Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources.

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.

Comments on "was hydrogen peroxide present before the arrival of oxygenic photosynthesis? The important role of iron(II) in the archean ocean".

Recent research has hypothesized that hydrogen peroxide (H2O2) may have emerged from abiotic geochemical processes during the Archean eon (4.0-2.5 Ga), stimulating the evolution of an enzymatic antioxidant system in early life. This eventually led to the evolution of cyanobacteria, and in turn, the accumulation of oxygen on Earth. In the latest issue of Redox Biology, Koppenol and Sies (vol. 29, no. 103012, 2024) argued against this hypothesis and suggested instead that early organisms would not have been exposed to H2O2 due to its short half-life in the ferruginous oceans of the Archean. We find these arguments to be factually incomplete because they do not consider that freshwater or some coastal marine environments during the Archean could indeed have led to H2O2 generation and accumulation. In these environments, abiotic oxidants could have interacted with early life, thus steering its evolutionary course.

Transient fertilization of a post-Sturtian Snowball ocean margin with dissolved phosphate by clay minerals.

Marine sedimentary rocks deposited across the Neoproterozoic Cryogenian Snowball interval, ~720-635 million years ago, suggest that post-Snowball fertilization of shallow continental margin seawater with phosphorus accelerated marine primary productivity, ocean-atmosphere oxygenation, and ultimately the rise of animals. However, the mechanisms that sourced and delivered bioavailable phosphate from land to the ocean are not fully understood. Here we demonstrate a causal relationship between clay mineral production by the melting Sturtian Snowball ice sheets and a short-lived increase in seawater phosphate bioavailability by at least 20-fold and oxygenation of an immediate post-Sturtian Snowball ocean margin. Bulk primary sediment inputs and inferred dissolved seawater phosphate dynamics point to a relatively low marine phosphate inventory that limited marine primary productivity and seawater oxygenation before the Sturtian glaciation, and again in the later stages of the succeeding interglacial greenhouse interval.

Ecological engineering of iron ore tailings into useable soils for sustainable rehabilitation.

Ecological engineering of soil formation in tailings is an emerging technology toward sustainable rehabilitation of iron (Fe) ore tailings landscapes worldwide, which requires the formation of well-organized and stable soil aggregates in finely textured tailings. Here, we demonstrate an approach using microbial and rhizosphere processes to progressively drive aggregate formation and development in Fe ore tailings. The aggregates were initially formed through the agglomeration of mineral particles by organic cements derived from microbial decomposition of exogenous organic matter. The aggregate stability was consolidated by colloidal nanosized Fe(III)-Si minerals formed during Fe-bearing primary mineral weathering driven by rhizosphere biogeochemical processes of pioneer plants. From these findings, we proposed a conceptual model for progressive aggregate structure development in the tailings with Fe(III)-Si rich cements as core nuclei. This renewable resource dependent eco-engineering approach opens a sustainable pathway to achieve resilient tailings rehabilitation without resorting to excavating natural soil resources.

Exogenous Electroactive Microbes Regulate Soil Geochemical Properties and Microbial Communities by Enhancing the Reduction and Transformation of Fe(III) Minerals.

Electroactive microbes can conduct extracellular electron transfer and have the potential to be applied as a bioresource to regulate soil geochemical properties and microbial communities. In this study, we incubated Fe-limited and Fe-enriched farmland soil together with electroactive microbes for 30 days; both soils were incubated with electroactive microbes and a common iron mineral, ferrihydrite. Our results indicated that the exogenous electroactive microbes decreased soil pH, total organic carbon (TOC), and total nitrogen (TN) but increased soil conductivity and promoted Fe(III) reduction. The addition of electroactive microbes also changed the soil microbial community from Firmicutes-dominated to Proteobacteria-dominated. Moreover, the total number of detected microbial species in the soil decreased from over 700 to less than 500. Importantly, the coexistence of N-transforming bacteria, Fe(III)-reducing bacteria and methanogens was also observed with the addition of electroactive microbes in Fe-rich soil, indicating the accelerated interspecies electron transfer of functional microflora.

A sedimentary record of the evolution of the global marine phosphorus cycle.

