Geochemistry and Origin of Layers in Single Manganese Nodule from the Philippine Sea and Manganese Nodules from Offshore Minami-Torishima,Western Pacific

Layers from one manganese nodule dredged from the Philippine Sea(16°56'N, 129°48'E; water depth, 5700 m) and 45 bulk nodules from offshore Minami-Torishima Island, Japan(23°3'N, 153°22'E; water depth, 1200 m) were analyzed chemically and their origin is discussed based on geochemical constraints. In general, Cu, Ni, Zn and Mo tend to increase with increasing Mn content, while Co, Pb, Ba, V, Sc, Th, and the rare earth elements(REEs) show less variation with increasing Mn content. Nodule 42 H from the Philippine Sea has an average Mn/Fe ratio close to 1 and shows a positive Ce anomaly, suggesting a predominant hydrogenous origin. Profiles of 230Th230 ex and Thex/232 Th ratios in the outer ~0.3 mm of nodule 42 H indicate a steady growth rate of ~1.7 mm/Myr. Nodule E30 from offshore Minami-Torishima is characterized by lower Mn, Fe, Mn/Fe(0.53) and Mo/V(0.2) ratios but higher P and Cu/Ni(0.31) ratio relative to other nodules from that area. The Ce content of E30 is unusually low(82 ppm) when compared with other nodules from the area and it is the only nodule analyzed with a negative Ce anomaly(-0.64). Based on the geochemical data we suggest that most nodules from offshore Minami-Torishima are primarily of hydrogenous origin except E30, which is dominated by hydrothermal input, and E45, which has about a 35% hydrothermal contribution.     

Rare elements and Nd and Sr isotopic composition in micronodules from the Brazil Basin,Atlantic Ocean

The Sr isotope stratigraphy of the biogenic apatite was used to determine the age of pelagic sediments in the Brazil Basin (Station 1541) that contain ferromanganese micronodules, nodules, and coatings on the weathered volcanic rocks. The age of sediments at horizons 0–5 and 86–90 cm was estimated at 24.1 ± 0.2 Ma and 24.8 ± 0.2 Ma, respectively. The average sedimentation rate in the Late Oligocene was about 13 mm/ka. The hydrogenous Fe–Mn nodule on the sediment surface with the Mn/Fe value of 1.05–1.95 was formed at a rate of 1.2–2.4 mm/Ma, which is 1000 times lower than the growth rate of buried nodule (Mn/Fe 0.4) at depth of 83 cm. Diagenesis provoked changes in the mineral composition of the buried nodule (asbolane-buserite partially replaced by goethite), leading to the loss of a part of Mn, Ni, Li, and Tl but accumulation of trace elements linked with iron oxyhydroxides (Ce, Th, Be, As, and V) were retained. The composition of manganese micronodules at two studied depths in sediments evolved in the course of two stages of ore formation: related to the oxic and suboxic diagenesis. The Sr isotopic composition in manganese micronodules from both horizons do not differ from that of dissolved Sr in the ocean water. The ¹⁴³Nd/¹⁴⁴Nd ratio, which reflects the Nd isotopic composition in the paleocean during the micronodule formation, varies in manganese micronodules from different horizons and is constant in different size fractions.     

Chronology of Late Weichselian glaciation in the western part of the East European Plain

A database consisting of radiocarbon (¹⁴C), optically stimulated luminescence (OSL), thermoluminescence (TL) and beryllium (¹⁰Be) dates was used for timing the advance of the Late Weichselian Scandinavian Ice Sheet (SIS), determining the age of the Last Glacial Maximum (LGM) and the rate of deglaciation. The study area encompasses the southeastern sector of the last SIS between the Baltic Sea and the LGM position in the western part of the East European Plain, covering the Karelian Ice‐Stream Complex (ISC) area in the east and the Baltic ISC area in the west. The linear advance and recession rates of the last SIS were estimated to be between 110 and 330 m a^?1 and between 50 and 170 m a^?1, respectively. The onset of the last SIS in the Karelian ISC area reached the western shores of Latvia not before 26 OSL ka, and in the Baltic ISC area, on the southern shores of the Gulf of Finland, not before 21 OSL ka. The last SIS reached close to the LGM position earliest in NW Belarus, not earlier than 22.6 cal. ¹⁴C ka BP, and latest in the NE of Belarus, not earlier than 19.1 cal. ¹⁴C ka BP. The Baltic ISC area between the LGM position and the western shores of Latvia was deglaciated in about 8 ka, and in the Karelian ISC area, between the LGM position and the southern shores of the Gulf of Finland, in about 2.6 ka. The whole area between the LGM position and the Baltic Sea was deglaciated between 14.2 ¹⁰Be ka and 13.3 cal. ¹⁴C ka BP.     

