Fe Corrosion Research Articles

A comparative study of different modification methods on zero-valent iron performance toward nitrate selective reduction to nitrogen

Although nanoscale zero-valent iron (nZVI) has been widely used for nitrate reduction, its application is always limited by the undesired generation of toxic ammonium. In this study, by selecting four commonly used nZVI modification methods (i.e., introducing Fe(II), activated carbon, Cu, and Pd), the roles of direct electron transfer and atomic hydrogen (H*) mediated reaction on nitrate selective reduction were examined. Results revealed that all the modification methods could enhance the reduction rates of nitrate with a promotion factor of 0.94–8.62, while the N2-selectivity could only be increased from ∼4.5 % to less than 25.7 % (in carbon amended system). The enhancing effect of these additives is determined to be highly associated with their ability to promote the direct electron transfer from Fe0 core to nitrate by forming galvanic couples or conductive magnetite layer. Unexpectedly, multiple lines of evidence suggested that H* was not the dominant reducing species responsible for nitrate reduction in Pd-modified nZVI system (and also the other tested systems), despite the presence of Pd could significantly accelerate H* generation. Correlation analysis further showed that there was no reasonable relationship between N2-selectivity and Fe0 corrosion tendency and hydrogen formation rates of different modified nZVI systems. All these finding could improve our understanding of nitrate selective reduction by Fe0.

Adaptation of a methanogen to Fe0 corrosion via direct contact

Due to unique genomic adaptations, Methanococcus maripaludis Mic1c10 is highly corrosive when in direct contact with Fe0. A critical adaptation involves increased glycosylation of an extracellular [NiFe]-hydrogenase, facilitating its anchoring to cell surface proteins. Corrosive strains adapt to the constructed environment via horizontal gene transfer while retaining ancestral genes important for intraspecies competition and surface attachment. This calls for a reevaluation of how the built environment impacts methane cycling.

Reactive transport modelling of iron bentonite interaction in the FEBEX in situ experiment

The evolution of steel/bentonite interfaces in engineered barrier systems of radioactive waste disposal is governed by the corrosion of the steel and the interaction of corrosion products with the bentonite. In the early post-closure phase of the repository, the transition from aerobic to anaerobic corrosion in combination with evolving temperature conditions and chemical gradients due to the hydration of the bentonite take place. In situ tests in underground laboratories provide a high degree of representativeness for the early transient evolution of the interfaces. Complex Fe-bentonite interaction patterns have been observed, which include a concave Fe accumulation front and distinct coloured halos around the corroding steel. A reactive transport model for the FEBEX in situ test is presented, which describes the transition from aerobic to anaerobic corrosion, the transport of O2 in the gas and liquid phase and the chemical evolution of the steel/bentonite interface during the 18 years of the experiment. The model successfully reproduces the major steps of the interface evolution: an aerobic corrosion phase characterized by accumulation of goethite in the corrosion layer, and an anaerobic corrosion phase, where Fe(II) and Fe(II)/Fe(III) corrosion products form, including a gradual re-dissolution of the aerobic corrosion products. In the anaerobic corrosion phase, some of the Fe(II) diffuses into the bentonite, where it partly reacts with remaining O2 to form Fe(III) precipitates or interacts with the clay minerals via surface complexation or cation exchange. Two different approaches for the implementation of a potential electron transfer from sorbed Fe(II) to structural Fe(III) are presented, but the lack of experimental data does not allow evaluation of their representativeness for the FEBEX in situ experiment. The model calculations qualitatively reproduce the concave shape of the Fe accumulation front in the bentonite and a distinct zonation with an iron-oxide precipitation dominated zone adjacent to the steel and a Fe(II) sorption dominated zone further into the bentonite. Sensitivity cases with respect to the hydration of the bentonite and the transport parameters point to the importance of the fast O2 diffusion in the gas phase for the formation of these characteristic interface features. The calculated thickness of the Fe-bentonite interaction zone varies from 1 to 4 cm, which is smaller than observed in some areas of the experiment, where locally this zone extended >10 cm into the bentonite. It is possible that this difference is due to a more complex flow pattern in the in situ experiment that is not captured by the model or due to an additional decoupled electron transport across oxide rich layers.

