Neuroblastoma is the most common extracranial cancer in childhood. High-risk neuroblastoma continues to have a poor prognosis and there is an urgent need to design biologically based therapies that ...specifically target the pathways responsible for malignant transformation and progression. One such pathway is the PI3K/Akt/mTOR pathway. In this article we outline the evidence for aberrant activation of the PI3K/Akt/mTOR pathway in neuroblastoma and discuss the possible mechanisms which mediate it. We also discuss the development of treatments targeting this pathway in neuroblastoma and the challenges that must be overcome before such treatments can enter routine clinical practice.
Large-scale olivine carbonation has been proposed as a potential method for sequestering CO2 emissions. For in situ carbonation techniques, understanding the relationship between the formation of ...carbonate and other phases is important to predict the impact of possible passivating layers on the reaction. Therefore, we have conducted reactions of olivine with carbonated saline solutions in unstirred batch reactors. Altering the reaction conditions changed the Mg-carbonate morphology. We propose that this corresponded to changes in the ability of the system to precipitate hydromagnesite or magnesite. During high-temperature reactions (200 °C), an amorphous silica-enriched phase was precipitated that was transformed to lizardite as the reaction progressed. Hematite was also precipitated in the initial stages of these reactions but dissolved as the reaction proceeded. Comparison of the experimental observations with reaction models indicates that the reactions are governed by the interfacial fluid composition. The presence of a new Mg-silicate phase and the formation of secondary products at the olivine surface are likely to limit the extent of olivine to carbonate conversion.
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IJS, KILJ, NUK, PNG, UL, UM
Serpentinization-fueled systems in the cool, hydrated forearc mantle of subduction zones may provide an environment that supports deep chemolithoautotrophic life. Here, we examine serpentinite clasts ...expelled from mud volcanoes above the Izu–Bonin–Mariana subduction zone forearc (Pacific Ocean) that contain complex organic matter and nanosized Ni–Fe alloys. Using time-of-flight secondary ion mass spectrometry and Raman spectroscopy, we determined that the organic matter consists of a mixture of aliphatic and aromatic compounds and functional groups such as amides. Although an abiotic or subduction slab-derived fluid origin cannot be excluded, the similarities between the molecular signatures identified in the clasts and those of bacteria-derived biopolymers from other serpentinizing systems hint at the possibility of deep microbial life within the forearc. To test this hypothesis, we coupled the currently known temperature limit for life, 122 °C, with a heat conduction model that predicts a potential depth limit for life within the forearc at ∼10,000 m below the seafloor. This is deeper than the 122 °C isotherm in known oceanic serpentinizing regions and an order of magnitude deeper than the downhole temperature at the serpentinized Atlantis Massif oceanic core complex, Mid-Atlantic Ridge. We suggest that the organic-rich serpentinites may be indicators for microbial life deep within or below the mud volcano. Thus, the hydrated forearc mantle may represent one of Earth’s largest hidden microbial ecosystems. These types of protected ecosystems may have allowed the deep biosphere to thrive, despite violent phases during Earth’s history such as the late heavy bombardment and global mass extinctions.
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BFBNIB, NMLJ, NUK, PNG, SAZU, UL, UM, UPUK
Abstract Vertebrates use the phosphate mineral apatite in their skeletons, which allowed them to develop tissues such as enamel, characterized by an outstanding combination of hardness and ...elasticity. It has been hypothesized that the evolution of the earliest vertebrate skeletal tissues, found in the teeth of the extinct group of conodonts, was driven by adaptation to dental function. We test this hypothesis quantitatively and demonstrate that the crystallographic order increased throughout the early evolution of conodont teeth in parallel with morphological adaptation to food processing. With the c -axes of apatite crystals oriented perpendicular to the functional feeding surfaces, the strongest resistance to uniaxial compressional stress is conferred along the long axes of denticles. Our results support increasing control over biomineralization in the first skeletonized vertebrates and allow us to test models of functional morphology and material properties across conodont dental diversity.