Phosphorus (P) is typically considered to be the ultimate limiting nutrient for Earth's biosphere on geologic timescales. As P is monoisotopic, its sedimentary enrichment can provide some insights into how the marine P cycle has changed through time. A previous compilation of shale P enrichments argued for a significant change in P cycling during the Ediacaran Period (635-541 Ma). Here, using an updated P compilation-with more than twice the number of samples-we bolster the case that there was a significant transition in P cycling moving from the Precambrian into the Phanerozoic. However, our analysis suggests this state change may have occurred earlier than previously suggested. Specifically in the updated database, there is evidence for a transition ~35 million years before the onset of the Sturtian Snowball Earth glaciation in the Visingsö Group, potentially divorcing the climatic upheavals of the Neoproterozoic from changes in the Earth's P cycle. We attribute the transition in Earth's sedimentary P record to the onset of a more modern-like Earth system state characterized by less reducing marine conditions, higher marine P concentrations, and a greater predominance of eukaryotic organisms encompassing both primary producers and consumers. This view is consistent with organic biomarker evidence for a significant eukaryotic contribution to the preserved sedimentary organic matter in this succession and other contemporaneous Tonian marine sedimentary rocks. However, we stress that, even with an expanded dataset, we are likely far from pinpointing exactly when this transition occurred or whether Earth's history is characterized by a single or multiple transitions in the P cycle.

Molecular dynamics simulation study of covalently bound hybrid coagulants (CBHyC): Molecular structure and coagulation mechanisms.

Covalently-bound organic silicate-aluminum hybrid coagulants (CBHyC) have been shown to efficiently remove low molecular weight organic contaminants from wastewater. However, the interaction dynamics and motivations during the coagulation of contaminant molecules by CBHyC are limited. In this study, a molecular dynamics (MD) simulation showed that CBHyC forms core-shell structure with the aliphatic carbon chains gather inside as a core and the hydrophilic quaternary ammonium-Si-Al complexes disperse outside as a shell. This wrapped structure allowed the coagulant to diffuse into solutions easily and capture target contaminants. The adsorption of anionic organic contaminants (e.g., diclofenac) onto the CBHyC aggregates was driven equally by van der Waals forces and electrostatic interactions. Cationic organic contaminants (e.g., tetracycline) were seldom bound to CBHyC because of substantial repulsive forces between cationic molecules and CBHyC. Neutrally-charged organic molecules were generally bound through hydrophobic interactions. For adenine and thymine deoxynucleotide, representatives of antibiotic resistance genes, van der Waals forces and electrostatic interaction became the dominant driving force with further movement for adenine and thymine, respectively. Driving forces between target contaminant and coagulant directly affect the size and stability of formed aggregate, following the coagulation efficiency of wastewater treatment. The findings of this study enrich the database of aggregation behavior between low molecular weight contaminants and CBHyC and contribute to further and efficient application of CBHyC in wastewater treatment.

Pyrolyzed biomass-derived nanoparticles: a review of surface chemistry, contaminant mobility, and future research avenues to fill the gaps.

Nanoparticles are abundant in the subsurface, soil, streams, and water bodies, and are often a critical control on elemental speciation, transport and cycling in the natural environment. This review provides an overview of pyrolyzed biomass-derived nanoparticles (PBNPs), their surface properties and reactivity towards aqueous species. We focus specifically on biochar-derived nanoparticles and activated carbon-derived nanoparticles which fall under our classification of PBNPs. Activated carbon-iron (nano)composites are included in some instances where there are significant gaps in literature because of their environmental relevance. Increased use of activated carbon, along with a resurgence in the manufacture and application of biochar for water treatment and soil amendment, has generated significant concerns about the mobility and toxicity of PBNPs derived from the bulk material in environmental applications. Recent examples are discussed to highlight current progress in understanding the influence of PBNPs on contaminant transport, followed by a critical discussion of gaps and future research directions.

Biofilms as agents of Ediacara-style fossilization.

