Textural history of recent basaltic-andesites and plutonic inclusions from Merapi volcano

Mt. Merapi in Central Java is one of the most active stratovolcanoes on Earth and is underlain by a multistage plumbing system. Crystal size distribution analyses (CSD) were carried out on recent Merapi basaltic-andesites and co-eruptive magmatic and plutonic inclusions to characterise the crystallisation processes that operate during storage and ascent and to obtain information on respective time scales. The basaltic-andesites exhibit log-linear, kinked-upwards CSD curves for plagioclase and clinopyroxene that can be separated into two main textural populations. Large plagioclase phenocrysts (≥1.6 mm) make up one population, but correspond to crystals with variable geochemical composition and reflect a period of crystal growth at deep to mid-crustal levels. This population was subsequently influenced by crystal accumulation and the onset of crustal assimilation, including the incorporation of high-Ca skarn-derived xenocrysts. Textural re-equilibration is required for these crystals to form a single population in CSD. A second episode of crystal growth at shallower levels is represented by chemically homogenous plagioclase crystals <1.6 mm in size. Crustal assimilation is indicated by, for example, oxygen isotopes and based on the CSD data, crystallisation combined with contamination is likely semi-continuous in these upper crustal storage chambers. The CSD data observed in the basaltic-andesite samples are remarkably consistent and require a large-volume steady state magmatic system beneath Merapi in which late textural equilibration plays a significant role. Plagioclase CSDs of co-eruptive magmatic and plutonic inclusions may contain a third crystal population (<1 mm) not found in the lavas. This third population has probably formed from enhanced degassing of portions of basaltic-andesite magma at shallow crustal levels which resulted in increased crystallinity and basaltic-andesite mush inclusions. A suite of coarse plutonic inclusions is also present that reflects crystallisation and accumulation of crystals in the deep Merapi plumbing system, as deduced from CSD patterns and mineral assemblages.     

Fe isotopic fractionation during mineral dissolution with and without bacteria

Fe released into solution is isotopically lighter (enriched in the lighter isotope) than hornblende starting material when dissolution occurs in the presence of the siderophore desferrioxamine mesylate (DFAM). In contrast, Fe released from goethite dissolving in the presence of DFAM is isotopically unchanged. Furthermore, Δ⁵⁶Fe_{solution-hornblende} for Fe released to solution in the presence of ligands varies with the affinity of the ligand for Fe. The extent of isotopic fractionation of Fe released from hornblende also increases when experiments are agitated continuously. The Fe isotope fractionation observed during hornblende dissolution with organic ligands is attributed predominantly to retention of ⁵⁶Fe in an altered surface layer, while the lack of isotopic fractionation during goethite dissolution in DFAM is consistent with the lack of an altered layer. When a siderophore-producing soil bacterium is added to the system (without added organic ligands), Fe released to solution from both hornblende and goethite differs isotopically from Fe in the bulk mineral: Δ⁵⁶Fe_{solution-starting material} = −0.56 ± 0.19 (hornblende) and −1.44 ± 0.16 (goethite). Increased isotopic fractionation is attributed in this case to the fact that as bacterial respiration depletes the system in oxygen and aqueous Fe is reduced, equilibration between aqueous ferrous and ferric iron creates a pool of isotopically heavy ferric iron that is assimilated by bacterial cells. Adsorption of isotopically heavy ferrous iron (Fe(II) enriched in the heavier isotope) or precipitation of isotopically heavy Fe minerals may also contribute to observed fractionations.To test whether these Fe isotope signatures are recorded in natural systems, we also investigated extractions of samples of soils from which the bacteria were isolated. These extractions show variability in the isotopic signatures of exchangeable Fe and Fe oxyhydroxide fractions from one soil sample to another, but exchangeable Fe is observed to be lighter than Fe in soil Fe oxyhydroxides and hornblende. This observation is consistent with isotopically light Fe-organic complexes in soil pore water derived from the Fe-silicate starting materials in the presence of growing microorganisms, as documented in experiments reported here. The contributions from phenomena including organic ligand-promoted nonstoichiometric dissolution of Fe silicates, uptake of ferric iron by organisms, adsorption of isotopically heavy ferrous iron, and precipitation of iron minerals should create complex isotopic signatures in soils. Better understanding of these processes and the timescales over which they contribute to fractionation is needed.