Nepheline Crystals Research Articles

Nepheline crystallization and the residual glass composition: Understanding waste glass durability

AbstractThe vast majority of High‐Level Waste (HLW) originating from defense nuclear programs is sequestered and immobilized in borosilicate glass. Borosilicate glass is universally accepted for immobilizing HLW, but its efficiency has limitations based on the compositional makeup of the waste stream. The chemical durability of the glass is the most important factor in determining the longevity and usefulness of the final glass waste form. The primary detriment to this durability in glasses containing high levels of aluminum is nepheline (NaAlSiO4) crystallization, as it is generally accompanied by a measurable decrease in the glass's chemical durability. This work seeks to understand nepheline crystallization, within the context of thermal history, and to elucidate the influence of compositional shifts in the residual glass (after crystallization) on the measured durability. The results presented within show a distinct deviation in leaching behavior as a function of structural makeup (calculated Q units). This understanding will provide practical information required for broadening glass compositional regions needed to more efficiently vitrify HLW.

Nonlinear logistic regression mixture experiment modeling for binary data using dimensionally reduced components

AbstractThis article motivates, presents, and illustrates an approach using nonlinear logistic regression (NLR) for modeling binary response data from a mixture experiment when the components can be partitioned into groups used to form dimensionally reduced components (DRCs). A DRC is formed from a linear combination of the components in a group having similar roles and/or effects of the same sign, where the linear combinations over all groups are normalized so that the DRC proportions sum to one. Linear combinations of a particular form provide for quantifying the effects of the remaining components in a group relative to a chosen component. This reason, plus dimensional reduction, are the primary motivations for the proposed DRC mixture experiment modeling approach. NLR is required because models expressed in terms of the DRCs are nonlinear in the parameters that specify the linear combinations. A method for obtaining nonparametric tolerance limits on the probability of a “success” for the binary response variable using a bootstrap approach is also presented. Finally, the article shows how DRCs provide for visualizing data and modeling results that otherwise would be impossible. A real database on the presence or absence of nepheline crystals in simulated nuclear waste glass is used to illustrate the NLR modeling and nonparametric tolerance limit approaches. The methodology is general and can be applied to other applications.

Developing a space-filling mixture experiment design when the components are subject to linear and nonlinear constraints

This article presents a case study of developing a space-filling design (SFD) for a constrained mixture experiment when the experimental region is specified by single-component constraints (SCCs), linear multiple-component constraints (LMCCs), and nonlinear multiple-component constraints (NMCCs). Traditional methods and software for designing constrained mixture experiments with SCCs and LMCCs (using either optimal design or SFD approaches) are not directly applicable because of the NMCCs. A SFD algorithm in the JMP® software was modified to accommodate the NMCCs; the modification is described in this article. The case study involves high-level waste (HLW) glass that is subject to the formation of nepheline crystals as the glass cools. This can significantly reduce the durability of HLW glass (which is undesirable). The goal of the study was to develop a SFD for the HLW glass compositional region where nepheline may form, and generate data for modeling nepheline formation as a function of HLW glass composition. The HLW glass composition region was specified in terms of eight components with SCCs, two LMCCs, and two NMCCs. The NMCCs were based on a nonlinear logistic regression model for a binary nepheline response that was developed from previous data. This article discusses the HLW glass example, the constraints specifying the experimental composition region, and how an existing algorithm for generating SFDs was modified to accommodate the NMCCs. The methodology discussed in this article can be applied to any example in which the experimental region is specified by one or more nonlinear constraints in addition to linear constraints on mixture components and/or non-mixture variables.

