Fe Oxide Minerals Research Articles

Importance of oxidation products in coumarin-mediated Fe(hydr)oxide mineral dissolution.

Due to the low iron solubility in alkaline soils, plants have evolved different iron acquisition strategies, which are either based on ferric iron reduction (strategy I) or complexation by phytosiderophores (strategy II). Recently, a prominent role of coumarins for iron acquisition has been discovered, but details of the respective mechanism remain unclear. Since coumarins may act as iron-binding ligands but also as reductants, various reaction sequences are possible, resulting in different iron species and oxidized coumarins. In this context, it is often overlooked that oxidized coumarins are not just byproducts of iron(III) reduction, but may be actively involved in further steps of iron mobilization. In order to verify this active role of oxidized coumarins in Fe(hydr)oxide dissolution, we complemented iron dissolution data with data of single coumarins (esculetin, scopoletin, fraxetin) and their oxidation products, as a function of time, pH, and mineral (goethite, lepidocrocite). Our results demonstrate that there are four different routes for coumarin oxidation, leading to quinones, dimers, hydroxylated coumarins, demethylated coumarins, and combinations of these. The time-dependent species pattern differs with respect to mineral, pH, and coumarin molecule. Oxidized coumarins are often more reactive than the original coumarins, explaining unexpected iron mobilization by scopoletin, which is demethylated to esculetin. Also oxidative hydroxylation and dimerization increase the number of phenolic groups and yield new chelating properties. Several iron-species are identified for the three coumarins. Since oxidation reactions are initiated directly at mineral surfaces, they are often very effective-but this does not always result in more iron mobilization.

Hydrogeochemical and health risk evaluation of arsenic in shallow and deep aquifers along the different floodplains of Punjab, Pakistan

The current study delineated the distribution, (hydro)geochemical behavior and health risk of arsenic (As) in shallow (depth < 35 m; handpumps and electric pumps) and deep (depth > 35 m; tube wells) aquifers in five areas along the Indus River (Bhakar, Kallur Kot), Jhelum River (Jhelum) and Chenab River (Hafizabad, Gujranwala) floodplains of Punjab, Pakistan. Relatively, greater As concentration was observed in deep wells (mean: 24.3 µg L−1) compared to shallow wells (19.4 µg L−1), with groundwater As spanning 0.1–121.7 µg L−1 (n = 133) in three floodplains. Groundwater from Hafizabad (Chenab River floodplain) possessed the highest As (121.7 µg L−1), Na+ (180 mg L−1), Ca2+ (95 mg L−1), Cl− (101 mg L−1) and SO42− (1353 mg L−1) concentrations. Arsenic health risk modeling indicated the potential carcinogenic (value > 10−4) and non-carcinogenic (hazard quotient > 1.0) risks for groundwater of all areas, with the utmost risk estimated for Chenab floodplain and deep aquifers. Positive saturation index values for Fe oxide mineral phases may suggest their potential role in As mobilization/release in these aquifer environments. This study provides critically-important and baseline knowledge for a widespread groundwater As examination along these three floodplains, which is vital for launching suitable As mitigation and remediation programs to reduce the potential health risk.

Using Zn isotopes to trace Zn sources and migration pathways in paddy soils around mining area

