Nature of co-bearing ferromanganese crusts of the Magellan Seamounts (Pacific Ocean): Communication 1. Geology, mineralogy, and geochemistry

Communication 1 of the present paper is devoted to various aspects of the hydrogenic ferromanganese crusts in the western and eastern clusters of the Magellan Seamounts in the Pacific. It was revealed that crusts are developed on guyots as a continuous sheet of Fe-Mn minerals on exposures of primary rocks. They commonly make up ring-shaped deposits along the periphery of the summit surface and in the upper sectors of slopes. Thickness of the crust varies from n to ～18 cm and shows irregular variations in separate layers. Irrespective of the geographic position, crusts are composed of four layers—two lower phosphatized (I-1 and I-2) and two upper nonphosphatized (II and III) layers. The crusts differ in terms of structure and texture, but they are sufficiently similar within separate layers (I-1, I-2, and others). The major ore minerals in crusts are commonly represented by poorly crystallized and low-ordered minerals (Fe-vernadite and Mn-feroxyhyte); the subordinate mineral, by the well-crystallized and ordered vernadite. It has been established that heavy and rare metal cations are concentrated extremely irregularly in ore minerals of the crusts, suggesting a pulsating mode of their input during different geological epochs.     

The Oligocene gap in the formation of Co-rich ferromanganese crusts and sedimentation in the Pacific Ocean and the effects of bottom currents

The Marcus Wake and Magellan guyots formed about 129–74 Ma ago at 10°–30° S and drifted 1700–4400 km to their present-day latitudinal position across the equatorial zone of maximum deposition. Cooling of the Pacific plate brought these guyots to the northern arid zone during the Turonian–Maastrichtian, to depths at which sediment accumulation rates were low and the conditions promoted precipitation of Co-rich Fe–Mn crusts from the Campanian to the present. Nonprecipitation of Co-rich Fe–Mn crusts during the Oligocene was caused by the action of bottom currents. The presence of a hiatus identified in cores from drill holes was used as the basis for reconstruction of the directions of bottom currents in the Oligocene.     

钴结壳矿区圈定和资源评价的参数指标

大洋海山钴结壳集海洋资源和环境双重信息, 各国对它的调查研究方兴未艾.钴结壳资源勘查的最终目的是圈定钴结壳矿区和开发钴结壳资源.迄今为止, 国内外尚未就钴结壳矿区圈定和资源评价给出具体的参数指标, 基于我国近十年对西太平洋26座海山钴结壳资源调查, 结合太平洋环境资料, 在深入分析钴结壳厚度、丰度、品位、覆盖率、资源量、面积, 海山坡度和水深资料的基础上, 对13座重点海山进行了钴结壳矿区圈定、资源评价和钴结壳分布规律的系统研究, 进而提出圈定钴结壳矿区的八项重要参数指标: 钴结壳矿区的结壳厚度为≥3cm或≥4cm, 取决于海山具体地理位置; 水深为≤2500m或≤3000m;Co含量为≥0.50%或≥0.60%;丰度为≥60kg/m2或≥70kg/m2; 坡度为≤15°; 结壳覆盖率为≥30%;钴结壳矿区的申请面积为17000~20000km2, 矿区最终保留面积为5000~6000km2.钴结壳矿区8项参数指标的提出, 将有力地促进大洋钴结壳矿区圈定、资源量计算和资源评价工作, 为我国积极参与联合国海底管理局制定钴结壳资源开发利用规章制度提供量化参考指标.      