Elucidating microbial iron corrosion mechanisms with a hydrogenase-deficient strain of Desulfovibrio vulgaris.

Sulfate-reducing microorganisms extensively contribute to the corrosion of ferrous metal infrastructure. There is substantial debate over their corrosion mechanisms. We investigated Fe0 corrosion with Desulfovibrio vulgaris, the sulfate reducer most often employed in corrosion studies. Cultures were grown with both lactate and Fe0 as potential electron donors to replicate the common environmental condition in which organic substrates help fuel the growth of corrosive microbes. Fe0 was corroded in cultures of a D. vulgaris hydrogenase-deficient mutant with the 1:1 correspondence between Fe0 loss and H2 accumulation expected for Fe0 oxidation coupled to H+ reduction to H2. This result and the extent of sulfate reduction indicated that D. vulgaris was not capable of direct Fe0-to-microbe electron transfer even though it was provided with a supplementary energy source in the presence of abundant ferrous sulfide. Corrosion in the hydrogenase-deficient mutant cultures was greater than in sterile controls, demonstrating that H2 removal was not necessary for the enhanced corrosion observed in the presence of microbes. The parental H2-consuming strain corroded more Fe0 than the mutant strain, which could be attributed to H2 oxidation coupled to sulfate reduction, producing sulfide that further stimulated Fe0 oxidation. The results suggest that H2 consumption is not necessary for microbially enhanced corrosion, but H2 oxidation can indirectly promote corrosion by increasing sulfide generation from sulfate reduction. The finding that D. vulgaris was incapable of direct electron uptake from Fe0 reaffirms that direct metal-to-microbe electron transfer has yet to be rigorously described in sulfate-reducing microbes.

Fe0-mediated mixotrophic denitrification enhanced by carbon fiber for secondary effluent with low C/N ratio

Compared with Fe0-mediated autotrophic denitrification (ADN), mixotrophic denitrification (MDN) can alleviate the problem of reduced denitrification efficiency due to Fe0 passivation. In this study, carbon fiber (CF) was added as an additional cathode material to Fe0-mediated MDN to promote Fe0 corrosion and advanced denitrification of secondary effluent with low chemical oxygen demand (COD) to nitrogen (C/N) ratio. The results showed that the average removal efficiencies of total nitrogen (TN) and nitrate nitrogen (NO3--N) in the experimental group with CF coupling Fe0 (CF/Fe0) were achieved as high as 80.08 % and 79.79 % in Phase VI (C/N ratio = 3, hydraulic retention time (HRT) = 48 h), respectively. Mechanistic investigation showed that part of Fe0 corroded during the reaction process and the reaction products (Fe3+, Fe2+) were adsorbed on CF surface, sustaining the reaction of NO3--N conversion and promoting denitrification performance. Furthermore, the iron ions attached to the CF surface will further stimulate the generation of extracellular polymeric substance (EPS) containing redox-active components such as flavins and Cytochrome c (Cyt c). Consequently, the activity of the electron transport system was promoted. CF dosing resulted in a high enrichment of dominant denitrifying bacteria such as Acinetobacter, Comamonas and Pseudomonas in MDN, and expression of narG, napA, nosZ and other microbial metabolic function genes. Based on the above, the efficiency and mechanism of CF enhanced Fe0-mediated MDN was elucidated, which is favorable for enhancing the nitrogen removal in secondary effluent containing NO3--N with low C/N ratio based on Fe0-mediated MDN.