Earth's earliest fossils of complex macroscopic life are recorded in Ediacaran-aged siliciclastic deposits as exceptionally well-preserved three-dimensional casts and molds, known as "Ediacara-style" preservation. Ediacara-style fossil assemblages commonly include both macrofossils of the enigmatic Ediacara Biota and associated textural impressions attributed to microbial matgrounds that were integral to the ecology of Ediacara communities. Here, we use an experimental approach to interrogate to what extent the presence of mat-forming microorganisms was likewise critical to the Ediacara-style fossilization of these soft-bodied organisms. We find evidence that biofilms can play an instrumental role in fostering fossilization. Rapid silica precipitation associated with macroorganism tissues is enhanced in the presence of mat- and biofilm-forming microorganisms. These results indicate that the occurrence of microbial mats and biofilms may have strongly shaped the preservational window for Ediacara-style fossils associated with early diagenetic silica cements, and therefore influenced the distribution and palaeoecological interpretation of the Ediacara Biota fossil record.

Complex impacts of hydraulic fracturing return fluids on soil microbial community respiration, structure and functional potentials.

The consequences of soils exposed to hydraulic fracturing (HF) return fluid, often collectively termed flowback and produced water (FPW), are poorly understood, even though soils are a common receptor of FPW spills. Here, we investigate the impacts on soil microbiota exposed to FPW collected from the Montney Formation of western Canada. We measured soil respiration, microbial community structure and functional potentials under FPW exposure across a range of concentrations, exposure time and soil types (luvisol and chernozem). We find that soil type governs microbial community response upon FPW exposure. Within each soil, FPW exposure led to reduced biotic soil respiration, and shifted microbial community structure and functional potentials. We detect substantially higher species richness and more unique functional genes in FPW-exposed soils than in FPW-unexposed soils, with metagenome-assembled genomes (e.g. Marinobacter persicus) from luvisol soil exposed to concentrated FPW being most similar to genomes from HF/FPW sites. Our data demonstrate the complex impacts of microbial communities following FPW exposure and highlight the site-specific effects in evaluation of spills and agricultural reuse of FPW on the normal soil functions.

Evaporative silicification in floating microbial mats: patterns of oxygen production and preservation potential in silica-undersaturated streams, El Tatio, Chile.

Microbial mats floating within multiple hydrothermally sourced streams in El Tatio, Chile, frequently exhibit brittle siliceous crusts (~1 mm thick) above the air-water interface. The partially silicified mats contain a diverse assemblage of microbial clades and metabolisms, including cyanobacteria performing oxygenic photosynthesis. Surficial crusts are composed of several amorphous silica layers containing well-preserved filaments (most likely cyanobacteria) and other cellular textures overlying EPS-rich unsilicified mats. Environmental logs, silica crust distribution, and microbial preservation patterns provide evidence for crust formation via repeated cycles of evaporation and silica precipitation. Within the mats, in situ microelectrode profiling reveals that daytime oxygen concentrations and pH values are diminished beneath silica crusts compared with adjacent unencrusted communities, indicating localized inhibition of oxygenic photosynthesis due to light attenuation. As a result, aqueous conditions under encrusted mats have a higher saturation state with regard to amorphous silica compared with adjacent, more active mats where high pH increases silica solubility, likely forming a modest feedback loop between diminished photosynthesis and crust precipitation. However, no fully lithified sinters are associated with floating encrusted mats in El Tatio streams, as both subaqueous and subaerial silica precipitation are limited by undersaturated, low-SiO2 (<150 ppm) stream waters. By contrast, well-cemented sinters can form by evaporation in silica-undersaturated solutions above 200 ppm SiO2 . Floating mats in El Tatio therefore represent a specific sinter preservation window, where evaporation in silica-undersaturated microbial mats produces crusts, which preserve cells and affect mat chemistry, but low-silica concentrations prevent the formation of lasting sinter deposits. Patterns of silica precipitation in El Tatio microbial communities show that the preservation potential of silicifying mats in the rock record is strongly dependent on aqueous silica concentrations.

An abiotic source of Archean hydrogen peroxide and oxygen that pre-dates oxygenic photosynthesis.

The evolution of oxygenic photosynthesis is a pivotal event in Earth's history because the O2 released fundamentally changed the planet's redox state and facilitated the emergence of multicellular life. An intriguing hypothesis proposes that hydrogen peroxide (H2O2) once acted as the electron donor prior to the evolution of oxygenic photosynthesis, but its abundance during the Archean would have been limited. Here, we report a previously unrecognized abiotic pathway for Archean H2O2 production that involves the abrasion of quartz surfaces and the subsequent generation of surface-bound radicals that can efficiently oxidize H2O to H2O2 and O2. We propose that in turbulent subaqueous environments, such as rivers, estuaries and deltas, this process could have provided a sufficient H2O2 source that led to the generation of biogenic O2, creating an evolutionary impetus for the origin of oxygenic photosynthesis.