Nepheline crystallization behavior in simulated high-level waste glasses

The U.S. Department of Energy immobilizes legacy nuclear high-level waste (HLW) in borosilicate glass. HLW glass with elevated Na2O and Al2O3 concentrations have a demonstrated propensity for precipitating nepheline (NaAlSiO4) during cooling, which adversely affects the waste form performance. Currently, nepheline is suppressed by controlling the HLW glass composition, but this can limit the waste loading and result in longer mission life and cost. Correlation between composition and thermal history experienced during processing with time-temperature relationships that enable nepheline crystal growth would facilitate a more realistic prediction of nepheline crystallization in HLW glass and allow for a wider range of compositions to be accessed. In this work, crystallization behavior in simulated HLW glass was investigated to identify key attributes that lead to nepheline formation, with results indicating that the rate of diffusion for crystal growth may be controlled by glass structure connectivity.

Chemical Composition and Petrogenetic Implications of Apatite in the Khibiny Apatite-Nepheline Deposits (Kola Peninsula)

Khibiny, one of the largest of the world’s peralkaline intrusions, hosts gigantic apatite deposits. Apatite is represented by F-apatite and it contains exceptionally high concentration of SrO. (4.5 wt % on average) and increased amounts of rare earth elements (REEs; up to 8891 ppm). Such enrichment of apatite ores in REEs defined Khibiny deposit as world-class deposit with resources reaching several millions tons REE2O3. Apatite from the Khibina alkaline complex is characterized by the significant enrichment in light REEs relative to the heavy REEs (with average Ce/Yb ratio of 682) and the absence of a negative Eu anomaly. The obtained geochemical signature of apatite suggests a residual character of the Khibiny alkaline magma and it indicates that the differentiation of the primary olivine-melanephelinitic magma developed without fractionation of plagioclase which is the main mineral-concentrator of Sr and Eu in basaltic magmatic systems. The compositional evolution of the Khibiny apatite in the vertical section of the intrusion reflects primary fractionation processes in the alkaline magma that differentiated in situ. The main mechanism for the formation of the apatite-nepheline deposits was the gravitational settling of large nepheline crystals in the lower part of the magma chamber, while very small apatite crystals were suspended in a convective magma, and, together with the melt, were concentrated in its upper part of the magmatic chamber.

Chiral Proportions of Nepheline Originating from Low-Viscosity Alkaline Melts. A Pilot Study

Chromatographic interaction between infiltrating solutions of racemic mixtures of enantiomers and enantiomorphic minerals with chiral excess has been proposed as a scenario for the emergence of biomolecular homochirality. Enantiomer separation is supposed to be produced by different partition coefficients of both enantiomers with regard to crystal faces or walls of capillary tubes in the enantiomorphic mineral. Besides quartz, nepheline is the only common magmatic mineral with enantiomorphic symmetry. It crystallizes from SiO2-undersaturated melts with low viscosity and is a promising candidate for chiral enrichment by autocatalytic secondary nucleation. Under liquidus conditions, the dynamic viscosity of silicate melts is mainly a function of polymerization. Melts with low concentrations of SiO2 (<55 wt%) and rather high concentrations of Na2O (>7 wt%) are only slightly polymerized and hence are characterized by low viscosities. Such melts can ascend, intrude or extrude by turbulent flow. Fourteen volcanic and subvolcanic samples from alkaline provinces in Africa and Sweden were chemically analyzed. Polished thin sections containing fresh nepheline phenocrysts were etched with 1% hydrofluoric acid at 20 °C for 15 to 25 min. Nepheline crystals suitable for a statistical evaluation of their etch figures were found in four samples. Crystals with chiral etch figures are mainly not twinned. Their chiral proportions in grain percentages of single crystals are close to parity in three samples. Only one sample shows a slight chiral excess (41.67% L-type vs. 58.33% D-type) but at a low level of significance (15 vs. 21 crystals, respectively).