Paddy soils around mining areas suffer from the great threat of heavy metal pollution. The traditional source-tracing methods based on metal concentrations limit our ability to quantify the sources of heavy metals and trace their transport processes to paddy soils. In this study, Zn isotope compositions of paddy soils in Dabaoshan mine area, a typical sulfide deposit in southern China, have been systematically studied. According to a plot between 1/Zn (i.e. inverse concentration) and δ66Zn value, all the polluted paddy soils fall on the mixing line between acid mine drainage precipitate (AMD-precipitate) and fertilizer while the unpolluted paddy soil falls on the mixing line between fertilizer and bedrock. This indicates the mixing of Zn sources at least three end-members: the mining end-member (i.e. AMD-precipitate), the agricultural end-member (i.e. fertilizer), and bedrock whose geochemical signature is often overprinted by the former two sources around the mining area. The quantitative calculations to apportion the end-member’s contributions show that the mining activity contributes most Zn in the paddy soils with an average of ∼66.2%. The contribution of mining activities has significant spatial variations. Specifically, the mining activities have relatively low impacts on the lower reach and the deep soil. Additionally, the apparent Zn isotope fractionation between AMD and AMD-precipitate (Δ66ZnAMD-precipitate − AMD of −0.35 to −0.08‰) in the tailings dam suggests that Zn cations in AMD coprecipitated with the secondary Fe-bearing minerals (e.g. jarosite and goethite). After being discharged from the tailings dam, Zn is mainly carried by the Fe-oxide minerals and migrated during surface runoff. Our study highlights the contribution of human activities to the Zn pollution in the paddy soils and the key role of Fe-bearing minerals in the migration of Zn. These findings provide a scientific base for the development of policy for pollution control in mining-affected region.

Interactions of xanthate molecule with different mineral surfaces: A comparative study of Fe, Pb and Zn sulfide and oxide minerals with coordination chemistry

Why are xanthates widely used in sulfide minerals flotation but seldom used in oxidized ore? Herein, the principle of coordination chemistry is introduced to study the interactions of methyl xanthate with sulfide (pyrite, galena and sphalerite) and oxide minerals (hematite, cerussite and smithsonite) under weak acidic and neutral conditions. The findings show that xanthate can strongly combine with the low-spin Fe atom of the pyrite surface, and the adsorption on the galena and cerussite surfaces is attributed to the strong ionic polarization induced by the center deviations between their Pb and S atoms. However, the adsorption configurations on both the sphalerite and smithsonite surfaces are rather weak due to the highly stable Zn 3d orbital. Further analysis shows that the orbital symmetry of the methyl xanthate molecule matches well with the pyrite, galena and cerussite. Moreover, very strong hybridization occurs in the pyrite, galena and cerussite configurations, but is rarely observed in other configurations. In addition, a remarkable d-p back-bonding is found in the pyrite adsorption configuration.

Spectroscopic Quantification of Inner- and Outer-Sphere Oxyanion Complexation Kinetics: Ionic Strength and Background Cation Effect on Sulfate Adsorption to Hematite

Sulfate adsorbs on Fe-oxide minerals by both inner- and outer-sphere modes; however, the time dependence of coexisting surface species is not clear. Using in situ attenuated total reflectance–Fouri...

Removal of heavy metals from contaminated paddy soils using chemical reductants coupled with dissolved organic carbon solutions

General acid washing is commonly used to treat heavy metal-contaminated soils, but it is sometimes difficult to achieve remediation aims in severely polluted soils. If we expose the surfaces of Fe oxide minerals to reductive dissolution during washing treatment, more of the metals initially adsorbed to these surfaces will be liberated, which may encourage the removal of heavy metals. Initially, the metal extraction capabilities of nine chemical reductants were compared in ten soil samples polluted by Cr, Cu, Zn, and Ni. Sodium dithionite (Na2S2O4) and ferrous sulfate (FeSO4) were screened for subsequent intensive research. In summary, the Na2S2O4 solutions had higher Cr, Cu, and Zn removal rates than either the FeSO4 or acid solution. Application of dissolved organic carbon (DOC) further increased the removal of heavy metals by complexation. About 15%, 86%, 32%, and 52% of the Cr, Cu, Zn, and Ni, respectively, were removed from the representative soil (M-2) by two-stage washing using 0.2 M Na2S2O4 coupled with 1,500 mg L−1 DOC solution at pH 2.0. Meanwhile, most soil fertility was preserved: ammonium nitrogen was increased 3.9 times; the increase in exchangeable potassium was 33%; and the reduction in available P was only 10%.

Immobilization and release risk of arsenic associated with partitioning and reactivity of iron oxide minerals in paddy soils.