Accelerated removal of organic pollutants by biochar-based iron carbon granule-activated periodate in chloride-containing water: The role of active chlorine

Ubiquitous in water environments, the chloride ion (Cl−) can impact the decontamination capacity of an oxidation system. However, minimal studies are available on its effects in periodate (PI)-based advanced oxidation processes. In this study, a novel biochar-based iron-carbon (FeBC) granule was synthesized to activate PI and remove organic pollutants from water containing Cl−. The FeBC/PI/Cl− system (FeBC: 0.5 g/L; PI: 0.5 mM; AO7: 20 mg/L; NaCl: 50 mM) exhibited excellent performance on various organic pollutants, with ＞ 85 % of Acid Orange (AO7) removal over a pH range of 3–10. Within 20 min after the tenth run, approximately 80 % of AO7 was removed. Inorganic ions and natural organic matter had a negligible effect on AO7 removal. Characterization results confirmed that the presence of Cl− enhanced Fe corrosion, thereby improving PI activation efficiency for removing AO7. Electron paramagnetic resonance spectroscopy and active species trapping experiments verified that radicals (•OH and O2•−) and nonradical (1O2, Fe(IV), and electron transfer) oxidation processes participated in the FeBC/PI system. Moreover, the presence of Cl− accelerated •OH, O2•−, 1O2, and Fe(IV) formation and generated active chlorine, such as HOCl. The main pathways involved in the generation of multiple reactive species were evaluated. AO7 degradation pathways were proposed, and numerous intermediates exhibited decreased toxicity. These findings provide new insights for the decontamination of organic contaminants in water containing Cl−.

Sulfide mediated zero valent iron for enhanced nickel removal under neutral condition: Reaction kinetic, mechanism, and stability

The application of sodium sulfide (Na2S) as sulfidation reagent of zero valent iron (ZVI) has been well studied, however, the effect of Na2S existence on ZVI reactivity remains obscure. In this study, Ni(II) removal performance, mechanism, and stability by ZVI with Na2S were investigated at neutral condition. The results showed that Ni(II) removal sharply increased from < 5–100% by ZVI within 60 min with the increase of Na2S concentration, but the subsequent Ni(II) release occurred. In addition to the slight Ni(II) removal by Na2S in aqueous phase, Ni(II) was mainly removed by the adsorption and reduction by Na2S mediated ZVI system. Characterization analysis indicated that Na2S could lead to the severe Fe0 corrosion and the main corrosion product on ZVI was lepidocrocite, which played the dominant role for Ni(II) immobilization. Meanwhile, the formation of iron sulfides on ZVI surface would enhance Ni(II) reduction and partially transform the adsorbed Ni(II) to NiS. Moreover, the higher ionic strength could further enhance the initial Ni(II) removal rate but the stability became poor. Regardless of the additive methods, the Ni(II) removal significantly enhanced in the system of ZVI and Na2S combination. Overall, this work reveals the sulfide mediated Fe0 corrosion and provides a potential method for enhancing the reactivity of ZVI in the treatment of Ni(II) pollution.

Enhanced uranium removal from aqueous solution by core–shell Fe0@Fe3O4: Insight into the synergistic effect of Fe0 and Fe3O4

In this study, Fe0@Fe3O4 was synthesized and used to remove U(VI) from groundwater. Different experimental conditions and cycling experiments were used to investigate the performance of Fe0@Fe3O4 in the U(VI) removal, and the XRD, TEM, XPS and XANES techniques were employed to characterize the Fe0@Fe3O4. The results showed that the U(VI) removal efficiency of Fe0@Fe3O4 was 48.5 mg/g that was higher than the sum of removal efficiency of Fe0 and Fe3O4. The uranium on the surface of Fe0@Fe3O4 mainly existed as U(IV), followed by U(VI) and U(V). The Fe0 content decreased after reaction, while the Fe3O4 content increased. Based on the results of experiments and characterization, the enhanced removal efficiency of Fe0@Fe3O4 was attributed to the synergistic effect of Fe0 and Fe3O4 in which Fe3O4 accelerated the Fe0 corrosion that promoted the progressively formation of Fe(II) that promoted the reduction of adsorbed U(VI) to U(IV) and incorporated U(VI) to U(V). The performance of Fe0@Fe3O4 at near-neutrality condition was better than at acidic and alkalic conditions. The chloride ions, sulfate ions and nitrate ions showed minor effect on the Fe0@Fe3O4 performance, while carbonate ions exhibited significant inhibition. The metal cations showed different effect on the Fe0@Fe3O4 performance. The removal efficiency of Fe0@Fe3O4 decreased with the number of cycling experiment. Ionizing radiation could regenerate the used Fe0@Fe3O4. This study provides insight into the U(VI) removal by Fe0@Fe3O4 in aqueous solution.