Ferromanganese Crusts in the Central Basin,Sea of Japan

The paper presents a comparative analysis of ferromanganese crusts and concretions (FMC) recovered during the dredging of 14 seamounts in the Central Basin, Sea of Japan. The major rock-forming elements in FMC are Mn, Fe, and Si. In terms of the Mn content, the studied 53 samples are divided into four groups: (1) less than 10% (given than concentrations of 2–8% are lacking); (2) 10?25%; (3) 25?42%; and (4) 42?63%. The (Mn + Fe)/Si ratio increases from group 1 to group 4, and average value in them is 1.6, 2.5, 6.7, and 70.7, respectively. Taking Fe/Si and Mn/Si values into consideration, concretions of these groups belong to the following varieties: (1) ferrosiliceous; (2) mangano-ferrosiliceous; (3) siliceous-ferromanganese, and (4) manganiferous. The highest concentration of nonferrous metals is observed in FMC of groups 2 and 3. Their concentration is slightly lower in group 4 and very low in group 1. The internal structure of FMC in these groups is variable, suggesting their different formation settings. Crusts of group 1 were formed during the precipitation of Mn from a hydrothermal plume on the older ferrosiliceous crusts. Crusts of groups 2 and 3 were likely formed by the diffuse percolation of Mn-bearing hydrothermal solutions along fractures and weakened zones in volcanic rocks, with their subsequent cementation by manganiferous hydroxides from sedimentary or volcaniclastic deposits on seamounts. Crusts of group 4 were formed at sites of the hydrothermal solution discharge on the seafloor. FMC of different groups are recovered during the dredging of most volcanic seamounts in the Central Basin (Sea of Japan). Since the dredging is accomplished at a depth interval of a few hundreds of meters, the detection of concretions of a certain type is governed by the distance to the nearest hydrothermal source.     

西太平洋海山富钴结壳的稀土和铂族元素特征及其意义

为了探讨富钴结壳的稀土和铂族元素是否有相似的形成机制,对西太平洋海山富钴结壳稀土和铂族元素进行了类比研究.结果表明:富钴结壳的∑REY范围为1 433.7×10-6~2 888.0×10-6,其中Ce占到近50%,北美页岩标准化后显示较平坦的稀土模式和显著的Ce正异常特征.根据稀土配分模式及已有的Nd同位素结果,富钴结壳具有亲陆壳属性.富钴结壳具有极高的Pt (115.5×10-9~1 132.0×10-9)、(Pt/Pd)_N和 (Pt/Os)_N值,Ir与Pt及Rh与Pt显示良好相关性.经球粒陨石标准化后显示较一致PGE (platinum-group elements) 配分模式,从Os到Pt逐渐富集,Pd元素强烈亏损.已有的Os同位素研究结果显示物源在地质历史时期从幔源属性向陆源属性变化,但富钴结壳PGE元素内部相对含量仍在一定程度上保持稳定.研究认为:富钴结壳对海水中的稀土清扫具有选择性,Ce的正异常恰恰是结壳对海水稀土中Ce的优先选择造成的,从而导致海水亏损Ce.然而海水中Ce的亏损并未改变新形成富钴结壳的稀土模式,原因是在海洋中存在适量的具有亏损Ce特征的磷酸盐等组分,理论上只需要氧化物类稀土与磷酸盐类稀土消耗的稀土与海水中的补给平衡即可.只是在相关过程中,海洋中氧化物类对稀土的选择更具有主动性,而磷酸盐类表现更多的继承关系.尽管Os同位素显示物源供给发生变化,然而富钴结壳PGE模式相对稳定.因此富钴结壳PGE模式同样可以用富钴结壳对PGE的选择性吸收解释,因富钴结壳优先选择Pt与Ir以及相对排斥Pd和Os,形成了现有独特的PGE模式.      

Pleistocene sea‐floor fibrous crusts and spherulites in the Danakil Depression (Afar,Ethiopia)