CO2-rich phonolitic melt and carbonatite immiscibility in early stage of rifting: Melt inclusions from Hanang volcano (Tanzania)

Hanang volcano is the southern volcano of, the southern area of the east part of the East African Rift (the North Tanzanian Divergence) and represents volcanic activity of the first stage of continental break-up. In this study, we investigate glassy melt inclusions in nepheline phenocrysts to constrain the late stage of Mg-poor nephelinite evolution and the behaviour of volatiles (CO2, H2O, S, F, Cl) during magma storage and ascent during early stage rifting. The melt inclusions have a green silicate glass, a carbonate phase and a shrinkage bubble free of gas phase indicating that carbonatite:silicate (18:82) liquid immiscibility occurred during nephelinite magmatic evolution. The silicate glasses have trachytic composition (Na + K/Al = 1.6–7.2, SiO2 = 54–65.5 wt%) with high CO2 (0.43 wt% CO2), sulfur (0.21–0.92 wt% S) and halogens (0.28–0.84 wt% Cl; 0.35–2.54 wt% F) contents and very low H2O content (<0.1 wt%). The carbonate phase is an anhydrous Ca-Na-K-S carbonate with 33 wt% CaO, 20 wt% Na2O, 3 wt% K2O, and 3 wt% S. The entrapped melt in nepheline corresponds to evolved interstitial CO2-rich phonolitic composition (Na + K/Al = 6.2–6.9) with 6 ± 1.5 wt% CO2 at pressure of 800 ± 200 MPa after crystallization of cpx (17%), nepheline (40%) garnet (6.5%) and apatite (1.7%) from Mg-rich nephelinitic magma. During ascent, immiscibility in phonolitic melt inclusions leads to Ca-Na carbonate melt with composition within the range of carbonate melt from Oldoinyo Lengai and Kerimasi, in equilibrium with trachytic silicate melt (closed-system, P < 500 MPa). The CO2-rich phonolitic melt inclusions from Hanang volcano may represent an early stage of differentiation before Na‑carbonatitic magmatism observed at Oldoinyo Lengai.

Crystallization of iron‐containing sodium aluminosilicate glasses in the NaAlSiO4‐NaFeSiO4 join

AbstractAlthough natural materials are the subject of most Earth science articles, fundamental studies on analogous synthetic materials, produced under laboratory‐controlled conditions, can provide significant insight into expected behavior of natural systems. Iron, a common element in natural aluminosilicates as well as high‐level nuclear wastes, plays a crucial role in crystallization behavior. In the present study, effects of Fe‐Al substitution in nepheline‐based aluminosilicate glasses (NaAl(1 − x)FexSiO4, x = 0.0–1.0) were investigated to assess the role of iron in crystallization, employing semiquantitative X‐ray diffraction (XRD), vibrating sample magnetometry (VSM), and electron probe microanalysis (EPMA). Fe promotes nepheline crystallization when substituted for Al in low additions (x &lt; 0.3), yet suppresses it at higher additions (x &gt; 0.5). Since effect of Fe is the subject of the present work and is the most common magnetic element, magnetic techniques were used to further analyze the phase assemblage. VSM measurements revealed that Fe oxides, i.e., hematite and magnetite, are present in cases even when their fractions are below the XRD detection limit, and backscattered electron micrographs confirm their presence. EPMA also shows that Fe incorporation in nepheline increases with increasing Fe‐Al substitution, up to a maximum of x = 0.37 for the nepheline crystals in the sample with starting glass of Na(Al0.3Fe0.7)SiO4. The residual glass, on the other hand, contains approximately constant Fe concentration x ~ 0.54–0.59 for all samples with starting Fe addition 0.4 ≤ x ≤ 0.8, and excess iron is expelled into Fe oxide phases. The significance of these results for geological processes and immobilization of high‐level nuclear waste is discussed.