Evaluation of in vitro corrosion behavior and biocompatibility of poly[xylitol-(1,12-dodecanedioate)](PXDD)-HA coated porous iron for bone scaffolds applications.

The present study evaluates the corrosion behavior of poly[xylitol-(1,12-dodecanedioate)](PXDD)-HA coated porous iron (PXDD140/HA-Fe) and its cell-material interaction aimed for temporary bone scaffold applications. The physicochemical analyses show that the addition of 20wt.% HA into the PXDD polymers leads to a higher crystallinity and lower surface roughness. The corrosion assessments of the PXDD140/HA-Fe evaluated by electrochemical methods and surface chemistry analysis indicate that HA decelerates Fe corrosion due to a lower hydrolysis rate following lower PXDD content and being more crystalline. The cell viability and cell death mode evaluations of the PXDD140/HA-Fe exhibit favorable biocompatibility as compared to bare Fe and PXDD-Fe scaffolds owing to HA's bioactive properties. Thus, the PXDD140/HA-Fe scaffolds possess the potential to be used as a biodegradable bone implant.

Removal of bisphenol A in a heterogeneous Fenton system via biochar synthesized using different Fe precursors: Properties, effects, and mechanisms

The reactivity and mechanism of the Fe-doped biochar (FeBC) Fenton reaction are typically influenced by the amount and type of Fe species in materials. This study investigated the effects of different Fe precursors (FeSO4, Fe(NO)3, FeCl2, and FeCl3) used to prepare Fenton catalyst FeBCs (FeSBC, FeNBC, FeC2BC, and FeC3BC) on the physicochemical characteristics, pH resistance, and reactivity for bisphenol A (BPA) removal. In addition to the FeSBC/H2O2 (0.007 min−1) system, FeNBC/H2O2 (1.143 min−1), FeC2BC/H2O2 (0.278 min−1), and FeC3BC/H2O2 (0.556 min−1) completely removed BPA within 20 min under the optimal conditions (FeBCs: 0.1 g/L; H2O2: 1 mM; BPA: 20 mg/L; pH 3). FeBCs/H2O2 systems demonstrated good stability and resistance to inorganic anions and natural organic matter under appropriate initial pH conditions. However, FeC2BC and FeC3BC exhibited better pH applicability than FeNBC. Characterization results indicated that the physicochemical properties of FeBCs were dependent on the Fe precursor, which correlated with the degree of Fe corrosion and the production of distinct reactive oxygen species (ROS). Quenching experiments and electron spin resonance detection results indicated that OH, 1O2, and O2− species were all engaged in BPA removal; the ROS concentrations were significantly influenced by the initial pH and Fe precursor. The results indicate that Fe precursors significantly impact the performance and characteristics of Fe-based biochar materials, which are tailorable to specific applications.

