Fe Minerals Research Articles

Iron isotope fractionation during transcrustal magmatic differentiation: Implications for continental crustal formation in subduction zones

Earth’s continental crust is hypothesized to originate from mantle melting in subduction zones. However, mantle melts are typically Fe-rich, with light Fe isotopes (δ56Fe = 0.05‰), unlike the Fe-depleted and heavy Fe isotope (δ56Fe can be up to 0.2‰) compositions of continental crust. The mechanisms responsible for this paradox remain elusive. Here, we report Fe isotope data from a suite of co-magmatic Middle Triassic continental arc rocks in the Ailaoshan tectonic zone (Yunnan, SW China). Gabbroic diorites have light Fe isotopes (δ56Fe = 0.04‰−0.09‰), while granodiorites and normal-arc granites have slightly heavier values (δ56Fe = 0.07‰−0.14‰). Adakitic granites, with high Sr/Y (61−183) and La/Yb (47−90) ratios, exhibit the heaviest δ56Fe (0.16‰−0.19‰). Rayleigh fractionation modeling results suggest that fractionation of isotopically light Fe minerals (e.g., olivine, pyroxene, and amphibole) can reproduce the Fe isotopic variations in most samples, but fails to explain the high Sr/Y, La/Yb, and δ56Fe values of adakitic granites, which would require Fe-rich garnet fractionation. Notably, the different Fe isotopes of the adakitic granites and non-adakitic rocks reveal two distinct transcrustal magmatic differentiation pathways: lower crustal, high-pressure, garnet-dominated fractionation; and middle−upper crustal, amphibole-dominated fractionation. The heavy Fe isotopic and Fe-depleted characteristics of the Ailaoshan magmatic arc suites are more comparable to the calc-alkaline arc magmas from normal to thick crust arcs (e.g., the Andean arc), but remarkably different from the tholeiitic arc magmas from thin crust arcs (e.g., the Mariana arc). This study highlights the role of amphibole and garnet fractionation in magmatic calc-alkaline differentiation. We propose that a thickened crust would permit a longer magmatic differentiation column, thus facilitating felsic and Fe-depleted continental crustal formation. The fractionated Fe-rich, garnet-bearing arc cumulates with light Fe isotopes are density-unstable and may be recycled into the mantle by lower crustal foundering.

Rare Earth Elements in Fe oxyhydroxides from biofilms containing iron-oxidizing bacteria

Fe oxyhydroxides extracted from modern-day biofilms with iron-oxidizing bacteria Arthrobacter spp., Gallionella spp и Leptothrix ochracea in the north-west of the East European platform display the enhanced content of rare earth elements – up to 1100 ppm. REE concentration in bacterial oxyhydroxides increase by one order in magnitude during 1 year suggesting the high sorption capacity of newly formed Fe mineral phases. La/YbN, Ce and Y anomalies in bacterial oxyhydroxides are consistent with geochemistry of the surface water facies where bacterial communities live. Isotopic composition of Nd in studied bacterial oxyhydroxides is controlled by the lithology of the Q-R underlying sediment and ambient water. 143Nd/144Nd values in Fe minerals of bacterial origin vary from 0.511570 to 0.512220 (eNd(0) from –21.8 to –9.2), the high proportion of radiogenic Nd is typical for the samples located on platform cover with Palaeozoic carbonate sediment.

The Influence of Seawater on Fe(II)-Catalyzed Ferrihydrite Transformation and Its Subsequent Consequences for C Dynamics.

Short-range-ordered minerals like ferrihydrite often bind substantial organic carbon (OC), which can be altered if the minerals transform. Such mineral transformations can be catalyzed by aqueous Fe(II) (Fe(II)aq) in redox-dynamic environments like coastal wetlands, which are inundated with seawater during storm surges or tidal events associated with sea-level rise. Yet, it is unknown how seawater salinity will impact Fe(II)-catalyzed ferrihydrite transformation or the fate of bound OC. We reacted ferrihydrite with Fe(II)aq under anoxic conditions in the absence and presence of dissolved organic matter (DOM). We compared treatments with no salts (DI water), NaCl-KCl salts, and artificial seawater mixes (containing Ca and Mg ions) with or without SO42-/HCO3-. Both XRD and Mössbauer showed that NaCl-KCl favored lepidocrocite formation, whereas Ca2+/Mg2+/SO42-/HCO3- ions in seawater overrode the effects of NaCl-KCl and facilitated goethite formation. We found that the highly unsaturated and phenolic compounds (HuPh) of DOM selectively bound to Fe minerals, promoting nanogoethite formation in seawater treatments. Regardless of salt presence, only 5-9% of Fe-bound OC was released during ferrihydrite transformation, enriching HuPh relative to aliphatics in solution. This study offers new insights into the occurrence of (nano)goethite and the role of Fe minerals in OC protection in coastal wetlands.

