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.     

南海海山铁锰结核元素赋存形式

铁锰结核中主微量元素的赋存形式研究对于理解铁锰结核的形成及其中元素的进入过程具有重要意义。选择采集自南海蛟龙海山水深约3 300 m的3个铁锰结核,根据其内部剖面上原位X荧光光谱分析(XRF)的主量元素含量差异分层进行了分层取样。对于分层样品开展了淋滤实验,分别提取样品中的碳酸盐相、锰矿物相、铁矿物相和残渣相组分,并将该4种组分以及原样中主微量元素加以分析比较。结果表明,蛟龙海山结核多数主要元素赋存方式基本上类似于大洋水成型结核结壳,但相对于大洋水成型结核结壳,Al、K、Mg、Li、Ti在碎屑相中赋存比例更高,呈现出边缘海水成型结核元素赋存方式的特点。圈层之间部分元素赋存形式略有变化,其中Mg、Cu、Ni、Zn从核心到边缘在锰矿物相中的赋存比例随着Mn/Fe比值的升高而增加,体现了不同生长阶段结核元素和矿物组成的变化。即Mn/Fe比值越高,说明锰氧化物/铁氧化物比值越高,而Mg、Cu、Ni、Zn主要赋存于锰氧化物中,所以Mg、Cu、Ni、Zn赋存于锰矿物相/铁矿物相的比例增加。此外,通过与前人关于南海蛟龙海山结核淋滤结果的对比发现,实验试剂与反应时间对于结核淋滤结果有较大影响。     

Mechanisms of enrichment of the rarer elements in marine manganese nodules

The rare-earth distribution has been determined in five manganese nodules from a range of marine environments. Manganese nodules from Loch Fyne, Scotland, and the Gulf of Aden are characterized by a low absolute abundance of the rare-earth elements and a low Ce/La ratio compared with deep-sea nodules. This difference is interpreted in terms of the diagenetic remobilization of manganese in the high sedimentation regimes leading to the effective fractionation of manganese from the rare-earth elements and the resultant depletion of the rare earths in nodules from these environments. The mechanism of incorporation of the rare-earth elements into manganese nodules is thought to be either the direct adsorption of these elements from seawater or the scavenging of the elements by colloidal iron oxide prior to their incorporation into the authigenic phase of nodules. There appears to be no evidence for the surface transfer of these elements from inorganic detritus into the authigenic phase of nodules as suggested by previous authors. The distribution of U and Th in the nodules is controlled by factors similar to those controlling the rare-earth abundance in nodules. The higher U/Th ratios in nodules from Loch Fyne and the Gulf of Aden is considered to be due to the preferential reduction of UO₂(CO₃)₃^4? to some lower-valency uranium species such as U₃O₈ in nodules from less oxidizing environments.     

西盘古海盆锰结核的元素地球化学特征及生长机制

通过对西盘古海盆(Cipangu Basin)15个锰结核样品开展系统的形态结构、显微构造、矿物组成、常微量元素和稀土元素含量特征差异性研究,进而探讨该区锰结核的成因类型和生长机制。西盘古海盆锰结核外观为椭球状或连生体状,表面光滑,组成矿物主要有水羟锰矿、石英、钙长石和石盐;其稀土元素配分模式图表现出明显的Ce正异常、Y负异常和轻稀土富集特征。样品Mn/Fe比值均<2.5,与Ni、Cu正相关,且Mn与Cu、Co和Ni高度正相关,这表明因Cu2+、Ni2+、Co2+更易占据层板结构锰氧八面体MnO6的空位而在锰矿物表面富集。锰结核显微构造区域可划分为Type-Ⅰ型和Type-Ⅱ型,其中Type-Ⅰ型为结构致密高反射率的层纹状、柱状、叠层状构造的显微构造区域,Type-Ⅱ型为结构疏松低反射率的掌状、混杂状、环状构造的显微构造区域;Type-Ⅰ型区域的Mn/Fe比值和Ni、Ni + Cu、Co含量均高于Type-Ⅱ型区域。构造致密的Type-Ⅰ型区域代表沉积环境变化较小,生长速率较小;构造疏松的Type-Ⅱ型区域代表沉积环境剧烈变化、结核生长速率较大。西盘古海盆锰结核具有典型的水成型成因特征,通过常微量元素测试数据估算得出西盘古海盆锰结核样品的形成时间为1.48 Ma。据微区分析数据估算得出其生长年龄为2.44 Ma。     