The consumption of agricultural products grown on paddy soils contaminated with toxic element has a detrimental effect on human health. However, the processes and mechanisms of iron (Fe) mineral-associated arsenic (As) availability and As reactivity in different paddy soil profiles are not well understood. In this study, the fractions, immobilization, and release risk of As in eleven soil profiles from the Changzhutan urban agglomeration in China were investigated; these studied soils were markedly contaminated with As. Sequential extraction experiments were used to analyze fractions of As and Fe oxide minerals, and kinetic experiments were used to characterize the reactivity of Fe oxide minerals. The results showed that concentrations of total As and As fractions had a downward trend with depth, but the average proportions of As fractions only showed relatively small changes, which implied that the decrease in the total As concentrations influenced the changes in fraction concentrations along the sampling depth. Moreover, we found that easily reducible Fe (Feox1) mainly controlled the reductive dissolution of the Fe oxides, which suggest that the reductive dissolution process could potentially release As during the flooded period of rice production. In addition, a high proportion of As was specifically absorbed As (As-F2) (average 20.4%) in paddy soils, higher than that in other soils. The total organic carbon (TOC) content had a positive correlation with the amount of non-specifically bound As (As-F1) (R = 0.56), which means that TOC was one factor that affected the As extractability in the As-F1. Consequently, high inputs of organic fertilizers may elevate the release of As and accelerate the diffusion of As. Graphical abstract.

Arsenic immobilization by in-situ iron coating for managed aquifer rehabilitation

A long-lasting challenge in eliminating the worldwide impact of geogenic arsenic (As)-contaminated groundwater is the development of efficient, in-situ treatment technologies that are applicable in decentralized and rural areas. Here we present a managed aquifer rehabilitation (MAR) approach based on the in-situ creation of Fe-oxide scavengers for remediating As-contaminated groundwater. The Fe-oxide coatings on sediment surfaces were generated via periodic injection of Fe2+ and ClO− solutions into an As-affected sandy aquifer at the Datong Basin, northern China for 25 days. This treatment prompted the buildup of weakly alkaline/circumneutral and oxidizing conditions to enhance As(III) oxidation in the target aquifer. Dissolved As concentrations decreased from the initial average 78.0 to 9.8 μg/L over the 25-d amendment. Sediment imaging by scanning electron microscope-X-ray energy dispersive spectroscopy confirms the deposition of Fe-rich precipitates on sediment surfaces with the simultaneous retention of As, and high density electrical tomography suggests the occurrence of such a process throughout the target zone. Further X-ray diffraction analysis and sequential chemical extraction reveal that the neo-formed Fe minerals comprised both poorly crystalline (e.g., ferrihydrite) and better crystalline (e.g., goethite) Fe oxides. The process-based reactive-transport modeling for the variations of As species in the treated groundwater supports that the new Fe-oxide minerals, most probably goethite, acted as efficient removers of aqueous As. The low As level of ∼10 μg/L was maintained during the following 215-d monitoring, demonstrating the long effectiveness of the MAR approach. This study highlights the feasibility of As immobilization by manipulating in-situ Fe-oxide coating on sandy sediments at the pilot scale. The MAR technology may be applicable for As-affected aquifers with controlled oxidizing conditions in the Datong Basin and likely other high-As regions with similar hydrogeochemical settings.

Evaluation of Fe isotope values as a provenance tool for chert artefacts from the north‐eastern United States

