Sunlight-Driven Direct/Mediated Electron Transfer for Cr(VI) Reductive Sequestration on Dissolved Black Carbon-Ferrihydrite Coprecipitates.

Surface runoff horizontally distributed chromium (Cr) pollution into various surface environments. Sunlight is a vital factor for the Cr cycle in the surface environment, which may be affected by photoactive substances such as ferrihydrite (Fh) and dissolved black carbon (DBC). Herein, sunlight-driven transformation dynamics of Cr species on DBC-Fh coprecipitates were studied. Under sunlight, the removal of aqueous Cr(VI) by DBC-Fh coprecipitates occurred through sunlight-driven reductive sequestration including adsorption, followed by surface reduction (pathway 1) and aqueous reduction, followed by precipitation (pathway 2). Additionally, coprecipitates with a higher DBC content exhibited a more effective reduction of both adsorbed (kapp,S_red) and aqueous Cr(VI) (kapp,A_red). Photoelectrons facilitated Cr(VI) reduction through direct electron transfer; notably, electron donating DBC promoted the production of photoelectrons by consuming photogenerated holes. Photogenerated Fe(II) species (mineral-phase and aqueous Fe(II)) mediated electron transfer for Cr(VI) reduction, which was reinforced via a ligand-to-metal charge transfer (LMCT) process between DBC-organic ligands and mineral Fe(III). Furthermore, ·O2- also mediated Cr(VI) reduction, although this impact was limited. Overall, this study demonstrates that photoelectrons and photogenerated electron mediators play a crucial role in Cr(VI) reductive sequestration on DBC-Fh coprecipitates, providing new insights into the geochemical cycle of Cr pollution in sunlight-influenced surface environments.

Synergistic Release of Cd(II) and As(V) from Ternary Sorption Systems Containing Ferrihydrite Nanoparticles: The Role of Binary and Ternary Surface Complexes.

Cadmium (Cd) and arsenic (As) generally exhibit mutually beneficial co-sorption behavior on iron oxyhydroxides through multiple mechanisms, including surface precipitation, ternary surface complexes, and electrostatic interactions. However, the numerous factors that control the immobilization of Cd and As in turn complicated the processes and mechanisms involved in their co-desorption from iron minerals, which hindered the full understanding of their geochemical behaviors. Here, the simultaneous release of Cd(II) and As(V) from newly precipitated ferrihydrite nanoparticles by either Ca or P was investigated through kinetics and isothermal desorption experiments. We showed that the Cd(II) and As(V) present two-phase desorption processes (rapid desorption and slow desorption) in both binary (Fe-Cd or Fe-As alone) and ternary systems (Fe-Cd-As co-presence). Compared to their binary counterparts, Cd(II) and As(V) in the ternary systems are more prone to detachment from ferrihydrite. Further desorption of Cd(II) and As(V) at different co-presence scenarios (different initial concentrations) demonstrated mutual promotion behaviour towards their counterparts; the co-presence of Cd(II) facilitates the desorption of As(V), while the co-presence of As(V) also promotes the desorption of Cd(II). XPS and FTIR results demonstrated that either Ca or P showed minor effects on the binding environment of Cd and As. Further results from the in-situ ATR-FTIR experiment and second derivative peak fitting analysis indicate that the enhanced detachment of Cd(II) and As(V) from the ternary system may be due to the synergistic desorption of the ternary surface complexes and other surface complex species. Our results provide new insights into the prediction of the environmental behaviour of the coexistence of Cd(II) and As(V) in iron-rich geological settings. The potential environmental risks of iron-based remediation methods should be considered due to the enhanced bioavailability of Cd(II) and As(V) in co-presence circumstances.

Tailoring phases of ferrihydrite/α-Fe2O3@C nanocomposites using syringyl and guaiacyl-rich biomass-derived carbon nanodots for electrochemical application.

