Cycling Of Trace Elements Research Articles

Biogeochemical cycling of trace elements and nutrients in ferruginous waters: Constraints from a deep oligotrophic ancient lake

AbstractIron‐rich, ferruginous waters were the dominant geochemical regime for most of Earth's history. Modern ferruginous waters are found in stratified, sulfur‐poor lakes, and serve as crucial analogs for biogeochemical cycling throughout Earth's past. Here we present the first depth‐resolved data of physical structure, nutrients and trace elements from Lake Poso (Indonesia), a deep oligotrophic ancient lake. Lake Poso is ferruginous, with anoxia below ~ 90 m depth, placing it among the world's largest ferruginous lakes. Physical stratification is weaker than other tropical anoxic lakes, indicating sensitivity for paleoclimate reconstructions. Trace elements and nutrients are predominantly shaped by the oxic–anoxic transition. Manganese– and Fe oxyhydroxide–driven biogeochemical cycling occurs at distinct depth horizons, with Co and Ni controlled by Mn and showing shallow release in anoxic waters, while V, Cr, P, and As are controlled by Fe, with release in surface sediments and diffusive transport. Chromium is nonquantitatively removed in anoxic waters, in contrast to widespread assumptions in Cr‐based paleoreconstructions. Oxycline U and Se removal corresponds to a local N minimum, suggesting biological reduction and/or uptake. These first ferruginous water Se data also show removal in sediments, indicating sediment signals reflect multiple removal processes and informing Se‐based paleoreconstructions, while the absence of sediment U removal contrasts other anoxic basins. A comparison with other ferruginous lakes demonstrates how local influences drive deviations from expectations in other systems, and highlight common, generalizable ferruginous basin features. Therefore, these data will guide research in ferruginous settings across space and time, and improve paleoreconstructions from ferruginous sediment records.

How tree species have modified the potentially toxic elements distributed in the developed soil–plant system in a post-fire site in highly industrialized region

The biogeochemical cycles of trace elements are changed by fire as a result of the mineralization of organic matter. Monitoring the accumulation of trace elements in both the environment and the tree biomass during the post-fire (PF) forest ecosystem regeneration process is important for tree species selection for reforestation in ecosystems under anthropogenic pressure. We analyzed the soil concentrations of different groups of potentially toxic elements (PTEs), including beneficial (Al), toxic (Cd, Cr, Pb), and microelements (Cu, Mn, Ni, Zn), and their bioaccumulation in the tree species (Pinus sylvestris, Betula pendula, Alnus glutinosa) biomass introduced after a fire in a forest weakened by long-term emissions of industrial pollutants. The results indicated no direct threat from the PTEs tested at the PF site. The tree species introduced 30 years ago may have modified the biogeochemical cycles of the PTEs through different strategies of bioaccumulation in the belowground and aboveground biomass. Alder had relatively high Al concentrations in the roots and a low translocation factor (TF). Pine and birch had lower Al concentrations in the roots and higher TFs. Foliage concentrations and the TF of Cd increased from alder to pine to birch. However, the highest concentration and bioaccumulation factor of Cd was found in the alder roots. The concentrations of Cr in the foliage and the Cr TFs in the studied species increased from pine to birch to alder. Higher concentrations of Cu and Ni were found in the foliage of birch and alder than of pine. Among the species, birch also had the highest Pb and Zn concentrations in the roots and foliage. We found that different tree species had different patterns of PTE phytostabilization and ways they incorporated these elements into the biological cycle, and these patterns were not dependent on fire disturbance. This suggests that similar patterns might also occur in more polluted soils. Therefore, species-dependent bioaccumulation patterns could also be used to design phytostabilization and remediation treatments for polluted sites under industrial pressure.