Uncovering interactions among ternary electron donors of organic carbon source, thiosulfate and Fe0 in mixotrophic advanced denitrification: Proof of concept from simulated to authentic secondary effluent

To offset the imperfections of higher cost and emission of CO2 greenhouse gas in heterotrophic denitrification (HDN) as well as longer start-up time in autotrophic denitrification (ADN), we synergized the potential ternary electron donors of organic carbon source, thiosulfate and zero-valent iron (Fe0) to achieve efficient mixotrophic denitrification (MDN) of oligotrophic secondary effluent. When the influent chemical oxygen demand to nitrogen (COD/N) ratio ascended gradually in the batch operation with sufficient sulfur to nitrogen (S/N) ratio, the MDN with thiosulfate and Fe0 added achieved the highest TN removal for treating simulated and authentic secondary effluents. The external carbon is imperative for initiating MDN, while thiosulfate is indispensable for promoting TN removal efficiency. Although Fe0 hardly donated electrons for denitrification, the suitable circumneutral environment for denitrification was implemented by OH− released from Fe0 corrosion, which neutralized H+generated during thiosulfate-driven ADN. Meanwhile, Fe0 corrosion consumed the dissolved oxygen (DO) and created the low DO environment suitable for anoxic denitrification. This process was further confirmed by the continuous flow operation for treating authentic secondary effluent. The TN removal efficiency achieved its maximum under the combination condition of influent COD/N ratio of 3.1–3.5 and S/N ratio of 2.0–2.1. Whether in batch or continuous flow operation, the coordination of thiosulfate and Fe0 maintained the dominance of Thiobacillus for ADN, with the dominant heterotrophic denitrifiers (e.g., Plasticicumulans, Terrimonas, Rhodanobacter and KD4–96) coexisting in MDN system. The interaction insights of ternary electron donors in MDN established a pathway for realizing high-efficiency nitrogen removal of secondary effluent.

Compositional transformation of Ni2+ and Fe0 during the removal of Ni2+ by nanoscale zero-valent iron and the implications to groundwater remediation.

The use of nanoscale zero-valent iron (nZVI) to remove heavy metal ions like Ni2+ from groundwater has been extensively studied; however, the compositional transformation of the Ni2+ and Fe0 during the removal is not clearly comprehensible. This study provides an insight into the componential, structural, and morphological transformations of Ni2+ and Fe0 at a solid-liquid interface using various characterization devices. The underlying mechanism of transformation was investigated along with the toxicity/impact of the transformed products on the groundwater ecosystem. The results indicated that Fe0 is transformed into lath-like lepidocrocite (γ-FeOOH), twin-crystal goethite (α-FeOOH), and spherical magnetite (Fe3O4), while Ni2+ is converted into Fe0.7Ni0.3 alloy and Fe-Ni composite (trevorite - NiFe2O4) with a fold-fan morphology. The Fe0 transformation mechanism includes the redox of Fe0 with Ni2+, H2O, and dissolved oxygen, the combination of Fe2+ and OH- produced by Fe0 corrosion to amorphous ferrihydrite, and the further mineralogical transformation to Fe oxides with the aid of Fe2+ adsorbed on ferrihydrite. The conversion of Ni2+ is accomplished by reduction by Fe0 and surface coordination with Fe oxides. Compared with Ni2+ and Fe0, the toxicity and bioavailability of the transformed products are significantly reduced, hence conducive to the application of zero-valent iron technology in groundwater remediation.

Iron corrosion concomitant with nitrate reduction by Iodidimonas nitroreducens sp. nov. isolated from iodide-rich brine associated with natural gas.

Microbially influenced corrosion (MIC) may contribute significantly to corrosion-related failures in injection wells and iron pipes of iodine production facilities. In this study, the iron (Fe0) corroding activity of strain Q-1 isolated from iodide-rich brine in Japan and two Iodidimonas strains phylogenetically related to strain Q-1 were investigated under various culture conditions. Under aerobic conditions, the Fe0 foil in the culture of strain Q-1 was oxidized in the presence of nitrate and yeast extract, while those of two Iodidimonas strains were not. The amount of oxidized iron in this culture was six times higher than in the aseptic control. Oxidation of Fe0 in aerobic cultures of nitrate-reducing bacterium Q-1 was dependent on the formation of nitrite from nitrate. This Fe0 corrosion by nitrate-reducing bacterium Q-1 started after initial nitrite accumulation by day 4. Nitrate reduction in strain Q-1 is a unique feature that distinguishes it from two known species of Iodidimonas. Nitrite accumulation was supported by the encoding of genes for nitrate reductase and the missing of genes for nitrite reduction to ammonia or nitrogen gas in its genome sequence. Phylogenetic position of strain Q-1 based on the 16S rRNA gene sequence was with less than 96.1% sequence similarity to two known Iodidimonas species, and digital DNA-DNA hybridization (dDDH) values of 17.2-19.3%, and average nucleotide identity (ANI) values of 73.4-73.7% distinguished strain Q-1 from two known species. In addition of nitrate reduction, the ability to hydrolyze aesculin and gelatin hydrolysis and cellular fatty acid profiles also distinguished strain Q-1 from two known species. Consequently, a new species, named Iodidimonas nitroreducens sp. nov., is proposed for the nitrate-reducing bacterium strain Q-1T.

