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The non-classical crystallization pathway of carbonate minerals proceeds through the initial formation of an amorphous precursor phase and commonly takes place during biomineralization. Although the isotopic composition of marine calcifiers is often used to reconstruct paleo-environmental conditions, the impact of the crystallization pathway followed by these organisms on the isotope composition of their skeletons has rarely been quantified. This study presents the first examination of B partitioning and isotope fractionation during CaCO3 formation via an amorphous calcium carbonate phase, which provides new insights into the incorporation of B into marine calcite and aragonite that form via this route. Boron concentrations and isotope compositions of the fluids and the formed solids were characterized during the course of experiments that lasted two years and were performed at 25 °C under controlled pH conditions. The results suggest that during Mg-ACC formation, B distribution coefficients are 1.5–4 orders of magnitude higher than those reported earlier in the literature for calcite and aragonite. Additionally, B isotope fractionation during Mg-ACC formation is strongly affected by the continuous exchange of solutes between the nanoporous solid phase and the bulk fluid. The isotope composition of the transient amorphous phase is not inherited in the crystalline carbonate mineral phase that ultimately forms, because crystallization proceeds via a continuous dissolution/re-precipitation process and/or chemical/isotope exchange between the solid surface and the fluid. Interestingly, the isotope fractionation between the fluid and the final crystalline products is different from those achieved in earlier studies where mineral growth proceeded via the standard mechanism of ion-by-ion addition of solutes to advancing steps. The B isotope fractionations measured in this study are in good agreement with results of equilibrium first principle calculations for calcite and aragonite (Balan et al., 2018) except in the case of calcite formed at pH = 8.9, suggesting that changes in aqueous speciation (i.e. increase of NaB(OH)4° and CO32− concentrations) may be responsible for slight changes of the calcite BO4 environment and isotope composition. It is expected that this study will help to better decipher the mechanisms controlling B isotope fractionation during the non-classical growth of calcium carbonates involving the formation of transient amorphous precursors.

International audience; In this study, to better understand the factors controlling the concentration and isotope composition of lithium (Li) in the ocean, we investigated the behaviour of Li during interaction of kaolinite with artificial seawater. Dissolution of kaolinite in Li-free seawater at acidic conditions (exp. 1) results in a strong preferential release of light Li isotopes, with △7Liaq-kaol ∼ −19‰, likely reflecting both the preferential breaking of 6Lisingle bondO bonds over 7Lisingle bondO bonds and the release of Li from the isotopically lighter AlO6 octahedral sites. Sorption experiments on kaolinite (exp. 2) revealed a partition coefficient between kaolinite and fluid of up to 28, and an isotopic fractionation of −24‰. Thermodynamic calculation indicates authigenic smectites formed from the dissolution of kaolinite in seawater at pH 8.4 (exp. 3). The formation of authigenic phase strongly removed Li from the solution (with a partition coefficient between the solid and the fluid equal to 89) and led to an increase of ca. 25‰ in seawater δ7Li. This fractionation can be described by a Rayleigh fractionation model at the early stage of the experiment during rapid clay precipitation, followed, at longer reaction time, by equilibrium isotope fractionation during the much slower removal of aqueous Li via co-precipitation and adsorption. Both processes are consistent with a fractionation factor between the solid and the aqueous solution of ∼−20‰. These experiments have implications for interpreting the Li isotopic composition of both continental and marine waters. For instance, the preferential release of 6Li observed during kaolinite far-from-equilibrium dissolution could explain the transient enrichments in 6Li observed in soil profiles. With regard to the evolution of seawater δ7Li over geological time scales, our experimental results suggest that detrital material discharged by rivers to the ocean and ensuing “reverse chemical weathering” have the potential to strongly impact the isotopic signature of the ocean through the neoformation of clay minerals.

A 4-electrode technique has been used to measure the ionic conductivity in the binary lithium borate system XLi2O-(100-X)B2O3 (X = 10–45 mol%) in a large temperature interval (300 °C-1100 °C). Above the glass transition temperature, the dc conductivity increases faster than in glassy state and it doesn't follow the Arrhenius law anymore. In the molten and the supercooled states, the conductivity data are well described by the phenomenological VFT law characteristic of a cooperative conduction mechanism. Moreover, at a given temperature, the conductivity increases with the Li2O content till 30 mol% of Li2O then slows down for additional Li2O oxide. This behavior, which is reported for the first time, could be associated to the signature of the “boron anomaly” in the molten state.

