Single-crystal X-ray diffraction and spectroscopic studies on humboldtine and lindbergite: weak Jahn–Teller effect of Fe<Superscript>2+</Superscript> ion

The single-crystal of humboldtine [Fe²⁺(C₂O₄) · 2H₂O] was first synthesized and the crystal structure has been refined. Single-crystal X-ray diffraction data were collected using an imaging-plate diffractometer system and graphite-monochromatized MoKα radiation. The crystal structure of humboldtine was refined to an agreement index (R1) of 3.22% calculated for 595 unique observed reflections. The mineral crystallizes in the monoclinic system, space group C2/c, with unit cell dimensions of a = 12.011 (11), b = 5.557 (5), c = 9.920 (9) Å, β = 128.53 (3)?, V = 518.0 (8) Å³, and Z = 4. In this crystal structure, the alternation of oxalate anions [(C₂O₄)^2?] and Fe²⁺ ions forms one-dimensional chain structure parallel to [010]; water molecules (H₂O)⁰ create hydrogen bonds to link the chains, where (H₂O)⁰ is essentially part of the crystal structure. The water molecules with the two lone electron pairs (LEPs) on their oxygen atom are tied obliquely to the chains, because the one lone electron pair is considered to participate in the chemical bonds with Fe²⁺ ions. Humboldtine including hydrogen bonds is isotypic with lindbergite [Mn²⁺(C₂O₄) · 2H₂O]. The donor–acceptor separations of the hydrogen bonds in humboldtine are slightly shorter than those in lindbergite, which suggests that the hydrogen bonds in the former are stronger than those in the latter. The infrared and Raman spectra of single-crystals of humboldtine and lindbergite confirmed the differences in hydrogen-bond geometry. In addition, Fe²⁺–O stretching band of humboldtine was split and broadened in the observed Raman spectrum, owing to the Jahn–Teller effect of Fe²⁺ ion. These interpretations were also discussed in terms of bond-valence theory.     

Degassing, crystallization and eruption dynamics at Stromboli: trace element and lithium isotopic evidence from 2003 ashes

During its 1800-year-long persistent activity the Stromboli volcano has erupted a highly porphyritic (HP) volatile-poor scoriaceous magma and a low porphyritic (LP) volatile-rich pumiceous magma. The HP magma is erupted during normal Strombolian explosions and lava effusions, while the LP one is related to more energetic paroxysms. During the March–April 2003 explosive activity, Stromboli ejected two typologies of juvenile glassy ashes, namely highly vesicular LP shards and volatile-poor HP shards. Their textural and in situ chemical characteristics are used to unravel mutual relationships between HP and LP magmas, as well as magma dynamics within the shallow plumbing system. The mantle-normalized trace element patterns of both ash types show the typical arc-lava pattern; however, HP glasses possess incompatible element concentrations higher than LP glasses, along with Sr and Eu negative anomalies. HP shards are generally characterized by higher Li contents (to ~20 ppm) and lower δ⁷Li values (+1.2 to −3.8‰) with respect to LP shards (Li contents of 7–14 ppm and δ⁷Li ranging between +4.6 and +0.9‰). Fractional crystallization models based on major and trace element compositions, combined with a degassing model based on open-system Rayleigh distillation and on the assumption that ^melt/fluidD_Li > 1, show that abundant (~30%) plagioclase precipitation and variable degrees of degassing can lead the more primitive LP magma to evolve toward a differentiated (isotopically lighter) HP magma ponding in the upper conduit and undergoing slow continuous degassing-induced crystallization. This study also evidences that in March 2003 Stromboli volcano poured out a small early volume of LP magma that traveled slower within the conduit with respect to later and larger volumes of fast ascending LP magma erupted during the April 5 paroxysm. The different ascent rates and cooling rates of the two LP magma batches (i.e., pre- and post-paroxysm) resulted in small, but detectable, differences in their chemical signatures. Finally, this study highlights the high potential of in situ investigations of juvenile glassy ashes in petrologic and geochemical monitoring the volcanic activity and of Li isotopes as tracers of degassing processes within the shallow plumbing system.