Biomass-derived carbon nanodots (CNDs) hold promise as effective reducing agents for metal oxide nanoparticles yet understanding the intricate interplay with CND structure remains challenging. This study explores the impact of lignin types, specifically syringyl (S), and guaiacyl (G) units in CNDs on metal oxide phases and their electrochemical activity toward dopamine oxidation. We design phases of ferrihydrite/α-Fe2O3@C nanocomposites, using hazelnut carbon nanodots (HS-CNDs (S-rich)) and beetroot carbon nanodots (BS-CNDs (G-rich)) via a one-pot hydrothermal technique. Our findings show S units in HS-CNDs promote α-FeOOH/α-Fe2O3@CHS, while G units in BS-CNDs favor α (ß)-FeOOH/α-Fe2O3@CBS. In contrast to α(ß)-FeOOH/α-Fe2O3@CBS, α-FeOOH/α-Fe2O3@CHS exhibits superior electrochemical performance in dopamine oxidation due to its larger electrochemical active surface area, higher absorbance capacity, and shortened electron transfer length. Moreover, α-FeOOH/α-Fe2O3@CHS nanocomposites demonstrate remarkable dopamine selectivity, achieving rapid detection response in 10 s with a low LOD of 4 nM within a broad linear range (0.05-0.3 µM), demonstrating impressive reproducibility (97.5 %), stability (96.4 %), and works in real-time human urine detection with a recovery rate of ranging from 94.57 % and 102.2 %. Therefore, the utilization of biomass-derived CNDs, particularly S and G units-rich CNDs, in tailoring the phases of ferrihydrite/α-Fe2O3@C nanocomposites for electrochemical dopamine detection is promising.

Sulfate-mediated Fe(III) mineral reduction accelerates arsenic mobilization by a Desulfovibrio strain isolated from paddy soil.

The biogeochemical cycling of arsenic (As) is often intertwined with iron (Fe) and sulfur (S) cycles, wherein Fe(III)- and sulfate-reducing bacteria (SRB) play a crucial role. Here, we isolated strain DS-1, a strictly anaerobic Fe(III)- and sulfate-reducing bacterium, from As-contaminated paddy soil. Using 16S rRNA gene sequence analysis, strain DS-1 was identified as a member of the genus Desulfovibrio. Strain DS-1 utilized energy derived from ferrihydrite reduction to support its cellular growth. Under anoxic sulfate-reducing conditions, the presence of strain DS-1 significantly increased As mobilization compared to sulfate-free conditions. Mechanistically, SRB-produced sulfide reacts with Fe(III) to form FeS, which disrupts Fe(III) minerals, thereby enhancing As release. These findings highlight the critical role of redox disequilibrium in As mobilization and suggest that SRB-produced sulfide may permeate to the rice rhizosphere, increasing As mobilization through Fe(III) reduction.

Biogenic amorphous FeOOH activated additional intracellular electron flow pathways for accelerating reductive dechlorination of tetrachloroethylene.

Dissimilatory iron-reducing bacteria (DIRB) with extracellular electron transfer (EET) capabilities have shown significant potential for bioremediating halogenated hydrocarbon contaminated sites rich in iron and humic substances. However, the role and microbial molecular mechanisms of iron-humic acid (Fe-HA) complexes in the reductive dehalogenation process of DIRB remains inadequately elucidated. In this study, we developed a sustainable carbon cycling approach using Fe-HA complexes to modulate the electron flux from sawdust (SD), enabling almost complete reductive dechlorination by most DIRB (e.g., Shewanella oneidensis MR-1) that lack complex iron-sulfur molybdo enzymes. The SD-Fe-HA/MR-1 system achieved a 96.52% removal efficiency of tetrachloroethylene (PCE) at concentrations up to 250 µmol/L within 60 days. Material characterization revealed that DIRB facilitated the hydrolysis of macromolecular carbon sources by inducing the formation of amorphous ferrihydrite (FeOOH) in Fe-HA complexes. More importantly, the bioavailable FeOOH activated additional intracellular electron flow pathways, increasing the activity of potential dehalogenases. Transcriptome further highlight the innovative role of biogenic amorphous FeOOH in integrating intracellular redox metabolism with extracellular charge exchange to facilitate reductive dechlorination in DIRB. These findings provide novel insights into accelerating reductive dechlorination in-situ contaminated sites lacking obligate dehalogenating bacteria.

Ferrihydrite Addition Activated Geobacteraceae, the Most Abundant Iron-reducing Diazotrophs, and Suppressed Methanogenesis by Heterogeneous Methanogens in Xylan-amended Paddy Soil Microcosms.

