Detrital and authigenic(?) baddeleyite (ZrO2) in ferromanganese nodules of Central Indian Ocean Basin

Occurrence of baddeleyite (ZrO2) which is a rare mineral has been recorded in ferromanganese nodules of Central Indian Ocean Basin (CIOB). The mineral occurs either as independent isolated sub-rounded to elliptical grains or in clusters forming fine subhedral crystals (<3 mm) within ferromanganese concretionary growth bands. The mode of occurrence, textural features and chemistry of the mineral suggest detrital and possibly an authigenic origin for baddeleyite. For authigenic origin it is proposed that zirconium might have got released either from the terrigenous sediments or the altered seafloor rocks forming halogen complexes and subsequently it has re-precipitated in the form of baddeleyite within manganese nodules under oxic to sub-oxic conditions.     

Composition and Genesis of Zeolitic Claystones from the Central Indian Ocean Basin

We examined more than fifty indurated sediments recovered from the Central Indian Ocean Basin （CIOB） during the course of collection for manganese nodules and crusts. The samples occur as slabs either over which ferromanganese oxides are present or over a substrate of altered oceanic basalt in conjunction with palagonite or within the nucleus of manganese nodules. Mineralogically and compositionally, the samples show a mixture of phillipsite, palagonite and montmorillonite. We suggest that the volcanogenic precursors occurring in the CIOB were subjected to varying degrees of alteration under the influence of low temperature conditions, resulting in the formation of zeolitic claystones. The CIOB samples have similarities to those reported from various sites in the world oceans.     

Geochemistry of ferromanganese nodule–sediment pairs from Central Indian Ocean Basin

Fourteen ferromanganese nodule–sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule–sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo – (307, 273), Ni – (71, 125), Mn – (64, 87), Cu – (43, 80), Co – (23, 75), Pb – (15, 24), Zn – (9, 11) and V – (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation (r ? 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.     

答《关于深海锰结核中“纳米级超微生物化石”的思考和建议》一文

本文详细讨论了东太平洋深海锰矿结核中新发现的中华微放线菌和太平洋螺球孢菌究竟是不是超微结构，首先，它们是笔者根据形态，结构和元素成分作为超微生物化石进行鉴定的，其次，透射电子显微镜中可以清楚地区分出完整的微生物结构，包括菌丝，孢子，孢囊和菌落等，它们之间的尺寸比例也是适当的，此外，透射电子显微像还揭示，深海锰质叠层石的纹层就是这些超微生物韵律性生长的结果，与滨海叠层中的纹层十分相似，笔者认为，已知微生物的最小尺寸不能作为否定新发现的超微生物化石的依据。本文还讨论了超微生物化石的术语问题。     

A note on chemical composition and origin of ferromanganese oxide coated and uncoated pumice samples from Central Indian Ocean Basin

Pumice are explosive volcanic product, occur as uncoated or coated with ferromanganese (Fe-Mn) oxide and resides in association with ferromanganese nodules on the seabed in Central Indian Ocean Basin (CIOB). The older Fe-Mn oxide coated and younger uncoated pumice clasts were leached with 6N HCl to remove Fe-Mn oxide coatings as well as the calcium carbonate present within the vesicles. The main objective of the present study is to understand the origin of these pumice by utilizing their chemical composition. Both coated and uncoated pumice samples are rhyoliteand medium K calc-alkaline series. Major, trace, rare earth elements (∑REE) concentration and chondrite-normalized REE patterns of both coated and uncoated pumice are nearly similar to each other suggesting a same source. Tectonomagmatic discrimination diagrams (Nb vs Y: Yb vs. Ta), triangular plot (TiO₂-Zr-Y) and High Field Strength Element ratios (La/Ta- 25; Ta/Hf- 0.2; Nb/Ta- 9; Zr/Nb- 22 and Ba/Ta-1084) indicate volcanic arc origin. These were probably sourced from the nearest Indonesian volcanic arc and drifted to the CIOB by currents.     