Iron (Fe) isotope compositions of prehistoric stone tools and geological sources were compared to evaluate the robustness of this isotopic fingerprinting technique. Artefacts and source materials were collected from the Hatch site in central Pennsylvania, United States, where both veined chert (Bald Eagle chert) and stone tools coexist within several metres. Yellow artefacts (δ56Fe = 0.38 ± 0.1, n = 7) and source materials (δ56Fe = 0.42 ± 0.1, n = 8) isotopically matched within error. The source values also overlap yellow chert samples from three other Bald Eagle chert locations in the area. These values are different from six other chert locations in the north‐eastern United States. These data suggest that the Fe isotope composition of chert artefacts reflect distinct geological sources. To enhance the mechanical characteristics of the stone tools, the chert experienced heat treatment, which induced a phase shift of the Fe oxide mineral goethite to hematite. This phase shift changes the colour of the chert to red. The red chert artefacts and source material also have overlapping Fe isotope values, but are 0.2‰ higher than the initial yellow chert. Experimental work where cherts were heated with different clays shows that Fe exchange with site soils induces the +0.2 fractionation. These data demonstrate that predictable Fe isotope fractionation occurs during heating, resulting in isotopically distinct artefacts.

Tracing water column euxinia in Eastern Mediterranean Sapropels S5 and S7

Sapropels S5 and S7 formed in the semi-enclosed Eastern Mediterranean Sea (EMS) during peak interglacial periods MIS5e and MIS7a, respectively, are considered among the most strongly developed Quaternary sapropels. This study investigates the redox dynamics of the water column during their formation, via Fe isotope and Fe speciation studies of cores taken at 2550 m depth at site ODP-967. Both sapropels show an inverse correlation between δ56Fe and FeT/Al, with slopes mostly matching that found for the Black Sea, pointing to a benthic shelf to basin shuttle of Fe and subsequent precipitation of Fe sulphides in euxinic bottom waters. An exception to these Black Sea-type trends occurs during the later, peak, stages of S7, where the negative δ56Fe - FeT/Al slope shallows. Fe speciation studies reveal that the dominant highly reactive Fe phase (FeHR) in the sapropels is pyrite, with Fe (oxyhydr)oxides forming the second major mineral component. Correspondingly, FeHR/FeT plots show increased strengthening of anoxic water conditions during the passage from pre-sapropel sediment into the sapropel. Nevertheless, despite the evidence for euxinic conditions from both Fe isotopes and high Mo concentrations in the sapropel, Fepy/FeHR ratios remain below values commonly used to identify water column euxinia. This apparent contradiction is ascribed to the sedimentary preservation of a high flux of crystalline Fe (oxyhydr)oxide minerals to the basin, which resulted in a relatively low degree of sulphidation, despite the presence of euxinic bottom waters. Thus, the operationally defined ferruginous/euxinic boundary for EMS sapropels is better placed at Fepy/FeHR = 0.6, which is somewhat below the usually ascribed lower limit of 0.7. Consistent with the significant presence of crystalline Fe (oxyhydr)oxides, the change in the δ56Fe - FeT/Al slope during peak S7 is ascribed to an enhanced monsoon-driven flux of detrital Fe(III) oxides from the River Nile into the EMS basin and comcomitant diagenetic sulphidation. Euxinic water column conditions in sapropel S5 and S7 are interpreted here to reflect the positive balance between dissolved sulphide formation and rates of reductive dissolution of Fe (oxyhydr)oxide minerals. Both of these parameters in turn depend on the extent to which water overturn times are reduced and export productivity increased during sapropel formation.

Threshold for labile phosphate in a sandy acid sulfate soil

In acid soils, plant availability of fertiliser P is affected by phosphate binding to Fe or Al oxide minerals. However, little is known about the P pools in acid sulfate soils after phosphate fertilisation, or the capacity of the oxyhydroxy sulfate mineral jarosite (KFe3(OH)6(SO4)2) found in these soils, to bind or release added phosphate. Sulfuric acid sulfate soil (initial pH 3.5, adjusted to 5.5) was amended with phosphate at 0, 96, 385, 578 and 770 mg P kg−1 and incubated under submerged conditions. Soil phosphate pools (labile phosphate, moderately labile phosphate, non-labile phosphate and residual phosphate) and amorphous Fe/Al were measured after two and four weeks. Phosphate sorption and its release were determined in incubated soils and jarosite, separately. In soil, maximum phosphate sorption was about 350 mg phosphate kg−1. Labile phosphate was higher than the control (without phosphate addition) at phosphate rates above 350 mg P kg−1 and was more than 50% of added phosphate. The length of submergence had little effect on phosphate pools. Below the threshold of 350 mg phosphate kg−1, absorbed phosphate was strongly bound to the soil whereas 50% of sorbed phosphate was released above the threshold. The high phosphate binding capacity of jarosite (maximal 360 mg phosphate kg−1) confirmed the importance of Fe oxyhydroxy sulfate minerals in P binding in acid soils. However, at maximal phosphate binding, up to 20% of bound phosphate could be released, suggesting that phosphate bound to jarosite may become plant available. The results of this study will help inform fertiliser requirements for crop growth or remediation of acid sulfate soils using plants.