Paddy fields are a major emission source of the greenhouse gas methane. In the present study, the addition of ferrihydrite to xylan-amended paddy soil microcosms suppressed methane emissions. PCR-based and metatranscriptomic ana-lyses revealed that the addition of ferrihydrite suppressed methanogenesis by heterogeneous methanogens and simultaneously activated Geobacteraceae, the most abundant iron-reducing diazotrophs. Geobacteraceae may preferentially metabolize xylan and/or xylan-derived carbon compounds that are utilized by methanogens. Geomonas terrae R111 utilized xylan as a growth substrate under liquid culture conditions. This may constitute a novel mechanism for the mitigation of methane emissions previously observed in ferric iron oxide-applied paddy field soils.

Coexisting ferrihydrite-enhanced contaminant degradation during pyrite oxygenation.

Oxygenation of pyrite (Py) is known to mediate generation of reactive oxygen species (ROS) with these species capable of inducing contaminants degradation, whereas the possible participation of coexisting Fe(III) minerals in these processes is still unclear. This study finds that freshly formed ferrihydrite (Fh) significantly enhances the Py-mediated sulfamethoxazole (SMX) degradation process. Through the 56Fe isotope tracer experiment and a series of control experiments, Fh is found to be reduced by Py to form secondary solid-phase Fe(II) species (Fe(II)RF) which in turn facilitates generation of H2O2 from the O2 reduction pathway. However, Py was found to mediate rapid structural transformation of Fh to form more thermodynamically stable goethite and hematite with these less redox active minerals unable to sustainably promote the Py-mediated SMX degradation process. Therefore, the improvement of Fh on Py-mediated SMX degradation process is not readily observable in reaction systems with low concentrations of coexisting Fh. In comparison, continuing input of 10 mM Fh increased the degradation efficiency of SMX by 60 % over three days. Our results demonstrate that the oxidative degradation of organic contaminants over the oxygenation of Py when coexisting with Fh can be more significant but currently underestimated.

Unveiling the Influence of Antimony Substitution on the Surface Properties and Adsorption Behavior of Ferrihydrite: From Molecular Mechanisms to Environmental Implications.

Antimony(V) substitution is common in secondary ferrihydrite, especially in mining areas and tailings. However, its impact on the adsorption behavior of ferrihydrite is still unclear. Therefore, this study investigated the influential mechanisms of Sb(V) substitution on the lattice structure and surface properties of Sb-substituted ferrihydrite (SbFh), and its adsorption of coexisting Sb(OH)6-. Antimony(V) is substituted at Fe1 sites and is primarily distributed on the surface. Substitution has opposing effects on the outer- and inner-sphere complexation of Sb(OH)6-. On one hand, substituted-Sb(V) transfers more positive charges to ≡FeOH, reducing the number of H bonds. Subsequently, the charge saturation of ≡FeOH decreases, surface charge increases, and outer-sphere complexation is promoted. On the other hand, the elevated bond valence of Sb-O increases charge saturation of ≡FeOH, reducing the charge capacity that ≡FeOH can accommodate from inner-sphere complexes. Thus, inner-sphere complexation is inhibited. Inner-sphere complexation plays a more important role, and Sb(OH)6- adsorption is inhibited. Additionally, the primary complexation modes of Sb(OH)6- transform from bidentate to monodentate complexation. This research has important implications for understanding the environmental behavior of ferrihydrite, as well as the fate and bioavailability of antimony in mining areas and tailings.

Enhancing assimilatory sulfate reduction with ferrihydrite-humic acid coprecipitate in anaerobic sulfate-containing wastewater treatment.

Sulfide produced from dissimilatory sulfate reduction can combine with hydrogen to form hydrogen sulfide, causing odor issues and environmental pollution. To address this problem, ferrihydrite-humic acid coprecipitate was added to improve assimilatory sulfate reduction (ASR), resulting in a decrease in sulfide production (190.2 ± 14.6 mg/L in the Fh-HA group vs. 246.3 ± 8.1 mg/L in the Fh group) with high sulfate removal. Humic acid, adsorbed on the surface of ferrihydrite, delayed secondary mineralization of ferrihydrite under sulfate reduction condition. Therefore, more iron-reducing species (e.g. Trichococcus, Geobacter) were enriched with ferrihydrite-humic acid coprecipitate to transfer more electrons to other species, which led to more COD reduction, an increase in electron transfer capacity, and a decrease in the NADH/NAD+ ratio. Metagenomic analysis also indicated that functional genes related to ASR was enhanced with ferrihydrite-humic acid coprecipitate. Thus, the addition of ferrihydrite-humic acid coprecipitate can be considered as a promising candidate for anaerobic sulfate wastewater treatment.