GEOCHEMISTRY OF ABYSSAL SEDIMENT IN THE PACIFIC OCEAN

The contents of Fe, Mn, Cu, Co, Ni, Pb and Zn in the seaiment associated with manganese nodules from the Northern Central Pacific Ocean and in their acid-soluble fractions were determined and correlations among the elements and between the trace metals and environmental parameters were discussed. It has been found that the contents of Mn, Cu and Ni in the sediment are one order of magnitude higher than those in the common sediment. As shown in the manganese nodules, they may mainly derive from seabed. The contents of all trace metals in the sediment are obviously governed by Fe-and Mn-oxides, organic matter, seawater depth, particle size and Eh. Multi-element correlation equations were developed for all trace metals. The trace metals in acid-soluble fraction of the sediment were also much higher than ihose of common sediment and negatively correlated with water depth, implying the possible influence of carbonate speciation.     

Factors regulating the distribution of elements in marine sediments predicted by a simulation model

The contents of oxyanionic elements (V, Se and Mo) and cationic transition metals (Mn, Fe, Co, Ni, Cu and Zn) in sediments from near-shore to deep-sea environments were measured to clarify factors regulating the distribution of these elements in marine sediments. For cationic transition metals of which contents increase from near-shore to deep-sea environments, the chemical composition of pelagic clays is modeled by a mixture of aluminosilicates having the chemical composition of average shale and Fe–Mn oxides having the chemical composition of associated manganese nodules. The content of V is fairly constant in sediments from near-shore to deep-sea areas. The mixture model of average shale and manganese nodules holds also for V, although most of the V is located in the aluminosilicate lattices. The content of Se in the near-shore sediments is higher and that in the deep-sea sediments is lower than that in average shale. The high content in the near-shore sediments is interpreted as the addition of biogenic materials to aluminosilicates with average shale composition and the low content in deep-sea sediments is explained by oxidative release of Se from aluminosilicates. The content of Mo in sediments increases from near-shore to deep-sea environments. The general distribution of Mo in marine sediments is expressed by the mixture model. An anomalously high content of Mo in a near-shore sediment is attributed to adsorption of molybdate on manganese oxides.     

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.     

Separation of iron from manganese and growth of manganese nodules as a consequence of diagenetic ageing of radiolarians

111 samples of diagenetically aged radiolarians sampled in the Central Pacific manganese nodules belt were investigated chemically and microscopically.

Authigenic clays of the smectite group are precipitated in the cavities of radiolarian tests; metal oxides are precipitated on the surfaces of radiolarian tests. During these processes a separation of iron from manganese takes place: about 96% of the iron is bound to smectites and all of the manganese is bound to the oxide coatings of the radiolarians.

With further diagenesis, radiolarian tests are dissolved together with their oxide coatings. This dissolution of the oxide coatings provides material for the growth of manganese nodules, material which is depleted in Fe and enriched in Mn, Cu, and Zn.

The smectite aggregates that fill the cavities of radiolarian tests contain iron bound to their crystal lattice. Whereas radiolarian tests are dissolved during the diagenesis, these smectite aggregates do not dissolve and thus become enriched in older samples.     

Ferromanganese nodules from the East Siberian Sea near Bennett Island

Ferromanganese nodules recovered from the bottom of the East Siberian Sea near Bennett Island are studied by coupled ultramicroscopic and ICP-MS methods. The majority of nodules are flattened dense formations 2.5 to 10 cm in cross section and circled by a thick rim, which is common in nodules from other Arctic basins. The major components of nodules are iron and manganese oxides in the form of ferruginous vernadite and magnetite, as well as accessory minerals, including apatite and titanomagnetite. The major and trace element compositions of nodules are comparable to Arctic nodules from other Arctic seas, but somewhat different compared to those from the Mendeleev Rise. A specific feature of these nodules is that they contain high amounts of mercury in all samples and a positive europium anomaly in one sample, along with gold; this may be related to the influence of endogenous gas-and-vapor exhalations.     