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.     

Non-destructive alpha-spectrometry and radiochemical studies of deep-sea manganese nodules

A deep-sea Mn nodule handpicked from top of a 20 cm diameter North Pacific tripod core was directly counted by an α-spectrometer with a silicon surface barrier detector. A distinct ²¹⁰Po peak was recorded for the nodule upper side in contact with bottom seawater. Based on the spectrum, the ²¹⁰Po (supported by ²¹⁰Pb with 22 year half life) is thought to be confined in the top few microns of the nodule. Since the ²¹⁰Po peak diminishes considerably for the bottom side resting on sediment, nondestructive α-spectrometry is useful for determining the sea floor orientation of nodules. This method was tested for a western North Pacific dredged Mn nodule, and was successful in identifying the orientation (and also surface loss of the nodule by dredging).Radiochemical analysis was also carried out for carefully scraped samples from the top and bottom of the two nodules. The growth rates of the hand-picked nodule based on excess ²³⁰Th and ²³¹Pa profiles were 1 to 4 mm/10⁶ y and apparently varied with time. The dredged sample has grown at 2 to 6 mm/ 10⁶ y and the growth has likely been episodic. The radionuclide composition was significantly different between the top and bottom. Evidence was found that the radionuclide fluxes of ²³⁰Th and ²³¹Pa into the nodules considerably changed during the growing histories. The ²³⁰Th/²³²Th activity ratios in the nodule tops are comparable with those in bottom seawater suggesting that the top is growing with metals of seawater origin. However it remains unresolved whether the nodule bottoms are growing by utilizing metals in the sediment pore water.     

Deposition of deep-sea manganese nodules

Manganese at equilibrium in seawater occurs dominantly as Mn²⁺ and inorganic complexes at a concentration ratio of about 1:0.72; solubility decreases exponentially with increasing pH or Eh. However, the nodule oxides birnessite and todorokite are at least four orders of magnitude undersaturated relative to the Mn concentrations of seawater, and are metastable relative to hausmannite and manganite. This apparent lack of equilibrium is explicable by the mechanism of precipitation.Surfaces assist Mn precipitation by catalyzing equilibration between dissolved and reactive O₂ and simultaneously also by adsorbing ionic Mn species. The effective Eh at the surface becomes 200–400 mV above that of seawater; the oxidation rate of Mn increases about 10⁸ ×, and the activation energies for Mn oxidation decrease ~ 11.5 kcal/mole. Consequently, marine Mn nodules and crusts form by adsorption and catalytic oxidation of Mn²⁺ and ferrous ions at nucleating surfaces such as sea-floor silicates, oxyhydroxides, carbonates, phosphates and biogenic debris. The resulting ferromanganese surfaces autocatalyze further growth. In addition, Mn-fixing bacteria may also significantly accelerate accretion rates on these surfaces.Mn which accumulates in submarine sediments may be diagenetically recycled in response to steep solubility gradients causing upward migration from more acidic and reducing horizons toward the sea floor. In contrast, the concentrations of the predominant ferric complexes, Fe(OH)₃⁰ and Fe(OH)₄^?, are relatively less sensitive to the Eh's and pH's found in this environment; Fe is therefore not as readily recycled within buried sediments. Consequently, Fe is not so effectively enriched on the sea floor, although it precipitates more readily than Mn because seawater is saturated in amorphous Fe(OH)₃.The metastable, perhaps kinetically-related, Mn oxides of nodules have a characteristic distribution: birnessite predominates in oxidizing environments of low sedimentation rate and todorokite where sedimentation rates and diagenetic Mn mobility are higher. Surface adsorption and cation substitution within the disordered birnessite-todorokite structure account for the high trace element content of Mn nodules.     