Tracing the origin of reservoir sediments using magnetic properties in Southeastern Brazil

Determining the origin of eroded soil is essential to design effective soil erosion control strategies which preserve the soil resource, enhance agricultural productivity, and reduce the negative impacts of soil erosion, in-field and off-field. Magnetic properties have been widely used in temperate environments to identify sediment sources, pathways and links, but there have been very few applications in tropical and subtropical environments. Therefore, in this paper we investigated reservoir sediment sources in the Upper Grande River Basin, Southeastern Brazil, using sediment tracing techniques based on magnetic parameters (low and high frequency magnetic susceptibility, frequency dependent susceptibility). The different parent materials and subtropical weathering conditions resulted in soils having different Fe oxide minerals and Fe oxide contents, promoting magnetic variability that allowed comparison and identification of possible sources of reservoir sediments in order to reduce water erosion impacts. The results indicate the suitability of magnetic properties as a tracer for soil erosion studies in tropical environments.

Transfer and transformation mechanisms of Fe bound-organic carbon in the aquitard of a lake-wetland system during reclamation

Organic carbon (OC) can help control greenhouse gas emissions by participating in biogeochemical reactions and preventing the migration of contaminants in groundwater systems. The association of OC with Fe (Iron) oxide minerals plays a significant role in stabilizing OC and regulating the biogeochemical cycles of OC on the earth’s surface. Reclaiming farmland from lakes changes an original lake into a wetland, but the destiny of Fe bound-OC in the underlying aquitard during this process has been poorly understood. The mechanisms of migration and transformation of Fe bound-OC were investigated in subsurface aquitard sediments of three typical boreholes in the Chen Lake wetland, central China. The Fe bound-OC content in the natural sedimentary conditions (borehole A), transition area (borehole B), and intensive reclamation area (borehole C) were 0.17–3.87, 0.28–3.98 and 0.13–7.08 mg g−1, respectively. The reclamation changed the redox, water, and infiltration conditions of the surface environment, resulting in a transformation of Fe oxides phases, and then cause the change of content and structure of Fe bound-OC. The fresh organic matter provided by undecomposed crops causes oxygen- and nitrogen-rich compounds to combine with Fe oxides extensively through adsorption, resulting in higher δ13C values of Fe bound-OC than non-Fe bound-OC. Fe bound-OC has strong resistance to biodegradation. The Fe bound-OC: total OC ratios generated by adsorption and coprecipitation on the surface layer (0 to −3.5 m) of borehole C was 10.37% and 18.86%, 6.92% and 12.46% higher than those of boreholes A and B, respectively. Coprecipitation has a stronger OC-binding ability and enriches more carboxylates and aromatics, while adsorption gradually assumed a dominant position in OC-Fe interaction in deep aquitard. The reduction dissolution of Fe oxide causes Fe bound-OC to transfer into pore water, leading to an increase of Fe ion and dissolved OC in deep strata.

