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. 相似文献
Garber Schlag (Q-GS) is one of the major springs of the Karwendel Mountains, Tyrol, Austria. This spring has a unique runoff pattern that is mainly controlled by the tectonic setting. The main aquifer is a moderately karstified and jointed limestone of the Wetterstein Formation that is underlain by nonkarstified limestone of the Reifling Formation, which acts as an aquitard. The aquifer and aquitard of the catchment of spring Q-GS form a large anticline that is bound by a major fault (aquitard) to the north. Discharge of this spring shows strong seasonal variations with three recharge origins, based on δ18O and electrical conductivity values. A clear seasonal trend is observed, caused by the continuously changing portions of water derived from snowmelt, rainfall and groundwater. At the onset of the snowmelt period in May, the discharge is composed mainly of groundwater. During the maximum snowmelt period, the water is dominantly composed of water derived from snowmelt and subordinately from rainfall. During July and August, water derived from snowmelt continuously decreases and water derived from rainfall increases. During September and October, the water released at the spring is mainly derived from groundwater and subordinately from rainfall. The distinct discharge plateau from August to December and the following recession until March is likely related to the large regional groundwater body in the fissured and moderately karstified aquifer of the Wetterstein Formation and the tectonic structures (anticline, major fault). Only a small portion of the water released at spring Q-GS is derived from permafrost.
International Journal of Earth Sciences - Three-dimensional geophysical modelling of the early Late Miocene Pásztori volcano (ca. 11–10 Ma) and adjacent area in the Little... 相似文献
The occurrence of increasing blooms of toxic cyanobacteria in freshwaters has received much attention due to the ability of many cyanobacteria to produce potent cyanotoxins. In this paper, the occurrence of dominant cyanobacteria and the concentration of microcystins (MCs) analysis were investigated monthly from July 2008 to April 2009 in the Hoan Kiem Lake and from February to April 2009 in the Nui Coc reservoir. Concentrations of intracellular MCs from water, bloom samples, and isolated strains were quantified by using high performance liquid chromatography (HPLC). During the study period, the microscopic examination of the phytoplankton samples showed the dominance of the genus Microcystis in the water environment of the Hoan Kiem Lake and the Nui Coc reservoir. The toxin analysis by HPLC demonstrated the presence of two MC variants: MC-LR and MC-RR in water samples. Total concentrations of the toxins in filtered samples from surface water ranged from non-detected to 0.91 μg L?1 at Nui Coc reservoir and they ranged from 2.1 to 46.0 μg L?1 at Hoan Kiem Lake. The results of the HPLC analysis confirmed the production of MCs in bloom samples (ranged from 115.9 to 184.6 μg L?1 in the Hoan Kiem Lake and from 726.5 to 1116 μg L?1 in the Nui Coc reservoir) and isolated strains of Anabaena sp. and Microcystis with the concentration of MC ranging from 152 to 396.2 μg g?1 dry mass, respectively. 相似文献
Throughout much of Earth's history, marine carbonates have represented one of the most important geological archives of environmental change. Several pivotal events during the Phanerozoic, such as mass extinctions or hyperthermal events have recently been associated with ocean acidification. Nevertheless, well‐defined geological proxies for past ocean acidification events are, at best, scarce. Here, experimental work explores the response of bivalve shell ultrastructure and isotope geochemistry (δ13C, δ18O and δ26Mg) to stressful environments, in particular to sea water acidification. In this study, the common blue mussel, Mytilus edulis, was cultured (from early juvenile stages to one year of age) at four pH regimes (pHNBS 7·2 to pH 8·0). Shell growth rate and ultrastructure of mainly the calcitic portion of the shells were compared between experimental treatments. Specimens exposed to low‐pH environments show patches of disordered calcitic fibre orientation in otherwise well‐structured shells. Furthermore, the electron backscattered diffraction analyses reveal that, under acidified conditions, the c‐axis of the calcite prisms exhibits a bimodal or multi‐modal distribution pattern. Similar shell disorder patterns have been reported from mytilids kept under naturally acidified sea water conditions. In contrast, this study found no evidence that different pH regimes affect shell carbon, oxygen or magnesium isotope ratios. Based on these observations, it is proposed that: (i) stressful environments, in this case low sea water pH, predictably affect bivalve biomineralization patterns; and (ii) these findings bear potential as a novel (petrographic) proxy for ancient sea water acidification. An assessment of the applicability of these data to well‐preserved fossil shell material from selected time intervals requires additional work. 相似文献
In this paper, we present the results of the first automated continuous multi-year high temporal frequency study of CO2 dynamics in a coastal coral reef ecosystem. The data cover 2.5?years of nearly continuous operation of the CRIMP-CO2 buoy spanning particularly wet and dry seasons in southern Kaneohe Bay, a semi-enclosed tropical coral reef ecosystem in Hawaii. We interpret our observational results in the context of how rapidly changing physical and biogeochemical conditions affect the pCO2 of surface waters and the magnitude and direction of air–sea exchange of CO2. Local climatic forcing strongly affects the biogeochemistry, water column properties, and gas exchange between the ocean and atmosphere in Kaneohe Bay. Rainfall driven by trade winds and other localized storms generates pulses of nutrient-rich water, which exert a strong control on primary productivity and impact carbon cycling in the water column of the bay. The “La Ni?a” winter of 2005–2006 was one of the wettest winters in Hawaii in 30?years and contrasted sharply with preceding and subsequent drier winter seasons. In addition, short-term variability in physical forcing adds complexity and helps drive the response of the CO2–carbonic acid system of the bay. Freshwater pulses to Kaneohe Bay provide nutrient subsidies to bay waters, relieving the normal nitrogen limitation of this system and driving phytoplankton productivity. Seawater pCO2 responds to the blooms as well as to physical forcing mechanisms, leading to a relatively wide range of pCO2 in seawater from about 250 to 650?