Pleistocene fibrous aragonite fabrics, including crusts and spherules, occur in the Danakil Depression (Afar, Ethiopia) following the deposition of two distinctive Middle and Late Pleistocene coralgal reef units and pre‐dating the precipitation of evaporites. Crusts on top of the oldest reef unit (Marine Isotope Stage 7) cover and fill cavities within a red algal framework. The younger aragonite crusts directly cover coralgal bioherms (Marine Isotope Stage 5) and associated deposits. Their stratigraphic position between marine and evaporitic deposits, and their association to euryhaline molluscs, suggest that the crusts and spherules formed in restricted semi‐enclosed conditions. The availability of hard substrate controls crust formation with crusts more often found on steep palaeo‐slopes, from sea level up to at least 80 m depth, while spherules mainly occur associated with mobile substrate. Crusts reach up to 30 cm in thickness and can be microdigitate, columnar (branching and non‐branching) or non‐columnar, with laminated and non‐laminated fabrics. Two different lamination types are found within the crystalline fabrics: (i) isopachous lamination; and (ii) irregular lamination. These two types of lamination can be distinguished by the organization of the aragonite fibres, as well as the lateral continuity of the laminae. Scanning electron microscopy with energy dispersive X‐ray spectroscopy analyses on well‐preserved samples revealed the presence of Mg‐silicate laminae intercalated with fibrous aragonite, as well as Mg‐silicate aggregates closely associated with the fibrous aragonite crusts and spherules. The variety of observed fabrics results from a continuum of abiotic and microbial processes and, thus, reflects the tight interaction between microbially mediated and abiotic mineralization mechanisms. These are the youngest known isopachously laminated, digitate and columnar branching fibrous crusts associated with a transition from marine to evaporitic conditions. Understanding the context of formation of these deposits in Afar can help to better interpret the depositional environment of the widespread Precambrian sea‐floor precipitates.     

A specific type of Fe-Mn mineralization on the Arctic seafloor

Three samples of Fe-Mn crusts overgrown on the surface of rocks are studied from the Mendeleev submarine rise located in the northern subpolar part of the Chukchi Sea. A massive crust up to 4–5 cm thick consists of an upper dense and lower denser layers similar in composition to the main one and contains 31–37% FeO and 11–13% MnO. Thin crusts and films are depleted in both components. Fe-vernadite is a major mineral of the crusts. The comparison of the major and trace element composition of the crusts with oceanic and marine nodules and hydrothermal crusts shows that they are mostly similar in composition to the nodules of the Bering Sea and are significantly distinct from the oceanic hydrothermal crusts. A small inclusion of the Pt-, Pd-, and Ru-rich (up to 1–2%) rock in one of the thin crusts points to the possible role of igneous rocks as a source of precious metals.     

Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements(REE) composition of the polymetallic crusts and nodules obtained from the South China Sea(SCS) were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances(∑REE) of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE(LREE), the markedly positive Ce anomaly(δCe), and the non-or weakly positive Eu anomaly(δEu), suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event(sea-level change) during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.     

Soil CO2 concentration in biological soil crusts and its driving factors in a revegetated area of the Tengger Desert,Northern China

Biological soil crusts (BSCs) are an important cover in arid desert landscapes, and have a profound effect on the CO₂ exchange in the desert system. Although a large number of studies have focused on the CO₂ flux at the soil–air interface, relatively few studies have examined the soil CO₂ concentration in individual layers of the soil profile. In this study, the spatiotemporal dynamics of CO₂ concentration throughout the soil profile under two typical BSCs (algae crusts and moss crusts) and its driving factors were examined in a revegetated sandy area of the Tengger Desert from Mar 2010 to Oct 2012. Our results showed that the mean values of the vertical soil CO₂ concentrations under algal crusts and moss crusts were 600–1,200 μmol/mol at the 0–40 cm soil profiles and increased linearly with soil depth. Daily CO₂ concentrations showed a single-peak curve and often had a 1–2 h time delay after the maximum soil temperature. During the rainy season, the mean soil CO₂ concentration profile was 1,200–2,000 μmol/mol, which was 2–5 times higher as compared to the dry season (400–800 μmol/mol). Annually, soil moisture content was the key limiting factor of the soil CO₂ concentration, but at the daily time scale, soil temperature was the main limiting factor. Combined with infiltration depth of crusted soils, we predicted that precipitation of 10–15 mm was the most effective driving factor in arid desert regions.     