Insights on the Contradiction between the Affinity and Capacity of Ferrihydrite toward As(III) and As(V): Surface Reaction Revisited.

Ferrihydrite is omnipresent in nature, and its adsorption of As(III/V) decides the migration of arsenic. Although As(III) is commonly recognized as the more mobile species of inorganic arsenic, it sometimes exhibits less mobility in ferrihydrite systems, which calls for further insights. In this study, we elucidated the adsorption behavior and mechanisms of As(III/V) on ferrihydrite under different loading levels (molar ratio As/Fe = 0-0.38), solution pH (3-10), and coexisting ions [P(V) and Ca(II)] based on batch adsorption experiments, surface complexation modeling, density functional theory calculations, and X-ray photoelectron spectroscopy. Our results show that As(III) exhibits weaker adsorption affinity but a larger capacity compared with that of As(V). On ferrihydrite, As(III) and As(V) are adsorbed mainly as bidentate mononuclear complexes at type-a sites [≡Fe(OH-0.5)2] and bidentate binuclear complexes at type-b sites (2≡FeOH-0.5), respectively. As the dosage increases, As(III) further forms mononuclear monodentate complexes at both surface sites, resulting in a higher site utilization efficiency, while As(V) does not due to repulsive electrostatic interaction. The difference in surface species of As(III/V) also leads to complex responses when coexisting with high concentrations of P(V) and Ca(II). This study helps us to understand environmental behavior of As(III/V) and develop remediation strategy in As(III/V) contaminated systems.

Molecular characterization on the fractionation of organic phosphorus induced by iron oxide adsorption using ESI-FT-ICR MS.

The interaction between organic phosphorus (OP) and iron oxide significantly influences the phosphorus cycle in the natural environment. In shallow lakes, intense oxidation-reduction fluctuations constantly alter the existing form of iron oxides, but little is known about their impact on the adsorption and fractionation of OP molecules. In this study, electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS) was used to investigate the fractionation of OP from alkali-extracted sediment induced by crystalline goethite and amorphous ferrihydrite adsorption at a molecular scale. The results showed that ferrihydrite and goethite both exhibited high OP adsorption, and the adsorption amount decreased as the pH increased. The adsorption kinetics matched the pseudo-second-order equation. The ESI-FT-ICR MS analysis showed that 91 P-containing formulas were detected in the alkaline-extracted sediment solution. Ferrihydrite and goethite adsorbed 51 and 24 P-containing formulas, respectively, with adsorption rates of 56.0 % and 26.4 %. Ferrihydrite could adsorb more OP compounds than goethite, but no obvious molecular species selectivity was observed during the adsorption. The P-containing compounds, including unsaturated hydrocarbons-, lignin/carboxyl-rich alicyclic molecule (CRAM)-, tannin-, and carbohydrate-like molecular compounds, were more suitable for iron oxide adsorption. The double bond equivalence (DBE) is a valuable parameter that indicates OP fractionation during adsorption, and P-containing compounds with lower DBE values such as lipid- and protein-like molecular were prone to remain in the solution after adsorption. These research results provide insights into the biogeochemical cycling process of P in the natural environment.

Interactions between Iron Minerals and Dissolved Organic Matter Derived from Microplastics Inhibited the Ferrihydrite Transformation as Revealed at the Molecular Scale.

Microplastic-derived dissolved organic matter (MP-DOM) is an emerging carbon source in the environment. Interactions between MP-DOM and iron minerals alter the transformation of ferrihydrite (Fh) as well as the distribution and fate of MP-DOM. However, these interactions and their effects on both two components are not fully elucidated. In this study, we selected three types of MP-DOM as model substances and utilized Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and extended X-ray absorption fine structure (EXAFS) spectroscopy to characterize the structural features of DOMs and DOM-mineral complexes at the molecular and atomic levels. Our results suggest that carboxyl and hydroxyl groups in MP-DOM increased the Fe-O bond length by 0.02-0.03 Å through interacting with Fe atoms in the first shell, thereby inhibiting the transformation of Fh to hematite (Hm). The most significant inhibition of Fh transformation was found in PS-DOM, followed by PBAT-DOM and PE-DOM. MP-DOM components, such as phenolic compounds and condensed polycyclic aromatics (MW > 360 Da) with high oxygen content and high unsaturation, exhibited stronger mineral adsorption affinity. These findings provide a profound theoretical basis for accurately predicting the behavior and fate of iron minerals as well as MP-DOM in complex natural environments.