Estimating growth rates of ferromanganese nodules from chemical compositions: implications for nodule formation processes

Using available information on the accretion rates and the bulk chemical compositions of oceanic ferromanganese nodules, it can be shown that the accumulation rate of manganese is proportional to the square of the accumulation rate of iron. This relationship has been used to derive an equation that predicts nodule growth rates from their chemical compositions. The equation accurately predicts growth rates up to about 50 mm/10⁶ yr, but yields incorrect rates for faster-growing concretions. From this relationship nodules underneath water of high primary productivity grow most rapidly and accumulate transition metals most rapidly; however, nodules from regions of highest primary productivity do not have the highest concentrations of nickel and copper. Reduction of manganese within the sediment column and remobilization of a fraction to the surface sediments adds manganese to nodules without substantially augmenting the supply of other transition elements. The addition of remobilized manganese to the nodule dilutes the concentrations of nickel, copper and iron, even though their rates of accumulation are also high.     

Geochemistry and U-series dating of Holocene and fossil marine hydrothermal manganese deposits from the Izu-Ogasawara arc

This study investigated Holocene and fossil hydrothermal manganese deposits in the Izu-Ogasawara arc. Mineralogically, these deposits comprise 10 Å and 7 Å manganate minerals, and the fossil samples showed higher 10 Å stabilities. Chemical compositions of the Holocene samples are typical of other hydrothermal manganese deposits, including low Fe/Mn ratios, low trace metals, and low rare earth elements. Although the fossil samples generally have similar chemical characteristics, they exhibit significant enrichment in Ni, Cu, Zn, Cd, Ba, REE, Tl, and Pb contents. Furthermore, the chondrite-normalized REE patterns showed more light REE enrichment trends. These chemical characteristics suggest post-depositional uptake of these metals from seawater. U-Th dating of a Holocene hydrothermal manganese deposit from the Kaikata Seamount indicated 8.8 ± 0.94 ka for the uppermost layer and downward growth beneath the seafloor with a growth rate of ca. 2 mm/kyr. This is approximately three orders of magnitude faster than that of hydrogenetic ferromanganese crusts. U-Pb age of a fossil hydrothermal manganese deposit from the Nishi-Jokyo Seamount showed 4.4 ± 1.6 Ma, which was contemporary with basaltic volcanism (5.8 ± 0.3 Ma). Hydrothermal manganese deposits contain high concentrations of high value Mn, but only small amounts of valuable minor metals; their ages constrain the periods of past hydrothermal activity and provide a vector to explore for polymetallic sulfide deposits.     

Composition and characteristics of the ferromanganese crusts from the western Arctic Ocean

Layered ferromanganese crusts collected by dredge from a water depth range of 2770 to 2200 m on Mendeleev Ridge, Arctic Ocean, were analyzed for mineralogical and chemical compositions and dated using the excess ²³⁰Th technique. Comparison with crusts from other oceans reveals that Fe-Mn deposits of Mendeleev Ridge have the highest Fe/Mn ratios, are depleted in Mn, Co, and Ni, and enriched in Si and Al as well as some minor elements, Li, Th, Sc, As and V. However, the upper layer of the crusts shows Mn, Co, and Ni contents comparable to crusts from the Atlantic and Indian Oceans. Growth rates vary from 3.03 to 3.97 mm/Myr measured on the uppermost 2 mm. Mn and Fe oxyhydroxides (vernadite, ferroxyhyte, birnessite, todorokite and goethite) and nonmetalliferous detrital minerals characterize the Arctic crusts. Temporal changes in crust composition reflect changes in the depositional environment. Crust formation was dominated by three main processes: precipitation of Fe-Mn oxyhydroxides from ambient ocean water, sorption of metals by those Fe and Mn phases, and fluctuating but large inputs of terrigenous debris.     