Sources of osmium to the modern oceans: new evidence from the Pt-Os system

High precision Os isotope analysis of young marine manganese nodules indicate that whereas the composition of modern seawater is radiogenic with respect to ¹⁸⁷Os/¹⁸⁸Os, it has ¹⁸⁶Os/¹⁸⁸Os that is within uncertainty of the chondritic value. Marine Mn nodule compositions thus indicate that the average continental source of Os to modern seawater had long-term high Re/Os compared to Pt/Os. Analyses of loess and freshwater Mn nodules support existing evidence that average upper continental crust (UCC) has resolvably suprachondritic ¹⁸⁶Os/¹⁸⁸Os, as well as radiogenic ¹⁸⁷Os/¹⁸⁸Os. Modeling the composition of seawater as a two-component mixture of oceanic/cosmic Os with chondritic Os compositions and continentally-derived Os demonstrates that, insofar as estimates for the composition of average UCC are accurate, congruently weathered average UCC cannot be the sole continental source of Os to seawater. Our analysis of four Cambrian black shales confirm that organic-rich sediments can have ¹⁸⁷Os/¹⁸⁸Os ratios that are much higher than average UCC, but ¹⁸⁶Os/¹⁸⁸Os compositions that are generally between those of chondrites and average-UCC. Preferential weathering of black shales can result in dissolved Os discharged to the ocean basins that has a much lower ¹⁸⁶Os/¹⁸⁸Os than does average upper crust. Modeling the available data demonstrates that augmentation of estimated average UCC compositions with less than 0.1% additional black shale and 1.4% additional ultramafic rock can produce a continental end-member Os isotopic composition that satisfies the requirements imposed by the marine Mn nodule data. The interplay of these two sources provides a mechanism by which the ¹⁸⁷Os/¹⁸⁸Os of seawater can change as sources and weathering conditions change, yet seawater ¹⁸⁶Os/¹⁸⁸Os varies only minimally.     

Radiochemical observations on manganese nodules from three sedimentary environments in the north Pacific

Decay-series isotopes were measured on manganese nodules from three sedimentary environments, characterized by substrates of red clay (R), siliceous ooze (S) and hemipelagic clay (H). Growth rates of nodules are shown to be site dependent: 1–2 mm/Myr at site R, 3–8 mm/Myr at sites S, and 20–50 mm/ Myr at site H. Correlation between growth rate and the parameter Mn/Fe² suggests that regional diagenetic variations control the compositions and growth rates of the nodules. The frequency of nodule turnover and the period of their growth are assessed from the “top” vs. “bottom” distributions of several nuclides. Based on the ²³⁰Th, ²³¹Pa and ²²⁶Ra data, turnover times of 10³ to 10⁵ years are estimated and they vary with relative size and shape of the specimens at a given site. The presence of unsupported ²¹⁰Pb and ²²⁸Th in the top surfaces but not in the bottom surfaces of the surface nodules suggests active growth during the last decades or years, despite their old ages. The data also indicate that turnover rates are not more frequent than once every several years or decades.The ²³⁰Th-²²⁶Ra, ²²⁶Ra-²¹⁰Pb and ²³²Th-²²⁸Th disequilibrium relationships in the nodules allow the migratory behavior of ²²⁶Ra, ²²²Rn and ²²⁸Ra and their fluxes to be deduced: thus radium leaves the top sides but enters the bottom sides of the surface nodules at sites R and S. At site R there is a net loss of radium to the sea; the opposite is true at site S. Surface nodules at site H trap radium from both sides, probably due to more intense diagenetic input of radium from sediment pore water. The effective diffusivities of ²²⁶Ra in nodules vary from $\text{3 × 10}{}^{\mathrm{?12}}$ to $\text{8 × 10}{}^{\mathrm{?14}}$ cm²/s, dependent on the textural variation of the nodule material, which crudely reflects the growth rate and hence sedimentary environment. ²²²Rn diffuses out of nodules from all sides, with an effective diffusivity of ca. $\text{(2–6) × 10}{}^{\mathrm{?8}}\text{cm}{}^2\text{/s}$. At all sites nodules serve as a more effective source of ²²²Rn to sea water than their adjacent sediments. The outward flux of ²²²Rn from nodules relative to that from adjacent sediments tends to be higher in more reduced environments, an effect caused by the fact that Mn-rich nodules from more reduced environment act as a more efficient trap for ²²⁶Ra.     