Exploration Potential of Fine-Fraction Heavy Mineral Concentrates from Till Using Automated Mineralogy: A Case Study from the Izok Lake Cu–Zn–Pb–Ag VMS Deposit, Nunavut, Canada

Exploration under thick glacial sediment cover is an important facet of modern mineral exploration in Canada and northern Europe. Till heavy mineral concentrate (HMC) indicator mineral methods are well established in exploration for diamonds, gold, and base metals in glaciated terrain. Traditional methods rely on visual examination of &gt;250 µm HMC material, however this study applies modern automated mineralogical methods (mineral liberation analysis (MLA)) to investigate the finer (&lt;250 µm) fraction of till HMC. Automated mineralogy of finer material allows for rapid collection of precise compositional and morphological data from a large number (10,000–100,000) of heavy mineral grains in a single sample. The Izok Lake volcanogenic massive sulfide (VMS) deposit, one of the largest undeveloped Zn–Cu resources in North America, has a well-documented fan-shaped indicator mineral dispersal train and was used as a test site for this study. Axinite, a VMS indicator mineral difficult to identify optically in HMC, is identified in till samples up to 8 km down ice. Epidote and Fe-oxide minerals are identified, with concentrations peaking proximal to mineralization. Corundum and gahnite are intergrown in till samples immediately down ice of mineralization. Till samples also contain chalcopyrite and galena up to 8 km down ice of mineralization, an increase from 1.3 km for sulfide minerals in till previously reported for coarse HMC fractions. Some of these sulfide grains occur as inclusions within chemically and physically robust mineral grains and would not be identified visually in the coarse HMC visual counts. Best practices for epoxy mineral grain mounting and abundance reporting are presented along with the automated mineralogy of till samples down ice of the deposit.

Accelerating Mineral Carbonation in Ultramafic Mine Tailings via Direct CO2 Reaction and Heap Leaching with Potential for Base Metal Enrichment and Recovery

Abstract Accelerated carbonation of ultramafic mine tailings has the potential to offset CO2 emissions produced by mining ores from Cu-Ni-platinum group element, podiform chromite, diamondiferous kimberlite, and historical chrysotile deposits. Treatments such as acid leaching, reaction of tailings with elevated concentrations of gaseous CO2, and optimization of tailings pore water saturation have been shown to enhance CO2 sequestration rates in laboratory settings. The next challenge is to deploy treatment technologies on the pilot and field scale while minimizing cost, energy input, and adverse environmental impacts. Implementation of accelerated tailings carbonation at field scale will ideally make use of in situ treatments or modified ore-processing routes that employ conventional technology and expertise and operate at close to ambient temperatures and pressures. Here, we describe column experiments designed to trial two geochemical treatments that address these criteria: (1) direct reaction of partially saturated ultramafic tailings with synthetic flue gas from power generation (10% CO2 in N2) and (2) repeated heap leaching of ultramafic tailings with dilute sulfuric acid. In the first experiment, we report rapid carbonation of brucite [Mg(OH)2] in the presence of 10% CO2 gas within tailings sampled from the Woodsreef chrysotile mine, New South Wales, Australia. Within four weeks, we observe a doubling of the amount of CO2 stored within minerals relative to what is achieved after three decades of passive mineral carbonation via air capture in the field. Our simulated heap leaching experiments, treated daily with 0.08 M H2SO4, produce high-Mg leachates that have the potential to sequester 21.2 kg CO2 m–2 y–1, which is approximately one to two orders of magnitude higher than the rate of passive carbonation of the Woodsreef mine tailings. Although some nesquehonite (MgCO3 · 3H2O) forms from these leachates, most of the Mg is precipitated as Mg sulfate minerals instead. Therefore, an acid other than H2SO4 could be used; otherwise, sulfate removal would be required to maximize CO2 sequestration potential from acid heap leaching treatments. Reactive transport modeling (MIN3P) is employed to simulate acid leaching experiments and predict the effects of heap leaching for up to five years. Finally, our synchrotron X-ray fluorescence microscopy results for leached tailings material reveal that valuable trace metals (Fe, Ni, Mn, Co, Cr) become highly concentrated within secondary Fe (hydr)oxide minerals at the pH neutralization horizon within our column experiments. This discrete horizon migrates downward, and our reactive transport models indicate it will become increasingly enriched in first-row transition metals in response to continued acid leaching. Acid-leaching treatments for accelerated mineral carbonation could therefore be useful for ore processing and recovery of base metals from tailings, waste rock, or low-grade ores.