Ferromanganese oxide deposits from the Central Pacific Ocean,I. Encrustations from the Line Islands Archipelago

Chemical and mineralogical analyses of a well-controlled suite of ferromanganese encrustations from the Line Islands Archipelago (Central Pacific) suggest that they represent purely hydrogenous deposits—i.e. they have formed through the slow accumulation of trace metal-enriched oxides directly from the water-column. Mineralogically they consist predominantly of δMnO₂ and amorphous FeOOHxH₂O. Compositionally, they are similar to δMnO₂ nodules from adjoining basinal areas but are enriched in both Mn (mean = 20.4%, max = 29.3%) and Co (mean = 0.55%, max = 1.57%). δMnO₂ is the most important trace metal bearing phase; strong associations are noted between it and Co, Mo, Ni, Zn, and Cd, whilst only Be is associated specifically with FeOOH. V, Sr and Pb are partitioned between the authigenic oxide phases, whilst Ti most probably occurs as TiO₂xH₂O. Cu is contained in both aluminosilicate contaminant phases and Fe oxide phases. These relations are considered to reflect the differing scavenging behaviour of Mn and Fe oxides in the water column.Crusts from ~1–2 km are enriched in Mn and the Mn-related elements and exhibit higher $\text{Mn}\text{Fe}$ ratios than deeper crusts, which are compositionally constant. The higher $\text{Mn}\text{Fe}$ ratios may result from a supply of Mn from continental borderland sediments at these depths, which is transported horizontally by advective-diffusive processes. Since manganophile elements are enriched relative to Mn in the 1–2 km crusts, it is considered that the supply of Mn is scavenged by existing oxides, is oxidised and effectively occludes them. A higher proportion of oxide particles thus exhibit Mn oxide scavenging properties in the 1–2 km depth zone. The increased vertical flux of Mn resulting from the supply at ~1–2 km is not reflected by higher $\text{Mn}\text{Fe}$ ratios in deeper crusts, so that the vertical flux of oxides is not simply related to the standing crop. The $\text{Mn}\text{Fe}$ ratios of the crusts thus reflect the composition of suspended oxides at similar depths.     

西太平洋富钴结壳的分布、组分及元素地球化学

本文以富钴结壳的研究意义,趋势、西太平洋的地区域地质特征为背景,较为详细地阐述了西太平洋富钴结壳的区域分布特征、局部富集规律及其在水下平顶海山上的产出形态;论述了富钴结壳的物质组分,探讨了其含量变化与古海洋环境的关系;研究了富钴结壳的化学成分特征及其在空间上的变化规律,指出西太平洋富钴结壳成矿的良好前景,这对进一步开展富钴结壳成矿规律以及找矿勘探都有重要指导意义。     

Middle Paleozoic crusts of weathering in northeastern Siberian Platform

Crusts of weathering on bituminous limestones and shales, diabases, and granites are described: profile, chemical and mineralogical composition, thermic analysis. Residual and redeposited crusts are distinguished. The dominant minerals are montmorillonite, beidellite and kaolinite, depending on parental rock; age is possibly Middle to Upper Carboniferous. Bauxite deposits are not encountered but the probability of their existence in the region is surmised. Some observations are made on mid-Paleozoic climate and paleogeography of the northeastern Siberian Platform. --B. V. Brajnikov.     

Metal cation exchange reactions of ore minerals in Fe–Mn crusts of the Marcus Wake Rise (Pacific Ocean) in aqueous–salt solutions

It is shown that the reaction ability of metal cations of ore minerals in Fe–Mn crusts of the Marcus Wake Rise increases in the following manner: (Co²⁺ < Cu²⁺ < Ni²⁺) < (Mg²⁺ < Mn²⁺ < K⁺ ≈ Ca²⁺ ≈ Na⁺). The composition of the exchange complex of the ore minerals is constant and includes these metal cations. Ca²⁺ and Na⁺ are major contributors to the exchange capacity of the ore minerals. The capacity of the ore minerals by cations of alkali and base metals is 0.43–0.60 and 2.08–2.70 mg-equiv/g, respectively. The exchange capacity of the ore minerals by cations of base metals increases linearly with the increase in the MnO₂ content of the crust and does not depend on the geographical locations of the Marcus Wake guyots.     

