Some geochemical controls on Ni and Co concentrations in marine ferromanganese deposits

The uptake of Ni and Co in the hydrous Mn oxide or the amorphous Fe-oxide phases of ferromanganese deposits in the oceans was studied by electron-microprobe analyses of 17 natural manganese nodules and by experiments on desorption-dissolution of these metals from synthetic Fe oxide or Mn oxides and natural nodule material. Ni was found to occur nearly always in the Mn-oxide phases of natural nodules, while Co occurs both in the Mn-oxide and Fe-oxide phases, with a slight preference for the latter. The solubility of Ni and Co (from coprecipitates of these metals with Fe hydroxides after aging) in seawater was found to depend strongly on the crystallinity of the host phase. The adsorption of Co by the synthetic Mn oxides from seawater was higher than that of Ni. The experimentally determined solubility of Ni and Co in seawater from natural nodule material is extremely low and matches the concentration range of these metals in ocean water.     

Biomineral nanostructures of manganese oxides in oceanic ferromanganese nodules

Manganese oxides, which are widespread and of great practical importance, are formed and transformed by the active role of microorganisms. Manganese aggregates occur as both crystallized varieties and disordered fine-grained phases with significant ore grade and up to 50–60 vol % of X-ray amorphous components. X-ray amorphous nanosized Mn oxides in Fe-Mn nodules from the Pacific Ocean floor were examined from the standpoint of their biogenic origin. SEM examination showed abundant mineralized biofilms on the studied samples. The chemical composition of bacterial mass is as follows (wt %): 28.34 MnO, 17.14 Fe₂O₃, 7.11 SiO₂, 2.41 CaO, 17.90 TiO₂, 1.74 Na₂O, 1.73 Al₂O₃, 1.30 MgO, 1.25 P₂O₅, 1.25 SO₃, 0.68 CoO, 0.54 CuO, 0.53 NiO, and 0.50 K₂O. The chemical composition of fossilized cyanobacterial mats within the interlayer space of nodulesis as follows (wt %): 48.35 MnO, 6.23 Fe₂O₃, 8.76 MgO, 5.05 Al₂O₃, 4.45 SiO₂, 3.63 NiO, 2.30 Na₂O, 2.19 CuO, 1.31 CaO, and 0.68 K₂O is direct evidence for participation of bacteria in Mn oxide formation. This phase consists of mineralized glycocalix consisting of nanosized flakes of todorokite. Native metals (Cu, Fe, and Zn) as inclusions 10–20 μm in size were identified in ferromanganese nodules as well. The formation of nativemetals can be explained by their crystallization at highly reducing conditions maintained by organic matter.     

The oxidation state of manganese in marine sediments and ferromanganese nodules

Marine sediments and ferromanganese nodules from the Pacific Ocean have been analyzed for the $\text{O}\text{Mn}$ ratio of solid manganese. We tested six chemical methods and concluded that the iodometric and oxalate methods were equivalent and were the best choice in terms of accuracy and precision on natural samples. We choose the iodometric method for most of our analyses because the oxalate procedure is a method of differences.The ferromanganese nodules that we analyzed were all from MANOP site H and had $\text{Mn}\text{Fe}$ ratios that ranged from 5.6 to 70. These nodules were invariably highly oxidized with $\text{O}\text{Mn}$ values ranging from 1.90 to 2.00. Our most precise analyses suggest that less than 1% of the total manganese is present as Mn(II).We also analyzed red clay and hemipelagic sediments from the eastern tropical Pacific (Baja borderland and MANOP site H) and carbonate ooze samples from the equatorial Pacific. These sediments are also highly oxidized ($\text{O}\text{Mn}\text{= 1.90 to 2.00}$) except when Mn(II) appears in the interstitial water. As dissolved Mn(II) increases the value of the $\text{O}\text{Mn}$ ratio in the solid phase decreases. The $\text{O}\text{Mn}$ ratio decreases to values as low as 1.40. This decrease appears to be due to a decrease in oxidized manganese by reduction, however, an increase in reduced manganese in the solid sediments by adsorption or MnCO₃ formation can not be ruled out in all cases.     

