10^‐6) and positive Eu anomalies of the crusts suggest rapid deposition of the iron oxyhydroxide near the hydrothermal vent. The high Fe/Mn ratio of vent fluids at hot spot volcanoes (8.5–5.6) may account for the formation of these iron‐rich crusts. The present data indicate that there may be differences in the nature of the iron‐rich crusts based on the depth of occurrence. This influences the temperature of the venting hydrothermal fluids and the possibility of occurrence of submarine phreatomagmatic eruptions.     

Ferromanganese crusts from the Sea of Okhotsk

New data on the microstructures and the mineral and chemical compositions of ferromanganese crusts obtained from the western slope of the Kuril Island Arc in the Sea of Okhotsk during cruises of the R/V Vulkanolog are discussed. The study of the crusts using analytical electron microscopy methods revealed that their manganese phase is represented by vernadite, Fe-vernadite, todorokite, asbolane, and asbolane-buserite, while the iron phase consists of hematite, hydrohematite, ferroxyhite, and magnetite. The assemblage of lithic minerals includes apatite, quartz, epidote, and montmorillonite. According to the chemical analysis, most of the crusts contain a significant share of volcanogenic and hydrothermal material, which is evident from the elevated values of the Mn and Ti modules, the low concentrations of some trace elements, and the positive Eu anomaly in the rare earth elements composition.     

Hydrothermal manganese oxide deposits from Baby Bare seamount in the Northeast Pacific Ocean

Manganese oxide crusts were recovered from Baby Bare seamount in order to investigate the history of off-axis hydrothermal venting. Baby Bare is a small basement high protruding from a regional sediment cover on the eastern flank of the Juan de Fuca Ridge that acts as a focus for discharging crustal fluids. Stratabound Mn-oxide crusts were collected where warm venting has been observed near the seamount summit. Mn-oxide crusts are composed primarily of 10 Å manganate ± pyrolusite, with minor nontronite, saponite, and/or barite. These assemblage and chemical characteristics such as high Mn/Fe ratios and low trace metal and REE concentrations are indicative of a hydrothermal origin. Minimum ages for these deposits, calculated using growth rates (324 to ∼ 1800 mm/Ma) and estimated thicknesses of manganese outcrops, show that Baby Bare has been hydrothermally active for at least 0.5 Myr, and possibly since its formation (1.7–2.7 Ma). Hydrothermal manganese oxide crusts such as these from Baby Bare record interactions between the hydrothermal fluids and seawater and are important tools for estimating the longevity of off-axis hydrothermal activity.     

Cerium anomaly variations in ferromanganese nodules and crusts from the Indian Ocean

Fifty analyses of rare earth elements as well as mineralogical studies have been carried out on a suite of manganese nodules and crusts from the Central Indian Basin and the Western Indian Ocean. The aim was to identify the processes controlling the REE patterns of the phases hosting the REE in the manganese nodules, with an emphasis on an understanding of the Ce anomaly. This has involved separating the encrusting layers and nuclei physically as well as Fe-Mn oxides from the aluminosilicate phase chemically (using a 2 M HCl leach) prior to analysis.

The presence of nodule nuclei seems to have little influence (mostly <5% to a maximum of 30%) on the overall magnitude of the Ce anomalies in these nodules. The ratios of concentrations of elements in the acid leachates and the corresponding bulk values yield flat REE patterns indicating that the aluminosilicate phase contributes very little to the Ce anomalies. Interelement relations indicate that the Ce anomalies are largely controlled by the amorphous mineral phase FeOOH.xH₂O. The relationship of Fe, Ce anomaly and δ-MnO₂ further suggests that Ce is chemisorbed onto iron oxyhydroxides which are epitaxially intergrown with δ-MnO₂.

The regional distribution of the Ce anomaly values appears to depend on many of the factors responsible for the uptake of other minor metals in nodules and crusts.     

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.     

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.     

Deposition of hydrogenetic and hydrothermal manganese minerals in the Ogasawara (Bonin) Arc Area,Northwest Pacific

A widespread distribution of hydrothermal and hydrogenetic manganese deposits is described in the results of the Hakurei‐Maru cruises conducted in the Bonin Arc areas of the West Pacific from 1984 to 1989. Manganese deposits occur in the active volcano chains, back‐arc basins, remnant back‐arc ridges, and oceanic seamounts.

The hydrogenetic iron‐manganese deposits commonly form earthly black crusts and nodules on the topographic highs of inactive ridges and old seamounts, sometimes as thick as 10 cm. They are always composed of the iron‐manganese mineral vernadite. Co and Ni contents are relatively high in the crusts from the seamounts in the open Pacific Ocean (up to 1.1% Co and 1.0% Ni). Two generations of distinct chemistry and texture are typical of these crusts, which can be compared to reported thick crusts from the Central Pacific seamounts.

The hydrothermal deposits, characterized by dense, submetallic, and gray appearance, are dominant in the recent and also in past submarine volcanoes of the island‐arc systems. Evidence of past hydrothermal activity was ascertained as fossil hydrothermal manganese deposits inside the hydrogenetic nodules or beneath the hydrogenetic crusts over the Tertiary island arc. Their component minerals are considered to be todorokite and bimessite (stable and contractible upon dehydration), having almost negligible amounts of Fe, Si, Al, Ni, Co, Zn, Pb, Cu, etc. In the small model site, the Kaikata Seamount hydrothermal area, the presumably recent hydrothermal activity has yielded thin slabs of pure manganate deposits growing downward within volcanic and sand layers.