Timing the evolution of antioxidant enzymes in cyanobacteria.

The ancestors of cyanobacteria generated Earth's first biogenic molecular oxygen, but how they dealt with oxidative stress remains unconstrained. Here we investigate when superoxide dismutase enzymes (SODs) capable of removing superoxide free radicals evolved and estimate when Cyanobacteria originated. Our Bayesian molecular clocks, calibrated with microfossils, predict that stem Cyanobacteria arose 3300-3600 million years ago. Shortly afterwards, we find phylogenetic evidence that ancestral cyanobacteria used SODs with copper and zinc cofactors (CuZnSOD) during the Archaean. By the Paleoproterozoic, they became genetically capable of using iron, nickel, and manganese as cofactors (FeSOD, NiSOD, and MnSOD respectively). The evolution of NiSOD is particularly intriguing because it corresponds with cyanobacteria's invasion of the open ocean. Our analyses of metalloenzymes dealing with reactive oxygen species (ROS) now demonstrate that marine geochemical records alone may not predict patterns of metal usage by phototrophs from freshwater and terrestrial habitats.

Lead (Pb) sorption to hydrophobic and hydrophilic zeolites in the presence and absence of MTBE.

The co-contamination of the environment by metals and organic pollutants is a significant concern, and one such example is lead (Pb) and methyl tert-butyl ether (MTBE) due to their historic use as fuel additives. Clinoptilolite is an abundant and efficient zeolite for metal removal, but the potential interference of co-existing organic pollutants on metal removal, such as MTBE, have rarely been discussed. In this study, a combination of batch sorption tests and synchrotron-based X-ray absorption spectroscopic analyses were employed to investigate Pb sorption mechanism(s) onto clinoptilolite in the presence and absence of MTBE. A comparison was made to synthetic ZSM-5 zeolite to gain insights into differences in Pb binding mechanisms between hydrophilic (clinoptilolite) and hydrophobic (ZSM-5) zeolites. Site occupancy and surface precipitation contributed equally to Pb removal by clinoptilolite, while surface precipitation was the main Pb removal mechanism for ZSM-5 followed by site occupancy. Despite the negligible effect of 100 mg/L MTBE on observed Pb removal from solution by both zeolites, a surface-embedded Pb removal mechanism, through the Mg site on clinoptilolite surface, arises when MTBE is present. This study provides an understanding of atomic-level Pb uptake mechanisms on zeolites, with and without co-contaminating MTBE, which aids in their application in water treatment at co-contaminated sites.

The dissolution of fluorapatite by phosphate-solubilizing fungi: a balance between enhanced phosphorous supply and fluorine toxicity.

Fluorapatite (FAp) is the largest phosphorous (P) reservoir on Earth. However, due to its low solubility, dissolved P is severely deficient in the pedosphere. Fungi play a significant role in P dissolution via excretion of organic acids, and in this regard, it is important to understand their impact on P cycling. The object of this study was to elucidate the balance between P release and F toxicity during FAp dissolution. The bioweathering of FAp was assisted by a typical phosphate-solubilizing fungus, Aspergillus niger. The release of elements and microbial activities were monitored during 5-day incubation. We found that the release of fluorine (F) was activated after day 1 (~90 mg/L), which significantly lowered the phosphate-solubilizing process by day 2. Despite P release from FAp being enhanced over the following 3 days, decreases in both the amount of biomass (52% decline) and the respiration rate (81% decline) suggest the strong inhibitory effect of F on the fungus. We thus concluded that F toxicity outweighs P supply, which in turn inhibits fungi growth and prevents further dissolution of FAp. This mechanism might reflect an underappreciated cause for P deficiency in soils.

The kaolinite shuttle links the Great Oxidation and Lomagundi events.