Effects of deep magmatic degassing and shallow seawater circulation on trace element and sulfur cycling in submarine hydrothermal systems: Insights from the Shijuligou analog, North China

Limited access to modern subseafloor sulfides hampers our understanding of the link between magmatic volatile influx and the cycling of trace elements and sulfur, as well as the effect of the subsequent shallow seawater circulation on these processes. Hence, we studied a well-preserved fossil analog of submarine hydrothermal systems – the Shijuligou volcanogenic massive sulfide (VMS) deposit from the North Qilian Mountains in North China to examine variations in elements and isotopes of subseafloor sulfides vertically.The vertical distribution of trace elements in subseafloor sulfides is strongly controlled by temperature gradients and redox states during the interaction between hot fluids and seawater beneath the paleo-seafloor. While the enrichment of elements like As, Sb, and Au (median: 1335, 43.7, and 0.30 ppm, respectively, n = 21) and negative δ34S values (mean: −3.07 ‰, n = 7) of euhedral pyrites in the jasper, along with the precipitation of high sulfidation minerals (e.g., enargite), suggest the input of magmatic volatiles into hydrothermal systems. During the shallow seawater-hydrothermal circulation, pyrites in the veined and stockwork zones exhibit distinctly elevated δ34S values (up to 15.74 ‰), accompanied by increased concentrations of wall-rock-derived elements (e.g., Cu, Ni, Si, and Ti) and low-temperature-responsive elements (e.g., Pb, Zn, and Cd). Sulfur isotopes of sulfides vary significantly from the surface to the deep ore zones, ranging from −3.36 to 19.84 ‰ (mean: 9.25 ‰, n = 37). The negative δ34S values of pyrites at the paleo-seafloor are due to the addition of H2S derived from the disproportionation of magmatic SO2. The increased δ34S values of stockwork and disseminated sulfides at depth are attributed to the progressive reduction of seawater sulfates by ferrous iron released from the alteration of fresh basalts. The trace elemental and isotopic characteristics of sulfides suggest the Shujuligou VMS deposit resembles the fossil analog of immature, subduction-related submarine hydrothermal systems.

Combined Genomic and Imaging Techniques Show Intense Arsenic Enrichment Caused by Detoxification in a Microbial Mat of the Dead Sea Shore

AbstractMicrobial mats and microbialites are essential tools for reconstructing early life and its environments. To better understand microbial trace element cycling, a microbial mat was collected from the sinkhole systems of the western shores of the Dead Sea, a dynamic environment exhibiting diverse extreme environments. Intense arsenic enrichment was measured (up to 6.5 million times higher than current concentrations in water, and 400 times the bulk concentration in the mat). Arsenic was found predominantly as As(V) in organic molecules, as shown by XANES spectra and high‐resolution elemental mapping. Arsenic cycling genes obtained from metagenomic analysis were associated with arsenic detoxification, supporting an active mechanism of As(V) uptake, As(III) efflux and organoarsenic accumulation in the extracellular polymeric substances (EPS) of the mat. Thus, we propose that such localized As enrichment can be attributed to a transient increase in As(V) concentrations in the circulating subsurface water of the Dead Sea shore and its subsequent incorporation into organoarsenic molecules through microbial detoxification processes. Our data set supports the possibility of metalloid enrichment recorded in very localized facies due to rapid geogenic fluctuations in the chemistry of the water flowing over a biofilm. In this context, this example calls for caution in interpreting metal(loid) enrichment in organic matter‐rich layers and microbialites of Paleoproterozoic origin. Arsenic signatures in Precambrian organic matter and carbonate rocks may host biosignatures, including evidence for extracellular polymeric substances, As‐binding and detoxification processes, without supporting arsenotrophy. However, they provide clues to better assess the paleoenvironmental conditions at the time of microbial mat formation.