Early diagenetic influence is negligible on nodules of this area.     

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.     

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。     

南海尖峰海山多金属结壳地球化学

南海尖峰海山多金属结壳富含30多种元素,其锰铁矿物主要由钡镁锰矿,δ-MnO_2和FeOOH·xH_2O组成。与其它海区的结壳相比,尖峰海山结壳富含Cu、Ni、Ba、Zn、Pb等元素,而Co、Ti、稀土元素(REE)、Sr等元素相对较贫。研究表明,HREE亏损,具明显的Ce正异常,较明显的Tb正异常和Yb负异常。这是氧化弱碱性海洋环境所致。结壳是水成作用的产物,它的形成受南海独特的古海洋环境所控制,海底火山热液作用,可能也是影响因素之一。     

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.     

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。     

Mössbauer studies and oxidized manganese ratio in ferromanganese nodules and crusts from the Central Indian Ocean

Ferromanganese nodules from siliceous and pelagic clays and crusts from a seamount in Central Indian Ocean were analyzed for chemical composition, mineralogy, iron oxidation as determined by Mössbauer spectroscopy, and oxidized manganese (O/Mn ratio) by iodometric method. Despite considerable variation in chemical composition (Mn/Fe ratio 1.42 to 7.4) and mineralogy, iron is present solely as Fe (III) in the paramagnetic or superparamagnetic phase. The oxidized manganese ratio showed that 73 to 81% of the manganese is Mn (IV). Mn (II) is detected qualitatively by electron spin resonance spectra in the nodules and crusts from the Central Indian Ocean.     

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。     

富钴结壳中矿物组成对稀土元素分布的制约

为探讨富钴结壳中矿物组成对稀土元素分布的制约,对约翰斯顿岛富钴结壳中矿物组成及稀土元素特征进行了研究。依据主要矿物组成,富钴结壳可以分为3种类型,分别命名为A、B、C。由A到C,水羟锰矿含量逐渐降低,B类中磷灰石含量最高,C类中水钠锰矿和钙锰矿含量最高。A类结壳中富集REE3+、Ce,B类结壳中富集Ce和Y。A类富钴结壳中,REE3+、Y以专属吸附的方式富集在铁氧化物上,Ce3+氧化成Ce4+与其他REE分离,吸附在锰矿物上。B类结壳中,稀土元素主要以独立矿物的形式存在,另有部分Ce、LREE3+吸附于铁相中,部分Y存在于磷灰石中。C类结壳中,稀土元素主要赋存在锰矿物中,部分Y存在于磷灰石中。     

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.     

富Co铁锰结壳铂族元素与铼-锇同位素组成及其意义

用ICP－MS测定了太平洋富Co铁锰结壳铂族元素和铼－锇同位素组成。富Co铁锰结壳不仅异常富集铂族元素，而且铂族元素及其它亲铁元素的配发与陨石特征非常相似。铁锰结壳的铼－锇同位素组成明显有别于大陆地壳岩石，和K－T界线沉积物相似，接近陨石值。世界大洋范围内的富Co铁锰结壳均产于远离海底构造热液活动区，几乎不可能受到地幔源热液作用的直接影响。因此，富Co铁锰结壳中的铂族元素可能部分来源于地外物质。     

Composition and Useful Properties of Tailings of Marine Manganese Nodules and Crusts

ABSTRACT

Marine manganese nodules and crusts, when processed, yield tailings which may be utilized for environmental and economic benefit. The key to the reasonable and effective utilization of these tailings lies in making a systematic appraisal of their composition and properties. This article gives an introduction to the investigation of manganese tailings properties. The tailings have a high iron and/or manganese content, high surface area, high porosity, and fine grain size. Some tailings have a high rare earth element content which is valuable. They may also have high SO₃, arsenic, and uranium contents which are harmful. Depending on the process used to produce the tailings, there will likely be some differences in chemical composition, mineral assemblages, surface area and adsorption capability, pore diameter and volume, density and pH. In assigning potentially beneficial applications for these tailings, these differences should be taken into account to optimize utilization.     

太平洋海山富钴结壳中铂族元素赋存状态与富集机理

通过选择性化学提取法,对太平洋采薇海山富钴结壳样品中铂族元素进行分级提取实验,利用电感耦合等离子体质谱仪(ICP-MS)测定了铂族元素含量。赋存状态结果显示,富钴结壳中铂族元素在各个化学相态中富集比例从大到小依次为:铁氧化物相、残渣态、锰氧化物相、碳酸盐相、吸附态,未磷酸盐化新壳层和磷酸盐化老壳层中铂族元素都主要赋存于铁氧化物相中,其富集比例为59.26%～82.19%,残渣态中磷酸盐对铂族元素具有一定的富集能力,其富集比例为17.23%～35.37%。不同类型地质体中铂族元素的赋存状态结果,也证实了富钴结壳和海山结核中铂族元素富集主要受到铁氧化物相和残渣态的影响。太平洋海山富钴结壳中铂族元素的富集机理推测为铁氧/氢氧化物胶体粒子的吸附作用,使海水中PtC l24-离子被吸附到铁氧化物相中,从而使富钴结壳中铂族元素富集。