Iron Oxyhydroxide Transformation in a Flooded Rice Paddy Field and the Effect of Adsorbed Phosphate.

The mobility and bioavailability of phosphate in paddy soils are closely coupled to redox-driven Fe-mineral dynamics. However, the role of phosphate during Fe-mineral dissolution and transformations in soils remains unclear. Here, we investigated the transformations of ferrihydrite and lepidocrocite and the effects of phosphate pre-adsorbed to ferrihydrite during a 16-week field incubation in a flooded sandy rice paddy soil in Thailand. For the deployment of the synthetic Fe-minerals in the soil, the minerals were contained in mesh bags either in pure form or after mixing with soil material. In the latter case, the Fe-minerals were labeled with 57Fe to allow the tracing of minerals in the soil matrix with 57Fe Mössbauer spectroscopy. Porewater geochemical conditions were monitored, and changes in the Fe-mineral composition were analyzed using 57Fe Mössbauer spectroscopy and/or X-ray diffraction analysis. Reductive dissolution of ferrihydrite and lepidocrocite played a minor role in the pure mineral mesh bags, while in the 57Fe-mineral-soil mixes more than half of the minerals was dissolved. The pure ferrihydrite was transformed largely to goethite (82-85%), while ferrihydrite mixed with soil only resulted in 32% of all remaining 57Fe present as goethite after 16 weeks. In contrast, lepidocrocite was only transformed to 12% goethite when not mixed with soil, but 31% of all remaining 57Fe was found in goethite when it was mixed with soil. Adsorbed phosphate strongly hindered ferrihydrite transformation to other minerals, regardless of whether it was mixed with soil. Our results clearly demonstrate the influence of the complex soil matrix on Fe-mineral transformations in soils under field conditions and how phosphate can impact Fe oxyhydroxide dynamics under Fe reducing soil conditions.

Facilitated transport of ferrihydrite with phosphate under saturated flow conditions.

With increasing phosphate (P) entering the environment during agricultural application, the subsurface flow of particular P has been recently discussed as a vital P transport pathway. Iron (oxyhydr)oxide colloid-facilitated P transport is critical for iron and P biogeochemical processes in the subsurface. This study investigated the ferrihydrite colloid-facilitated P transport through adsorption and column experiments under different P concentrations and three pH conditions. Increased P loading on ferrihydrite colloids decreased the transport of ferrihydrite colloids (< 8.0%) under acid conditions through pore straining and irreversible attachment. Under neutral and alkaline conditions, ferrihydrite colloids exhibited more negative surfaces and smaller diameters with increasing P, which further enhanced ferrihydrite colloid transport (maximum to 95.6%). Ferrihydrite colloid-facilitated P transport was limited under acid conditions, and it was 10% - 57% enhancement under neutral and alkaline conditions with increasing P adsorption. Under neutral conditions, ferrihydrite colloid-facilitated P transport was strongest (maximum to 68.84%) because of its stronger ferrihydrite colloid transport than under acid conditions and larger P adsorption capacity than under alkaline conditions. Our findings indicate that the facilitated transport of ferrihydrite colloids in the presence of P may be appreciable in iron and phosphate-rich soil and subsurface systems, which is essential for evaluating the fate of iron and iron-facilitated P and potential environmental risks of P transport in the subsurface.

Dimerization of Fe(III) Ion in an Aqueous Medium: Mechanistic Modelling and Effects of Ligands.