Jurassic microbial communities in hydrothermal manganese crust of the Rifian Calcareous Chain,Northern Morocco

The stratigraphic record of the Middle and Upper Jurassic in the Western Tethys is characterized by successive eustatic and tectonic events recorded as stratigraphic unconformities, which are revealed by hardgrounds, palaeokarsts, palaeosoils, and by the deposition of Fe–Mn crusts. The study of a Mn crust from the Middle-Upper Jurassic discontinuity in the Jbel Moussa Group (Rifian Cordillera), from stratigraphic, geomicrobiologic, mineralogical, and geochemical standpoints allows us to establish its hydrothermal origin. The manganese crust is composed by Ca-birnessite, cryptomelane and coronadite. Major- and trace-elements analyses of the whole crust show high contents in MnO (> 70 wt.%), a negative Ce anomaly and a positive Eu anomaly. Analysis of the microstructures under scanning electron microscopy reveals crystalline and microbial laminations, probably owing to fungal mycelium. Mineralogical and geochemical composition, together with microbial structures, suggest that this Mn crust formed as a result of venting hydrothermal fluids through synsedimentary faults. Chemosynthetic microbes were probably involved in the precipitation of Mn.     

Tube fossils from gossanites of the Urals VHMS deposits,Russia: Authigenic mineral assemblages and trace element distributions

The occurrence, types, morphology, and mineralogical characteristics of tube microfossils were studied in gossanites from twelve VHMS deposits of the Urals. Several types of tube microfossils were recognized, including siboglinids, polychaetes and calcerous serpulids, replaced by a variety of minerals (e.g. hematite–quartz, hematite–chlorite, carbonate–hematite) depending on the nature of the substrate prior to the formation of the gossanites. Colonial hematite tube microfossils (~ 150 μm across,1–2 mm long) are composed of hematitic outer and inner walls, and may exhibit a cellular structure within their cavities. Spherical forms are saturated with Fe-oxidizing bacteria inside the tubes – probably analogues of trophosomes. Colloform stromatolitic outer wall surfaces are characterized by the presence of numerous interlaced filaments of hematite (2–3 μm diameter, up to 1–2 mm long). Between tube microfossils, the hematitized cement contains bundles of hematitized filaments with structures similar to the hyphae of fungi. Hematite–chlorite tube microfossils are scattered in gossanites, mostly as biological debris. They are typically 30 to 300 μm in diameter and 1 to 5 mm long. The layered structure of their tube walls is characterized by hematite–quartz and chlorite layers. Abundant filamentous bacteria coated by glycocalix and chlorite stromatolite are associated with hematite–chlorite tubes. The carbonate–hematite tube microfossils (up to 300 μm across, 2–3 mm long) occur in carbonate-rich gossanites. The tubes are characterized by fine (~ 10 μm thick) walls of hematite and cavities dominated by relatively dark carbonate or hematite. Carbonates may be present both in walls and cavities. Stromatolite-like leucoxene or hematite–carbonate aggregates were also found in association with tubes. Randomly oriented filaments are composed of ankerite. Single filaments are composed of individual cells, typically smaller than 100 nm across, similar to that of magnetotactic bacteria.Three dimensional tomographic images of all types of tube microfossils demonstrate a clear wavy microlayering from outer and inner walls, which may reflect segmentation of the tube worms. The traces of burrowing or fragments of glycocalix with relict spheres are typical of tube microfossils from gossanites.The carbon isotopic composition of carbonates associated with tube microfossils from hematite–quartz, hematite–carbonate, and hematite–chlorite gossanites average − 7.2, − 6.8, –22.8‰, PDB, respectively. These values are indicative of a biogenic origin for the carbonates. The oxygen isotopic composition of these carbonates is similar in all three gossanite types averaging + 13.5, + 14.2, + 13.0‰ (relative to SMOW), and indicative of active sulfate reduction during the diagenetic (and anadiagenetic) stages of the sediments evolution. The trace element characteristics of hematite from tube microfossils are characterized by high contents of following trace elements (average, ppm): Mn (1529), As (714), V (540), W (537), Mo (35), and U (5). Such high contents are most likely the result of metal and metalloid sorption by fine particles of precursor iron hydroxides during the oxidation of sulfides and decomposition of hyaloclasts via microbially-mediated reactions.     

