Enhanced terrestrial Fe(II) mobilization identified through a novel mechanism of microbially driven cave formation in Fe(III)-rich rocks.

Most cave formation requires mass separation from a host rock in a process that operates outward from permeable pathways to create the cave void. Given the poor solubility of Fe(III) phases, such processes are insufficient to account for the significant iron formation caves (IFCs) seen in Brazilian banded iron formations (BIF) and associated rock. In this study we demonstrate that microbially-mediated reductive Fe(III) dissolution is solubilizing the poorly soluble Fe(III) phases to soluble Fe(II) in the anoxic zone behind cave walls. The resultant Fe(III)-depleted material (termed sub muros) is unable to maintain the structural integrity of the walls and repeated rounds of wall collapse lead to formation of the cave void in an active, measurable process. This mechanism may move significant quantities of Fe(II) into ground water and may help to explain the mechanism of BIF dissolution and REE enrichment in the generation of canga. The role of Fe(III) reducing microorganism and mass separation behind the walls (outward-in, rather than inward-out) is not only a novel mechanism of speleogenesis, but it also may identify a previously overlooked source of continental Fe that may have contributed to Archaean BIF formation.

Hydrologic Alteration and Enhanced Microbial Reductive Dissolution of Fe(III) (hydr)oxides Under Flow Conditions in Fe(III)-Rich Rocks: Contribution to Cave-Forming Processes.

Previous work demonstrated that microbial Fe(III)-reduction contributes to void formation, and potentially cave formation within Fe(III)-rich rocks, such as banded iron formation (BIF), iron ore and canga (a surficial duricrust), based on field observations and static batch cultures. Microbiological Fe(III) reduction is often limited when biogenic Fe(II) passivates further Fe(III) reduction, although subsurface groundwater flow and the export of biogenic Fe(II) could alleviate this passivation process, and thus accelerate cave formation. Given that static batch cultures are unlikely to reflect the dynamics of groundwater flow conditions in situ, we carried out comparative batch and column experiments to extend our understanding of the mass transport of iron and other solutes under flow conditions, and its effect on community structure dynamics and Fe(III)-reduction. A solution with chemistry approximating cave-associated porewater was amended with 5.0 mM lactate as a carbon source and added to columns packed with canga and inoculated with an assemblage of microorganisms associated with the interior of cave walls. Under anaerobic conditions, microbial Fe(III) reduction was enhanced in flow-through column incubations, compared to static batch incubations. During incubation, the microbial community profile in both batch culture and columns shifted from a Proteobacterial dominance to the Firmicutes, including Clostridiaceae, Peptococcaceae, and Veillonellaceae, the latter of which has not previously been shown to reduce Fe(III). The bacterial Fe(III) reduction altered the advective properties of canga-packed columns and enhanced permeability. Our results demonstrate that removing inhibitory Fe(II) via mimicking hydrologic flow of groundwater increases reduction rates and overall Fe-oxide dissolution, which in turn alters the hydrology of the Fe(III)-rich rocks. Our results also suggest that reductive weathering of Fe(III)-rich rocks such as canga, BIF, and iron ores may be more substantial than previously understood.

Author Correction: Global karst springs hydrograph dataset for research and management of the world's fastest-flowing groundwater.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Global karst springs hydrograph dataset for research and management of the world's fastest-flowing groundwater.

Karst aquifers provide drinking water for 10% of the world's population, support agriculture, groundwater-dependent activities, and ecosystems. These aquifers are characterised by complex groundwater-flow systems, hence, they are extremely vulnerable and protecting them requires an in-depth understanding of the systems. Poor data accessibility has limited advances in karst research and realistic representation of karst processes in large-scale hydrological studies. In this study, we present World Karst Spring hydrograph (WoKaS) database, a community-wide effort to improve data accessibility. WoKaS is the first global karst springs discharge database with over 400 spring observations collected from articles, hydrological databases and researchers. The dataset's coverage compares to the global distribution of carbonate rocks with some bias towards the latitudes of more developed countries. WoKaS database will ensure easy access to a large-sample of good quality datasets suitable for a wide range of applications: comparative studies, trend analysis and model evaluation. This database will largely contribute to research advancement in karst hydrology, supports karst groundwater management, and promotes international and interdisciplinary collaborations.

Mammal tooth traces in a ferruginous cave in southeastern Brazil and their relevance to cave legal protection.