Olivine-Hosted Melt Inclusions Track Progressive Dehydration Reactions in Subducting Slabs Across Volcanic Arcs

Abstract The stability and breakdown of mineral phases in subducting slabs control the cycling of trace elements through subduction zones. Stability of key minerals and the partitioning of trace elements between these minerals and liquid phases of interests have been charted by natural sample analysis and experimental constraints. However, systematic study from arc front to far back arc has rarely shown that the expected geochemical variations of the slab liquid are actually recorded by natural samples. Complexities arise by uncertainties on the nature of the slab component (melts, fluids and supercritical liquids), source heterogeneities and transport processes. Using data from olivine-hosted melt inclusions sampled along and across the NE Japan and southern Kurile arcs, we demonstrate that experimentally and thermodynamically constrained phase stabilities in subducted materials indeed control the trace element signatures as predicted by these models and experiments. The main reactions that can be traced across arc are progressive breakdown of light rare earth element-rich accessory phases (e.g. allanite), enhanced dehydration of the lithospheric mantle (serpentine breakdown) and changes in the nature of the slab component. This work elucidates subduction zone elemental cycling in a well-characterized petrogenetic setting and provides important constraints on the interpretation of trace element ratios in arc magmas in terms of the prograde metamorphic reactions within the subducting slab.

Speciation of iodine on biogenic iron oxyhydroxides by I K-edge and LIII-edge XANES

Abstract The host phase of iodine (I) in biogenic iron oxyhydroxides (BIOS) was determined using X-ray absorption near-edge structure (XANES). I K-edge and LIII-edge XANES analyses of BIOS collected from deep-sea hydrothermal environments revealed that the primary form of I in the BIOS is an organic species. Furthermore, LIII-edge XANES fitting implied the dominance of aromatic-bound I among BIOS. Our first observation of organic–trace element association in natural BIOS can explain the enhanced adsorption of I on BIOS compared to synthetic ferrihydrite. This further suggests the importance of various chemistry on this organic–mineral composite for understanding the geochemical cycling of trace elements.

Timekeepers for Trace Elements in the Global Ocean: The Thorium Stopwatches

The various isotopes of thorium offer oceanographers tools for tracking particulate matter in the ocean across multiple timescales. To learn about the cycling of trace elements in the ocean, in this perspective we focus on the latest applications of thorium’s longest-lived naturally occurring isotopes: 232Th, 230Th, 228Th, and 234Th. From desert dust to marine snow to sediment porewaters, thorium measurements can be used to derive rates of trace element input and removal, using the assumptions of radioactive disequilibrium. Opportunities exist to fine tune and improve the application of these already versatile stopwatches, but GEOTRACES-era data clearly demonstrate their utility.

A Needle in the Haystack

For the past 20 years, the GEOTRACES program has produced transformative insights into the cycling of trace elements and isotopes (TEIs) in the ocean. Modeled after the 1970s GEOSECS (Geochemical Ocean Sections Study) program, the goals of this ambitious study were to conduct large-scale measurements of TEI concentrations and to determine the biogeochemical processes that controlled their distributions throughout the global ocean. Perhaps the biggest hurdle to overcome was how to accurately measure less than nanomolar concentrations of TEIs from the deck of a 3,000 gross tonnage steel ship. Contaminants were literally everywhere, requiring scientists and crew to become innovative in their attempts to maintain clean conditions for sample collection, storage, and measurement. GEOTRACES encouraged international partnerships while instilling a collaborative approach in the next generation of scientists. The practices GEOTRACES developed led to consistent high-quality measurements across diverse lab groups and provided an extensive and open database. GEOTRACES has truly been a labor of love among all the scientists and crews involved, and the program continues as a lofty example of the discoveries possible when conducting such wide-ranging collaborative research.

Advances in Understanding the Marine Nitrogen Cycle in the GEOTRACES Era

Because nitrogen availability limits primary production over much of the global ocean, understanding the controls on the marine nitrogen inventory and supply to the surface ocean is essential for understanding biological productivity and exchange of greenhouse gases with the atmosphere. Quantifying the ocean’s inputs, outputs, and internal cycling of nitrogen requires a variety of tools and approaches, including measurements of the nitrogen isotope ratio in organic and inorganic nitrogen species. The marine nitrogen cycle, which shapes nitrogen availability and speciation in the ocean, is linked to the elemental cycles of carbon, phosphorus, and trace elements. For example, the majority of nitrogen cycle oxidation and reduction reactions are mediated by enzymes that require trace metals for catalysis. Recent observations made through global-scale programs such as GEOTRACES have greatly expanded our knowledge of the marine nitrogen cycle. Though much work remains to be done, here we outline key advances in understanding the marine nitrogen cycle that have been achieved through these analyses, such as the distributions and rates of dinitrogen fixation, terrestrial nitrogen inputs, and nitrogen loss processes.