Amino acid imidazole ionic liquids as green corrosion inhibitors for mild steel in neutral media: Synthesis, electrochemistry, surface analysis and theoretical calculations

The corrosion inhibition properties of three amino acid imidazole ionic liquids ([CyVIm][AA]) as corrosion inhibitors for mild steel in a 3.5 wt% NaCl corrosion medium were evaluated by electrochemical measurements. The polarization experiments show that [CyVIm][AA] influences anode reaction processes, demonstrating that [CyVIm][AA] is an anodic inhibitor type corrosion inhibitor. [CyVIm]Try outperforms [CyVIm]His and [CyVIm]Pro in terms of corrosion inhibition. The results of surface analysis and quantum chemical calculations show that [CyVIm]Try can form a protective film on the surface of mild steel and inhibit surface corrosion. Furthermore, by applying molecular dynamics simulations, after investigating the corrosion inhibitor adsorption trends on the Fe (110) surface, the interaction order between the molecular framework of the Fe corrosion inhibitor and the Fe (110) surface for entanglement was determined. According to the radial distribution function, the corrosion inhibitor adsorption mode on the metal surface is composite adsorption with chemisorption as the major mode and physical adsorption as the secondary mode.

Organic carbon source excites extracellular polymeric substances to boost Fe0-mediated autotrophic denitrification in mixotrophic system

Fe0-mediated autotrophic denitrification (ADN) can be suppressed by iron oxide coverage resulting from Fe0 corrosion. The mixotrophic denitrification (MDN) coupling Fe0-mediated ADN with heterotrophic denitrification (HDN) can circumvent the weakening of Fe0-mediated ADN over operation time. But the interaction between HDN and Fe0-mediated ADN for nitrogen removal of secondary effluent with deficient bioavailable organics remains unclear. When the influent COD/NO3−-N ratio increased from 0.0 to 1.8–2.1, the TN removal efficiency was promoted significantly. The increased carbon source did not inhibit ADN, but promoted ADN and HDN synchronously. The formation of extracellular polymeric substances (EPS) was also facilitated concomitantly. Protein (PN) and humic acid (HA) in EPS increased significantly, which capable of accelerating electron transfer of denitrification. Due to that the electron transfer of HDN occurs intracellularly, the EPS with the capacity of accelerating electron transfer had a negligible influence on HDN. But for Fe0-mediated ADN, the increased EPS as well as corresponding PN and HA facilitated TN and NO3−-N removal significantly, while accelerated the electron release originating from Fe0 corrosion. The bioorganic-Fe complexes were generated on Fe0 surface after used, meaning that the soluble EPS and soluble microbial products (SMP) participated in the electron transfer of Fe0-mediated ADN. The coexistence of HDN and ADN denitrifiers demonstrated the synchronous enhancement of HDN and ADN by the external carbon source. From the perspective of EPS and related SMP, the insight of enhancing Fe0-mediated ADN by external carbon source is beneficial to implement high-efficiency MDN for organics-deficient secondary wastewater.

