Formation of todorokite from vernadite in Ni-rich hemipelagic sediments

Todorokite is considered to form from vernadite in nature and commonly concentrates nickel. However, this mineralogical transformation has never been imaged nor explained mechanistically, and its effect on the uptake of nickel has never been quantified at the molecular-level. We have characterized these reactions at the macroscopic, microscopic, nanoscopic and atomic scales in a marine manganese concretion by combining transmission electron microscopy, electron and X-ray microprobe analysis, powder and micro X-ray diffraction, and Mn and Ni K-edge EXAFS spectroscopy. The concretion was collected during the Ticoflux II expedition near the Nicoya Peninsula, Costa Rica, and is representative of Mn deposits in hemipelagic sediments. It consists of 5 to 25 μm aggregates, shaped like sea-urchins, with a core of 7Å-vernadite (1.0 wt% Ni), a rim of 10Å-vernadite (3.8 wt% Ni), and an outermost region of todorokite fibers (1.9 wt% Ni) that extend outwards. The crystallites of 7Å-vernadite are single- to bi-layered, with hexagonal layer symmetry (a = b = 2.83 Å), and an average structural formula of . The crystallites of 10Å-vernadite contain 10 to 20 layers semi-coherently stacked in the ab plane and uniformly separated in the [0 0 1] direction by ∼9 Å due to the intercalation of hydrated Mg²⁺ cations. The average structural formula of 10Å-vernadite is if the layers contain vacancy sites, or alternately , if they contain Mn³⁺. The average formula of todorokite is .A genetic model is proposed based on combining these new data with previously published results. The thermodynamically unstable 7Å-vernadite transforms via dissolution-recrystallization to semi-ordered Mg-rich 10Å-vernadite. Nickel is released from dissolved biogenic silica or reduced organic matter, and taken up mainly in the Mn layer of 10Å-vernadite. Interlayer magnesium serves as a template to the further topotactic transformation of 10Å-vernadite to todorokite. The dimension of the todorokite tunnels in the [0 0 1] direction is uniform and determined by the size of the hydrated Mg²⁺ ion (8.6 Å). The tunnel dimension in the [1 0 0] direction depends on the density of Mg²⁺ in the interlayer and the superstructure of the phyllomanganate layer. If the parent phyllomanganate contains high amounts of Mg²⁺ (i.e., high layer charge), or Mn³⁺ and Mn⁴⁺ cations ordered following the Mn³⁺-Mn⁴⁺-Mn⁴⁺ sequence as in synthetic triclinic birnessite, then the tunnel dimension is ideally 3 × 3 octahedral chain widths in both crystallographic directions. Otherwise, the tunnel dimension is incoherent in the [1 0 0] direction (i.e., T(3,n) tunnel structure), as has been observed in all natural todorokites. Natural todorokite is defective because the precursor natural phyllomanganates either have a layer charge deficit below 0.33e per octahedral site, or rarely are triclinic birnessite. The abundance of Mg in seawater and its key role in converting phyllomanganate to tectomanganate with T(3,n) tunnel structure explain why todorokite is common in marine ferromanganese oxides, and seldom present in terrestrial environments. The topotactic phase transformation described here is the only known route to todorokite crystallization. This implies that all natural todorokites may be authigenic because they are formed in situ from a phyllomanganate precursor.     

Neutral Hydrogen and Its Emission Lines in the Solar Corona

Since the Lyman-\(\alpha\) rocket observations of Gabriel (Solar Phys. 21, 392, 1971), it has been realized that the hydrogen (H) lines could be observed in the corona and that they offer an interesting diagnostic for the temperature, density, and radial velocity of the coronal plasma. Moreover, various space missions have been proposed to measure the coronal magnetic and velocity fields through polarimetry in H lines. A necessary condition for such measurements is to benefit from a sufficient signal-to-noise ratio. The aim of this article is to evaluate the emission in three representative lines of H for three different coronal structures. The computations have been performed with a full non-local thermodynamic-equilibrium (non-LTE) code and its simplified version without radiative transfer. Since all collisional and radiative quantities (including incident ionizing and exciting radiation) are taken into account, the ionization is treated exactly. Profiles are presented at two heights (1.05 and 1.9 solar radii, from Sun center) in the corona, and the integrated intensities are computed at heights up to five solar radii. We compare our results with previous computations and observations (e.g. L\(\alpha\) from Ultraviolet Coronal Spectrometer) and find a rough (model-dependent) agreement. Since the H\(\alpha\) line is a possible candidate for ground-based polarimetry, we show that in order to detect its emission in various coronal structures, it is necessary to use a very narrow (less than 2 Å wide) bandpass filter.     