Geochemistry of the Manganese Ore Process in the Ocean: Evidence from Rare Earth Elements

Processes governing the formation of rare earth elements (REE) composition are considered for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different fractions) within the Clarion–Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity, the size of micronodules has a positive correlation with the Mn content and Mn/Fe and P/Fe ratios and a negative correlation with Fe, P, REE, and Ce anomaly. The behavior of REE in micronodules from sediments within bioproductive zones is related to increase of the influence of diagenetic processes in sediments as a response to the growth of the size of micronodules. Distinctions in the chemical composition of micronodules and nodules are related to their interrelations with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in the labile fraction of sediments reworked during diagenesis. Sources of the material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from the bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to the sorption of phosphate-ion from bottom and pore waters. The sorption of phosphate-ion results in an additional sorption of REE.     

A high-resolution geochemical record from Lake Edward,Uganda Congo and the timing and causes of tropical African drought during the late Holocene

High-resolution analyses of the elemental composition of calcite and biogenic silica (BSi) content in piston cores from Lake Edward, equatorial Africa, document complex interactions between climate variability and lacustrine geochemistry over the past 5400 years. Correlation of these records from Lake Edward to other climatically-forced geochemical and lake level records from Lakes Naivasha, Tanganyika, and Turkana allows us to develop a chronology of drought events in equatorial East Africa during the late Holocene. Major drought events of at least century-scale duration are recorded in lacustrine records at about 850, 1500, ∼2000, and 4100 cal year BP. Of these, the most severe event occurred between about 2050 and 1850 cal year BP, during which time Lake Edward stood about 15 m below its present level. Numerous additional droughts of less intensity and/or duration are present in the Lake Edward record, some of which may be correlated to other lacustrine climate records from equatorial East Africa. These events are superimposed on a long-term trend of increasingly arid conditions from 5400 to about 2000 cal year BP, followed by a shift toward wetter climates that may have resulted from an intensification of the winter Indian monsoon. Although the causes of decade- to century-scale climate variability in the East African tropics remain obscure, time-series spectral analysis suggests no direct linkage between solar output and regional rainfall. Rather, significant periods of ∼725, ∼125, 63–72, 31–25, and 19–16 years suggest a tight linkage between the Indian Ocean and African rainfall, and could result from coupled ocean-atmosphere variability inherent to the tropical monsoon system.     

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.     

Timing of supergene enrichment of low-grade sedimentary manganese ores in the Kalahari Manganese Field,South Africa

Low-grade carbonate-rich manganese ore of sedimentary origin in the giant Kalahari Manganese Field, South Africa, is upgraded to high-grade todorokite–manganomelane manganese ore by supergene alteration below the unconformity at the base of the Cenozoic Kalahari Formation. Incremental laser-heating ⁴⁰Ar/³⁹Ar dating of samples from the supergene altered manganese ore suggest that chemical weathering processes below the Kalahari unconformity peaked at around 27.8 Ma, 10.1 Ma and 5.2 Ma ago. Older ages are dominant in the upper part of the weathering profile, while younger ages are characteristic of the deeper part of the profile. Younger ages partially overprint older ages in the upper part of the weathering profile and demonstrate the downward progression of the weathering front by as little as 10 cm per million years. The oldest age obtained in the weathering profile, namely 42 Ma, is considered a minimum estimate for the onset of the post African I cycle of weathering and erosion that followed the break up of Gondwanaland and formation of the Cretaceous to early Cenozoic African land surface. The youngest ages, recorded at around 5 Ma, in turn, correspond well to the Pliocene transition from humid to arid climatic conditions in Southern Africa.     