Antimony Sorption to Goethite: Effects of Fe(II)-Catalyzed Recrystallization

The environmental mobility and bioavailability of antimony (Sb) are strongly influenced by sorption to Fe(III) oxide minerals, such as goethite (αFeOOH). Exposure to aqueous Fe(II), as occurs, for ...

Linking microbial community composition to hydrogeochemistry in the western Hetao Basin: Potential importance of ammonium as an electron donor during arsenic mobilization

Various functional groups of microorganisms and related biogeochemical processes are likely to control arsenic (As) mobilization in groundwater systems. However, spatially-dependent correlations between microbial community composition and geochemical zonation along groundwater flow paths are not fully understood, especially with respect to arsenic mobility. The western Hetao Basin was selected as the study area to address this limitation, where groundwater flows from a proximal fan (geochemical-group I: low As, oxidizing), through a transition area (geochemical-group II: moderate As, moderately-reducing) and then to a flat plain (geochemical-group III: high As, reducing). High-throughput Illumina 16S rRNA gene sequencing showed that the microbial community structure in the proximal fan included bacteria affiliated with organic carbon degradation and nitrate-reduction or even nitrate-dependant Fe(II)-oxidation, mainly resulting in As immobilization. In contrast, for the flat plain, high As groundwater contained Fe(III)- and As(V)-reducing bacteria, consistent with current models on As mobilization driven via reductive dissolution of Fe(III)/As(V) mineral assemblages. However, Spearman correlations between hydrogeochemical data and microbial community compositions indicated that ammonium as a possible electron donor induced reduction of Fe oxide minerals, suggesting a wider range of metabolic pathways (including ammonium oxidation coupled with Fe(III) reduction) driving As mobilization in high As groundwater systems.

An expanded shale δ98Mo record permits recurrent shallow marine oxygenation during the Neoarchean

Multiple attempts have been made using the ancient shale record to track the molybdenum isotope composition (δ98Mo) of seawater during the final two-hundred million years of the Archean Eon (2.7 to 2.5 billion-years-ago, or Ga). This seawater δ98Mo value is important because it should have scaled with levels of ocean oxygenation during the runup to the Great Oxidation Event (GOE). Unfortunately, however, it is difficult to tell if the majority of the existing late-Archean shale δ98Mo record tracks an ancient seawater value. Here, we further attempt to track pre-GOE seawater δ98Mo using an expanded and well-characterized shale sample set from Western Australia (Jeerinah, Wittenoom, and Mt. Sylvia formations) and South Africa (Nauga and Klein Naute formations). Most importantly, and in contrast to most previous Mo isotope studies of similarly aged shales, local redox conditions for our shales have been independently constrained using the iron (Fe) speciation proxy and bottom-water Mo contents at the time of deposition have been qualitatively estimated using Mo/TOC ratios. Local redox conditions and bottom water Mo availability are important parameters because transfer of the seawater δ98Mo to sediments today is shown to be dependent on these conditions. According to our updated sedimentary δ98Mo record, seawater δ98Mo commonly exceeded 1.0‰ between ~2.69 Ga and 2.50 Ga. In order to drive such a heavy seawater δ98Mo, there must have been a marine sink with a strong preference for lighter-mass Mo isotopes frequently present over this timeframe. The operation of some anaerobic processes in late-Archean marine settings could theoretically explain the heavier seawater δ98Mo. Such processes are known to promote the preferential retention of lighter-mass Mo isotopes in marine sediments today (e.g., interactions between Mo and organic matter or the formation of thio-complexes). Alternatively, or in addition, adsorption of lighter-mass Mo isotopes to Fe and Mn oxide minerals formed in oxygenated marine environments can explain the heavier seawater δ98Mo. A compilation of previous work suggests that oxygenated shallow marine environments were fairly common during the late-Archean, and thus Mo adsorption to FeMn oxides formed in these settings probably played an important role in driving heavy seawater δ98Mo over this timeframe.