Effect of Li, Fe, and B Addition on the Crystallization Behavior of Sodium Aluminosilicate Glasses as Analogues for Hanford High Level Waste Glasses

ABSTRACTCrystallization of aluminosilicates during the conversion of Hanford high-level waste (HLW) to glass is a function of the composition of the glass-forming melt. In high-sodium, high-aluminum waste streams, the crystallization of nepheline (NaAlSiO4) removes chemically durable glass-formers from the melt, leaving behind a residual melt that is enriched in less durable components, such as sodium and boron. We seek to further understand the effect of lithium, boron, and iron addition on the crystallization of model silicate glasses as analogues for the complex waste glass. Boron and iron behave as glass intermediates which allow for crystallization when present in low additions but frustrate crystallization in high additions. In this work, we seek to compare the average structures of quenched and heat treated glasses through Raman spectroscopy, X-ray diffraction, vibrating sample magnetometry, and X-ray pair distribution function analysis. The endmembers of this study are feldspathoid-like (LiAlSiO4, NaAlSiO4, NaBSiO4, and NaFeSiO4), pyroxene-like (LiAlSi2O6, NaAlSi2O6, NaBSi2O6, and NaFeSi2O6), and feldspar-like (LiAlSi3O8, NaAlSi3O8, NaBSi3O8, and NaFeSi3O8). Such a comparison will provide further insight on the complex relationship between the average chemical ordering and topology of glass on crystallization.

Genesis of apatite ores of the Magan massif (northern East Siberia)

Having applied the methods of comprehensive melt inclusion studies, we elucidated the formation conditions for one of the largest apatite deposits in the Maimecha–Kotui province, located in the exocontact zone of the Magan alkaline ultramafic carbonatite massif, in apoquartzite fenite-aegirinites. We examined the most P-enriched exocontact nepheline-containing aegirinites and ijolite veins in them. In veined ijiolite, primary silicate–salt melt inclusions in nepheline and syngenetic primary silicate, alkali sulfate–carbonate, and carbonate melt inclusions in apatite were found. Primary alkali sulfate–carbonate melt inclusions were also identified in apatite from exocontact nepheline-containing aegirinites. Detailed analysis of the inclusions showed that nepheline of the apatite-containing ijolite veins crystallized at 1100–1120 °C from homogeneous nephelinite melt, which was enriched in SO3, Cl, CO2, and H2O and locally contaminated with quartz sandstones and quartzites. At lower temperatures (either at the final stages of nepheline crystallization or at the early stages of apatite formation), the melt was already heterogeneous (probably, because of immiscibility) and consisted of more Si-saturated, alkali sulfate–carbonate, and carbonate fractions. Apatite crystallized mainly from separated alkali sulfate–carbonate melts: at 1080–980 °C in veined ijolites and at 940–760 °C in aegirinites. Alkali sulfate–carbonate melts in veined ijolites were enriched in SO3 but depleted in P as compared with those in aegirinites. At the final stage, apatite crystallized from P-poor carbonate melts.

Nepheline structural and chemical dependence on melt composition

Nepheline crystallizes upon slow-cooling in some melts concentrated in Na2O and Al2O3, which can result in a residual glass phase of low chemical durability. Nepheline can incorporate many components often found in high-level waste radioactive borosilicate glass, including glass network ions (e.g., Si, Al, Fe), alkali metals (e.g., Cs, K, Na, and possibly Li), alkaline-earth metals (e.g., Ba, Sr, Ca, Mg), and transition metals (e.g., Mn, and possibly Cr, Zn, Ni). When crystallized from melts of different compositions, nepheline composition varies as a function of starting melt composition. Five simulated high-level nuclear waste borosilicate glasses shown to crystallize large fractions of nepheline on slow-cooling were selected for study. These starting melt compositions contained a range of Al2O3, B2O3, CaO, Na2O, K2O, Fe2O3, and SiO2 concentrations. Compositional analyses of nepheline crystals in glass by electron probe micro-analysis (EPMA) indicate that nepheline is generally rich in silica, whereas boron is unlikely to be present in any significant concentration, if at all, in nepheline. Also, several models are presented for calculating the fraction of vacancies in the nepheline structure.