Effects of climate change on bioclimatic indices in vineyards along Lake Neuchatel,Switzerland

Theoretical and Applied Climatology - In this study, we investigated the consequences of climate change on bioclimatic indices in vineyards along the edge of Lake Neuchatel in Switzerland. Like in...     

Discrimination between different water bodies from a multilayered aquifer (Kaluvelly watershed,India): Trace element signature

In the multilayered aquifer of Kaluvelly (India), comprising various sedimentary layers overlying a charnockitic basement, concentrations of trace elements were measured in aquifer formations and in groundwaters to identify geochemical tracers for water bodies. The two main sandstones (Cuddalore and Vanur) originate from the charnockites and the Cuddalore sandstone has experienced lateritization. In the studied area, two charnockite end-members were identified: a dioritic and a granitic one. Mineralogical composition and whole-rock Ti concentrations confirmed the charnockite which displayed the granitic composition as the parent rock of the two sandstones. Titanium distribution indicates that the Cuddalore sandstone originates from a more intense weathering of the parent material than the Vanur sandstone. Despite extensive differences in trace element contents recorded in aquifer formations, only a few trace elements were suitable to distinguish the water bodies. Among soluble elements, Li (in the Vanur aquifer) and Ba (in the charnockite and carbonaceous aquifers) can be used as tracers. As the input of these elements in solution is mainly regulated by the available stock, for a given mineralogical origin there is a direct link between the aquifer formation composition and water signature. With the exception of As, concentrations of redox-sensitive elements were not preserved during pumping because of oxidation, preventing their use as tracers. Low-mobility elements such as La, Ce, Th, Zr, Nb, Hf, or Ta were too insoluble to be detected in waters and/or to record the aquifer formation signature. Their input in solution was not regulated by the available stock but by the dissolution rate of rock-forming minerals. Only Ti can be used to distinguish between two out of the three aquifers (charnockite and Vanur). The specific behavior of Ti recorded in these waters may be linked to rutile inclusions within plagioclases and to the influence of climate on Ti solubility.     

A New Interlaboratory Characterisation of Silicon,Rare Earth Elements and Twenty‐Two Other Trace Element Concentrations in the Natural River Water Certified Reference Material SLRS‐6 (NRC‐CNRC)

The natural river water reference material SLRS‐6 (NRC‐CNRC) is the newest batch of a quality control material routinely used in many international environmental laboratories. This work presents a nine‐laboratory compilation of measurements of major and trace element concentrations and their related uncertainties, unavailable in the NRC‐CNRC certificate (B, Cs, Li, Ga, Ge, Hf, Nb, P, Rb, Rh, Re, S, Sc, Se, Si, Sn, Th, Ti, Tl, W, Y, Y, Zr and REEs). Measurements were mostly made using inductively coupled plasma‐mass spectrometry. The results are compared with equivalent data for the last batch of the material, SLRS‐5, measured simultaneously with SLRS‐6 in this study. In general, very low concentrations, close to the quantification limits, were found in the new batch. The Sr isotopic ratio is also reported.     

Experimental transport of Si,Al and Mg in hydrothermal solutions: an application to vein mineralization during high-pressure,low-temperature metamorphism in the French Alps

A study of hydrothermal vein mineralization in meta-argillites subjected to high-pressure, low-temperature metamorphism reveals that ferromagnesian (e.g., chlorite) and pure aluminosilicate (e.g., pyrophyllite) mineralization can be correlated with regimes of increasing and decreasing temperature, respectively. An experimental study of the transport of silica, aluminum and magnesium in hydrothermal solutions has been undertaken to simulate variations in the physical conditions during metamorphism and the accompanying mass transport in a closed system. Thermodynamic and kinetic analysis of the experimental results indicates that local equilibrium among aqueous and mineral phases controls the distribution and composition of hydrothermal vein mineralization and that vein mineralogy can be used to infer the sense of variation of pressure and temperature during metamorphism.     

Public expectation as an element of human perception of climate change

Human expectations regarding weather and climate sometimes lead to perceptions of climate change which are not supported by observational evidence. This paper analyses two very characteristic complaints about current climate in Switzerland, i.e., the lack of snow in winter and the lack of sunshine in summer, through a statistical investigation of climatological data. As one major problem of public perception of climate in mid-latitude regions is linked to the strong variability of the climatic parameters, the paper suggests means of presenting climatic data which include a measure of this variability. Such presentations would help overcome the common confusion between the terms weather and climate, and stress the fact that short-term extreme events are not necessarily indicative of a long-term shift in climate.     