International audience; We report a detailed structural investigation of Ca-Na aluminosilicate glasses containing 0-20 wt% ZrO2 using X-ray absorption spectroscopy, Raman spectroscopy and 27 Al and 29 Si NMR. The X-ray absorption spectroscopy data reveal that Zr is predominantly present in ZrO6 octahedra but a significant Zr coordination change occurs with increasing ZrO2 content. Though Al and Zr are competing to be surrounded by charge balancing cations, 27 Al NMR data do not show the presence of high-coordinated Al species; thus charge-balancing cations are preferentially localized close to AlO4 tetrahedra rather than Zr polyhedra, explaining the increase in Zr coordination number that ultimately leads to limit Zr solubility in glasses. Raman and 29 Si NMR data indicates that Zr atoms are linked to the silicate network with a trend for higher degree of network connectivity at high zirconia content. Change in network connectivity and in Zr environment provide insights to understand chemical durability or crystallization in glasses.

For the handling of high level nuclear waste (HLW), new glass formulations with a high waste capacity and an enhanced thermal stability, chemical durability, and processability are under consideration. This study focuses on the durability of peraluminous glasses in the SiO2–Al2O3–B2O3–Na2O–CaO–La2O3 system, defined by an excess of Al3+ ions compared with the network-modifying cations Na+ and Ca2+. To qualify the behavior of such a peraluminous glass in a geological storage situation, its chemical durability was studied in various environments (pure water, groundwater, and alkaline solutions related to a cement environment) and glass alteration regimes (initial rate, residual rate, and resumption of alteration). The alteration solution was characterized by inductively coupled plasma, and the altered glass by scanning electron microscopy, X-ray diffraction and secondary ion mass spectrometry. A comparative study of the chemical durability of these and reference glasses (ISG and SON68) over all timescales highlights the remarkable properties of the former. While their initial dissolution rate is of the same order as the reference glasses, the gel formed under silica saturation conditions is more passivating, making its dissolution rate at least one order of magnitude lower, while its low alkalinity makes it less susceptible to clayey groundwater and highly alkaline solutions. How a ‘peraluminous’ glass—of interest in nuclear waste storage—changes in solution has been studied. The long term behaviour of borosilicate nuclear glasses, used to store high-level nuclear waste, has important safety ramifications and it is known that dissolution and precipitation processes in water can affect their durability. A team, led by Maxime Fournier at the CEA, Marcoule, France, has now studied the durability of a ‘peraluminous’ glass, which is defined by its excess of Al3+ ions as compared to more standard ‘peralkaline’ glasses. Such materials are known to form passivating layers on their surface in aqueous solution and the researchers observe that the layer that forms on the surface of the ‘peraluminous’ glass is more passivating than that on the peralkaline reference glasses used for comparison, resulting in a significantly lower dissolution rate.

International audience; Calcium is an essential component of osteogenesis and is often required for imparting significant bioactivity to synthetic bone substitutes and, in particular, silicate-based materials. However, the mechanism of calcium incorporation inside sol–gel silicates is poorly understood. In this work, we shed light on the determinant parameters for incorporation of calcium into acid–base-catalyzed sol–gel silicates at ambient temperature: increasing the pH above the isoelectric point of silicic acid and the nature of the calcium counterion in the calcium precursor are found to be the key. Based on our proposed reaction sequence, we were able to compare calcium precursors and select an ideal candidate compound for the synthesis of bioactive glasses (BG) and organic–inorganic hybrids at ambient temperature. Reproducible syntheses and gel times of SiO2–CaO BG were obtained using calcium hydroxide (CH), and we demonstrate its usability in the synthesis of promising BG–polycaprolactone hybrid scaffolds. BG and hybrids prepared with CH were able to form nanocrystalline nonstoichiometric apatite in simulated body fluid. The increased reliability of low-temperature syntheses associated with the use of a stable and inexpensive alkaline-earth precursor are major steps toward the translation of calcium silicate hybrids or other alkaline-earth silicates from bench to clinic.