A Young Scientist’s Perspective on GEOTRACES

GEOTRACES is an international endeavor to elucidate the biogeochemical cycles of trace elements and their isotopes in the ocean. Inherently, this interdisciplinary program provides ample opportunities for students to develop professional, academic, and seagoing skills. This perspective recalls first-hand experiences gained from five years in the GEOTRACES community, spanning undergraduate and graduate research, including international engagement in Germany and seagoing oceanography in the South Pacific and Southern Ocean. Description of these opportunities reveals the framework that makes the GEOTRACES program a success and the culture that will ensure its ongoing legacy.

Introduction to the special issue on twenty years of GEOTRACES: An international study of the marine biogeochemical cycles of trace elements and isotopes

This special issue of Oceanography celebrates the transformational findings of the international GEOTRACES program in chemical oceanography, 20 years after drafting of the GEOTRACES Science Plan in 2004 (GEOTRACES Planning Group, 2006). With the section cruise phase of the program ending soon, and a planned pivot toward smaller-​scale process studies, this is an opportune time to look back at the achievements of GEOTRACES during the last two decades and to highlight some of the advances in our understanding of the processes that determine the oceanic distributions of trace elements and isotopes (TEIs).

Novel Insights into Ocean Trace Element Cycling from Biogeochemical Models

Ocean biogeochemical models have become critical tools for interpreting trace element and isotope (TEI) distributions observed during the GEOTRACES program and understanding their driving processes. Models stimulate new research questions that cannot be addressed with observations alone, for instance, concerning processes that occur over vast spatial scales and linkages between TEIs and other elemental cycles. A spectrum of modeling approaches has been applied to date, including (1) fully prognostic models that couple TEIs to broader biogeochemical frameworks, (2) simpler element-specific mechanistic models that allow for assimilation of observations, and (3) machine learning models that have no mechanistic underpinning but allow for skillful extrapolation of sparse data. Here, we evaluate the strengths and weaknesses of these approaches and review three sets of novel insights they have facilitated. First, models have advanced our understanding of global-scale micronutrient distributions, and their deviations from macronutrients, in terms of a “ventilation-regeneration-scavenging” balance. Second, models have yielded global-scale estimates of TEI inputs to and losses from the ocean, revealing, for instance, a rapid iron (Fe) cycle with an oceanic residence time on the order of decades. Third, models have identified novel links among various TEI cycling processes and the global ocean carbon cycle, such as tracing the supply of hydrothermally sourced Fe to iron-starved microbial communities in the Southern Ocean. We foresee additional important roles for modeling work in the next stages of trace element research, including synthesizing understanding from the GEOTRACES program in the form of TEI state estimates, and projecting the responses of TEI cycles to global climate change.

Trace Element Geochemistry in North Pacific Red Clay Sediment Porewaters and Implications for Water‐Column Studies