Contrasting trace element geochemistry in two American and French salt marshes

Trace metals were analyzed in the bulk fine phase of two contrasting salt marsh cores on the North Atlantic east (Baie de l'Aiguillon, LaRochelle, France) and west (Lewes, DE, USA) coasts. The purpose is to gauge how the different clay mineral sources and surface sedimentary diagenetic conditions affect the respective trace element geochemistries. It has been established that there is considerably more clay mineral diagenesis at the zone of redox transition in the Delaware core than in the l'Aiguillon core. The Delaware core shows unweathered glacial sedimentary material directly deposited from the continental shelf whereas the l'Aiguillon core is formed from soil clays deposited after river and estuarine transport. Although there is strong Mn redox depletion in the Delaware salt marsh core, and enrichment in the French one at l'Aiguillon, transition elements seem to follow iron content in both cores. The trace pollutant elements Pb, Sn and Zn show pronounced depth profiles in both North Atlantic cores. The Pb, Sn and Zn appear to be carried by clay sources into the French marshes, while appearing to be largely deposited by atmospheric processes as well into the Delaware marsh.Upon deposition, the Zn appears to become decoupled from lead, which is probably more strongly fixed on clays. The Sn seems to be both air transported, and carried as well on non-clay phases contaminated by industrial organo-tins, including antifouling bottom paints. Copper while uniformly enriched in France, probably from use in regional vineyards, appears enriched only near the top at Delaware, suggesting diagenetic recycling in the more abundant peat in the surface. The Cs and Li appear to be tracers for specific soil-derived clay sources in the French core source materials. These observations suggest that clay is a very important carrier in fixing trace elements for historical records as salt marsh sediments.     

The clay mineralogy of particulate material from some surface seawaters of the eastern Atlantic Ocean

The concentrations of the clay minerals montmorillonite and illite have been determined in 28 samples of particulate material from surface (0–～5 m) waters along the eastern margins of the Atlantic Ocean, and the concentrations of chlorite and kaolinite have been determined in nineteen of the samples.The average concentration of the four clays in the particulate material decreases in the following order: illite (～42%) > kaolinite (～25%) > chlorite (～19%) > montmorillonite (～14%). There are specific trends in the latitudinal distributions of illite and kaolinite in the particulate material; illite decreases and kaolinite increases towards low latitudes. These trends are also found in eolian dusts and deep-sea sediments from the same region, and these clays are considered to have a detrital origin.The concentrations of montmorillonite in the particulate material and deep-sea sediments are similar in the North Atlantic. However, in the South Atlantic the sediments contain about twice as much montmorillonite as does the particulate material. It is suggested that whereas the montmorillonite in North Atlantic deep-sea sediments is largely detrital, that in South Atlantic sediments is both detrital and authigenic.     

Atmospheric inputs of trace metals to the northeast Atlantic Ocean: the importance of southeasterly flow

The study of aerosols and rainwater presented here demonstrates that episodic atmospheric deposition events associated with southeasterly flow are quantitatively significant for large areas of the North Atlantic Ocean. This paper considers aluminium and manganese, with predominantly crustal sources, and lead and zinc, which are mobilised into the atmosphere primarily through anthropogenic activity. High levels of all trace metals are associated with southeasterly flow from Europe as the air passes over heavily populated and industrialised regions before reaching the northeast Atlantic Ocean. Fluxes calculated using the 1% HNO₃ acid soluble metal concentration show that, although the climatological norm for this area is westerly flow, short-lived southeasterly transport events dominate the input of trace metals to this ocean region. This material may be toxic to phytoplankton or may be represent a new source of nutrients to the biological community. A significant decrease in atmospheric lead levels in polluted air is seen between June 1996 and May 1997, reflecting the decrease in use of leaded fuels in Europe. Comparing atmospheric flux values to sediment trap metal fluxes shows that the atmosphere represents the dominant source of zinc to the deep ocean, whereas an additional, non-atmospheric, manganese source this required, perhaps from mobilisation of sedimentary material from the continental shelf or long range advection of manganese rich Saharan material.     

Composition of the inorganic fraction of the particulate organic matter in seawater

Na, K, Mg, Ca, Fe, and Mn have been measured in both naturally occurring particulate matter and artificially created aggregates taken from water from the Nova Scotian coastal region and from the North Atlantic Ocean. The order of concentration of these elements is the same in both the aggregates and the natural particulate matter as it is in seawater. There is an inverse relationship between depth of the water and the amount of inorganic matter in artificially created aggregates, while a direct relationship is found with the naturally occurring particles. This direct relationship may reflect the utilization of organic material in the surface waters. Iron and manganese are enriched in both kinds of particles.     

