Hydrothermal experiments were carried out with powder from an almost fully amorphous, natural zircon under various
P–
T–
t conditions mainly in a 0.1 N HCl solution. Powder infrared spectroscopic ...measurements on the experimental products reveal that first structural changes occurred at a fluid temperature as low as 75 °C. Significant recrystallization started at 200 °C, as indicated by an increase in the absorption intensity of the zircon fundamental IR bands and the formation of sharp OH stretching bands at 3385 and 3420 cm
−1. Although the powder has fully reacted at 400 °C, the zircon fundamental absorption bands are not fully recovered, indicating the occurrence of significant amounts of amorphous remnants. The experimental results in neutral to acidic solutions are consistent with the idea that water (H
+ and possibly H
2O) diffuses into the amorphous network where it ‘catalyses’ solid state recrystallization. During this process, Zr and Si were leached from the amorphous network.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
It is widely known that post mortem diagenetic alteration processes cause modifications and overprinting of the chemical and isotopic proxies incorporated in vivo in bone apatite and collagen. ...Understanding the processes occurring during the interaction between fluids and bones in an early diagenetic setting is fundamental to determining the extent to which the commonly-used geochemical proxies in bone get modified during fossilization. The present study experimentally investigates the structural and chemical changes in bone induced by controlled in vitro aqueous alteration experiments under simulated early diagenetic conditions. It is intended to derive a deeper phenomenological and quantitative understanding of the transport and reaction processes that occur in the early stage of fossilization. For this purpose, 3.5 mm-sized cylinders were drilled from modern ostrich cortical bone and immersed in different experimental solutions enriched with tracers such as Zn, Sr, rare earth elements, and U. The experiments ran for several hours to weeks at 30, 60, and 90 °C - the latter two temperatures were chosen to accelerate anticipated early diagenetic modifications of the bone samples. Both the bone samples and the experimental solutions were analyzed using micro-analytical techniques such as Raman spectroscopy, electron microprobe, high-resolution inductively coupled plasma-mass spectrometry, nanoscale ion microprobe, and atom probe tomography to assess mineralogical, chemical, and structural changes from the millimeter to the atomic scale. The results show that element uptake into the bone samples occurs within hours after they have been exposed to an aqueous solution instead of years, as previously assumed. Additionally, distinct modifications of the organic phase were observed, accompanied by the growth of new apatite phases by dissolution-reprecipitation and recrystallization processes. Carbonate-poor or -free hydroxylapatite formed in the sample center and more stable carbonated fluorapatite in the sample rim. From these data, a phenomenological model is derived that explains the interaction between bone and aqueous solutions during the earliest stages of fossilization. This study also demonstrates the importance of using a comprehensive methodological approach when investigating alteration processes whose effects range from the millimeter down to the atomic scale.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The mineral zircon is used widely to constrain the age of rocks and the processes that formed them. Although zircon is robust to a range of physical and chemical processes, it may show evidence for ...rapid re-equilibration that is generally considered to reflect interaction with hydrous fluids. Here, we show that zircon grains that crystallized from melt produced during the catastrophic meltdown of the Chernobyl nuclear reactor exhibit re-equilibration textures that occurred in an environment without free water. The process of re-equilibration involved a melt-mediated interface-coupled dissolutionreprecipitation that took place over a few days to produce textures that are commonly observed in igneous and anatectic systems. Thus, the composition of zircon can be modified even in the absence of hydrous fluids in a short time frame. Through this process, zircon crystals may track the timing of the last silicate melt they interacted with.
•In operando observation of silicate glass alteration in a hyperalkaline solution.•Coupling of glass dissolution, precipitation, transport, and solution chemistry in space and time.•Non-linearity ...driven by shielding, precipitation and surface effects.•Experiments can guide improvement of models.