Tropical glacier fluctuations in the Cordillera Blanca,Peru between 12.5 and 7.6 ka from cosmogenic 10Be dating

We report cosmogenic surface exposure ¹⁰Be ages of 21 boulders on moraines in the Jeullesh and Tuco Valleys, Cordillera Blanca, Peru (～10°S at altitudes above 4200 m). Ages are based on the sea-level at high-latitude reference production rate and scaling system of Lifton et al. (2005. Addressing solar modulation and long-term uncertainties in scaling secondary cosmic rays for in situ cosmogenic nuclide applications. Earth and Planetary Science Letters 239, 140–161) in the CRONUS-Earth online calculator of Balco et al. (2008. A complete and easily accessible means of calculating surface exposure ages or erosion rates from ¹⁰Be and ²⁶Al measurements. Quaternary Geochronology 3, 174–195). Using the Lifton system, large outer lateral moraines in the Jeullesh Valley have a ¹⁰Be exposure age of 12.4 ka, inside of which are smaller moraine systems dated to 10.8, 9.7 and 7.6 ka. Large outer lateral moraines in the Tuco Valley have a ¹⁰Be exposure age of 12.5 ka, with inner moraines dated to 11.3 and 10.7 ka. Collectively, these data indicate that glacier recession from the Last Glacial Maximum (LGM) in the Cordillera Blanca was punctuated by three to four stillstands or minor advances during the period 12.5–7.6 ka, spanning the Younger Dryas Chronozone (YDC; ～12.9–11.6 ka) and the cold event identified in Greenland ice cores and many other parts of the world at 8.2 ka. The inferred fluctuations of tropical glaciers at these times, well after their withdrawal from the LGM, indicate an increase in precipitation or a decrease in temperature in this region. Although palaeoenvironmental records show regional and temporal variability, comparison with proxy records (lacustrine sediments and ice cores) indicate that regionally this was a cold, dry period so we ascribe these glacier advances to reduced atmospheric temperature rather than increased precipitation.     

Thorium and uranium isotopes in a manganese nodule from the Peru basin determined by alpha spectrometry and thermal ionization mass spectrometry (TIMS): Are manganese supply and growth related to climate?

Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution²³⁰Th_excess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06–0.59 ppb (²³⁰Th), 0.43–1.40 ppm (²³²Th), 0.09–0.49 ppb (²³⁴U) and 1.66–8.24 ppm (²³⁸U). The uranium activity ratio in the uppermost samples (1–6 mm) and in two further sections in the nodule at 12.5±1.0 mm and 27.3–33.5 mm comes close to the present ocean water value of 1.144±0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the²³⁰Th_excess concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant²³⁰Th_excess concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11–15 and 28–33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.     

Petrology of mafic lavas within the Onega plateau, central Karelia: evidence for 2.0 Ga plume-related continental crustal growth in the Baltic Shield

The Onega plateau constitutes part of a vast continental flood basalt province in the SE Baltic Shield. It consists of Jatulian-Ludikovian submarine volcanic, volcaniclastic and sedimentary sequences attaining in places 4.5?km in thickness. The parental magmas of the lavas contained ～10% MgO and were derived from melts generated in the garnet stability field at depths 80–100?km. The Sm-Nd mineral and Pb-Pb whole-rock isochron ages of 1975?±?24 and 1980?±?57 Ma for the upper part of the plateau and a SHRIMP U-Pb zircon age of 1976?±?9 Ma for its lower part imply the formation of the entire sequence within a short time span. These ages coincide with those of picrites in the Pechenga-Imandra belt (the Kola Peninsula) and komatiites and basalts in the Karasjok-Kittilä belt (Norway and Finnmark). Together with lithostratigraphic, chemical and isotope evidence, these ages suggest the derivation of the three provinces from a single large (～2000?km in diameter) mantle plume. These plume-generated magmas covered ～600,000?km² of the Baltic Shield and represent a major contribution of juvenile material to the existing continental crust at 2.0 Ga. The uppermost Onega plateau lavas have high (Nb/Th)_N?=?1.4–2.4, (Nb/La)_N= 1.1–1.3, positive ?Nd(T) of +3.2 and unradiogenic Pb-isotope composition (μ₁?= 8.57), comparable with those of modern oceanic plume-derived magmas (oceanic flood basalt and ocean island basalt). These parameters are regarded as source characteristics. The lower sequences have (Nb/Th)_N= 0.58–1.2, (Nb/La)_N= 0.52–0.88 and ?Nd(T) =?2.6. They have experienced mixing with 10–30% of continental crust and resemble contaminated lavas from other continental flood basalt provinces. The estimated Nb/U ratios of 53?±?4 in the uncontaminated rocks are similar to those found in the modern mantle (～47) suggesting that by 2.0 Ga a volume of continental crust similar to the present-day value already existed.     