The pseudomorphic replacement of Carrara marble by calcium phosphates was used as a model system in order to study the influence of different fluid pathways for reaction front propagation induced by ...fluid–rock interaction. In this model, grain boundaries present in the rock as well as the transient porosity structures developing throughout the replacement reaction enable the reaction front to progress further into the rock as well as to the center of each single grain until transformation is complete. Hydrothermal treatment of the marble using phosphate bearing solutions led to the formation of hydroxylapatite and β-TCP; the formation of the latter phase was probably promoted by the presence of ∼0.6 wt.% Mg in the parent carbonate phase. Completely transformed single grains show a distinctive zoning, both in composition and texture. Whereas areas next to the grain boundary consist of nearly pure hydroxylapatite and show a coarse porosity, areas close to the center of the single grains show a high amount of β-TCP and a very fine porous microstructure. If fluorine was added as an additional solution component, up to 3 wt.% of F were incorporated into the product apatite and the formation of β-TCP was avoided. The use of the isotope 18O as a chronometer for the replacement reaction makes it possible to reconstruct the chronological development of the calcium phosphate reaction front. Raman analysis revealed that the incorporation of 18O in the PO4 tetrahedron of hydroxylapatite results in the development of distinct profiles in the calcium phosphate reaction front perpendicular to the grain boundaries of the marble. Through the use of the 18O chronometer, it is possible to estimate and compare the time effectiveness of the different fluid pathways in this model system. The results demonstrate that the grain boundaries are an effective pathway enabling the fluid to penetrate the rock more than one order of magnitude faster compared to the newly developing channel-like porosity structures, which act as pathways towards the center of single mineral grains. Thus, after only short reaction durations, it may be possible for the fluid to progress relatively large distances along the grain boundaries without developing broad reaction fronts along the path.
•Hydrothermal replacement of marble by hydroxylapatite and β-TCP.•Formation of β-TCP is avoided if fluorine is present in solution.•18O used as a chronometer to study time effectiveness of different fluid pathways.•Grain boundaries represent more effective fluid pathways than porosity structures.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Calcium carbonate and cadmium-rich fluid interactions have been studied at the nano and microscale with fluid flow and static fluid conditions for three forms of CaCO3: calcite in single crystals of ...Iceland Spar, calcite in a polycrystalline Carrara marble, and aragonite single crystals. Atomic Force Microscopy (AFM) showed the nanoscale effect of cadmium on CaCO3 dissolution and growth under flow-through conditions at ambient temperature, with the modification of calcite dissolution behaviour and simultaneous precipitation of a Cd-rich phase on all the different samples. Hydrothermal experiments at 200 °C revealed that the reactivity of single calcite crystals is passivated by epitaxial growth of the less soluble Cd-rich endmember of the (Ca,Cd)CO3 solid-solution on the sample surface due to the similar crystallographic structures of calcite and otavite (CdCO3). Conversely, the presence of grain boundaries in Carrara marble or the change of crystallographic structure and reaction-induced fracturing in aragonite allowed, to some extent, the pseudomorphic replacement of Carrara marble and aragonite samples by a porous (Ca,Cd)CO3 solid-solution phase of variable composition. These phenomena have been observed in solutions undersaturated with respect to all solid phases and are the result of an interface-coupled dissolution-precipitation mechanism where the dissolving CaCO3 provides ions to supersaturate the mineral-fluid interfacial layer, leading to the precipitation of a Cd-containing phase on the samples' surfaces. This coupled dissolution-precipitation mechanism could potentially be used as a remediation process to sequester cadmium from contaminated effluents.