We describe the first occurrence of biogenic traces made by mammals within an iron formation cave located in the Serra da Ferrugem Ridge, in Southeastern Brazil. These bioerosions are tooth traces produced in boulders, walls and floor within the cave. The traces occur as sets of two or more grooves, which are highly variable in size. The grooves were compared to tooth traces artificially produced by imprinting the incisors of different mammal species collected in the cave region on soft clay. Among those, the following taxa are potential tracemakers: Akodon sp., Oligoryzomys sp., Necromys lasiurus, Rhipidomys mastacalis, Oecomys gr. concolor, Trinomys moojeni, and Hydrochoerus hydrochaeris. The age of the traces is unknown; therefore, any discussion on its fossil nature is circumstantial. Regardless of its relevance to paleontology, the presence of ichnological features should be considered as an additional cave value, according to the current Brazilian legislation regarding cave protection.

South American monsoon response to iceberg discharge in the North Atlantic.

Heinrich Stadials significantly affected tropical precipitation through changes in the interhemispheric temperature gradient as a result of abrupt cooling in the North Atlantic. Here, we focus on changes in South American monsoon precipitation during Heinrich Stadials using a suite of speleothem records covering the last 85 ky B.P. from eastern South America. We document the response of South American monsoon precipitation to episodes of extensive iceberg discharge, which is distinct from the response to the cooling episodes that precede the main phase of ice-rafted detritus deposition. Our results demonstrate that iceberg discharge in the western subtropical North Atlantic led to an abrupt increase in monsoon precipitation over eastern South America. Our findings of an enhanced Southern Hemisphere monsoon, coeval with the iceberg discharge into the North Atlantic, are consistent with the observed abrupt increase in atmospheric methane concentrations during Heinrich Stadials.

Hydroclimate changes across the Amazon lowlands over the past 45,000 years.

Reconstructing the history of tropical hydroclimates has been difficult, particularly for the Amazon basin-one of Earth's major centres of deep atmospheric convection. For example, whether the Amazon basin was substantially drier or remained wet during glacial times has been controversial, largely because most study sites have been located on the periphery of the basin, and because interpretations can be complicated by sediment preservation, uncertainties in chronology, and topographical setting. Here we show that rainfall in the basin responds closely to changes in glacial boundary conditions in terms of temperature and atmospheric concentrations of carbon dioxide. Our results are based on a decadally resolved, uranium/thorium-dated, oxygen isotopic record for much of the past 45,000 years, obtained using speleothems from Paraíso Cave in eastern Amazonia; we interpret the record as being broadly related to precipitation. Relative to modern levels, precipitation in the region was about 58% during the Last Glacial Maximum (around 21,000 years ago) and 142% during the mid-Holocene epoch (about 6,000 years ago). We find that, as compared with cave records from the western edge of the lowlands, the Amazon was widely drier during the last glacial period, with much less recycling of water and probably reduced plant transpiration, although the rainforest persisted throughout this time.

Climate change patterns in Amazonia and biodiversity.

Precise characterization of hydroclimate variability in Amazonia on various timescales is critical to understanding the link between climate change and biodiversity. Here we present absolute-dated speleothem oxygen isotope records that characterize hydroclimate variation in western and eastern Amazonia over the past 250 and 20 ka, respectively. Although our records demonstrate the coherent millennial-scale precipitation variability across tropical-subtropical South America, the orbital-scale precipitation variability between western and eastern Amazonia exhibits a quasi-dipole pattern. During the last glacial period, our records imply a modest increase in precipitation amount in western Amazonia but a significant drying in eastern Amazonia, suggesting that higher biodiversity in western Amazonia, contrary to 'Refugia Hypothesis', is maintained under relatively stable climatic conditions. In contrast, the glacial-interglacial climatic perturbations might have been instances of loss rather than gain in biodiversity in eastern Amazonia, where forests may have been more susceptible to fragmentation in response to larger swings in hydroclimate.

Wet periods in northeastern Brazil over the past 210 kyr linked to distant climate anomalies.

The tropics are the main source of the atmosphere's sensible and latent heat, and water vapour, and are therefore important for reconstructions of past climate. But long, accurately dated records of southern tropical palaeoclimate, which would allow the establishment of climatic connections to distant regions, have not been available. Here we present a 210,000-year (210-kyr) record of wet periods in tropical northeastern Brazil--a region that is currently semi-arid. The record is obtained from speleothems and travertine deposits that are accurately dated using the U/Th method. We find wet periods that are synchronous with periods of weak East Asian summer monsoons, cold periods in Greenland, Heinrich events in the North Atlantic and periods of decreased river runoff to the Cariaco basin. We infer that the wet periods may be explained with a southward displacement of the Intertropical Convergence Zone. This widespread synchroneity of climate anomalies suggests a relatively rapid global reorganization of the ocean-atmosphere system. We conclude that the wet periods probably affected rainforest distribution, as plant fossils show that forest expansion occurred during these intermittent wet intervals, and opened a forest corridor between the Amazonian and Atlantic rainforests.