International audience; The structural and microstructural properties of both homogeneous and phase separated lanthanum aluminosilicate (La$_2$O$_3$-Al$_2$O$_3$-SiO$_2$ i.e. LaAS system) glasses were investigated. The microstructural observations and the structural characterization by X-ray Diffraction and by Nuclear Magnetic Resonance have highlighted the role of aluminum to favor a homogeneous vitreous aluminosilicate network by a high-level of Al/Si intermixing. A qualitative and simplified structure description is proposed from $^{29}$Si nuclear magnetic resonance spectra assignment according to Q$^n$(mAl) species by controlling the deviation of chemical parameters. According to this approach, a homogeneous distribution of non-bridging oxygen in the aluminosilicate network and Al-O-Al linkages are considered for homogeneous glasses with high Al/Si atomic ratio. Phase separated samples are characterized by a low Al/Si atomic ratio inducing spinodal or nucleation/growth phase separation according to the depolymerization level. Homogeneity degree of the samples is discussed according to the intermixing level between silicon tetrahedra and aluminum polyhedra as a function of the proportion of Q$^n$ and Q$^n$(mAl) species.

Thanks to their active promotion of bone formation, bioactive glasses (BG) offer unique properties for bone regeneration, but their brittleness prevents them from being used in a wide range of applications. Combining BG with polymers into a true hybrid system is therefore an ideal solution to associate toughness from the polymer and stimulation of bone mineralization from the glass. In this work, we report the synthesis and characterization of hybrid scaffolds based on SiO2–CaO bioactive glass and gelatin, a hydrolyzed form of bone type-I collagen. Incorporation of calcium ions, known to trigger bone formation and cellular activity, into the hybrid structure was achieved at ambient temperature through careful control of chemistry of the sol–gel process. Thorough characterization of the materials highlights the effect of grafting an organoalkoxysilane coupling molecule to covalently link networks of BG and gelatin, and proves it a successful means to take control over the degradation and bioactive properties of hybrids. Importantly, BG–gelatin hybrids are synthesized in a process fully conducted at ambient temperature that allows obtaining open-porous scaffolding structures, with well-controlled and tuneable porosity with regards to both pore and interconnection sizes. Mechanical properties of the scaffolds under compression are similar to that of trabecular bone and their apatite-forming ability is even higher than that of pure BG scaffold foams.

Structural properties and ionic conductivity have been correlated in the XLi2O-(100 − X)B2O3 vitreous system over a wide range of composition (X = 0–50 mol%). The structural evolution of the vitreous network as a function of the lithium oxide content was established at ambient temperature by 11B and 7Li high resolution solid state NMR, while electrical conductivity has been measured by complex impedance spectroscopy from room temperature up to the glass transition temperature Tg. The 11B NMR spectra indicate that starting from pure boron trioxide glass, the addition of alkali leads to a gradual transformation of BO3 units into BO4−. From X ≈ 30, the increase of Li+ content is also accompanied by the formation of Non-Bridging Oxygen (NBO). These specific structural changes have been used to interpret the conductive behavior of vitreous lithium borates. Indeed, measured on a wide range of composition, the direct conductivity (σdc) increases with the Li2O content and exhibits a clear regime change at X ≈ 32, which can be correlated to the interaction of cations with BO4− units and NBO.

International audience; The alkylation of sulfur-containing compounds (benzothiophene and thiophene) with 2-methyl-1-pentene was investigated over MgF2-supported heteropoly acid (H3PW12O40: HPW) as catalysts under mild conditions (85 degrees C, atmospheric pressure). The magnesium fluoride used as support was prepared by a sal-gel method and exhibited a high specific surface area (186 m(2) g(-1)). Several solids containing various amounts of HPW (in the range of 5 wt% to 46 wt%) were prepared by incipient wetness impregnation and fully characterized (ICP-OES, XRD, N-2 adsorption, TEM, IR, adsorption of pyridine followed by IR, F-19 and P-31 MAS NMR). For all solids, it was observed that the Keggin structure of HPW was preserved and that the heteropoly acid was finely dispersed on the MgF2 support. A significant modification of the textural properties of the sample containing the higher amount of HPW (46 wt%) was observed and attributed to a pore blocking phenomenon by HPW. As expected, the HPW loading in the range of 5-30 wt% allowed an increase of the Bronsted acidity. Whatever the catalyst, benzothiophene was only transformed by mono-alkylation, whereas the olefin underwent alkylation, oligomerization and isomerization, the latter being largely predominant and yielded 2-methyl-2-pentene. The increase of the HPW loading until 30 wt% led to an increase of the catalytic activity, the selectivity being not modified. In addition, a significant deactivation of catalysts containing 30 wt% and 40 wt% of HPW was observed and attributed to a strong adsorption of the alkylated products. Thiophene presented a poor reactivity through alkylation compared to benzothiophene.