Enhanced organic pollutant removal in saline wastewater by a tripolyphosphate-Fe0/H2O2 system: Key role of tripolyphosphate and reactive oxygen species generation

The effects of tripolyphosphate (TPP) on organic pollutant degradation in saline wastewater using Fe0/H2O2 were systematically investigated to elucidate its mechanism and the main reactive oxygen species (ROS). Organic pollutant degradation was dependent on the Fe0 and H2O2 concentration, Fe0/TPP molar ratio, and pH value. The apparent rate constant (kobs) of TPP-Fe0/H2O2 was 5.35 times higher than that of Fe0/H2O2 when orange II (OGII) and NaCl were used as the target pollutant and model salt, respectively. The electron paramagnetic resonance (EPR) and quenching test results showed that •OH, O2•−, and 1O2 participated in OGII removal, and the dominant ROS were influenced by the Fe0/TPP molar ratio. The presence of TPP accelerates Fe3+/Fe2+ recycling and forms Fe-TPP complexes, which ensures sufficient soluble Fe for H2O2 activation, prevents excessive Fe0 corrosion, and thereby inhibits Fe sludge formation. Additionally, TPP-Fe0/H2O2/NaCl maintained a performance similar to those of other saline systems and effectively removed various organic pollutants. The OGII degradation intermediates were identified using high-performance liquid chromatography–mass spectrometry (HPLC–MS) and density functional theory (DFT), and possible degradation pathways for OGII were proposed. These findings provide a facile and cost-effective Fe-based AOP method for removing organic pollutants from saline wastewater.

Understanding the process of phosphate removal in Fe0/H2O systems using the methylene blue method

The removal mechanisms of contaminants in Fe0/H2O are still poorly understood, and characterized by contradictory findings. Therefore, the present study aims to improve the understanding of the processes involved in phosphate removal in Fe0/H2O system. Herein, the methylene blue method (MB method) is used to trace the dynamics within the investigated systems. The MB method utilizes the differential adsorptive affinity of MB onto sand and sand coated with iron corrosion products to evaluate the degree of Fe0 corrosion in Fe0/H2O systems. The extent of MB discoloration and phosphate removal in various Fe0-based systems was characterized in parallel quiescent batch experiments for two weeks and two months. Parallel experiments with Orange II (O-II) as a model contaminant allowed an improved discussion of the results. The investigated systems were: (i) Fe0 alone, (ii) MnO2 alone, (iii) sand alone, (iv) Fe0 + sand, (v) Fe0 + MnO2, and (vi) Fe0 + sand + MnO2. Additional experiments were conducted to test the influence of Fe0 type, Fe0 and sand mass loadings on dye discoloration and phosphate removal in Fe0/sand system. Each system was characterized by: (i) pH value, (ii) Fe concentration, (iii) dye discoloration (MB, O-II), and (iv) phosphate concentration. Results showed that the MB method was capable of tracing the extent of iron corrosion in the various investigated systems and clarified the role of in-situ generated iron corrosion products (FeCPs) in the removal of phosphate. The suitability of mixing sand aggregates with Fe0 for efficient phosphate removal is demonstrated through the MB method. Overall, the appropriateness of the MB method to characterize the dynamics of Fe0/H2O systems is validated.

Hydrophilic sulfurized nanoscale zero-valent iron for enhancing in situ biocatalytic denitrification: Mechanisms and long-term column studies

The aim of this study was to investigate the effects of hydrophilic sulfur-modified nanoscale zero-valent iron (S-nZVI) as a biocatalyst for denitrification. We found that the denitrifying bacteria Cupriavidus necator (C. necator) promoted Fe corrosion during biocatalytic denitrification, reducing surface passivation and sulfur species leaching from S-nZVI. As a result, S-nZVI exhibited a higher synergistic factor (fsyn = 2.43) for biocatalytic NO3- removal than nanoscale zero-valent iron (nZVI, fsyn = 0.65) at an initial nitrate concentration of 25 mg L−1-N. Based on kinetic profiles, SO42- was the preferred electron acceptor over NO3- when using C. necator and S-nZVI for biocatalytic denitrification. Up-flow column experiments demonstrated that biocatalytic denitrification using S-nZVI achieved a total nitrogen removal capacity of up to 2004 mg L−1 for 127 d. Notably, microbiome taxonomic profiling showed that the addition of S-nZVI to the groundwater promoted the growth of Geobacter, Desulfosporosinus, Streptomyces, and Simplicispira spp in the column experiments. Most of those microbes can reduce sulfate, promote denitrification, and match the batch kinetic profile obtained using C. necator. Our results not only discover the great potential of S-nZVI as a biocatalyst for enhancing denitrification via microbial activation but also provide a deep understanding of the complicated abiotic-biotic interaction.