Rare earth elements in ferromanganese nodules and other marine phases

The concentrations of rare-earth elements (REE) have been measured in 31 ferromanganese nodules from the Pacific and Indian Oceans and vary by almost a factor of 5. Too few nodules have been analyzed to define possible regional trends. The shale-normalized patterns, however, permit division of nodules into two groups: those from depth greater than 3000–3500 m and those from less depth. The factors that determine this change in the relative concentration of REE may be related to the mineralogy of manganese phases and/or the transport of REE to the deep ocean by particulate matter.Comparison of the REE patterns of nodules with those of phillipsite, phosphorite, clays, CaCO₃ and seawater suggests that the patterns of these phases reflect fractionation from an initial pattern closely resembling that of shale. By assuming that the accumulation rate of REE in clays, CaCO₃ and nodules is represented by that for surface sediments, it has been possible to estimate an accumulation rate of phillipsite in pelagic sediments of the Pacific of 0.02 mg/cm²/yr.     

The uptake of cobalt into ferromanganese nodules,soils, and synthetic manganese (IV) oxides

Strong enrichments of cobalt occur in marine manganese nodules, soils, wads, and natural and synthetic minerals such as hollandite, cryptomelane, psilomelane, lithiophorite, birnessite, and δ-MnO₂. Previously, it was suggested that Co³⁺ ions in these minerals replace either Mn³⁺ or substitute for Fe³⁺ in incipient goethite epitaxially intergrown with δ-MnO₂. Neither of these interpretations is now considered to be satisfactory on account of the large discrepancy of ionic radius between octahedrally coordinated low-spin Co³⁺ and high-spin Mn³⁺ or Fe³⁺ in oxide structures. The close agreement between the ionic radii of Co³⁺ and Mn⁴⁺ suggests that some cobalt substitutes for Mn⁴⁺ ions in edge-shared [MnO₆] octahedra in many manganese(IV) oxide mineral structures. It is proposed that hydrated cations, including Co²⁺ ions, are initially adsorbed on to the surfaces of certain Mn(IV) oxides in the vicinity of essential vacancies found in the chains or sheets of edge-shared [MnO₆] octahedra. Subsequently, fixation of cobalt takes place as a result of oxidation of adsorbed Co²⁺ ions by Mn⁴⁺ and replacement of the displaced manganese by low-spin Co³⁺ ions in the [MnO₆] octahedra or vacancies.     

Molecular-scale mechanisms of distribution and isotopic fractionation of molybdenum between seawater and ferromanganese oxides

The distribution of Mo between seawater and marine ferromanganese oxides has great impacts on concentration and isotopic composition of Mo in modern oxic seawater. To reveal the adsorption chemistry of Mo to ferromanganese oxides, we performed (i) detailed structural analyses of Mo surface complexes on δ-MnO₂, ferrihydrite, and hydrogenetic ferromanganese oxides by L₃- and K-edge XAFS, and (ii) adsorption experiments of Mo to δ-MnO₂ and ferrihydrite over a wide range of pHs, ionic strengths, and Mo concentrations. XAFS analyses revealed that Mo forms distorted octahedral (Oh) inner-sphere complexes on δ-MnO₂ whereas it forms a tetrahedral (Td) outer-sphere complex on ferrihydrite. In the hydrogenetic ferromanganese oxides, the dominant host phase of Mo was revealed to be δ-MnO₂. These structural information are consistent with the macroscopic behaviors of Mo in adsorption experiments, and Mo concentration in modern oxic seawater can be explained by the equilibrium adsorption reaction on δ-MnO₂. In addition, the large isotopic fractionation of Mo between seawater and ferromanganese oxides detected in previous studies can be explained by the structural difference between and adsorbed species on the δ-MnO₂ phase in ferromanganese oxides. In contrast, smaller fractionation of Mo isotopes on ferrihydrite is due to little change in the Mo local structures during its adsorption to ferrihydrite.The structures of Mo species adsorbed on crystalline Fe (oxyhydr)oxides, goethite, and hematite were also investigated at pH 8 and I = 0.70 M (NaNO₃). Our XAFS analyses revealed that Mo forms inner-sphere complexes on both minerals: Td edge-sharing (46%) and Oh double corner-sharing (54%) for goethite, and Td double corner-sharing (14%) and Oh edge-sharing (86%) for hematite. These structural information, combined with those for amorphous ferrihydrite and δ-MnO₂, show the excellent correlation with the magnitude of adsorptive isotopic fractionation of Mo reported in previous studies: the proportion of Oh species or their magnitude of distortion in Mo surface complexes become larger in the order of ferrihydrite < goethite < hematite < δ-MnO₂, a trend identical to the magnitude of isotopic fractionation.Based on the comparison with previous reports for Mo surface species on various oxides, the chemical factors that affect Mo surface complex structures were also discussed. The hydrolysis constant of cation in oxides, log K_OH (or the acidity of the oxide surfaces, PZC) is well correlated with the mode of attachment (inner- or outer-sphere) of Mo surface complexes. Furthermore, the symmetric change in Mo species from Td to Oh is suggested to be driven by the formation of inner-sphere complexes on specific sites of the oxide surfaces.     