Critical metals in manganese nodules from the Cook Islands EEZ,abundances and distributions

The Cook Islands (CIs) Exclusive Economic Zone (EEZ) encompasses 1,977,000 km² and includes the Penrhyn and Samoa basins abyssal plains where manganese nodules flourish due to the availability of prolific nucleus material, slow sedimentation rates, and strong bottom currents. A group of CIs nodules was analyzed for mineralogical and chemical composition, which include many critical metals not before analyzed for CIs nodules. These nodules have varying sizes and nuclei material; however all are composed predominantly of δ-MnO₂ and X-ray amorphous iron oxyhydroxide. The mineralogy, Fe/Mn ratios, rare earth element contents, and slow growth rates (mean 1.9 mm/10⁶ years) reflect formation primarily by hydrogenetic precipitation. The paucity of diagenetic input can be explained by low primary productivity at the surface and resultant low organic matter content in seafloor sediment, producing oxic seafloor and sub-seafloor environments. The nodules contain high mean contents of Co (0.41%), Ni (0.38%), Ti (1.20%), and total rare earth elements plus yttrium (REY; 0.167%), and also high contents of Mo, Nb, V, W, and Zr.Compiled data from a series of four cruises by the Japan International Cooperation Agency and the Mining agency of Japan from 1985 to 2000 were used to generate a map that defines the statistical distribution of nodule abundance throughout the EEZ, except the Manihiki Plateau. The abundance distribution map shows a belt of high nodule abundance (19–45 kg/m²) that starts in the southeast corner of the EEZ, runs northwest, and also bifurcates into a SW trending branch. Small, isolated areas contain abundances of nodules of up to 58 kg/m². Six ~ 20,000 km² areas of particularly high abundance were chosen to represent potential exploration areas, and maps for metal concentration were generated to visualize metal distribution and to extrapolate estimated metal tonnages within the six sites and the EEZ as a whole. Grades for Mn, Cu, and Ni are low in CIs nodules in areas of high abundance; however, Ti, Co, and REY show high contents where nodule abundances are high. Of the six areas identified to represent a range of metal contents, one at the northern end of the N-S abundance main belt optimizes the most metals and would yield the highest dry metric tons for Mn (61,002,292), Ni (1,247,834), Mo (186,166), V (356,247), W (30,215), and Zr (195,323). When compared with the Clarion–Clipperton Zone, the CIs nodules show higher nodule abundances (> 25 kg/m² over ~ 123,844 km²), and are more enriched in the green-tech, high-tech, and energy metals Co, Ti, Te, Nb, REY, Pt, and Zr. The CIs EEZ shows a significant resource potential for these critical metals due to their high prices, high demand, and the high nodule abundance, which will allow for a smaller footprint for a 20-year mine site and therefore smaller environmental impact.     

Diagenetic mobilization of manganese in Peru Basin sediments

The Mn contents and sedimentation rates of two cores from different areas of the Peru Basin have been determined. The southern core is associated with Mn nodules of conventional slow accretion rates (~ mm/10⁶ yr) while the northern one accompanies nodules with very high growth rates (~10² mm/10⁶ yr). The depletion of Mn observed within the top 40 cm of the cores is interpreted as resulting from a diagenetic remobilization of Mn⁺² due to the oxidative characteristics of the sedimentary column. In both cores, the calculated flux of Mn provided by the sediment is higher than the total Mn recovered in the overlying nodules. This indicates that the Mn content of the Peru Basin nodules can be supplied by diagenetic processes from the sediment, not only for the slowly growing nodules but also for the extremely fast growing concretions found in the north of the basin.     