•Cadmium modifies CaCO3 dissolution and growth under flow-through conditions at ambient temperature.•Cadmium in solution passivates calcite single crystal on long term exposure.•The presence of fluid pathways/change of crystallographic structure allows the replacement of CaCO3 by a (Ca,Cd)CO3 phase.•CaCO3 as limestone, marble or aragonite can be used to sequester Cd in solutions.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
One possible carbon dioxide sequestration strategy is via the carbonation of dissolved Mg2+ obtained through olivine ((Mg,Fe)2SiO4) dissolution. However, silica is also produced during the breakdown ...of olivine. This component may have a detrimental effect on the yield of Mg-carbonate as Mg2+ incorporation into complex Mg silicate phases would limit CO2 uptake by this system. Yet this potential competition is currently not considered. Here, we use crystal growth experiments at temperatures applicable for potential coastal applications to test the effect of silica on the formation of the hydrated Mg-carbonate phase nesquehonite (MgCO3·3H2O). Solution chemistry analysis coupled with phase identification demonstrates that the presence of silica in the solution can actually assist the formation of nesquehonite and increase its yield by as much as 60 times. Our findings suggest that the presence of silica changes interfacial stabilities, lowering the energetic barrier for nesquehonite nucleation. In addition, in situ attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) transformation experiments demonstrated that nesquehonite precipitating in a solution containing a high concentration of dissolved silica exhibits enhanced stability against its transformation into hydromagnesite. These findings will help to better constrain what we expect for applications of olivine during carbon remediation strategies as well as assist yields for industrial applications that use Mg-based cement as building materials to facilitate a CO2-neutral or negative footprint.
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IJS, KILJ, NUK, PNG, UL, UM
Hydrothermal treatment is a common method used to modify the physicochemical properties of zeolite‐based catalyst materials. It alters the number and type of acid sites through dealumination and ...increases molecular diffusion by mesopore formation. Steaming also reduces the structural integrity of zeolite frameworks. In this study, Raman microscopy has been used to map large zeolite ZSM‐5 crystals before and after steaming. 3D elemental maps of T−O (T: Al or Si) sites of the zeolite were obtained. The Raman active vibrational bands were determined, which are indicative of (non‐) framework Al, as well as of structural integrity. Zeolite steaming caused the introduction of additional heterogeneities within the zeolite framework. Al migration and the formation of extra‐framework Al species were observed. The described experiments demonstrate the capability of 3D Raman spectroscopy as a valuable tool to obtain information on the spatial distributions of framework elements as well as defects within a zeolite‐based material.
On the map: Raman spectroscopy has been used to visualize the elemental distribution of large zeolite ZSM‐5 crystals to gain insights in the modifications caused by a hydrothermal treatment. The 3D distribution of Al and Si inside the zeolite ZSM‐5 framework has been revealed before and after steaming. It was found that the steaming pretreatment promoted the formation of heterogeneities in the near‐surface zeolite regions, most probably via the extraction of framework Al.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Siderite, the iron carbonate mineral, occurs in several geological environments and contributes to both the global iron and CO2 cycles. Under crustal conditions, this mineral may dissolve, releasing ...iron that becomes oxidized and then precipitates in the form of iron oxides and oxyhydroxides that have a high affinity for pollutants, such as arsenic. The process of siderite dissolution, dissolved iron oxidation, and oxyhydroxide precipitation is coupled in time and space. Here, we study the entire process using time-lapse in-situ atomic force microscopy. Natural siderite crystals were dissolved at room temperature in acidic aqueous solutions in the presence or absence of arsenic. The dissolution process, whose rate could be measured at a nanometer scale, occurred by the nucleation and growth of etch pits, the retreat of step edges, and the deepening of cleavage steps. Precipitation of iron oxyhydroxide phases coupled to siderite dissolution was imaged in-situ. Nucleated particles have an initial height of 1–2nm after 1minute reaction and then grow with time into aggregate precipitates 130–220nm wide and up to 80nm high after 24h of reaction. Ex-situ stirred-flow reactor measurements confirm the same sequence of siderite dissolution and iron oxyhydroxide precipitation. The arsenic is adsorbed by iron oxyhydroxides and its presence does not change significantly the rate of dissolution-precipitation of the overall process. Results provide a basis for understanding and quantifying the interactions between reduced-iron minerals and aqueous-phase oxidants, as well as potential sequestration of toxic elements such as arsenic.
•Siderite dissolution is coupled to iron oxyhydroxides precipitation in acidic conditions.•Siderite dissolution occurs by etch pits propagation, step retreat, and cleavage plane widening.•Arsenic is adsorbed by the precipitated iron oxyhydroxides.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
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