Incorporation of Be isotopes and other trace metals into marine ferromanganese deposits

Two-to threefold inward increase of ¹⁰Be, ⁹Be, Cu and Ni have been found in surface layers of marine ferromanganese deposits. We interpret this phenomenon as reflecting the manner in which the Be isotopes and probably other trace metals (e.g. Cu and Ni) are incorporated. On reaching the sea floor exchangeable Be is released from its carrier phase to the pore water of the ferromanganese deposits, diffuses inward and gets fixed into the deposits. The fixation process may be related to the mineralogical reorganizations suggested by previous studies. We have modeled this concept and applied it to a Mn crust on which detailed analyses of Cu, Ni and natural decay-series nuclides, as well as Be isotopes are made. Post-depositional fixation of Th isotopes may also occur. The redistributions of Be and Th isotopes are confined to regions very close to the surface of the deposits. For all practical purposes, they will not affect growth rate determinations conventionally done using these isotopes. The “linearly” extrapolated ${}^{10}\text{Be}{}^9\text{Be}$ ratio to the surface from deep layers of a Mn deposit does not necessarily represent that ratio in sea water.     

Energy transfer among Pb, Ce and Mn in fluorescent calcite from Kuerle, Xinjiang, China

Natural calcite from Kuerle, Xinjiang, China, shows orange-red fluorescence when exposed to short-wave ultraviolet (UV) light (Hg 253.7 nm). Photoluminescence (PL) emission and excitation spectra of the calcite are observed at room temperature in detail. The PL emission spectrum under 208 nm excitation consists of three bands: two UV bands at 325 and 355 nm and an orange-red band at 620 nm. The three bands are ascribed to Pb²⁺, Ce³⁺ and Mn²⁺, respectively, as activators. The Pb²⁺ excitation band is observed at 243 nm, and the Ce³⁺ excitation band at 295 nm. The Pb²⁺ excitation band is also observed by monitoring the Ce³⁺ fluorescence, and the Pb²⁺ and Ce³⁺ excitation bands, in addition to six Mn²⁺ excitation bands, are also observed by monitoring the Mn²⁺ fluorescence. These indicate that four types of the energy transfer can occur in calcite through the following processes: (1) Pb²⁺ → Ce³⁺, (2) Pb²⁺ → Mn²⁺, (3) Ce³⁺ → Mn²⁺ and (4) Pb²⁺ → Ce³⁺ → Mn²⁺.     

Sc,Cr, Co and Ni partitioning between minerals from spinel peridotite xenoliths

The partitioning of divalent (Co, Ni) and trivalent (Sc, Cr) trace elements between olivine, ortho- and clinopyroxene and spinel from spinel peridotite xenoliths has been investigated. These peridotites cover a wide range in modal composition from dunite to primitive lherzolites and have equilibrated in the upper mantle between >900° C and <1,200° C.The distribution of Co and Ni shows only minor variation through the whole sequence. In contrast, Sc partitioning between ortho- and clinopyroxene and olivine and clinopyroxene as well as Cr partitioning between olivine and clinopyroxene or olivine and orthopyroxene display high but systematic variations which can be assigned to dependences upon equilibration temperatues. Empirical temperature calibrations are given for Sc-orthopyroxene/clinopyroxene, Sc-olivine/clinopyroxene and Cr-olivine/clinopyroxene which, in principle, may permit to estimate equilibration temperatures not only for lherzolites or harzburgites but for orthopyroxene-free peridotites, too.Sc and Ni partition coefficients between spinel and mantle silicate minerals are primarily dependent upon the major element composition of spinel (e.g. Cr and Al) although a temperature dependence can still be identified. Probably such compositional effects are not observed for trace element partitioning between pyroxenes and olivine or ortho- and clinopyroxene only for the reason that in normal spinel peridotites these minerals show much less variation in major element composition than their coexisting spinels.     