Mineral vs. organic matter supply as a limiting factor for the formation of mineral-associated organic matter in forest and agricultural soils

Physical and chemical interactions between soil organic matter (OM) and minerals is one of the primary mechanisms for stabilizing OM in terrestrial ecosystems. Focusing on OM association with mineral surfaces, this study sought to examine mineral-associated OM from the perspectives of both mineral surface characteristics and organic matter chemistry. The research was conducted at paired-sites under North American Mid-Atlantic Coastal forest and crop production with shared environmental factors. Using carbon (C) and nitrogen (N) 1s micro- X-ray absorption near-edge fine structure (XANES) spectroscopy, we investigated the amounts and types of mineral-associated OM. Mineral specific surface area (SSA) of bulk soil was determined for three conditions: untreated, post OM removal and post iron (Fe) (oxyhydr)oxides removal. Amounts of mineral-associated OM were smaller in the agricultural soil, where greater SSA sourced from clay-sized phyllosilicates and Fe (oxyhydr)oxide minerals did not result in greater OM coverage of the mineral surface area. Although agricultural surface soil showed less abundance of phenolic C, speciation of mineral-associated OM did not differ between comparable horizons. Our results suggest that despite the plow-derived mixing of soil, which increased SSA and secondary minerals available to interact physically and chemically with OM in the plowed layer, the formation of mineral-associated OM in agricultural soil is ultimately limited by available OM.

Shelf-to-basin iron shuttle in the Guaymas Basin, Gulf of California

Enrichments of highly reactive iron (Fe) (sum of Fe (oxyhydr)oxide, carbonate and sulfide minerals) in marine sediments and sedimentary rocks are commonly interpreted as an indication of anoxic conditions in the bottom water at the time of deposition. The model system for this proxy rationale is the semi-restricted Black Sea, where sediments underneath the anoxic and sulfidic (i.e., euxinic) deep-water are enriched in reactive Fe, which was mobilized from the surrounding shelf areas. To test whether such a shelf-to-basin Fe shuttle can operate in semi-restricted basins without euxinic deep water, we investigated sedimentary Fe speciation and Fe isotope compositions in sediments of the Guaymas Basin, Gulf of California. Sediments on the slope underneath the eastern equatorial Pacific oxygen minimum zone and sediments within the oxic deep basin are both enriched in reactive Fe, with reactive Fe making up 45 ± 11% of the total Fe pool. The following mechanisms may contribute to these Fe enrichments: (1) Release of dissolved Fe from anoxic shelf and slope sediments followed by lateral transport of dissolved and/or particulate Fe in the water column; (2) preferential transport of fine-grained, terrigenous particles with a high reactive Fe content into the basin; (3) microbially mediated conversion of non-reactive silicate minerals to reactive Fe minerals during transport; (4) hydrothermal venting and lateral Fe transport within the deep water. The first process can explain reactive Fe enrichments in slope sediments, whereas all processes may contribute to sedimentary Fe enrichments in the deeper basin. The δ 56 Fe value of sediments increases from shelf to slope and decreases from the slope into the basin. This lateral pattern of δ 56 Fe, as well as the pattern of Fe enrichment, is similar to that observed in other marine systems with a Fe shuttle. However, the size of the Fe enrichment, and the range in δ 56 Fe (−0.06 to +0.16‰) is smaller. This difference is due to higher terrigenous sedimentation rates in the Guaymas Basin and, therefore, more intense dilution of shuttle-derived reactive Fe. We argue that, depending on the extent of bathymetric restriction and terrigenous background sedimentation, reactive Fe enrichments can form under a broad range of redox conditions and in diverse sedimentary environments. The concepts applied in this study can be used to identify those circumstances in the paleo-record.