Aqueous iron solutions generally undergo spontaneous hydrolysis followed by aggregation resulting in the precipitation of nanocrystalline oxyhydroxide minerals. The mechanism of nucleation of such multinuclear oxyhydroxide clusters are unclear due to limited experimental evidence. Here, we investigate the mechanistic pathway of dimerization of Fe(III) ions using density functional theory (DFT) in aqueous medium considering effects of other ligands. Two hydrolyzed monomeric Fe(III) ions in aqueous medium may react to form two closely related binuclear products, the µ-oxo and the dihydroxo Fe2 dimer. Our studies indicate that the water molecules in the second coordination sphere and those co-ordinated to the Fe(III) ion, both participate in the dimerization process. The proposed mechanism effectively explains the formation of dihydroxo and µ-oxo Fe2 dimers with interconversion possibilities, for the first time. Results show, with only water molecules present in the second co-ordination sphere, dihydroxo Fe2 dimer is the thermodynamically and kinetically favored product with a low activation free energy. We calculated the step-wise reaction free energies of dimerization in the presence of nitrate ions in the first and second coordination sphere of Fe(III) ion separately, which shows that with nitrate ions in the second co-ordination sphere, the µ-oxo Fe2 dimer is the kinetically favored product.

Effects of surfactants on the adsorption of norfloxacin onto ferrihydrite: comparison between anionic and cationic surfactants.

There is little information on how widespread surfactants affect the adsorption of norfloxacin (NOR) onto iron oxide minerals. In order to elucidate the effects of various surfactants on the adsorption characteristics of NOR onto typical iron oxides, we have explored the different influences of sodium dodecylbenzene sulfonate (SDBS), an anionic surfactant, and didodecyldimethylammonium bromide (DDAB), a cationic surfactant, on the interactions between NOR and ferrihydrite under different solution chemistry conditions. Interestingly, SDBS facilitated NOR adsorption, whereas DDAB inhibited NOR adsorption. The adsorption-enhancement effect of SDBS was ascribed to the enhanced electrostatic attraction, the interactions between the adsorbed SDBS on ferrihydrite surfaces and NOR molecules, and the bridging effect of SDBS between NOR and iron oxide. In comparison, the adsorption-inhibition effect of DDAB owning to the adsorption site competitive adsorption between NOR and DDAB for the effective sites as well as the steric hindrance between NOR-DDAB complexes and the adsorbed DDAB on ferrihydrite surfaces. Additionally, the magnitude of the effects of surfactants on NOR adsorption declined with increasing pH values from 5.0 to 9.0, which was related to the amounts of surfactant binding to ferrihydrite surfaces. Moreover, when the background electrolyte was Ca2+, the enhanced effect of SDBS on NOR adsorption was caused by the formation of NOR-Ca2+-SDBS complexes. The inhibitory effect of DDAB was due to the DDAB coating on ferrihydrite, which undermined the cation-bridging effect. Together, the findings from this work emphasize the essential roles of widely existing surfactants in controlling the environmental fate of quinolone antibiotics.

Hidden Role of Organic Matter in the Immobilization and Transformation of Iodine on Fe-OM Associations.

The biogeochemical processes of iodine are typically coupled with organic matter (OM) and the dynamic transformation of iron (Fe) minerals in aquifer systems, which are further regulated by the association of OM with Fe minerals. However, the roles of OM in the mobility of iodine on Fe-OM associations remain poorly understood. Based on batch adsorption experiments and subsequent solid-phase characterization, we delved into the immobilization and transformation of iodate and iodide on Fe-OM associations with different C/Fe ratios under anaerobic conditions. The results indicated that the Fe-OM associations with a higher C/Fe ratio (=1) exhibited greater capacity for immobilizing iodine (∼60-80% for iodate), which was attributed to the higher affinity of iodine to OM and the significantly decreased extent of Fe(II)-catalyzed transformation caused by associated OM. The organic compounds abundant in oxygen with high unsaturation were more preferentially associated with ferrihydrite than those with poor oxygen and low unsaturation; thus, the associated OM was capable of binding with 28.1-45.4% of reactive iodine. At comparable C/Fe ratios, the mobilization of iodine and aromatic organic compounds was more susceptible in the adsorption complexes compared to the coprecipitates. These new findings contribute to a deeper understanding of iodine cycling that is controlled by Fe-OM associations in anaerobic environments.

Probiotics Armed with In Situ Mineralized Nanocatalysts and Targeted Biocoatings for Multipronged Treatment of Inflammatory Bowel Disease.