Geochemical and mineralogical control of different genetic types of deep-sea nodules from the Pacific Ocean

Deep-sea nodules from the Northeast Pacific nodule belt and the Southeast Pacific (Sonne Basin), being formed in areas bordering the equatorial zone of high biological productivity, accumulate by two basically different growth processes: (A) early diagenetic growth by supply from pore water and (B) hydrogenetic growth by supply from near-bottom sea-water. These growth processes lead to different genetic types of nodules: early diagenetic type A, hydrogenetic type B, and mixed-type AB; a further type A_C, very rich in Mn, is being formed by increasing influence of early diagenesis. These types can clearly be distinguished by their shapes, surface textures, mineral constituents of oxide fraction, internal microstructures, and geochemistry. A genetical classification is being proposed on the basis of statistically computed interelement relationships. Todorokite, very poor in Fe, is the main Mn phase in the early diagenetic substance; -MnO₂ intimately intergrown with FeOOH · xH₂O is the main phase in the hydrogenetic substance. Consequently an important difference can be pointed out: the metal supply for the growth of the early diagenetic nodules is based on an ionic solution of Me²⁺ (e. g. Mn²⁺, Ni²⁺, Cu²⁺, Zn²⁺), whereas the supply for the hydrogenetic nodules is caused by transport of colloidal particles. Mobilization of Mn²⁺ and fractionation from Fe is controlled by the amount of decomposing organic matter in the "peneliquid" layer of the sediments. The main factor controlling the intensity of early diagenesis is the biological productivity in surface waters. The crucial "point of reversal" at a Mn/Fe ratio of about 5, obtained by hyperbolical regression of the analyses of nodules from the Southeast Pacific, represents best concentrations in Ni and Cu. Mn/Fe quotients greater than 5 cause a decrease of Ni and Cu content. Nodules from the Northeast Pacific nodule belt generally contain higher concentrations in Cu than nodules from the Southeast Pacific. This can be explained by an additional supply of Cu transported below CCD by siliceous plankton.     

Origin of spheroidal chert nodules, Drunka Formation (Lower Eocene), Egypt

Chert nodules of the Drunka Formation (Lower Eocene) are mostly spherical, have diameters from 40 to 120 cm, are quasi-uniformly spaced 2–3 m apart in the plane of bedding, have concentric internal structure and, except for rare small (<6 cm) solid chert nodules, are less than 85% chertified. Nodules formed after moderate alteration of limestone by meteoric water (δ¹⁸O_calcite = –4 to –8‰) at shallow (<100 m) burial depths; more extensive alteration of limestone (δ¹⁸O = –10 to –16‰) by meteoric water followed nodule growth. Chertification was by low-temperature meteoric water (δ¹⁸O_quartz = +18‰ in margins to +22‰ in nuclei) at shallow burial depths. Meteoric water may have invaded the Drunka Formation in association with shelf progradation during the Early Eocene, or during the development of a Middle Eocene unconformity. Replacement of carbonate mud by microcrystalline quartz was the dominant chertification process, but fossils were replaced in part by fine-grained equant megaquartz, quartzine and chalcedony; the last of these occurs in places as beekite. Opal A-secreting marine organisms are the inferred source of silica, but none are preserved. There is no compelling evidence of an opal-CT precursor, so quartz may have formed by direct precipitation. Self-organization processes of enigmatic character established the spacing pattern of the nodules and also the Liesegang-banded internal structure of the chert nodules. Nodules grew chiefly by diffusive supply of silica, although one locality has elongate nodules that grew when there was some porewater advection. Chertification patterns and δ¹⁸O values of both calcite and quartz indicate that nodule growth was complex and variable. Some nodules probably grew from the centre outwards. Many nodules, however, initially grew simultaneously across the entire nodule, but late-stage growth was predominantly at the outer margins or at selective internal sites.     

Composition of manganese nodules and manganese carbonates from Loch Fyne,Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn_47.7 Ca_45.1 Mg_7.2) CO₃. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.     

南海边缘海多金属结核与大洋多金属结核对比

本文通过系统对比分析前人研究成果,研究了南海边缘海多金属结核的成矿特征,结果表明：南海边缘海结核的矿物组成与大洋结核相似,均主要由锰相矿物和铁相矿物组成,其中锰相矿物主要为水羟锰矿和钡镁锰矿,铁相矿物主要以无定型铁氧化/氢氧化物形式存在,另外南海边缘海结核中含有大量硅酸盐矿物,表明在南海结核成矿过程中受到大量的陆源碎屑矿物混杂;相对于大洋主要经济成矿区的多金属结核,南海边缘海多金属结核中主要的经济元素如Mn、Cu、Co、Ni和Zn质量分数较低,而亲陆源性元素如Fe、Ti、P、Nb、Pb、Rb、Sc、Ta、Sr、Th和REY（REE和Y）等质量分数较高;南海边缘海多金属结核的元素地球化学特征和REE配分模式显示其为水成成因,并呈现更低的Mn/Fe值;同时南海边缘海结核也具有较快的平均生长速率及较高的δCe正异常,表明其生长在更为氧化的海水环境。虽然较快的沉积物沉积速率和动荡的海水环境影响了南海边缘海结核的成矿,但大量陆源物质进入海洋也为南海边缘海结核提供了丰富的成矿物质来源,便于南海边缘海结核的快速生长成矿。南海边缘海结核富集有Fe、Ti、Pb、Rb、Th和REY等金属元素,同样可以作为极具潜力的海洋矿产资源。南海边缘海多金属结核具有其独特的地球化学特征,与大洋多金属结核存在着明显差异。     