太平洋水下海山磷酸盐的成因及形成环境

笔者首次对太平洋与大洋富钴结壳密切相关的海山磷酸盐的成因及形成环境进行了比较深入的研究。研究发现 ,各种产出形态的磷酸盐都不同程度地交代碳酸盐等含钙物质 ,而呈现出交代生物结构、交代凝灰结构、交代角砾状结构及交代填间结构等各种交代结构 ,反映了磷酸盐的交代成因。此外 ,其δ13 C值 (变化于 0 .7‰～ 2 .0‰之间 )也证实其属于交代成因。磷酸盐中Na、Mg、Sr、F、P2 O5含量以及Na/P2 O5、Mg/P2 O5、Sr/P2 O5、F/P2 O5的比值 ,特别是晶格中结构CO2 的含量 (变化于 5 .7%～ 6 .2 %之间 ) ,与形成于氧化环境下的Blakeplateau、ChathamRise、AgulhasBank等处的磷酸盐相近 ,表明调查区磷酸盐亦形成于氧化环境。氧同位素测定结果表明 ,磷酸盐的形成温度为 5 .8～ 14 .8℃ ,平均为 11.5℃ ,显示其形成于正常的海水温度环境。西、中太平洋海山磷酸盐形成环境十分接近的事实暗示 ,西、中太平洋广大区域内的成磷事件存在着时间上和成因上的统一性和相似性。     

Ferromanganese oxide deposits from the Central Pacific Ocean,II. Nodules and associated sediments

Bulk chemical, mineralogical and selective leach analyses have been made on a suite of abyssal ferromanganese nodules and associated sediments from the S.W. equatorial Pacific Ocean. Compositional relations between nodules, sediment oxyhydroxides and nearby ferromanganese encrustations are drawn assuming that the crusts represent purely hydrogenetic ferromanganese material. Crusts, δMnO₂-rich nodules and sediment oxyhydroxides are compositionally similar and distinct from diagenetic todorokitebearing nodules. Compared to Fe-Mn crusts, sediment oxyhydroxides are however slightly enriched, relative to Mn and Ni, in Fe, Cu, Zn, Ti and Al, and depleted in Co and Pb, reflecting processes of non-hydrogenous element supply and diagenesis. δMnO₂ nodules exhibit compositions intermediate between Fe-Mn crusts and sediment oxyhydroxides and thus are considered to accrete oxides from both the water column and associated sediments.Deep ocean vertical element fluxes associated with large organic aggregates, biogenic calcite, silica and soft parts have been calculated for the study area. Fluxes associated with organic aggregates are one to three orders of magnitude greater than those associated with the other phases considered, are in good agreement with element accumulation rates in sediments, and are up to four orders of magnitude greater than element accumulation rates in nodules. Metal release from labile biogenic material in surface sediments can qualitatively explain the differences between the composition of Fe-Mn crusts and sediment oxyhydroxides.Todorokite-rich diagenetic nodules are confined to an eastwards widening equatorial wedge. It is proposed that todorokite precipitates directly from interstitial waters. Since the transition metal chemistry of interstitial waters is controlled dominantly by reactions involving the breakdown of organic carbon, the supply and degradation rate of organic material is a critical factor in the formation of diagenetic nodules. The wide range of (trace metal/Mn) ratios observed in marine todorokite reflects a balance between the release of trace metals from labile biogenic phases and the reductive remobilisation of Mn oxide, both of which are related to the breakdown of organic carbon.     

