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Nitridic Analogs of Micas AESi₃ P₄ N₁₀ (NH)₂ (AE=Mg, Mg_0.94 Ca_0.06 , Ca, Sr).

ABSTRACT: We present the first nitridic analogs of micas, namely AESi₃ P₄ N₁₀ (NH)₂ (AE=Mg, Mg_0.94 Ca_0.06 , Ca, Sr), which were synthesized under high-pressure high-temperature conditions at 1400 °C and 8 GPa from the refractory nitrides P₃ N₅ and Si₃ N₄ , the respective alkaline earth amides, implementing NH₄ F as a mineralizer. The crystal structure was elucidated by single-crystal diffraction with microfocused synchrotron radiation, energy-dispersive X-ray spectroscopic (EDX) mapping with atomic resolution, powder X-ray diffraction, and solid-state NMR. The structures consist of typical tetrahedra-octahedra-tetrahedra (T-O-T) layers with P occupying T and Si occupying O layers, realizing the rare motif of sixfold coordinated silicon atoms in nitrides. The presence of H, as an imide group forming the SiN₄ (NH)₂ octahedra, is confirmed by SCXRD, MAS-NMR, and IR spectroscopy. Eu²⁺ -doped samples show tunable narrow-band emission from deep blue to cyan (451-492 nm).

SUBMITTER: Eisenburger L

PROVIDER: S-EPMC9300002 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Acesta excavata (Fabricius, 1779) is a slow growing bivalve from the Limidae family and is often found associated with cold-water coral reefs along the European continental margin. Here we present the compositional variability of frequently used proxy elemental ratios (Mg/Ca, Sr/Ca, Na/Ca) measured by laser-ablation mass spectrometry (LA-ICP-MS) and compare it to in-situ recorded instrumental seawater parameters such as temperature and salinity. Shell Mg/Ca measured in the fibrous calcitic shell section was overall not correlated with seawater temperature or salinity; however, some samples show significant correlations with temperature with a sensitivity that was found to be unusually high in comparison to other marine organisms. Mg/Ca and Sr/Ca measured in the fibrous calcitic shell section display significant negative correlations with the linear extension rate of the shell, which indicates strong vital effects in these bivalves. Multiple linear regression analysis indicates that up to 79% of elemental variability is explicable with temperature and salinity as independent predictor values. Yet, the overall results clearly show that the application of Element/Ca (E/Ca) ratios in these bivalves to reconstruct past changes in temperature and salinity is likely to be complicated due to strong vital effects and the effects of organic material embedded in the shell. Therefore, we suggest to apply additional techniques, such as clumped isotopes, in order to exactly determine and quantify the underlying vital effects and possibly account for these. We found differences in the chemical composition between the two calcitic shell layers that are possibly explainable through differences of the crystal morphology. Sr/Ca ratios also appear to be partly controlled by the amount of magnesium, because the small magnesium ions bend the crystal lattice which increases the space for strontium incorporation. Oxidative cleaning with H2O2 did not significantly change the Mg/Ca and Sr/Ca composition of the shell. Na/Ca ratios decreased after the oxidative cleaning, which is most likely a leaching effect and not caused by the removal of organic matter.

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Nitridic Analogs of Micas AESi₃ P₄ N₁₀ (NH)₂ (AE=Mg, Mg_0.94 Ca_0.06 , Ca, Sr).

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Nitridic Analogs of Micas AESi3 P4 N10 (NH)2 (AE=Mg, Mg0.94 Ca0.06 , Ca, Sr).

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Nitridic Analogs of Micas AESi₃ P₄ N₁₀ (NH)₂ (AE=Mg, Mg_0.94 Ca_0.06 , Ca, Sr).