Assimilation and fractional crystallization of foid-bearing alkaline rocks:Buzlukdağ intrusives, Central Anatolia, Turkey

Felsic intrusive rocks within the Central Anatolian Crystalline Complex provide a window into the geodynamic processes in operation during the final closure of the Neotethys Ocean. Previous studies were largely restricted to the calc-alkaline granitoids, and the structural and petrogenetic relations of syenitoids are poorly studied. The Buzlukdag Intrusive Complex is a silica-undersaturated alkaline syenite that is differentiated into three concentric subgroups according to texture and grain size. Mineral compositions do not vary between the subgroups but differentiation has resulted in different mineral proportions. Mafic microgranular enclaves are present throughout the suite, indicating mingling and mixing between the coeval felsic and mafic magmas. Major element concentrations are consistent with fractional crystallization of nepheline + K feldspar ± Na rich plagioclase + Na amphibole + pyroxene ± melanite ± cancrinite. Mineral chemistry reveals that the syenites are crystallized under a wide range of pressures (1.5-3.7 kbar), at varying temperatures (732-808 °C), and are likely emplaced at depths of 6-14 km. Large-ion lithophile element and light rare earth element enrichments with respect to high field-strength elements and heavy rare earth elements are consistent with their derivation from an incompatible element-enriched magma source. Incompatible trace element concentrations (e.g., Sr, Ba, Th, Ta, Pb, La, Ce, and Yb) revealed that the magma has a subduction fluid component, which can be distinguished from crustal assimilation. The Buzlukdag alkaline intrusive rocks are likely to be derived from decompressional melting of the lithospheric mantle above asthenospheric upwelling as a result of crustal thinning of Central Anatolia during the Late Mesozoic-Early Cenozoic.

Eudialyte-group minerals in rocks of Lovozero layered complex at Mt. Karnasurt and Mt. Kedykvyrpakhk

Eudialyte-bearing interbeds within layers I-4 (Mt. Karnasurt) and II-4 (Mt. Kedykvyrpakhk) in the layered complex of the Lovozero Pluton are localized symmetrically relative to the loparite-bearing ijolite–malignite layer; the content of eudialyte decreases from underlying nepheline syenite to overlying foidolite. Eudialyte-group minerals fill the interstices between nepheline, sodalite, and microcline-perthite crystals in all rock types and are partially replaced with georgechaoite and minerals of the lovozerite group as a result of hydrothermal alteration. Variations in the chemical composition of the eudialyte-group minerals are mainly controlled by block substitution NaFeZrCl ↔ LnMn(Nb,Ti)S producing eudialyte proper, manganoeudialyte (sharply predominant), kentbrooksite, alluaivite, and a phase intermediate between manganoeudialyte and alluaivite. As the total Ln2O3 content increases, the relative amounts of Ce and La oxides increases linearly in the proportion Ce2O3: La2O3 = 2.5: 1. In the phases containing lower than 3 wt % La2O3, Nd becomes the next REE after Ce. It is very likely that (mangano)eudialyte was mostly formed after parakeldyshite and other anhydrous zirconium-silicate under effect of residual fluids enriched in Ca and Mn, which took part in fenitization of basalt, tuff, and tuffite of the Lovozero Formation.

Role of volatiles (S, Cl, H2O) and silica activity on the crystallization of haüyne and nosean in phonolitic magmas (Eifel, Germany and Saghro, Morocco)