International audience; Part of the Research and Development program concerning high level nuclear waste (HLW) glasses aims to assess new glass formulations able to incorporate a high waste content with enhanced properties in terms of thermal stability, chemical durability, and process ability. This study focuses on peraluminous glasses of the SiO2 – Al2O3 – B2O3 – Na2O – Li2O – CaO – La2O3 system, defined by an excess of aluminum ions Al3+ in comparison with modifier elements such as Na+, Li+ or Ca2+. To understand the effect of composition on physical properties of glasses (viscosity, density, Tg), a Design Of Experiments (DOE) approach was applied to investigate the peraluminous glass domain. The influence of each oxide was quantified to build predictive models for each property. Lanthanum and lithium oxides appear to be the most influential factors on peraluminous glass properties.

The acidity of amorphous B2O3−SiO2 has been investigated by infrared spectroscopy using the following three probe molecules presenting a wide range of basic strength: pyridine, acetonitrile, and carbon monoxide. The results are compared to those obtained on γ-Al2O3. No coordination of carbon monoxide is observed on B2O3−SiO2 even at low temperatures, whereas strongly coordinated CO species are formed on γ-Al2O3 under such conditions. Coordinated pyridine and acetonitrile show important infrared frequency shifts on both metal oxides, indicating strong charge transfer from the probe molecules to the surface Lewis acid centers. However, the thermal stability of coordinated species is much lower on B2O3−SiO2 than on γ-Al2O3, which suggests that there is no direct correlation between charge transfer and adsorption energy. Density functional theory (DFT) calculations on the interaction of these probe molecules with simple models representing Al3+ and B3+ Lewis acid sites adequately reproduce experimental obser...

When using the boron isotopic composition (δ11B) of marine carbonates as a seawater pH proxy, it is assumed that only the tetrahedral borate ion is incorporated into the growing carbonate crystals and that no boron isotope fractionation occurs during uptake. However, the δ11B of the calcium carbonate from most modern foraminifera shells or corals skeletons is not the same as the δ11B of seawater borate, which depends on pH, an observation commonly attributed to vital effects. In this study, we combined previously published high-field 11B MAS NMR and new δ11B measurements on the same synthetic calcite and aragonite samples precipitated inorganically under controlled environments to avoid vital effects. Our results indicate that the main controlling factors of δ11B are the solution pH and the mineralogy of the precipitated carbonate mineral, whereas the aqueous boron concentration of the solution, CaCO3 precipitation rate and the presence or absence of growth seeds all appear to have negligible influence. In aragonite, the NMR data show that boron coordination is tetrahedral (BO4), in addition, its δ11B is equal to that of aqueous borate, thus confirming the paleo-pH hypothesis. In contrast, both trigonal BO3 and tetrahedral BO4 are present in calcite, and its δ11B values are higher than that of aqueous borate and are less sensitive to solution pH variations compared to δ11B in aragonite. These observations are interpreted in calcite as a reflection of the incorporation of decreasing amounts of boric acid with increasing pH. Moreover, the fraction of BO3 measured by NMR in calcite is higher than that inferred from δ11B which indicates a coordination change from BO4 to BO3 upon boron incorporation in the solid. Overall, this study shows that although the observed differences in δ11B between inorganic and biological aragonite are compatible with a pH increase at calcification sites, the B speciation and isotope composition of biological calcites call for a more complex mechanism of boron incorporation.

About 20 years ago, the boron isotopic composition of marine carbonates was proposed as a proxy of ancient seawater pH. Since that time, a large body of studies has used boron isotopes in carbonates to reconstruct seawater paleo-pH and atmospheric paleo-CO2 concentration. To date, however, no systematic investigation of the physicochemical parameters that control boron incorporation in calcite and aragonite (pH, temperature, precipitation rate, etc.) has been performed. To fill this gap, we have experimentally investigated the inorganic co-precipitation of boron with calcite and aragonite at 5 and 25 °C in the presence and absence of seed crystals and over the pHNBS range 7.4 D B = ( X B / X CO 3 ) CaCO 3 ( [ B ] / [ CO 3 2 - ] ) fluid with Xi and [i] standing for the mole fraction and molality of the ith species in the solid and fluid, respectively. DB measured in this study are very small (DB ⩽ 10−3 and ⩽10−4 for aragonite and calcite, respectively) and exhibit a strong dependence on the solution pH and the calcium carbonate precipitation rate. High field 11B MAS NMR analyses of the precipitated carbonates show that boron in aragonite is mostly in the form of tetragonal B (⩾85% [IV]B) but that both trigonal and tetragonal B are present in calcite. A significant amount of tetragonal boron in calcite may be in non-lattice (defect) sites, in addition to the structural site. The relative abundance of [III]B and [IV]B in calcite is independent of the parent solution pH but appears to decrease with increasing precipitation rate. The change in boron coordination during its incorporation in calcite and its distribution in, at least, two different sites strongly suggest that the mechanisms controlling B incorporation in this mineral are more complex than for aragonite. It follows that calcite-based calibrations may be less reliable than aragonite calibrations for ocean paleo-pH reconstructions.