The ~2.22-2.06 Ga Lomagundi Event was the longest positive carbon isotope excursion in Earth's history and is commonly interpreted to reflect perturbations in continental weathering and the phosphorous cycle. Previous models have focused on mechanisms of increasing phosphorous solubilization during weathering without focusing on transport to the oceans and its dispersion in seawater. Building from new experimental results, here we report kaolinite readily absorbs phosphorous under acidic freshwater conditions, but quantitatively releases phosphorous under seawater conditions where it becomes bioavailable to phytoplankton. The strong likelihood of high weathering intensities and associated high kaolinite content in post-Great-Oxidation-Event paleosols suggests there would have been enhanced phosphorus shuttling from the continents into marine environments. A kaolinite phosphorous shuttle introduces the potential for nonlinearity in the fluxes of phosphorous to the oceans with increases in chemical weathering intensity.

Microbial processes during deposition and diagenesis of Banded Iron Formations.

Banded Iron Formations (BIFs) are marine chemical sediments consisting of alternating iron (Fe)-rich and silica (Si)-rich bands which were deposited throughout much of the Precambrian era. BIFs represent important proxies for the geochemical composition of Precambrian seawater and provide evidence for early microbial life. Iron present in BIFs was likely precipitated in the form of Fe3+ (Fe(III)) minerals, such as ferrihydrite (Fe(OH)3), either through the metabolic activity of anoxygenic photoautotrophic Fe2+ (Fe(II))-oxidizing bacteria (photoferrotrophs), by microaerophilic bacteria, or by the oxidation of dissolved Fe(II) by O2 produced by early cyanobacteria. However, in addition to oxidized Fe-bearing minerals such as hematite (FeIII 2O3), (partially) reduced minerals such as magnetite (FeIIFeIII 2O4) and siderite (FeIICO3) are found in BIFs as well. The presence of reduced Fe in BIFs has been suggested to reflect the reduction of primary Fe(III) minerals by dissimilatory Fe(III)-reducing bacteria, or by metamorphic (high pressure and temperature) reactions occurring in presence of buried organic matter. Here, we present the current understanding of the role of Fe-metabolizing bacteria in the deposition of BIFs, as well as competing hypotheses that favor an abiotic model for BIF deposition. We also discuss the potential abiotic and microbial reduction of Fe(III) in BIFs after deposition. Further, we review the availability of essential nutrients (e.g. P and Ni) and their implications on early Earth biogeochemistry. Overall, the combined results of various ancient seawater analogue experiments aimed at assessing microbial iron cycling pathways, coupled with the analysis of the BIF rock record, point towards a strong biotic influence during BIF genesis.

Reusable magnetite nanoparticles-biochar composites for the efficient removal of chromate from water.

Biochar (BC) and magnetite (Fe3O4) nanoparticles (MNP) have both received considerable recent attention in part due to their potential use in water treatment. While both are effective independently in the removal of a range of anionic metals from aqueous solution, the efficacy of these materials is reduced considerably at neutral pH due to decreased metal adsorption and MNP aggregation. In addition to synthetic metal oxide-biochar composites for use in treatment and remediation technologies, aggregates may also occur in nature when pyrolytic carbon is deposited in soils. In this study, we tested whether magnetite synthesized in the presence of biochar leads to increased removal efficiency of hexavalent chromium, Cr(VI), at the mildly acidic to neutral pH values characteristic of most natural and contaminated aqueous environments. To do so, magnetite nanoparticles and biochar produced from ground willow were synthesized to form composites (MNP-BC). Batch studies showed that MNP-BC markedly enhanced both adsorption and reduction of Cr(VI) from aqueous solution at acidic to neutral pH as compared to MNP and BC separately, suggesting a strong synergetic effect of hybridizing Fe3O4 with BC. Mechanistically, the Cr(VI) removal processes occurred through both adsorption and intraparticle diffusion followed by reduction to Cr(III). Synchrotron-based X-ray absorption spectroscopy analyses confirmed that Cr(VI) was reduced at the surface of MNP-BC, with electrons derived directly from both biochar and magnetite at low pH, while at near-neutral pH, biochar increased Cr(VI) reduction by inhibiting MNP aggregation. Extended X-ray absorption fine structure fitting results confirmed that the Cr(III) precipitates consist of Cr(OH)3 and chromite (Cr2FeO4) nanoparticles. Our results demonstrate that MNP-BC composites have great potential as a material for the treatment of chromate-containing aqueous solutions across a wide range of pH values, and provide information valuable broadly relevant to soils and sediments that contain biochar.