Post-collisional potassic magmatism in the eastern Lhasa terrane,South Tibet: Products of partial melting of mélanges in a continental subduction channel

Post-collisional, potassic magmatic rocks widely distributed in the eastern Lhasa terrane provide significant information for comprehensive understanding of geodynamic processes of northward subduction of the Indian lithosphere and uplift of the Tibetan Plateau. A combined dataset of whole-rock major and trace elements, Sr–Nd–Pb isotopes, and in situ zircon U–Pb dating and Hf–O isotopic analyses are presented for the Yangying potassic volcanic rocks (YPVR) in the eastern part of the Lhasa terrane, South Tibet. These volcanic rocks consist of trachytes, which are characterized by high K₂O (5.46–9.30 wt.%), SiO₂ (61.34–68.62 wt.%) and Al₂O₃ (15.06–17.36 wt.%), and relatively low MgO (0.47–2.80 wt.%) and FeO_t (1.70–4.90 wt.%). Chondrite-normalized rare earth elements (REE) patterns display clearly negative Eu anomalies. Primitive mantle-normalized incompatible trace elements diagrams exhibit strong enrichment in large ion lithophile elements (LILE) relative to high field strength elements (HFSE) and display significantly negative Nb–Ta–Ti anomalies. Initial isotopic compositions indicate relatively radiogenic Sr [(⁸⁷Sr/⁸⁶Sr)_i = 0.711978–0.712090)] and unradiogenic Nd [(¹⁴³Nd/¹⁴⁴Nd)_i = 0.512121–0.512148]. Combined with their Pb isotopic compositions [(²⁰⁶Pb/²⁰⁴Pb)_i = 18.615–18.774, (²⁰⁷Pb/²⁰⁴Pb)_i = 15.708–15.793, (²⁰⁸Pb/²⁰⁴Pb)_i = 39.274–39.355)], these data are consistent with the involvement of component from subducted continental crustal sediment in their source region. The whole-rock Sr–Nd–Pb isotopic compositions exhibit linear trends between enriched mantle-derived mafic ultrapotassic magmas and relatively depleted crustal contaminants from the Lhasa terrane. The enrichment of the upper mantle below South Tibet is considered to result from the addition of components derived from subducted Indian continental crust to depleted MORB-source mantle during northward underthrusting of the Indian continental lithosphere beneath the Lhasa terrane since India–Asia collision at ~ 55 Ma. Secondary Ion Mass Spectrometry (SIMS) U–Pb zircon analyses yield the eruptive ages of 10.61 ± 0.10 Ma and 10.70 ± 0.18 Ma (weighted mean ages). Zircon Hf isotope compositions [Ɛ_Hf(t) = −4.79 to −0.17], combined with zircon O isotope ratios (5.51–7.22‰), imply an addition of crustal material in their petrogenesis. Clinopyroxene-liquid thermobarometer reveals pressure (2.5–4.1 kbar) and temperature (1029.4–1082.9 °C) of clinopyroxene crystallization, suggesting that depth of the magma chamber was 11.6–16.4 km. Energy-constrained assimilation and fractional crystallization (EC–AFC) model calculation indicates depth of assimilation and fractional crystallization in the region of 14.40–18.75 km underneath the Lhasa terrane, which is in consistent with depth of the magma chamber as suggested by clinopyroxene-liquid thermobarometer. Based on the whole-rock major and trace elements and Sr–Nd–Pb isotope compositions, combined with EC–AFC modeling simulations and zircon Hf–O isotope data, we propose that the YPVR resulted from assimilation and fractional crystallization (AFC) process of the K-rich mafic primitive magmas, which were caused by partial melting of the Indian continental subduction-induced mélange rocks.     