Formation and distribution of manganese nodule deposit in the northwestern margin of Clarion-Clipperton fracture zones,northeast equatorial Pacific

In the northwestern margin of the Clarion and Clipperton fracture zones, manganese nodules are latitudinally variable in character, resulting from the progressive (re)generation of nodules since the Oligocene as the Pacific Plate migrates northwestward beneath the equatorial production zone. Complemented by the surface water productivity, bottom current activities have concentrated nodules in the Oligocene to Miocene siliceous clay. Resedimentation processes on nodules form three types of nodules with concentric structures and 10 Å-manganaterich bottoms, by periodically causing the diagenetic growth of nodules within the topmost sediment layer.     

Distribution of total Al,Cd, Co,Cu, Ni and Zn in the tongue of the ocean and the northwestern Atlantic Ocean

The elements Al, Cd, Co, Cu, Ni and Zn were concentrated from seawater using tetraethylenepentamine resin and analysed by atomic absorption spectrophotometry. The spatial distribution of these elements in the northwest Atlantic Ocean is discussed with respect to possible riverine inputs to the area from Puerto Rico.     

太平洋多金属结核中铁锰矿物分析及成因研究

铁锰矿物是大详多金属结核的重要组成,了解不同类型结核中主要铁锰矿物种类、形态、分布特点和结晶程度等,不仅有助于对锰矿物乃至多金属结核成因的研究,而且对选矿冶炼和资源的综合利用也具有现实意义.本文通过透射电子显微镜等多种手段综合分析与鉴定,指出多金属结核中主要铁锰矿物有钙锰矿、水羟锰矿、水钠锰矿、方锰矿、锰铁矿和针铁矿等.结晶程度普遍较差,钙锰矿结晶相对好于其他矿物,并在粗糙型结核中含量高,外层至核心含量稳定,变化小.水羟锰矿广为分布,但结晶差.铁矿物含量东区低于西区,结核外壳铁含量高于内核.锰矿物分布在叠层石柱体和纹层内,呈束状、纤维状和树枝状,与建造多金属结核的超微生物菌丝体形态一致.粗糙型结核是选冶的主要对象.     

中太平洋北部锰结核的主要元素化学

本文测定了中太平洋北部锰结核的主要化学元素的含量。研究表明,元素的含量分布与组成锰结核的主要矿物有关;与共生元素及渗入锰结核中的粘土矿物和其他碎屑矿物有关。文中还指出了锰结核中富Mn贫Ca,沉积物中富Ca贫Ti,而沉积物对Ca的富集又与海洋生物相关。同时说明,Mg在锰结核与沉积物之间的交换比例约为1∶1。锰结核区的海水深度、pH和Eh值的大小对锰结核的形成产生重要影响。     

Study on the managanese nodule

Chemical and X-ray analyses were performed on the fifteen manganese nodules collected from the Pacific Ocean floor. The results were discussed compared with the previous data on the manganese nodules. Minerals were found to be todorokite, δ-MnO₂ and other silicates, montmorillonite, illite, phillipsite and α-SiO₂. Average composition shows that copper is concentrated on the deep sea nodules more than the shallow ones, and that the todorokite rich nodules contain more copper and nickel than the δ-MnO₂ rich ones. The analyses of fresh water iron-manganese precipitates by bacterial activity suggest that biological process is one of the important factors on the genesis of the sedimentary iron-manganese deposits, including the manganese nodule. The Institute of Physical and Chemical Research     

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.     

The distribution of zinc,nickel, manganese,cadmium, copper,and iron in some surface waters from the world ocean

Determinations of Zn, Ni, Mn, Cd, Cu, and Fe have been carried out on 51 near-shore and 38 open-ocean surface seawaters from various regions of the World Ocean.The concentrations of the trace metals have been established in the open-ocean waters, and have been used as “baselines” to evaluate trace-metal enhancement in near-shore regions. The factors by which the trace metals are enriched in near-shore regions vary from one element to another and, according to the highest concentration factors found, decrease in the order Zn = Mn > Cd = Cu = Ni.These elements exhibit differences in their distributions between near-shore and open-ocean waters, and they have been divided into two types on this basis: Type I, in which the largest number of samples in both shelf and open-ocean waters lie in the same concentration range. Zinc, cadmium, and copper are Type I elements. Type 2, in which the largest number of samples of near-shore waters lie in a higher concentration range than the largest number of samples of open-ocean waters. Nickel and manganese are Type 2 elements.The concentrations of Mn, Cd and Zn are similar in open-ocean surface waters from the South Atlantic and Indian Ocean, but Cu and Ni have higher concentrations in the former ocean.There is considerable variation in the concentrations of the trace metals in near-shore surface waters from various regions of the World Ocean. These variations are discussed in detail.