ALBERT

Description: Synthetic materials based on calcium phosphate (CaP) are frequently used as bone graft substitutes when natural bone grafts are not available or not suitable. Chemical similarity to bone guarantees the biocompatibility of synthetic CaP materials, whereas macroporosity enables their integration into the natural bone tissue. To restore optimum mechanical performance after the grafting procedure, gradual resorption of CaP implants and simultaneous replacement by natural bone is desirable. Mg and Sr ions released from implants support osteointegration by stimulating bone formation. Furthermore, Sr ions counteract osteoporotic bone loss and reduce the probability of related fractures. The present study aimed at developing porous Ca carbonate biominerals into novel CaP-based, bioactive bone implant materials. Macroporous Ca carbonate biominerals, specifically skeletons of corals (aragonite) and sea urchins (Mg-substituted calcite), were hydrothermally converted into pseudomorphic CaP materials with their natural porosity preserved. Sr ions were introduced to the mineral replacement reactions by temporarily stabilizing them in the hydrothermal phosphate solutions as Sr-EDTA complexes. In this reaction system, Na, Mg, and Sr ions favored the formation of correspondingly substituted β-tricalcium phosphate over hydroxyapatite. Upon dissolution, the incorporated functional ions became released, endowing these CaP materials with bioactive and potentially osteoporotic properties.

Description: Primary subduction-related magmas build up modern continental crust and counterbalance massive recycling of crustal material into the deep mantle occurring at this tectonic setting. Melt inclusions in Mg-rich olivine are believed to be the best probes of primary subduction-related melts. However, unexpectedly, most of such inclusions are SiO2-undersaturated, in contrast to predominantly SiO2-saturated island-arc rocks. The origin of these melts has been explained by melting of amphibole-bearing pyroxenites in the lower crust or upper mantle. The current models fail, however, to explain the high abundance of SiO2-undersaturated melts as well as their compositional difference with host rocks for the major elements but not for incompatible trace elements. Here we report results from the investigation of rocks and melt inclusions in olivine from Klyuchevskoy volcano in Kamchatka. We show that experimental re-hydration of SiO2-undersaturated melt inclusions in olivine Fo85−90 at 300 MPa pressure and 1200 °C causes a concomitant enrichment of melt in H2O and SiO2 so that re-hydrated inclusions (4–5 wt% H2O) become as silica-saturated as primitive Klyuchevskoy rocks. An experimental dehydration of previously re-hydrated inclusions also resulted in coupled depletion of melt in H2O and SiO2. The estimated stoichiometry of SiO2 and H2O gain/loss is consistent with dissolution/crystallization of metal-defect olivine on inclusion walls. The migration mechanism of water is controlled by hydrogen diffusion in the octahedral metal (Mg, Fe) vacancies through olivine structure as confirmed by FTIR spectroscopy. We conclude that the previously reported SiO2-undersaturated composition of many melt inclusions from hypersthene-normative island-arc rocks can be explained by the coupled loss of up to several weight percent of H2O and SiO2 from the initially trapped primitive SiO2-saturated hydrous melts. Thus, SiO2-undersaturated melt inclusions may not be representative of primitive island-arc magmas. The discovery of the coupled SiO2 and H2O loss from inclusions allowed us to propose a method for reconstruction of the initial water content even for completely dehydrated inclusions. The results of this study may indicate that the majority of primitive island-arc inclusions have not preserved their initial H2O content, and that primary arc melts contain on average ≥4 wt% H2O. The higher H2O concentration in primary arc melts implies the existence of a ‘crustal filter’ controlling the water content, which can be preserved in melt inclusions, and also the lower mantle melting temperatures and higher output H2O fluxes in subduction zones than previously estimated based on direct determination of H2O in potentially dehydrated melt inclusions.

Description: Highlights • New experiments with melt inclusions in olivine at 1200 °C and 300 MPa. • Coupled behavior H2O and SiO2 in inclusions during re-hydration and dehydration. • SiO2 mobility results from formation/destruction of metal vacant olivine. • SiO2-undersaturated arc melt inclusions may originate by dehydration. • New method to assess initial H2O in dehydrated inclusions. Abstract Primary subduction-related magmas build up modern continental crust and counterbalance massive recycling of crustal material into the deep mantle occurring at this tectonic setting. Melt inclusions in Mg-rich olivine are believed to be the best probes of primary subduction-related melts. However, unexpectedly, most of such inclusions are SiO2-undersaturated, in contrast to predominantly SiO2-saturated island-arc rocks. The origin of these melts has been explained by melting of amphibole-bearing pyroxenites in the lower crust or upper mantle. The current models fail, however, to explain the high abundance of SiO2-undersaturated melts as well as their compositional difference with host rocks for the major elements but not for incompatible trace elements. Here we report results from the investigation of rocks and melt inclusions in olivine from Klyuchevskoy volcano in Kamchatka. We show that experimental re-hydration of SiO2-undersaturated melt inclusions in olivine Fo85−90 at 300 MPa pressure and 1200 °C causes a concomitant enrichment of melt in H2O and SiO2 so that re-hydrated inclusions (4–5 wt% H2O) become as silica-saturated as primitive Klyuchevskoy rocks. An experimental dehydration of previously re-hydrated inclusions also resulted in coupled depletion of melt in H2O and SiO2. The estimated stoichiometry of SiO2 and H2O gain/loss is consistent with dissolution/crystallization of metal-defect olivine on inclusion walls. The migration mechanism of water is controlled by hydrogen diffusion in the octahedral metal (Mg, Fe) vacancies through olivine structure as confirmed by FTIR spectroscopy. We conclude that the previously reported SiO2-undersaturated composition of many melt inclusions from hypersthene-normative island-arc rocks can be explained by the coupled loss of up to several weight percent of H2O and SiO2 from the initially trapped primitive SiO2-saturated hydrous melts. Thus, SiO2-undersaturated melt inclusions may not be representative of primitive island-arc magmas. The discovery of the coupled SiO2 and H2O loss from inclusions allowed us to propose a method for reconstruction of the initial water content even for completely dehydrated inclusions. The results of this study may indicate that the majority of primitive island-arc inclusions have not preserved their initial H2O content, and that primary arc melts contain on average ≥4 wt% H2O. The higher H2O concentration in primary arc melts implies the existence of a ‘crustal filter’ controlling the water content, which can be preserved in melt inclusions, and also the lower mantle melting temperatures and higher output H2O fluxes in subduction zones than previously estimated based on direct determination of H2O in potentially dehydrated melt inclusions.