Independent and synergistic bio-reductions of uranium (VI) driven by zerovalent iron in aquifer

Zerovalent iron [Fe(0)] can donate electron for bioprocess, but microbial uranium (VI) [U(VI)] reduction driven by Fe(0) is still poorly understood. In this study, Fe(0) supported U(VI) bio-reduction was steadily achieved in the 160-d continuous-flow biological column. The maximum removal efficiency and capacity of U(VI) were 100% and 46.4 ± 0.52 g/(m3·d) respectively, and the longevity of Fe(0) increased by 3.09 times. U(VI) was reduced to solid UO2, while Fe(0) was finally oxidized to Fe(III). Autotrophic Thiobacillus achieved U(VI) reduction coupled to Fe(0) oxidation, verified by pure culture. H2 produced from Fe(0) corrosion was consumed by autotrophic Clostridium for U(VI) reduction. The detected residual organic intermediates were biosynthesized with energy released from Fe(0) oxidation and utilized by heterotrophic Desulfomicrobium, Bacillus and Pseudomonas to reduce U(VI). Metagenomic analysis found the upregulated genes for U(VI) reduction (e.g., dsrA and dsrB) and Fe(II) oxidation (e.g., CYC1 and mtrA). These functional genes were also transcriptionally expressed. Cytochrome c and glutathione responsible for electron transfer also contributed to U(VI) reduction. This study reveals the independent and synergistic pathways for Fe(0)-dependent U(VI) bio-reduction, providing promising remediation strategy for U(VI)-polluted aquifers.

An insight into the fate of Cu2+ and zero-valent iron during removal of Cu2+ by nanoscale zero-valent iron

Aim: The transformation of zero-valent iron (Fe0) and Cu2+ during Cu2+ removal by nanoscale zero-valent iron (nZVI) has not been properly investigated using modern analytical techniques, despite its importance in environmental toxicology and surface chemistry associated with wastewater treatment/groundwater remediation. This study critically examines the phenomenon using a variety of modern instruments that characterize the physical and chemical properties of materials and provides extensive comprehension of the subject. Methods: As-prepared nZVI was used to remove Cu2+ in 5 mmol/L CuSO4. The morphological and structural characteristics of the Cu2+ and nZVI after removal were investigated with the aid of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectrometry (XPS). Results: Complete removal of Cu2+ by the nZVI was achieved within 60 min and remained constant till 120 min. The Cu2+ got reduced into cuprite (Cu2O) and copper metal (Cu0) (the crystals of both transformation products were cubic), while the Fe0 nanoparticles transformed into lath-like lepidocrocite (γ-FeOOH) and twin-rod goethite (α-FeOOH). The mechanism of Fe0 transformation was that the Fe2+ produced by Fe0 corrosion and oxidation by Cu2+ was hydrolyzed and oxidized to form hydropyrite, which was later converted into lepidocrocite and goethite with the assistance of Fe2+. The transformation of Cu2+ was due to the strong reduction property of Fe0. The toxicity and bioavailability of the transformed products were lower than those of Cu2+ and Fe0 nanoparticles. Conclusion: The findings are critical in understanding the fate of Fe0 nanoparticles and Cu2+ during Cu2+ removal by nZVI and can provide guidance for the application of nZVI technology.