Mechanisms, feedbacks and resulting non-linearity during silicate glass alteration in a hyperalkaline carbonate solution were studied through hyperspectral Raman imaging of heated fluid-cells. Our experimental setup enabled in operando visualization and rate measurements of glass dissolution and secondary phase precipitation, complemented by spectral characterization of the phases involved and semi-quantitative monitoring of the ionic strength of the solution close to the glass interface. After initial congruent dissolution of the Ba-bearing soda-lime boroaluminosilicate glass, the formation of a crystalline, saponite-based surface alteration layer (SAL), as well as subsequent zeolite precipitation, witherite coating, and carbonate precipitation within pore spaces of the saponite layer were observed. Two in operando experiments were conducted at ∼ 90 °C for 180 and 260 h that otherwise solely differed in the solution volume (SV) while keeping the surface area constant. The high SV experiment exhibited a transient upward excursion of initial dissolution rates, followed by continuously rapid glass dissolution along with slow SAL growth and sustained oscillations in ionic strength. Contrastingly, in the low SV experiment, glass dissolution monotonically decreased after the onset of rapid SAL growth and no sustained oscillations were observed. We find that growth conditions and resulting properties of the SAL exert dominant, non-linear effects on the evolution of glass dissolution rates. In turn, SAL formation depends on nucleation/growth kinetics and the accumulation of glass-derived solutes at the reaction front. Both, dissolution and precipitation, feedback with solution chemistry and transport processes, together controlling the evolution of the corrosion process. Additionally, fracturing, delamination, and the evolution of surface morphology may affect glass dissolution rates and transport pathways. Such interpretations of decelerating reaction rates in response to the growth of a protective layer are consistent in micro-scale experiments and in outcrop- to global-scale observations, as is the accelerating effect of surface area creation by physical disruption and morphology. Thus, these µm-scale mechanistic insights could help elucidating local to global environmental feedbacks (e.g., erosion or weathering patterns) as well as process dynamics in engineered environments (e.g., nuclear waste disposal) and may assist the improvement predictive models.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Stable isotope ratios and trace element concentrations of fossil bones and teeth are important geochemical proxies for the reconstruction of diet and past environment in archaeology and ...palaeontology. However, since diagenesis can significantly alter primary diet-related isotope signatures and elemental compositions, it is important to understand and quantify alteration processes. Here, we present the results of in-vitro alteration experiments of dental tissues from a modern African elephant molar reacted in aqueous solutions at 30 °C and 90 °C for 4 to 63 days. Dental cubes with ≈ 3 mm edge length, comprising both enamel and dentin, were placed into 2 mL of acidic aqueous solution enriched in different isotopes (25Mg, 44Ca, 67Zn, 86Sr, initial pH 1). Element and isotope distribution profiles across the reacted cubes were measured with LA-(MC-)ICP-MS and EMPA, while potential effects on the bioapatite crystal structure were characterised by Raman spectroscopy. In all experiments isotope ratios measured by LA-(MC-)ICP-MS revealed an alteration of the enamel in the outer ≈ 200–300 μm. In contrast, dentin was fully altered (≈ 1.4 mm) after one week at 90 °C while the alteration did not exceed a depth of 150–200 μm during the 30 °C experiments. Then, the tracer solution started also to penetrate through the enamel-dentin junction into the innermost enamel, however, leaving the central part of the enamel unaltered, even after three months. The Raman spectra suggest an initial demineralisation in the acidic environment while organic matter (i.e. collagen) is still preserved. In the 90 °C experiment, Raman spectra of the v1(PO4) band of the dentin shift over time towards synthetic hydroxylapatite patterns and the Ca (and Sr) concentrations in the respective solutions decrease. This indicates precipitation of newly formed apatite. Isotope and element concentration profiles across the dental tissues reveal different exchange mechanisms for different isotope systems. Magnesium is leached from enamel and dentin, while Zn is incorporated into the apatite crystal structure. However, the distribution of both elements is not affected in the innermost enamel where their concentrations do not change over the whole duration of the experiments. We found no correlation of reaction depth in the cubes and experimental duration, which might be caused by natural variability of the dental material already at the beginning of the experiment. Our alteration experiments in a closed system at high temperatures ≤90 °C and low initial pH demonstrate that at least the central part of mm-thick mammalian enamel apatite seems to be resistant against alteration preserving its pristine bioapatite mineral structure as well as its in-vivo elemental and isotopic composition. The experiments assess diagenetic alteration in a novel multi-proxy approach using in-situ analyses in high spatial resolution. It is demonstrated that the isotopes of Ca, Sr, Zn and Mg in the dentin are prone for diagenetic alteration, while enamel is more resistant against alteration and could be used for dietary and physiological reconstructions in fossil teeth.