To constrain the crystallization of alkaline and volatile-rich lavas present in intraplate settings, we studied the petrological features and the geochemical composition of major, trace, and volatile elements of mineral and bulk-rock of two sodalite-bearing phonolites: (1) hauyne-plagioclase-bearing Si-K-rich phonolite from Laacher See (Germany) and (2) nosean-nepheline-bearing Si-poor phonolite from Saghro (Morocco). In hauyne-bearing phonolites (55–59 wt% SiO2, K > Na, Na+K/Al = 0.96–1.08), we found that the low silica and low sodium activity promoted the early crystallization of S-rich hauyne (13.7–13.9 wt% SO3, 0.4 wt% Cl) + S-rich apatite (0.7–0.9 wt% SO3), titanite, and rare pyrrhotite followed by clinopyroxene-plagioclase-sanidine at relatively low pressure and temperature (P = 250 MPa and T = 850 °C) and oxidized condition (ΔNNO-NNO+1, where NNO is nickel-nickel oxide buffer). The crystallization of hauyne occurred at fluid-undersaturated conditions from a silicate melt with 6 wt% H2O, 0.17–0.23 wt% Cl, 0.11–0.4 wt% S, and 0.07–0.14 wt% F. Nosean-bearing phonolites from Saghro are silica-poor and peralkaline (52–54 wt% SiO2, Na > K, Na+K/Al = 1.2) and crystallized at higher P and T (300 MPa and 950 °C) and more reduced conditions (NNO) compared to hauyne-bearing phonolites. The incongruent reaction to form nosean requires high silica and Na2O activity. The mineral assemblage and composition suggest early crystallization of nepheline followed by nosean (7.8–8.8 wt% SO3; 1–1.1 wt% Cl). The sequence of crystallization is: clinopyroxene + nepheline + S-poor apatite (<0.04 wt% SO3) + pyrrhotite followed by nosean and titanite. Nosean-bearing magmas are fluid-undersaturated with relatively low volatile content (4 wt% H2O, <0.25 wt% Cl, <0.056 wt% S, 0.08–0.1 wt% F), although Cl may have exsolved during ascent and formed a fluid phase (NaCl-bearing). Both hauyne- and nosean-bearing phonolites are last equilibrated at relatively low pressure and high temperature. Hauyne and nosean crystallized at oxidized and volatile-rich pre-eruptive conditions. They record the volatile concentrations at depth and may be used as oxybarometer. The incongruent reactions involved to form hauyne and nosean suggest that phonolitic magmas became more oxidized during crystallization. The initial volatile concentrations in basanite/nephelinite magmas, from partial melting of volatile-bearing K2O-rich mantle rock, should have been one important factor influencing the crystallization of hauyne-bearing Si-K-rich phonolite and nosean-bearing Si-poor phonolite in intracontinental setting.

High performance transparent glass-ceramics for optical components

Glass-ceramics based on nepheline crystal (Na3(Na,K)[Al4Si4O16]) system was modified to satisfy the thermal and optical properties required for a band-pass filter (BPF) in telecommunication systems using optical fibers. The suitable coefficient of thermal expansion was achieved in a glass-ceramic containing more potassium oxide than the conventional nepheline glass-ceramics, in nepheline–kalsilite (K[AlSiO4]) binary system. An addition of the moderate amount of nucleating agents is a key parameter to obtain high transparency of the glass-ceramics. The optimized nepheline–kalsilite glass-ceramic showed higher mechanical strength as compared with the monolithic glassy material used in the same application.

Nepheline crystallization in boron-rich alumino-silicate glasses as investigated by multi-nuclear NMR, Raman, & Mössbauer spectroscopies

A spectroscopic study was conducted on six simulant nuclear waste glasses using multi-nuclear NMR, Raman, and Mössbauer spectroscopies exploring the role of Si, Al, B, Na, and Fe in the glass network with the goal of understanding melt structure precursors to deleterious nepheline crystal formation. NMR showed two sites each for Al, Si, and Na in the samples which crystallized significant amounts of nepheline, and B speciation changed, typically resulting in more B(IV) after crystallization. Raman spectroscopy suggested that some of the glass structure is composed of metaborate chains or rings, thus significant numbers of non-bridging oxygen and a separation of the borate from the alumino-silicate network. Mössbauer, combined with Fe redox chemical measurements, showed Fe playing a minor role in these glasses, mostly as Fe3+, but iron oxide spinel forms with nepheline in all cases. A model of the glass network and allocation of non-bridging oxygens (NBOs) was computed using experimental B(IV) fractions which predicted a large amount of NBO consistent with Raman spectra of metaborate features.