AbstractGeochemical analyses of trace elements in the ocean water column have suggested that pelagic clay‐rich sediments are a major source of various elements to bottom‐waters. However, corresponding high‐quality measurements of trace element concentrations in porewaters of pelagic clay‐rich sediments are scarce, making it difficult to evaluate the contributions from benthic processes to global oceanic cycles of trace elements. To bridge this gap, we analyzed porewater and bulk sediment concentrations of vanadium, chromium, cobalt, nickel, copper, arsenic, molybdenum, barium and uranium, as well as concentrations of the major oxidants nitrate, manganese, iron, and sulfate in the top 30 cm of cores collected along a transect from Hawaii to Alaska. The data show large increases in porewater concentrations of vanadium, manganese, cobalt, nickel, copper, and arsenic within the top cm of the sediment, consistent with the release of these elements from remineralized organic matter. The sediments are a sink for sulfate, uranium, and molybdenum, even though conditions within the sampled top 30 cm remain aerobic. Porewater chromium concentrations generally increase with depth due to release from sediment particles. Extrapolated to the global aerial extent of pelagic clay sediment, the benthic fluxes in mol yr−1 are Ba 3.9 ± 3.6 × 109, Mn 3.4 ± 3.5 × 108, Co 2.6 ± 1.3 × 107, Ni 9.6 ± 8.6 × 108, Cu 4.6 ± 2.4 × 109, Cr 1.7 ± 1.1 × 108, As 6.1 ± 7.0 × 108, V 6.0 ± 2.5 × 109. With the exception of vanadium, calculated fluxes across the sediment–water interface are consistent with the variability in bottom‐water concentrations and ocean residence time of the studied elements.

Local Biogeochemical Cycles of Trace Elements in Agroecosystems of Western Siberia

Local Biogeochemical Cycles of Trace Elements in Agroecosystems of Western Siberia

Local biogeochemical cycles of trace elements in agroecosystems of Western Siberia

The article presents the results of long-term field experiments (2005-2022) to study the distribution and migration of trace elements in the soil-plant-animal system on the example of agrocenoses of the southern forest-steppe of Western Siberia. A biogeochemical assessment of the content of trace elements (Pb, Cu, Zn, Ni, Cd, Cr, Se) in trophic chains under certain agroecological conditions is given. The analysis of geochemical factors affecting the accumulation of trace elements in various types of soils and plants growing on them has been carried out. Normative quantitative characteristics of the action of trace elements on the chemical composition of the soil, productivity and quality of plants of grain, fodder and vegetable crops have been established. The relationship of macro- and microelements when they enter plants is shown, depending on the level and ratio of chemical elements in the soil, the physiological needs of the plant organism at different stages of ontogenesis.The parameters of the intake of trace elements into the body of animals with plant food under the conditions of model experiments have been established. Structural and functional changes in animal organs during feeding with crop products grown with different content of trace elements are analyzed.

Formation and transformation of Fe(III)- and Ca-precipitates in aqueous solutions and effects on phosphate retention over time

Exfiltration of anoxic phosphate-rich groundwater into surface water leads to the oxidation of dissolved Fe(II) and the formation of Fe(III)-precipitates that can retain phosphate (PO4) and thereby attenuate eutrophication. Fresh Fe(III)-precipitates transform into more stable phases over time, and retained PO4 may be released again. In parallel, CO2 outgassing can promote the formation of Ca-phosphates or -carbonates that also sequester PO4. In laboratory experiments, we studied the effects of Mg, Ca, silicate (SiO4) and PO4 on these processes. Fresh Fe(III)-precipitates were formed in bicarbonate-buffered aqueous solutions at pH ∼ 7.0 via the oxidation of 0.5 mM Fe(II) in the presence of 0.15 or 0.025 mM PO4, at Mg or Ca concentrations of 0, 0.4, 1.2 or 4 mM and in the absence or presence of 0.5 mM SiO4. After CO2 outgassing, the suspensions were allowed to age for 100 d at pH ∼ 8. Changes in the composition and structure of Fe(III)- and Ca-precipitates over time were probed with spectroscopic and microscopic techniques and were linked to variations in the retention of PO4. The oxidation of Fe(II) led to effective PO4 removal via the formation of Fe(III)-precipitates that consisted of amorphous (Ca-)Fe(III)-phosphate ((Ca)FeP), ferrihydrite (Fh) and, in SiO4-free treatments, lepidocrocite (Lp). During aging, FeP and Fh that had formed in the absence of Mg, Ca and SiO4 rapidly and nearly completely transformed into Lp. Via effects on molecular- and nanoscale precipitate structure, Mg slowed down FeP transformation into Fh, stabilized Fh, and decreased the crystallinity of Lp (in SiO4-free suspensions), Ca stabilized CaFeP against transformation into Fh, and SiO4 stabilized Fh and (Ca)FeP. Core/shell CaFeP/Fh particles formed in electrolytes that contained Ca and SiO4 hardly transformed within 100 d. Calcite only formed at low dissolved PO4 concentrations and, by incorporation of PO4, contributed to PO4 retention. Higher levels of dissolved PO4 inhibited calcite formation but could induce Ca-phosphate precipitation. Differences in precipitate formation and transformation pathways and kinetics were reflected in the extents of PO4 release over the 100-d aging period, ranging from rapid release of 77% of the total PO4 in the treatment without Mg, Ca and SiO4 at 0.15 mM total PO4 to slow release of only 0.1% of the total PO4 at initial concentrations of 4 mM Ca, 0.5 mM SiO4, and 0.025 mM PO4. In summary, this study reveals the conditions and the extents and timescales over which Fe(III)- and Ca-precipitates form and transform and how these processes affect PO4 immobilization in near-neutral natural waters. The detailed new insights into the coupling between Fe(III)- and Ca-precipitate formation and into the interdependent effects of Mg, Ca, SiO4 and PO4 are not only relevant with respect to PO4 but also with respect to the cycling of trace elements in natural and engineered systems.