Electron probe microanalysis and microscopy: Principles and applications in characterization of mineral inclusions in chromite from diamond deposit

Electron probe microanalysis and microscopy is a widely used modern analytical technique primarily for quantifying chemical compositions of solid materials and for mapping or imaging elemental distributions or surface morphology of samples at micrometer or nanometer-scale. This technique uses an electromagnetic lens-focused electron beam, generated from an electron gun, to bombard a sample. When the electron beam interacts with the sample, signals such as secondary electron, backscattered electron and characteristic X-ray are generated from the interaction volume. These signals are then examined by detectors to acquire chemical and imaging information of the sample. A unique part of an electron probe is that it is equipped with multiple WDS spectrometers of X-ray and each spectrometer with multiple diffracting crystals in order to analyze multiple elements simultaneously. An electron probe is capable of analyzing almost all elements (from Be to U) with a spatial resolution at or below micrometer scale and a detection limit down to a few ppm.Mineral inclusions in chromite from the Wafangdian kimberlite, Liaoning Province, China were used to demonstrate the applications of electron probe microanalysis and microscopy technique in characterizing minerals associated with ore deposits, specifically, in this paper, minerals associated with diamond deposit. Chemical analysis and SE and BSE imaging show that mineral inclusions in chromite include anhydrous silicates, hydrous silicates, carbonates, and sulfides, occurring as discrete or single mineral inclusions or composite multiple mineral inclusions. The chromite–olivine pair poses a serious problem in analysis of Cr in olivine using electron probe. Secondary fluorescence of Cr in chromite by Fe in olivine drastically increases the apparent Cr₂O₃ content of an olivine inclusion in a chromite. From the chemical compositions obtained using electron probe, formation temperatures and pressures of chromite and its mineral inclusions calculated using applicable geothermobarometers are from 46 kbar and 980 °C to 53 kbar and 1130 °C, which are within the stability field of diamond, thus Cr-rich chromite is a useful indication mineral for exploration of kimberlite and diamond deposit. A composite inclusion in chromite composed of silicate and carbonate minerals has a bulk composition of 33.2 wt.% SiO₂, 2.5 wt.% Al₂O₃, 22.0 wt.% MgO, 7.5 wt.% CaO, 2.5 wt.% BaO, 0.8 wt.% K₂O, 25.5 wt.% CO₂, and 0.8 wt.% H₂O, similar to the chemical composition of the Wafangdian kimberlite, suggesting that it is trapped kimberlitic magma.     

Structural controls and timing of fault-hosted manganese at Woodie Woodie,East Pilbara,Western Australia

High-grade fault-hosted manganese deposits at the Woodie Woodie Mine, East Pilbara, are predominantly hydrothermal in origin with a late supergene overprint. The dominant manganese minerals are pyrolusite, braunite, and cryptomelane. The ore bodies are located on, or near the unconformities between the Neoarchean Carawine Dolomite and the Paleoproterozoic Pinjian Chert breccia (weathering product of Carawine Dolomite), and sedimentary units of the overlying ca 1300–1100 Ma Manganese Group. Stratabound manganese is typically located above or adjacent to steep fault-hosted manganese. The ore bodies range in size from 0.2 to 5.5 Mt with an average of 0.5 Mt. Historically, over 35 Mt of manganese has been mined at Woodie Woodie, and current ore resources are 29.94 Mt at 39.94% Mn, 6.96% Fe (resource and reserves statement, June 2011, Consolidated Minerals Pty Ltd).Manganese mineralization at Woodie Woodie is related to northwest–southeast directed extension and basin formation during the Mesoproterozoic. Basin architecture is generally well preserved and major manganese occurrences are localised along growth faults which down-throw the Pinjian Chert Breccia into local extensional basins. Manganese ore bodies are typically located on steep 2nd and 3rd order structures that extend off the major growth faults. Mineralized structures display a dominant northeast-trend reflecting the direction of maximum dilation during northwest–southeast extension.A paragenetic sequence is identified for the manganese ore at Woodie Woodie, with early hydrothermal braunite–pyrolusite–cryptomelane–todorokite–hausmannite, overprinted by late supergene oxides. Preliminary fluid inclusion studies in quartz crystals intergrown with pyrolusite and cryptomelane indicate that primary and pseudosecondary inclusions display a range of salinities from 1 to 18 eq. wt.% NaCl and trapping temperatures estimated to be from 220º to 290º at 1 kbar pressure.A lead–manganese oxide (coronadite) is common in manganese ores at Woodie Woodie, and Pb-isotope studies of 40 lead-rich ore samples from 16 pits indicate mineralization occurred within an age range of 955–1100 Ma. A mixed source is suggested for the lead, but was predominantly basalts and/or volcanogenic sedimentary units (e.g., Jeerinah Formation) of the ca 2700 Ma Fortescue Group. The typically high Mn:Fe ratios and enrichment in elements such as Pb, As, Cu, Mo, Zn are consistent with a dominantly hydrothermal origin for the manganese at Woodie Woodie. Supergene manganese is distinguished from hypogene manganese by a marked enrichment in REE in the supergene manganese.An early structural framework, established during Neoarchean rifting, provides a major structural control on manganese ore distribution. The Woodie Woodie mine corridor is located in a zone of oblique strike-slip extension on major northwest-trending transform faults and north-trending oblique normal faults. A major transform structure at the southern end of the Woodie Woodie mine corridor (Jewel-Southwest Fault Zone) likely acted as a major fluid conduit for manganese-bearing hydrothermal fluids and this would account for the concentration of significant manganese ore occurrences to the north and south of this structure.     