太平洋西北平顶海山上环礁型碳酸盐建造与白垩纪赤道洋流

深海钻探揭示构成环礁的浅水碳酸盐建隆覆盖沉积在太平洋西北部平顶海山之上。相对于现今珊瑚藻类生物构成的环礁而言,白垩纪和古新世孤立的环礁的四周边缘生物含量甚少,造礁能力下降。这些环礁浅水碳酸盐沉积在火山基座的顶部,在Albian初期、Albian末期、Maastrichtian晚期和始新世中期发生沉没。早期研究认为这些碳酸盐体系经历了地面暴露阶段以及随后的海侵淹没阶段。然而,一个事实是,环礁沉没仅发生在当太平洋板块背负着平顶海山向北漂移过程中,并且是经过南纬7°以后。几个不同的假说用来解释该时期环礁沉没现象,包括环礁暴露、喀斯特化、地面侵蚀、增强赤道上升洋流、缺氧和/或者富营养的浑浊水的出现等。文中在太平洋平顶海山深海钻孔的沉积、生物地层和古纬度数据综合研究基础上,提出一种新模式用于解释晚白垩世—古新世浅水碳酸盐建造的沉没。与以前的模式不同的是,文中提出,这些晚白垩世—古新世“环礁”之所以发生沉没,原因是受到原始环南赤道洋流(pSEC)的影响,导致一种对分泌碳酸盐的生物不利环境的产生。而且,当这些平顶海山漂移到南纬5°时,即赤道古纬度带,许多浅水碳酸盐建造之上,铁锰结核开始沉积。同时,平顶海山下沉到溶解氧极小层(海平面之下400~1 100 m)和原始环南赤道中层洋流( pEI     

An integrated method for the quantitative evaluation of mineral resources of cobalt-rich crusts on seamounts

Cobalt-rich crusts on seamounts potentially have the economic value of multiple metals. In the field of exploration, it is important to perform quantitative evaluations of mineral resources and delineate promising areas in survey regions for future mining. Accordingly, this study, based on prior knowledge, develops an integrated method to quantitatively evaluate mineral resources of cobalt-rich crusts on seamounts and gives an application example to demonstrate this method. The method includes four steps: first, defining units with certain areas and shapes on the target seamount (a 20 km² square block in the application example) and estimating characteristic values of the cobalt-rich crust for each unit with known geological survey data using a space interpolation method such as Kriging; second, presenting several model algorithms, i.e. Regional Coverage of Crusts, Suitable Slope Percentage for Mining and Fitting Area on Slopes, to extract the corresponding regional metallogenic factors for each unit by inputting regional surveying data (such as bathymetry data) into these models; third, considering both the features and regional metallogenic factors of cobalt-rich crusts in each unit to estimate their distribution of mineral resources on the entire seamount; and last, according to the distribution of the mineral resources and international social and economic requirements (such as the regulations of the International Seabed Authority), delineating a promising area for future mining.     

Zur Geologie und Mineralogie der Kalk- und Gipskrusten Algeriens

Caliches: Large areas of the northern Sahara and the Algerian High Planes are covered by mostly 1–5 m thick caliches. Their age (Pliocene in the Sahara) decreases to the north and their precipitation is generally independent of groundwater. Their profile is composed (from top to base) as follows:

Upper soil, loose and mostly of eolian origin.

Upper part of caliche, with very characteristic, dense, partly layered-knobby texture, formed slowly by solutional and reprecipitational processes of ± freely outcropping caliches under addition of eolian material.

Under part of caliche, highly porous, somewhat chalky and greyish-white; precipitated mainly by capillar rise of solutions in permeable and calcareous rocks.

Substratum, preferentially calcareous sandstones, alluvial deposits and marls.

The mineralogy of the caliches (whose main components are represented in fig. 4 A-C) is rather monotonous: in addition to relicts of the substratum (partly dissolved or pushed aside by precipitation of calcite), there are only newly formed low-Mg-calcite and some quarzine (length-slow quartz). Sr-contents of calcite rise clearly from substratum to upper part of caliche. Gypsiferous Crusts (or Cementations): They are found mainly in the surroundings of Chotts (flat, ± saline lakes) and in oases of the NE-Algerian Sahara. Their formation began — mostly caused climatically — after the period of caliche formation and is still continuing in some places. Most of these gypsum-crusts are formed by evaporation of near-surface groundwaters in sandy soils. Water saturated in gypsum precipitates large crystals of gypsum (relatively low in Sr), partly filled by sand, at groundwater-surface. Fine crystalline crusts (relatively high in Sr) are formed by ascendent waters with lower gypsum content ± directly under the landsurface.     

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element.We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases.Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO₂, carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO₂.Thermodynamic calculations indicate that Te occurs predominantly as H₅TeO₆⁻ in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO₂ in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.