Seawater–Groundwater Interaction Governs Trace Metal Zonation in a Coastal Sandy Aquifer

AbstractTrace metals in the groundwater of coastal sandy aquifers significantly influence the coastal ecosystem, yet the spatiotemporal controls of these metals remain unclear. In this paper, we comprehensively revealed the distribution patterns, key controlling factors, potential ecological risks, and fluxes to the ocean of groundwater trace metals (As, Ba, Cr, Cd, Fe, Mn, Pb, and Zn) in a coastal deep sandy aquifer. The results showed a clear zonation of trace metals in the groundwater in relation to the mixing extent between seawater and terrestrial freshwater. The freshwater zone exhibited a relatively low concentration of trace metals, whereas the freshwater‐seawater transition zone showed a substantial quantity of dissolved Fe, Mn, As, and Ba. Seawater‐groundwater interactions significantly affected the Fe, Mn, As, and Ba concentrations through redox potential and pH gradients. The tide‐driven saline water zone was vulnerable to oceanic environments and anthropogenic activities, resulting in the enrichment of trace metals such as Zn and Cd. Driven by recirculated submarine groundwater discharge (SGD), the concentrations of trace metals in the density‐driven saline circulation zone were found to be higher than those in the surrounding areas. The ecological risk index suggested that the freshwater‐seawater transition zone posted the highest ecological risks. Trace metal fluxes (i.e., Fe, Mn, and As) via SGD significantly contributed to the total input into the sea, which may have potential impacts on the coastal environments. Our study highlighted the importance of seawater‐groundwater interactions on trace element cycling in coastal sandy aquifers.

Control of particulate manganese (Mn) cycling in halocline Arctic Ocean waters by putative Mn‐oxidizing bacterial dynamics

AbstractParticulate Mn, given its high adsorptive capacity and oxidation potential, has profound impacts on the cycling of various trace elements and organic matter in the ocean. Moreover, particulate Mn acts as a sink (via oxidation and adsorption) or as a source (via remineralization and photoreduction) term of bioactive dissolved Mn(II). In the Canadian Arctic Ocean, particulate Mn distributions in the water column revealed the presence of distinctively high particulate Mn concentrations and an overwhelming dominance of the non‐lithogenic component to the bulk particulate Mn pool. This phenomenon is of particular importance in halocline waters in the Canada Basin, the Canadian Arctic Archipelago and Baffin Bay, and near‐bottom samples in Baffin Bay. Enhanced microbially‐mediated Mn oxidation in the water column is suggested as the main mechanism driving the non‐lithogenic dominance. Indeed, the microbial community composition data associated with high non‐lithogenic particulate Mn (i.e., Mn oxides) display a high relative abundance of taxa (e.g., f.Pirellulaceae, o.Phycisphaerales, f.Cryomorphaceae, g. Moritella) that have been identified in Mn oxide enriched environments. Furthermore, numerous taxa identified in the Canada Basin halocline water, where non‐lithogenic particulate Mn peaked, are phylogenetically related to known (cultured) Mn‐oxidizing bacteria (MnOB; e.g., Rhodobacteraceae, Oceanospirillaceae, Rhizobiaceae, and other Alphaproteobacteria). Putative MnOB appears to proliferate in certain water masses having a unique set of environmental conditions: low light intensity—alleviating photoinhibition—and high dissolved Mn concentrations, the main drivers known to influence MnOB dynamic, and hence, Mn oxidation.