Petrogenetic variability along the North–South Propagating Spreading Center of the North Fiji Basin

Summary Previous studies on propagating rifts suggested that segmentation of a spreading axis could represent the superficial mark of mantle behavior (Sinton et al., 1983; Nicolas, 1989; Gente et al., 1995). The study of North–South Propagating Spreading Center (NS-PSC) from the North Fiji Basin (NFB) brings new insights to this debate. Basalts from the central part of the propagator have more variable incompatible and isotopic ratios then those from its northern tip. A model of dynamic partial melting of a thermally and slightly geochemically and isotopically heterogeneous mantle is proposed. Beneath the central segment, the partial fusion starts deeper (ca. 30km) and reaches a higher rate (ca. 22%). Further open system differentiation occurs within shallow permanent magma reservoirs along most of the central segment. Below the segment closest to the tip of the propagator the partial fusion starts shallower (ca. 25km) and stays at a lower rate (ca. 16%). The maximum of differentiation occurs close to the propagator, in small, periodically disconnected, magma bodies resulting in the production of ferrobasalts close to the tip. In order to explain these variations, the presence of an asthenospheric diapir focused beneath the central part of the NS-PSC is proposed. The petrogenetic processes of propagating spreading centers of mature oceanic basins or back-arc basins are identical.     

Eastern Mediterranean palaeoclimates from 26 to 5 ka B.P. documented by pollen and isotopic analysis of a core in the anoxic Bannock Basin

Continuous pollen and isotopic records were established for core BAN 84 09 GC retrieved from the anoxic Bannock Basin in the Eastern Mediterranean. On the basis of two ¹⁴C dates, they document the palaeoclimate between about 25.7 ka B.P. and 5.2 ka B.P. in the northern borderlands of the Ionian Basin. The upper half of the core has been redeposited.

The isotopic record displays a correlation with pollen percentages that is strong and positive for Artemisia (sage-brush) and negative for Quercus (oak). The last glacial maximum and the deglaciation are identified by these combined taxa, together with Chenopodiaceae. The glacial maximum around 18 ka B.P. (which has elsewhere been dated from 20 to 15 ka B.P.) has pollen percentages that are high for Artemisia and low for Quercus. The climate in the pollen source area was arid, cold in winter, briefly warm in summer and sustained the vegetation of a semi-desert. The onset of deglaciation after 18 ka B.P. coincides with that of the decline in Artemisia pollen percentage. However, this decline does not indicate reduced aridity, because it is accompanied by a pollen percentage rise of the even more arid herbs Chenopodiaceae and Ephedra. Throughout the deglaciation from 18 to 11 ka B.P., the aridity progressively increases, culminating at 11 ka B.P. This trend is briefly interrupted by a more humid event, shown by a peak in Artemisia pollen percentage and a smaller peak in oak; these two peaks are coeval with the Bölling-Alleröd chronozone (13-11 ka B.P.). Maximum aridity occurs during the Younger Dryas chronozone (11-10 ka B.P.). Afterwards, the oak pollen percentage begins a steady increase, and its maximum value is coeval with the lowest isotopic value, dated at 8760 ± 170 yr B.P. This period was one of high moisture, warm summers, and, according to altitude, mild to cool winters. This climate sustained forests that were Mediterranean in the lowlands and warm temperate in the uplands. A high pollen concentration is observed during this period and reveals the presence of sapropel S1, which is otherwise unrecognizable in this entirely black core. During the following period between 8760 ± 170 and 5200 yr B.P., the δ¹⁸0 reverts to slightly higher values and the Quercus pollen percentage decreases, while the pollen percentage of the wetter Ostrya, the oriental hornbeam, increases. The high pollen concentration during the deposition of sapropel S1 cannot have been caused by increased pollen input into the sea, this pollen being wind-borne, nor by increased pollen production for all taxa, both trees and herbs. We conclude that it is entirely due to increased preservation of this allochtonous organic material by the deep anoxia of the bottom water, below a thick anoxic water column. The coincidence of sapropel deposition with warm and humid local climate as well as with the second global meltwater pulse suggests that the cessation of bottom-water ventilation was due to decreased surface water density, resulting from less saline incoming Atlantic surface water, increased local runoff, and warmer winters.