International audience; Bioactive glass hybrids are among the most promising materials for bone regeneration, but the incorporation of calcium, a key element for mineralization properties of the implant, into the inorganic part of the hybrid network is challenging. We present here a new synthesis route to both class I and II gelatin-bioactive glass hybrids allowing the efficient incorporation of calcium ions at low temperature.

We report new measurements of NMR parameters for 71 Ga in gallium bearing oxide reference compounds, ranging from perfectly ordered systems to disordered crystalline structures and their aluminate counterparts. Static, MAS, and QPASS spectra are obtained at magnetic fields ranging from 7.0 to 18.8 T. With these results we enhance the previously established correlation between isotropic chemical shifts of 71 Ga and 27 Al and propose a correlation between gallium and aluminum electric field gradients (EFG). This correlation shows that the EFG at 71 Ga sites are generally three times greater than those at equivalent 27 Al sites.

Considering the interest of developing new glass matrices able to immobilize higher concentration of high level nuclear wastes than currently used nuclear borosilicate compositions, glasses containing high rare earth contents are of particular interest. This study focuses on a peraluminous aluminoborosilicate system SiO2–B2O3–Al2O3–Na2O–CaO–Nd2O3 defined by a peralkaline/peraluminous ratio RP = ([Na2O] + [CaO])/([Na2O] + [CaO] + [Al2O3])

Over the years, solid-state nuclear magnetic resonance (NMR) spectroscopy has become an important tool for materials science, with its local point of view that is highly complementary to the structural information provided by diffraction techniques, electron microscopy, and molecular modeling, for example. As compared to other interactions that determine the spectral expression of the local structure of the observed nuclei in solid-state NMR experiments, the J coupling, characteristic of the chemical bonds, has received far less attention because of its being generally so small that it is masked in the line-widths. Nevertheless, the scalar or isotropic part of J couplings, which is not averaged by magic angle spinning (MAS), can be evidenced in many systems, and exploited to unequivocally characterize the extended coordination sphere. In a first step we describe the different experiments that permit the observation and the measurement of J couplings, even when dealing with quadrupolar nuclei. We then present new and recently-published results that illustrate the state of the art of NMR methodologies based on or intended for measuring J couplings in solids and the novel perspectives that they open towards better understanding of ordered and disordered materials at the subnanometric scale, a length scale that is otherwise difficult to access.

International audience; Over the years, solid-state nuclear magnetic resonance (NMR) spectroscopy has become an important tool for materials science, with its local point of view that is highly complementary to the structural information provided by diffraction techniques, electron microscopy, and molecular modeling for example. As compared to other interactions that determine the spectral expression of the local structure of the observed nuclei in solid-state NMR experiments, the J coupling, characteristic of the chemical bonds, has received far less attention because of its being generally so small that it is masked in the line-widths. Nevertheless, the scalar or isotropic part of J couplings, which is not averaged by magic angle spinning (MAS), can be evidenced in many systems, and exploited to unequivocally characterize the extended coordination sphere. In a first step we describe the different experiments that permit the observation and the measurement of J couplings, even when dealing with quadrupolar nuclei. We then present new and recently-published results that illustrate the state of the art of NMR methodologies based on or intended for measuring Jcouplings in solids and the novel perspectives that they open towards better understanding of ordered and disordered materials at the sub-nanometric scale, a length scale that is otherwise difficult to access.

We report new measurements of NMR parameters for 71Ga in gallium bearing oxide reference compounds, ranging from perfectly ordered systems to disordered crystalline structures and their aluminate counterparts. Static, MAS, and QPASS spectra are obtained at magnetic fields ranging from 7.0 to 18.8 T. With these results we enhance the previously established correlation between isotropic chemical shifts of 71Ga and 27Al and propose a correlation between gallium and aluminum electric field gradients (EFG). This correlation shows that the EFG at 71Ga sites are generally three times greater than those at equivalent 27Al sites.