A New Approach for Investigating Iron Mineral Transformations in Soils and Sediments Using 57Fe-Labeled Minerals and 57Fe Mössbauer Spectroscopy.

Iron minerals in soils and sediments play important roles in many biogeochemical processes and therefore influence the cycling of major and trace elements and the fate of pollutants in the environment. However, the kinetics and pathways of Fe mineral recrystallization and transformation processes under environmentally relevant conditions are still elusive. Here, we present a novel approach enabling us to follow the transformations of Fe minerals added to soils or sediments in close spatial association with complex solid matrices including other minerals, organic matter, and microorganisms. Minerals enriched with the stable isotope 57Fe are mixed with soil or sediment, and changes in Fe speciation are subsequently studied by 57Fe Mössbauer spectroscopy, which exclusively detects 57Fe. In this study, 57Fe-labeled ferrihydrite was synthesized, mixed with four soils differing in chemical and physical properties, and incubated for 12+ weeks under anoxic conditions. Our results reveal that the formation of crystalline Fe(III)(oxyhydr)oxides such as lepidocrocite and goethite was strongly suppressed, and instead formation of a green rust-like phase was observed in all soils. These results contrast those from Fe(II)-catalyzed ferrihydrite transformation experiments, where formation of lepidocrocite, goethite, and/or magnetite often occurs. The presented approach allows control over the composition and crystallinity of the initial Fe mineral, and it can be easily adapted to other experimental setups or Fe minerals. It thus offers great potential for future investigations of Fe mineral transformations in situ under environmentally relevant conditions, in both the laboratory and the field.

The DynaDeep observatory – a unique approach to study high-energy subterranean estuaries

Subterranean estuaries are connective zones between inland aquifers and the open sea where terrestrial freshwater and circulating seawater mix and undergo major biogeochemical changes. They are biogeochemical reactors that modify groundwater chemistry prior to discharge into the sea. We propose that subterranean estuaries of high-energy beaches are particularly dynamic environments, where the effect of the dynamic boundary conditions propagates tens of meters into the subsurface, leading to strong spatio-temporal variability of geochemical conditions. We hypothesize that they form a unique habitat with an adapted microbial community unlike other typically more stable subsurface environments. So far, however, studies concerning subterranean estuaries of high-energy beaches have been rare and therefore their functioning, and their importance for coastal ecosystems, as well as for carbon, nutrient and trace element cycling, is little understood. We are addressing this knowledge gap within the interdisciplinary research project DynaDeep by studying the combined effect of surface (hydro- and morphodynamics) on subsurface processes (groundwater flow and transport, biogeochemical reactions, microbiology). A unique subterranean estuary observatory was established on the northern beach of the island of Spiekeroog facing the North Sea, serving as an exemplary high-energy research site and model system. It consists of fixed and permanent infrastructure such as a pole with measuring devices, multi-level groundwater wells and an electrode chain. This forms the base for autonomous measurements, regular repeated sampling, interdisciplinary field campaigns and experimental work, all of which are integrated via mathematical modelling to understand and quantify the functioning of the biogeochemical reactor. First results show that the DynaDeep observatory is collecting the intended spatially and temporally resolved morphological, sedimentological and biogeochemical data. Samples and data are further processed ex-situ and combined with experiments and modelling. Ultimately, DynaDeep aims at elucidating the global relevance of these common but overlooked environments.