Geochemistry and mineralogy of REY-rich mud in the eastern Indian Ocean

Deep-sea sediments in parts of the Pacific Ocean were recently found to contain remarkably high concentrations of rare-earth elements and yttrium (REY) of possible economic significance. Here we report similar REY-rich mud in a core section from Deep Sea Drilling Project Site 213 in the eastern Indian Ocean. The sediments consist mainly of siliceous ooze, with subordinate zeolitic clay that contains relatively high REY concentrations. The maximum and average total REY (ΣREY) contents of this material are 1113 and 629 ppm, respectively, which are comparable to those reported from the Pacific Ocean. The REY-rich mud at Site 213 shows enrichment in heavy rare-earth elements, negative Ce anomalies, and relatively low Fe₂O₃/ΣREY ratios, similar to those in the Pacific Ocean. In addition, the major-element composition of the Indian Ocean REY-rich mud indicates slight enrichment in lithogenic components, which probably reflects a contribution from southern African eolian dust. A volcaniclastic component from neighboring mid-ocean ridges or intraplate volcanoes is also apparent. Elemental compositions and X-ray diffraction patterns for bulk sediment, and microscopic observation and elemental mapping of a polished thin section, demonstrate the presence of phillipsite and biogenic apatite, such as fish debris, in the REY-rich mud. The strong correlation between total REY content and apatite abundance implies that apatite plays an important role as a host phase of REY in the present deep-sea sediment column. However, positive correlations between ΣREY and elements not present in apatite (e.g., Fe₂O₃, MnO, and TiO₂) imply that the REY-rich mud is not formed by a simple mixture of REY-enriched apatite and other components.     

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.     

Paleomagnetic study of ferromanganese crusts recovered from the northwest Pacific — Testing the applicability of the magnetostratigraphic method to estimate growth rate

Previous studies have shown that ferromanganese crusts in the Pacific Ocean commonly record paleomagnetic reversals and that the reversal patterns can be used to estimate growth rates. In order to investigate the applicability of the magnetostratigraphic method, we conducted paleomagnetic measurements of crust samples recovered from five locations in the northwest Pacific. A series of thin slices, with thicknesses of 0.5–1.0 mm, was prepared for each sample, and a paleomagnetic polarity was determined for each slice. In all five samples, we found a consistent reversal pattern of N1–R1–N2–R2–N3 from the surface to the inner part of the crust. In three samples, another polarity interval (R3) was recognized below the N3 section of the crust. These data suggest that ferromanganese crusts in the northwest Pacific recorded paleomagnetic reversals and that reversal patterns can be used for ocean-scale correlations. The magnetostratigraphic method suggests constant growth rates of 1.49, 2.54, 3.56 and 3.67 mm/Ma for four samples, three of which are consistent with those estimated using ¹⁰Be/⁹Be dating at the 2σ (standard deviation) level.