A new biocompatible and antibacterial phosphate free glass-ceramic for medical applications.

In the attempt to find valid alternatives to classic antibiotics and in view of current limitations in the efficacy of antimicrobial-coated or loaded biomaterials, this work is focused on the development of a new glass-ceramic with antibacterial performance together with safe biocompatibility. This bactericidal glass-ceramic composed of combeite and nepheline crystals in a residual glassy matrix has been obtained using an antimicrobial soda-lime glass as a precursor. Its inhibitory effects on bacterial growth and biofilm formation were proved against five biofilm-producing reference strains. The biocompatibility tests by using mesenchymal stem cells derived from human bone indicate an excellent biocompatibility.

Non-isothermal crystallisation behaviour of fluorophlogopite/nepheline glass ceramics

Fluorophlogopite/nepheline glass ceramics were formed from the system of SiO2–Al2O3–MgO–K2O–Na2O–F, and the thermodynamic, crystallisation behaviour and microstructure were investigated using differential thermal analysis, X-ray diffraction, and scanning electron microscopy. It was found that fluorophlogopite crystals and nepheline crystals crystallised simultaneously, and bulk nucleation was the main crystallisation mechanism. Crystal growth was prone to follow the two-dimensional direction and controlled by diffusion. Activation energy for glass transition was 797·43 kJ mol−1, and crystallisation activation energy was 433·16 kJ mol−1.

Micro-Raman spectroscopy and SIMS characterization of oxykinoshitalite in an olivine nephelinite from the Hyblean Plateau (Sicily, Italy)

A Ba-Ti rich oxymica occurs in an olivine nephelinite from S. Demetrio High in the northern margin of the Hyblean Plateau (Sicily, Italy). The rock sample exhibits a porphyritic texture formed by olivine, clinopyroxene, nepheline, titanian magnetite, apatite, and rare subhedral tabular mica crystals, which have a perfect cleavage on {001}, and a strong pleochroism with X pale brown and YZ brown. The studied oxykinoshitalite, characterized by micro-Raman spectroscopy, electron microprobe WDS (wavelength- dispersive system), and secondary-ion mass spectrometry (SIMS), was compared with the type material from the Fernando de Noronha island (Pernambuco, Brazil). Structural formula of the Hyblean oxykinoshitalite, calculated on the basis of 7 (Si, Al, Fe, Mg, Ti), is (Ba0.51K0.41Na0.04Ca0.01)0.97(Mg1.98Fe0.55Ti0.48)3.01(Si2.42Al1.56)3.98 O10(O1.17F0.62(OH)0.21)2.00. The lack of chemical zoning and the enrichment in Zr and Nb in the groundmass crystals of the Hyblean oxykinoshitalite suggest formation during the final crystallization stage of a basaltoid magma with ocean island basalt (OIB) affinity. Most likely, the magma originated by partial melting of metasomatized ultramafic rocks in the Hyblean crustal basement.

Structural analysis of some sodium and alumina rich high-level nuclear waste glasses

Sodium- and aluminum-rich high-level nuclear waste glasses are prone to nepheline (NaAlSiO4) crystallization. Since nepheline removes three moles of glass-forming oxides (Al2O3 and SiO2) per mole of Na2O, the formation of this phase can result in severe deterioration of the chemical durability in a given glass. The present study aims to investigate the relationships between the molecular-level structure and the crystallization behavior of sodium alumino-borosilicate-based simulated high-level nuclear waste glasses with infrared spectroscopy (FTIR) and X-ray diffraction, respectively. The molecular structure of most of the investigated glasses comprise a mixture of Q2 and Q3 (Si) units while aluminum and boron are predominantly present in tetrahedral and trigonal coordination, respectively. The increasing boron content has been shown to suppress the nepheline formation in the glasses. The structural influence of various glass components on nepheline crystallization is discussed.