厚结壳的形成条件及控制因素分析

当前对于大洋厚结壳的研究较少,而厚结壳是未来开发利用的重点,同时它记录的地质历史长,控制和影响结壳生长发育的各种因素必然能在厚结壳上充分体现出来。因此,开展厚结壳的形成条件及控制因素的研究,具有重要的理论与现实意义。文章利用GIS空间分析技术与地质统计方法,对厚结壳的定义、结壳厚度与水深、结壳厚度与基岩、结壳生长与构造活动、结壳厚度与沉积速率、结壳厚度与经纬度、结壳厚度与主成矿元素之间的关系进行了分析,结果表明,结壳的厚度变化受控于水深、基岩、构造活动、沉积速率、经纬度等因素,同时结壳厚度与主成矿元素之间存在明显的相关性。     

深港西部通道填海区地下水Zn、Co、Pb、Mn迁移影响因素的研究

填海工程会扰动滨海地区的环境平衡,导致区域地下水中多种重金属浓度的变化.为探明重金属浓度发生变化的确切原因,为最大限度减少填海工程对环境影响提供参考依据,本文以深港西部通道填海区为例,通过实验室模拟填海条件,研究了填海区重金属迁移的关键影响因素.结果表明,填海区地下水中Zn含量升高与地下水淡化、淤泥氧化过程及填料风化有关;Co、Mn含量升高则主要与填料风化释放有关;Pb则保持较稳定的状态.     

炼锌固体废渣中重金属(Pb、Zn)的存在状态及环境影响

利用XRD、TEM/EDS和连续提取实验研究了土法炼锌固体废渣中重金属的矿物学特征及不同粒度中重金属的相态分布特征。与通常发现的重金属一般富集在小粒径废渣中的情况不同,本工作所研究的废渣样品中大粒径废渣与细粒径废渣相似,甚至有更高的金属含量。化学形态研究表明,冶炼过程形成的矿物(或玻璃质)集合体和堆积后的风化过程形成的次生矿物是废渣中重金属存在的主要化学相。同时发现Pb的残渣态很少(0.39%～15.75%),而Zn的残渣态较高(14.3%～46.2%),这可能与冶炼工艺所形成较多Zn的硅酸盐矿物有关。尽管可交换态Pb、Zn在不同相态中的相对比例非常小(Pb0.03%～1.30%;Zn0.03%～3.30%),但其绝对含量却比一般土壤或沉积物要高(Pb1.5～385μg/g;Zn3～590μg/g)。由于重金属可交换态有比其他化学相态更高的活动性和生物可利用性,因此,对环境有较大的潜在影响。废渣样品的微束分析表明,Pb在废渣中见有金属Pb存在形式或呈纳米金属Pb颗粒包裹于其他矿物或铁合金及熔球集合体中。同时不排除有Pb的碳酸盐矿物存在的可能。而以硅锌矿Zn2(SiO4)、锰硅锌矿(Zn,Mn)2犤SiO4犦和纤维状的丝锌铝石Zn8Al4犤(OH)8(SiO4)5犦·7H2O等矿物形式存在以及Fe、Mn等的铝硅酸盐形式存在的Zn,可能是导致Zn的残渣态较高的原因。与连续提     

Co,Hf, Ce,Cr, Th,and REE Charateristics of Modern Bottom Sediments of the Barents Sea

Doklady Earth Sciences - The Co, Hf, Ce, Cr, Th, and REE characteristics are analyzed for modern sediments collected by a bottom grab during the 67th and 68th cruises of R/V Akademik Mstislav...     

