Iron (hydr)oxide formation in Andosols under extreme climate conditions.

Redox-driven biogeochemical cycling of iron plays an integral role in the complex process network of ecosystems, such as carbon cycling, the fate of nutrients and greenhouse gas emissions. We investigate Fe-(hydr)oxide (trans)formation pathways from rhyolitic tephra in acidic topsoils of South Patagonian Andosols to evaluate the ecological relevance of terrestrial iron cycling for this sensitive fjord ecosystem. Using bulk geochemical analyses combined with micrometer-scale-measurements on individual soil aggregates and tephra pumice, we document biotic and abiotic pathways of Fe released from the glassy tephra matrix and titanomagnetite phenocrysts. During successive redox cycles that are controlled by frequent hydrological perturbations under hyper-humid climate, (trans)formations of ferrihydrite-organic matter coprecipitates, maghemite and hematite are closely linked to tephra weathering and organic matter turnover. These Fe-(hydr)oxides nucleate after glass dissolution and complexation with organic ligands, through maghemitization or dissolution-(re)crystallization processes from metastable precursors. Ultimately, hematite represents the most thermodynamically stable Fe-(hydr)oxide formed under these conditions and physically accumulates at redox interfaces, whereas the ferrihydrite coprecipitates represent a so far underappreciated terrestrial source of bio-available iron for fjord bioproductivity. The insights into Fe-(hydr)oxide (trans)formation in Andosols have implications for a better understanding of biogeochemical cycling of iron in this unique Patagonian fjord ecosystem.

Sources of dehydration fluids underneath the Kamchatka arc.

Fluids mediate the transport of subducted slab material and play a crucial role in the generation of arc magmas. However, the source of subduction-derived fluids remains debated. The Kamchatka arc is an ideal subduction zone to identify the source of fluids because the arc magmas are comparably mafic, their source appears to be essentially free of subducted sediment-derived components, and subducted Hawaii-Emperor Seamount Chain (HESC) is thought to contribute a substantial fluid flux to the Kamchatka magmas. Here we show that Tl isotope ratios are unique tracers of HESC contribution to Kamchatka arc magma sources. In conjunction with trace element ratios and literature data, we trace the progressive dehydration and melting of subducted HESC across the Kamchatka arc. In succession, serpentine (<100 km depth), lawsonite (100-250 km depth) and phengite (>250 km depth) break down and produce fluids that contribute to arc magmatism at the Eastern Volcanic Front (EVF), Central Kamchatka Depression (CKD), and Sredinny Ridge (SR), respectively. However, given the Tl-poor nature of serpentine and lawsonite fluids, simultaneous melting of subducted HESC is required to explain the HESC-like Tl isotope signatures observed in EVF and CKD lavas. In the absence of eclogitic crust melting processes in this region of the Kamchatka arc, we propose that progressive dehydration and melting of a HESC-dominated mélange offers the most compelling interpretation of the combined isotope and trace element data.

Element mobility related to rock weathering and soil formation at the westward side of the southernmost Patagonian Andes.

Rock weathering and pedogenesis are fundamental processes for element mobility in terrestrial bio-geochemical cycles and for the regulation of primary productivity in adjacent coastal marine ecosystems. Here, soils developed from volcanic ash under extreme climate conditions could play a particular role. We therefore investigated rock weathering, soil formation and the associated mobilization of trace elements and micronutrients in a pristine South Patagonian ecosystem. Weathered and unweathered basement lithologies, tephra of the 4.216 kyrs BP Mt. Burney eruption and four soil profiles are considered. The approach combines mineralogical (XRD, SEM) and inorganic geochemical (XRF, ICP-OES/MS) with organic geochemical analyses (TOC, TN, δ13C, δ15N, DOC extracts) of representative samples. Chemical weathering is quantified by mass balance calculations and 14C age constraints allow a correlation of pedogenic processes with the paleoenvironmental history of the area. Our data document that pedogenesis with initial peat formation occurred since ~2.5 kyrs BP. In these acidic peaty Andosols, intensive alteration of volcanic glass mobilized large quantities of elements, considerably surpassing leachates provided by basement rock weathering. Clay production is limited in favor of the formation of amorphous Al- and crystalline Fe-(hydr)oxides. However, tephra alteration, soil organic matter turnover rates, enhanced dissolved organic carbon export, and Fe-/Al-(hydr)oxide precipitation are closely linked and ultimately controlled by rainfall-induced water-level fluctuations, highlighting the dominant influence of the southern westerly wind belt. The transport of mobilized trace elements and micronutrients adsorbed onto suspended colloids (dissolved organic carbon, Al-humus complexes and Fe-(hydr)oxides) is redox-pH-dependent, highly variable and ultimately regulated by westerly intensity. Broader implications of this work include a new perspective on the climate-controlled micronutrient delivery for primary productivity in South Patagonian fjords, which is strongly affected by Andosol formation. Furthermore, a careful evaluation of 'ordinary' geochemical proxies in regional paleoenvironmental archives is needed to account for these unique pedogenic processes.

An andesitic source for Jack Hills zircon supports onset of plate tectonics in the Hadean.

The composition and origin of Earth's early crust remains hotly debated. Here we use partition coefficients to invert the trace element composition of 4.3-3.3 Gyr Jack Hills zircons to calculate the composition of the melts from which they crystallised. Using this approach, the average SiO2 content of these melts was 59 ± 6 wt. % with Th/Nb, Dy/Yb and Sr/Y ratios of 2.7 ± 1.9, 0.9 ± 0.2 and 1.6 ± 0.7, respectively. Such features strongly indicate that the protolith for the Jack Hills zircons was not an intra-plate mafic rock, nor a TTG (tondjhemite-tonalite-granodiorite) or a Sudbury-like impact melt. Instead, the inferred equilibrium melts are much more similar to andesites formed in modern subduction settings. We find no evidence for any secular variation between 4.3 and 3.3 Gyr implying little change in the composition or tectonic affinity of the Earth's early crust from the Hadean to Mesoarchaean.

Growth of, and diffusion in, olivine in ultra-fast ascending basalt magmas from Shiveluch volcano.

Complex core-rim zoning of Mg-Fe-Ni-Ca-Cr-Al-P in high-Mg olivine crystals from a tuff ring of Shiveluch volcano, Kamchatka, enables reconstruction of the entire olivine crystallization history from mantle conditions to eruption. Bell-shaped Fo86-92 and Ni profiles in crystal cores were formed by diffusion after mixing with evolved magma. Diffusion proceeded to the centres of crystals and completely equilibrated Fo and Ni in some crystals. Diffusion times extracted from Fo and Ni core profiles range from 100 to 2000 days. During subsequent mixing with mafic mantle-equilibrated melt, the cores were partially dissolved and overgrown by Fo90 olivine. Times extracted from Fo and Ni diffusion profiles across the resorption interface between the core and its overgrowth range within 1-10 days, which corresponds to the time of magma ascent to the surface. The overgrowth shows identical smooth Fo-Ni decreasing zoning patterns for all crystals towards the margin, indicating that all crystals shared the same growth history after last mixing event prior to eruption. At the same time, Ca, and to an even greater extent Cr, Al, and P have oscillatory growth patterns in the crystals overgrowth. Our data show that magma ascent can be extremely short during maar/tuff ring eruption.