μatm, depending on conditions. Large drawdowns in pCO2 following storms occasionally cause bay waters to switch from being a source of CO2 to the atmosphere to being a sink. Yet, during our study period, the southern sector of Kaneohe Bay remained a net source of CO2 to the atmosphere on an annualized basis. The integrated net annual flux of CO2 from the bay to the atmosphere varied between years by a factor of more than two and was lower during the wet “La Ni?a” year, than during the following year. Over the study period, the net annualized flux was 1.80?mol?C?m?2?year?1. Our CO2 flux estimates are consistent with prior synoptic work in Kaneohe Bay and with estimates in other tropical coral reef ecosystems studied to date. The high degree of climatological, physical, and biogeochemical variability observed in this study suggests that automated high-frequency observations are needed to capture the short-, intermediate-, and long-term variability of CO2 and other properties of these highly dynamic coastal coral reef ecosystems. 相似文献
Natural and anthropogenic forcing factors and their changes significantly impact water resources in many river basins around the world. Information on such changes can be derived from fine scale in situ and satellite observations, used in combination with hydrological models. The latter need to account for hydrological changes caused by human activities to correctly estimate the actual water resource. In this study, we consider the catchment area of the Garonne river (in France) to investigate the capabilities of space-based observations and up-to-date hydrological modeling in estimating water resources of a river basin modified by human activities and a changing climate. Using the ISBA–MODCOU and SWAT hydrological models, we find that the water resources of the Garonne basin display a negative climate trend since 1960. The snow component of the two models is validated using the moderate-resolution imaging spectroradiometer snow cover extent climatology. Crop sowing dates based on remote sensing studies are also considered in the validation procedure. Use of this dataset improves the simulated evapotranspiration and river discharge amounts when compared to conventional data. Finally, we investigate the benefit of using the MAELIA multi-agent model that accounts for a realistic agricultural and management scenario. Among other results, we find that changes in crop systems have significant impacts on water uptake for agriculture. This work constitutes a basis for the construction of a future modeling framework of the sociological and hydrological system of the Garonne river region. 相似文献
The mechanical efficiency of the biocementation process is directly related to the microstructural properties of the biocemented sand, such as the volume fraction of calcite, its distribution within the pore space (localized at the contact between grains, over the grain surfaces) and the contact properties: coordination number, contact surface area, contacts orientation and types of contact. In the present work, all these micromechanical properties are computed, for the first time, from 3D images obtained by X-ray tomography of intact biocemented sand samples. The evolution of all these properties with respect to the volume fraction of calcite is analyzed and compared between each other (from untreated sand to highly cemented sand). Whatever the volume fraction of calcite, it is shown that the precipitation of the calcite is localized at the contacts between grains. These results are confirmed by comparing our numerical results with analytical estimates assuming that the granular medium is made of periodic simple cubic arrangements of grains and by considering two extreme cases of precipitation: (1) The calcite is localized at the contact, and (2) the grains are covered by a uniform layer of calcite. In overall, the obtained results show that a small percentage of calcite is sufficient to get a large amount of cohesive contacts.
An experimental study has been performed to investigate the effect of the biocalcification process on the microstructural and the physical properties of biocemented Fontainebleau sand samples. The microstructural properties (porosity, volume fraction of calcite, total specific surface area, specific surface area of calcite, etc.) and the physical properties (permeability, effective diffusion) of the biocemented samples were computed for the first time from 3D images with a high-resolution images obtained by X-ray synchrotron microtomography. The evolution of all these properties with respect to the volume fraction of calcite is analysed and compared with success to experimental data, when it is possible. In general, our results point out that all the properties are strongly affected by the biocalcification process. Finally, all these numerical results from 3D images and experimental data were compared to numerical values or analytical estimates computed on idealized microstructures constituted of periodic overlapping and random non-overlapping arrangements of coated spheres. These comparisons show that these simple microstructures are sufficient to capture and to predict the main evolution of both microstructural and physical properties of biocemented sands for the whole range of volume fraction of calcite investigated. 相似文献
A thorough literature review has been undertaken to establish the first complete account of polychaetes recorded from the area around the volcanic island of Jan Mayen. The annotated checklist lists 121 species-level taxa, representing an increase from the 75 species previously recorded. The checklist is based on existing records, supplemented with material sampled in 1999, from which 42 species new to the area were reported. Some previously reported species from the area have been excluded because of inadequate documentation. The polychaete fauna of Jan Mayen is comparable with that of the mainland Norwegian coast and the Svalbard area. No taxa unique to the island were found. However, knowledge of the marine invertebrate fauna in general at Jan Mayen is sparse because few surveys have been undertaken there. It is expected that future expeditions will reveal further new taxon records for the area. 相似文献