Implications from concentrations and isotopic data for Pb partitioning processes in soils

Lead concentrations and stable isotopic measurements were examined in the different chemical fractions of Czech forest soils to investigate the mechanisms of Pb partitioning. A method of selective sequential dissolution (SSD) was employed that distinguished between five different fractions: exchangeable, surface bound, organic matter, Fe-oxides, and silicates (non-labile).From an analysis of the concentrations and isotopic compositions associated with the different fractions, it is apparent that Pb in the deep Czech mineral soils is of predominantly natural origin and is primarily associated with silicates (69-81%) and Fe-oxides (11-19%). Natural Pb associated with surface bound and organic matter fractions in mineral soils accounts for only 7 to 15%. Anthropogenic Pb in the Czech soils is concentrated primarily in the organic horizons and is strongly associated with the surface-bound and organic matter fractions in which the proportion of total Pb is 33 to 50% and 23 to 47%, respectively.At high and low levels of contamination, Pb isotopic signatures within the labile fractions of the same soil samples are generally homogenous, although a degree of heterogeneity among these fractions is noted in samples of intermediate degrees of contamination. Such heterogeneity probably reflects different levels of natural and anthropogenic Pb mixing.Determination of the mass-normalized affinity of Pb to the primary components using solid-solution distribution coefficients suggests that in Czech forest soils, the order of affinity may be summarized as Fe-oxides > organic matter > silicates. A similar treatment of the data reported for semiarid Mediterranean soils indicates the prevailing order to be Fe-oxides > carbonates > organic matter > silicates. The general similarity of the behaviour of Pb with respect to the different soil components in both temperate and semiarid soils suggests that these orders of affinity may have wider significance for a variety of other soil types.     

Transition metals in the transition zone: partitioning of Ni,Co, and Zn between olivine,wadsleyite, ringwoodite,and clinoenstatite

Ni, Co, and Zn are widely distributed in the Earth’s mantle as significant minor elements that may offer insights into the chemistry of melting in the mantle. To better understand the distribution of Ni²⁺, Co²⁺, and Zn²⁺ in the most abundant silicate phases in the transition zone and the upper mantle, we have analyzed the crystal chemistry of wadsleyite (Mg₂SiO₄), ringwoodite (Mg₂SiO₄), forsterite (Mg₂SiO₄), and clinoenstatite (Mg₂Si₂O₆) synthesized at 12–20 GPa and 1200–1400 °C with 1.5–3 wt% of either NiO, CoO, or ZnO in starting materials. Single-crystal X-ray diffraction analyses demonstrate that significant amounts of Ni, Co, and Zn are incorporated in octahedral sites in wadsleyite (up to 7.1 at%), ringwoodite (up to 11.3 at%), olivine (up to 2.0 at%), and clinoenstatite (up to 3.2 at%). Crystal structure refinements indicate that crystal field stabilization energy (CFSE) controls both cation ordering and transition metal partitioning in coexisting minerals. According to electron microprobe analyses, Ni and Co partition preferentially into forsterite and wadsleyite relative to coexisting clinoenstatite. Ni strongly prefers ringwoodite over coexisting wadsleyite with \({D}_{\text{Ni}}^{\text{Rw}/\text{Wd}}\)?=?4.13. Due to decreasing metal–oxygen distances with rising pressure, crystal field effect on distribution of divalent metal ions in magnesium silicates is more critical in the transition zone relative to the upper mantle. Analyses of Ni partitioning between the major upper-mantle phases implies that Ni-rich olivine in ultramafic rocks can be indicative of near-primary magmas.     

Errors in atomic absorption spectrophotometric determination of Pb,Zn, Ni and Co in geologic materials

Errors in atomic absorption spectrophotometric determinations of Pb, Zn, Ni and Co may occur due to the presence of Fe, Al, Ca, Mg, Na and K in the sample solution. At low concentrations of trace element in solution (i.e., up to about 1 p.p.m.) and low concentrations of major elements (up to about 4,000 p.p.m. total cations), the main source of interference is enhancement due to background absorption; this may be corrected by the hydrogen continuum or by use of a non-absorbing wavelength. At higher concentrations of trace element the enhancement due to molecular absorption is partly or completely nullified through suppression caused by major element interference. Similarly, at higher concentrations of major elements, suppression occurs which is probably a function of atomizer efficiency. In these situations, correction for total molecular absorption results in a residual negative error.The errors in determination of Pb, Zn, Ni and Co in geological materials are often ignored in exploration geochemistry work. This restriction on the accuracy of the analytical data is becoming more important with the increasing use of exploration methods based on rock analyses. The errors may be minimized by ensuring that the concentration of both trace element and major element in solution is too low to cause significant suppression effects. Under these circumstances, reasonable results should be obtained through correction for background absorption.     