Helium accumulation in groundwater,I: An evaluation of sources and the continental flux of crustal 4He in the Great Artesian Basin,Australia

The rate of accumulation of ⁴He in the groundwaters of the J-aquifer of the Great Artesian Basin, Australia has been determined using ¹⁴C and hydrologic ages. For groundwaters less than 50 Kyr in age, the ⁴He accumulation rate is 4.6 × 10^?12 HeAU (where ) in close agreement with in-situ production rate of ⁴He (3.95 × 10^?12 HeAU) based on U and Th concentrations of 1.7 and 6.1, respectively, of the sandstone. For groundwaters older than 100 Kyr, the rate of ⁴He accumulation is 2.91 × 10^?10 HeAU based on hydrologic ages; or 74 × the rate of in-situ production. The rate of ⁴He “production” due to weathering of the aquifer rock is calculated to be ~10^?16 HeAU, indicating that the weathering input of ⁴He is insignificant. If the groundwater of the GAB can be considered as a trap for the total crustal production of ⁴He, the rate of ⁴He accumulation under a steady-state flux is calculated to be 3.02 × 10^?10 HeAU, in agreement with the measured accumulation rate. It is concluded that over long times the ⁴He accumulation rate in groundwater aquifers may be controlled by the whole crust flux of ⁴He.     

Paired bedrock and boulder 10Be concentrations resulting from early Holocene ice retreat near Jakobshavn Isfjord,western Greenland

We measured in situ cosmogenic ¹⁰Be in 16 bedrock and 14 boulder samples collected along a 40-km transect outside of and normal to the modern ice margin near Sikuijuitsoq Fjord in central-west Greenland (69°N). We use these data to understand better the efficiency of glacial erosion and to infer the timing, pattern, and rate of ice loss after the last glaciation. In general, the ages of paired bedrock and boulder samples are in close agreement (r² = 0.72). Eleven of the fourteen paired bedrock and boulder samples are indistinguishable at 1σ; this concordance indicates that subglacial erosion rates are sufficient to remove most or all ¹⁰Be accumulated during previous periods of exposure, and that few, if any, nuclides are inherited from pre-Holocene interglaciations. The new data agree well with previously-published landscape chronologies from this area, and suggest that two chronologically-distinct land surfaces exist: one outside the Fjord Stade moraine complex (～10.3 ± 0.4 ka; n = 7) and another inside (～8.0 ± 0.7 ka; n = 21). Six ¹⁰Be ages from directly outside the historic (Little Ice Age) moraine show that the ice margin first reached its present-day position ～7.6 ± 0.4 ka. Early Holocene ice margin retreat rates after the deposition of the Fjord Stade moraine complex were ～100–110 m yr^?1. Sikuijuitsoq Fjord is a tributary to the much larger Jakobshavn Isfjord and the deglaciation chronologies of these two fjords are similar. This synchronicity suggests that the ice stream in Jakobshavn Isfjord set the timing and pace of early Holocene deglaciation of the surrounding ice margin.     

Cosmogenic isotope and track records in meteorites and their implications to cosmic ray fluxes

Study of several cosmic ray effects, such as VH track density, spallogenic²⁶Al and⁵³Mn activity,²¹Ne and²²Ne/²¹Ne ratio, made in the same sample or in cores taken from different meteorites can identify parameters related to the exposure history of meteorites and cosmic ray flux variations. Meteorites with single or multiple exposure can be distinguished from a track production rate —²²Ne/²¹Ne correlation diagram and cosmic ray flux variations over 10⁶–10⁷ years can be deduced from a three-isotope correlation diagram of²⁶Al,⁵³Mn and²¹Ne. Isotopic data based on chondrites with simple, one-stage exposure are consistent with the same average galactic cosmic ray intensity over the past 2 million years as that during the past 10⁷ years.