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.

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.

Curcuminoid-BF2 complexes: Synthesis, fluorescence and optimization of BF2 group cleavage.

Eight difluoroboron complexes of curcumin derivatives carrying alkyne groups containing substituents have been synthesized following an optimised reaction pathway. The complexes were received in yields up to 98% and high purities. Their properties as fluorescent dyes have been investigated. Furthermore, a strategy for the hydrolysis of the BF2 group has been established using aqueous methanol and sodium hydroxide or triethylamine.

Glacial reduction and millennial-scale variations in Drake Passage throughflow.

The Drake Passage (DP) is the major geographic constriction for the Antarctic Circumpolar Current (ACC) and exerts a strong control on the exchange of physical, chemical, and biological properties between the Atlantic, Pacific, and Indian Ocean basins. Resolving changes in the flow of circumpolar water masses through this gateway is, therefore, crucial for advancing our understanding of the Southern Ocean's role in global ocean and climate variability. Here, we reconstruct changes in DP throughflow dynamics over the past 65,000 y based on grain size and geochemical properties of sediment records from the southernmost continental margin of South America. Combined with published sediment records from the Scotia Sea, we argue for a considerable total reduction of DP transport and reveal an up to ∼ 40% decrease in flow speed along the northernmost ACC pathway entering the DP during glacial times. Superimposed on this long-term decrease are high-amplitude, millennial-scale variations, which parallel Southern Ocean and Antarctic temperature patterns. The glacial intervals of strong weakening of the ACC entering the DP imply an enhanced export of northern ACC surface and intermediate waters into the South Pacific Gyre and reduced Pacific-Atlantic exchange through the DP ("cold water route"). We conclude that changes in DP throughflow play a critical role for the global meridional overturning circulation and interbasin exchange in the Southern Ocean, most likely regulated by variations in the westerly wind field and changes in Antarctic sea ice extent.