While oral probiotics show promise in treating inflammatory bowel disease, the primary challenge lies in sustaining their activity and retention within the inflamed gastrointestinal environment. In this work, we develop an engineered probiotic platform that is armed with biocatalytic and inflamed colon-targeting nanocoatings for multipronged management of IBD. Notably, we achieve the in situ growth of artificial nanocatalysts on probiotics through a bioinspired mineralization strategy. The resulting ferrihydrite nanostructures anchored on bacteria exhibit robust catalase-like activity across a broad pH range, effectively scavenging ROS to alleviate inflammation. The further envelopment with fucoidan-based shields confers probiotics with additional inflamed colon-targeting functions. Upon oral administration, the engineered probiotics display markedly improved viability and colonization within the inflamed intestine, and they further elicit boosted prophylactic and therapeutic efficacy against colitis through the synergistic interplay of nanocatalysis-based immunomodulation and probiotics-mediated microbiota reshaping. The robust and multifunctional probiotic platforms offer great potential for the comprehensive management of gastrointestinal disorders.

Extracellular polymeric substances altered ferrihydrite (trans)formation and induced arsenic mobilization.

The behavior of As is closely related to trans(formation) of ferrihydrite, which often coprecipitates with extracellular polymeric substances (EPS), forming EPS-mineral aggregates in natural environments. While the effect of EPS on ferrihydrite properity, mineralogy reductive transformation, and associated As fate in sulfate-reducing bacteria (SRB)-rich environments remains unclear. In this research, ferrihydrite-EPS aggregates were synthesized and batch experiments combined with spectroscopic, microscopic, and geochemical analyses were conducted to address these knowledge gaps. Results indicated that EPS blocked micropores in ferrihydrite, and altered mineral surface area and susceptibility. Although EPS enhanced Fe(III) reduction, it retarded ferrihydrite transformation to magnetite by inhibiting Fe atom exchange in systems with low SO42-. As a result, 16% of the ferrihydrite was converted into magnetite in the Fh-0.3 treatment, and no ferrihydrite transformation occurred in the Fh-EPS-0.3 treatment. In systems with high SO42-, however, EPS promoted mackinawite formation and increased As mobilization into the solution. Additionally, the coprecipitated EPS facilitated As(V) reduction to more mobilized As(III) and decreased conversion of As into the residual phase, enhancing the potential risk of As contamination. These findings advance our understanding on biogeochemistry of elements Fe, S, and As and are helpful for accurate prediction of As behavior.

Distinct photochemistry of adsorbed and coprecipitated dicarboxylates with ferrihydrite: Implications for iron reductive dissolution and carbon stabilization.

Although ligand-promoted photodissolution of ferrihydrite (FH) has long been known for low molecular weight organic acids (LMWOAs), such as oxalate (Oxa) and malonate (Mal), photochemistry of coprecipitated FH with Oxa and Mal remains unknown, despite the importance of these mineral-organic associations in carbon retention has been acknowledged recently. In this study, ferrihydrite-LMWOAs associations (FLAs) were synthesized under circumneutral conditions. Photo-dissolution kinetics of FLAs were compared with those of adsorbed LMWOAs on FH surface and dissolved Fe-LMWOAs complexes through monitoring Fe(II) formation and organic carbon decay. For aqueous Fe(III)-LMWOAs complexes, Fe(II) yield was controlled by the initial concentration of LMWOAs and nature of photochemically generated carbon-centered radicals. Inner-sphere mononuclear bidentate (MB) configuration dominated while LMWOAs were adsorbed on the FH surface. MB complex of FH-Oxa was more photoreactive, leading to the rapid depletion of Oxa. Oxa can be readsorbed but in the form of binuclear bidentate and outer-sphere complexation, with much lower photoreactivity. While LMWOAs was coprecipitated with FH, the combination mode of LMWOAs with FH includes surface adsorption with a mononuclear bidentate structure and internal physical inclusion. Higher content of LMWOAs in the FLAs promoted the photo-production of Fe(II) as compared to pure FH, while it was not the case for FLAs containing moderate amounts of LMWOAs. The distinct photochemistry of adsorbed and coprecipitated Fe-LMWOAs complexes is attributed to ligand availability and configuration patterns of LMWOAs on the surface or entrapped in the interior structure. The present findings have significant implications for understanding the photochemical redox cycling of iron across the interface of Fe-organic mineral associates.