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Biomineralization provides living organisms with various materials for the formation of resilient structures. Calcium phosphate is the main component of teeth and bones in vertebrates, whereas ...especially silica serves for the protection against herbivores on many plant surfaces. Functional calcium phosphate structures are well-known from the animal kingdom, but had not so far been reported from higher plants. Here, we document the occurrence of calcium phosphate biomineralization in the South-American plant group Loasaceae (rock nettle family), which have stinging trichomes similar to those of the well-known stinging nettles (Urtica). Stinging hairs and the smaller, glochidiate trichomes contained nanocrystalline hydroxylated apatite, especially in their distal portions, replacing the silica found in analogous structures of other flowering plants. This could be demonstrated by chemical, spectroscopic, and diffraction analyses. Some species of Loasaceae contained both calcium phosphate and silica in addition to calcium carbonate. The intriguing discovery of structural hydroxylated apatite in plants invites further studies, e.g., on its systematic distribution across the family, the genetic and cellular control of plant biomineralization, the properties and ultrastructure of calcium phosphate. It may prove the starting point for the development of biomimetic calcium phosphate composites based on a cellulose matrix.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Oligoclase and labradorite crystals have been experimentally replaced by albite in an aqueous sodium silicate solution at 600°C and 2 kbars. The replacement is pseudomorphic and is characterised by a ...sharp chemical interface which progresses through the feldspar while preserving the crystallographic orientation. Reaction rims of albite, up to 50 μm thick, can be readily achieved within 14 days. Re-equilibration of plagioclase in an
18
O-enriched sodium- and silica-bearing solution results in oxygen isotope redistribution within the feldspar framework structure. The observed characteristics of the reaction products are similar to naturally albitised plagioclase and are indicative of an interface-coupled dissolution–reprecipitation mechanism. Chemical analyses demonstrate that the albitisation is accompanied by the mobilisation of major, minor and trace elements also including elements such as Al and Ti which are commonly regarded as immobile during hydrothermal alteration. The results contribute to developing our understanding of the close association between large-scale albitisation and secondary ore mineralisation which is common in nature.
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DOBA, EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, IZUM, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, SIK, UILJ, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200
°C using single inorganic aragonite crystals as a starting material. ...The initial saturation state and the total Ca
2+:CO
3
2− ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy.
Experiments using carbonate solutions prepared with water enriched in
18O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of
18O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the
18O distribution in the calcite replacement. An activation energy of 109
kJ/mol was calculated for the exchange of oxygen isotopes between C
16O
3
2−
aq and H
2
18O and the time for oxygen isotope exchange in the fluid at 200
°C was estimated at ∼0.9
s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution–reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
It was proposed to utilize siderite FeCO3 in mid to late Archaean Superior type banded as a proxy to constrain the CO2 partial pressure of Archaean atmospheres. Implicit in this proposition is that ...siderite was a primary carbonate mineral that crystallized directly from Fe2+ enriched Archaean seawater, in equilibrium with atmospheric CO2. To our knowledge that proposition has not been demonstrated to be valid. We test with water-gas exchange experiments under controlled CO2 partial pressures if siderite can be stabilized as a primary mineral in Fe2+ bearing seawater. Reduced seawater proxies enriched in Fe2+ and Mn2+ are equilibrated with reduced N2-CH4-CO2-H2 gas phases with variable CO2. The solid phases stabilized in Fe2+ enriched water compositions are amorphous ferrous iron hydroxy carbonates. Crystalline siderite FeCO3 is not found to be a stable phase. The phases precipitating from Mn2+ enriched water include crystalline rhodochrosite MnCO3 and possibly amorphous Mn-enriched phases. Based on these results we advise against using siderite in banded iron formations as a CO2 sensor for the Archaean atmosphere.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
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