Remobilisation features and structural control on ore grade distribution at the Konkola stratiform Cu–Co ore deposit,Zambia

The Konkola deposit is a high grade stratiform Cu–Co ore deposit in the Central African Copperbelt in Zambia. Economic mineralisation is confined to the Ore Shale formation, part of the Neoproterozoic metasedimentary rocks of the Katanga Supergroup. Petrographic study reveals that the copper–cobalt ore minerals are disseminated within the host rock, sometimes concentrated along bedding planes, often associated with dolomitic bands or clustered in cemented lenses and in layer-parallel and irregular veins. The hypogene sulphide mineralogy consists predominantly of chalcopyrite, bornite and chalcocite. Based upon relationships with metamorphic biotite, vein sulphides and most of the sulphides in cemented lenses were precipitated during or after biotite zone greenschist facies metamorphism. New δ³⁴S values of sulphides from the Konkola deposit are presented. The sulphur isotope values range from −8.7‰ to +1.4‰ V-CDT for chalcopyrite from all mineralising phases and from −4.4‰ to +2.0‰ V-CDT for secondary chalcocite. Similarities in δ³⁴S for sulphides from different vein generations, earlier sulphides and secondary chalcocite can be explained by (re)mobilisation of S from earlier formed sulphide phases, an interpretation strongly supported by the petrographic evidence. Deep supergene enrichment and leaching occurs up to a km in depth, predominantly in the form of secondary chalcocite, goethite and malachite and is often associated with zones of high permeability. Detailed distribution maps of total copper and total cobalt contents of the Ore Shale formation show a close relationship between structural features and higher copper and lower cobalt contents, relative to other areas of the mine. Structural features include the Kirilabombwe anticline and fault zones along the axial plane and two fault zones in the southern limb of the anticline. Cobalt and copper behave differently in relation to these structural features. These structures are interpreted to have played a significant role in (re)mobilisation and concentration of the metals, in agreement with observations made elsewhere in the Zambian Copperbelt.     

Mn, Fe, Zn and As speciation in a fast-growing ferromanganese marine nodule

The speciation of Mn, Fe, As, and Zn in a fast-growing (0.02mm/yr), shallow-marine, ferromanganese nodule has been examined by micro X-ray fluorescence, micro X-ray diffraction, and micro X-ray absorption spectroscopy. This nodule exhibits alternating Fe-rich and Mn-rich layers reflecting redox variations in water chemistry. Fe occurs as two-line ferrihydrite. The As is strictly associated with Fe and is mostly pentavalent, with an environment similar to that of As sorbed on or coprecipitated with synthetic ferrihydrite. The Mn is in the form of turbostratic birnessite with ∼10% trivalent manganese in the layers and probably ∼8% corner-sharing metal octahedra in the interlayers. The Zn is enriched on the rim of the nodule, associated with Mn. The Zn is completely (>90%) tetrahedrally coordinated and sorbed in the interlayers of birnessite on vacant layer Mn sites. The Zn and Mn species are similar to ones found in soils, suggesting common structural principles despite the differing formation conditions in these systems.     

Diagenetic control on arsenic partitioning in sediments of the Meghna River delta,Bangladesh

A stratigraphic profile of solid phase As was measured to investigate the diagenetic cycling of arsenic and related elements in fluvial sediments of the Meghna River delta plain. The distributions of Fe, Mn, and Al are typically characterized by surficial solid phase enrichment, and As is distributed down to 36.6 m showing similar alternate layers of maxima and minima with Fe, Mn and TOC, which reflects the diagenetic remobilization and periodical differences in source materials of As. Lithological characteristics and geochemical data suggest that elevated levels of As are found in organic-matter-rich clay and silty sand rather than sand samples, with occasionally enriched As content in iron-oxyhydroxide-coated sand grains. Arsenic demonstrates a positive and significant co-variation with total organic carbon in sediments, which suggests the important role of particulate and colloidal organic matter and biological activity in controlling the distribution of arsenic in the Bengal delta. However, the concentrations of Fe and Mn weakly correlate with As contents, whereas Al contents show no relationship with As. The results of this study suggest that reactive oxides or hydroxides of Fe and Mn, rather than Fe and Mn with other minerals, might control arsenic distribution.