Magnetite Survivability and Non‐Stoichiometric Magnetite Formation in Presence of Oxyhalogen Brines on Mars

AbstractThe mixed Fe(II)/Fe(III) mineral magnetite [Fe3O4] of various stoichiometric and non‐stoichiometric compositions have been reported in Martian soils and rocks by several rover missions. Magnetite is an important paleomagnetic indicator mineral and can serve as a ‘biogeobattery’ as a consequence of its magnetic properties and the mixed valence state of iron in its structure. Here, we assess the extent of oxidative weathering of magnetite in presence of chlorate and bromate containing solutions that are likely important oxidants on Mars. Oxyhalogen species, chlorate and bromate, produced non‐stoichiometric magnetite [Fe(II)/Fe(III) < 0.5] in Mars‐relevant, near‐neutral pH fluids; no other ferric minerals were produced. The same results were observed in highly acidic fluids with or without oxyhalogens. Owing to its resistance to extensive oxidation, magnetite can serve as an important archive of geochemical, paleomagnetic, and astrobiological information in samples that will be returned by the Mars Sample Return mission.

Time-dependent redistribution of soil arsenic induced by transformation of iron species during zero-valent iron biochar composites amendment: Effects on the bioaccessibility of As in soils

Zero-valent iron biochar composites (ZVI/BC) are considered as effective amendments for arsenic (As)-contaminated soils. However, the mechanisms of transformation of various soil As species during ZVI/BC amendments remain unclear. This study investigated As transformation in four soils (namely, GX, ZJ, HB, and HN) treated with ZVI/BC for 65 days under two soil moisture conditions, unsaturated and oversaturated. Results showed that the 65-day treatment was divided into two stages based on the variation of labile As content. Within 2 days (stage 1), ZVI/BC addition quickly reduced labile As content by 5.91–90.3 % in soils under unsaturated conditions. During days 2–65 (stage 2), labile As ultimately decreased by 0.06–0.31 mg/kg in GX, ZJ, and HB while increasing by 22.1 mg/kg in HN soil, due to its lower pH value and Fe content. The variations of labile As were attributed to changes in multiple Fe minerals and associated As species. In stage 1, the corrosion of ZVI/BC generated amorphous Fe oxides to immobilize labile As, resulting in the accumulation of meta-stable As. In stage 2, amorphous Fe oxides were transformed into crystalline Fe oxides, resulting in the release and re-precipitation of As along with transformation, thus redistributing immobilized As into labile and stable As, which was evidenced by multiple methods, including chemical extraction, XRD, and TEM-EDX. The elevated soil moisture condition would enhance the corrosion of ZVI/BC in stage 1, further forming a reductive environment to facilitate the transformation of Fe minerals in stage 2. Besides, As bioaccessibility in soils was reduced by 10.8–38.7 % after ZVI/BC treatment in in-vitro gastrointestinal simulations. Overall, our study revealed the time-dependent transformation mechanism of soil As species and associated Fe minerals under different soil moisture with ZVI/BC treatments, and highlighted the effectiveness of ZVI/BC as a long-term amendment for As-contaminated soils.

Regulating the interlayer SO42--induced rebound of SeO42- in green rust coupled with iron nanoparticles for groundwater remediation

Green rust (GR) is an interlayer anion-containing Fe(II)/Fe(III) mineral material that is versatile in removing a series of ionic contaminants in water. Taking SeO42- (Se(VI)) as the target contaminant, this study identified that the removal processes of Se(VI) by GR could be divided into three stages: initial rapid interlayer exchange, followed by a rebound, and finally slow removal. In addition, as the percentage of SO42- in GR interlayer increased, the Se(VI) removal by GR gradually decreased. To mediate the SO42--induced rebound of Se(VI), the coupling of GR with iron nanoparticles (nFe0@GR) was proposed in this study and it was found that the removal efficiency of Se(VI) by nFe0@GR was 3.53 folds greater than that of GR. This study further revealed that the enhanced reactivity of nFe0@GR with Se(VI) could be attributed to the re-equilibration of SO42- driven by the formed GR in situ. Since it had a weaker electrostatic repulsion with interlayer SeO42- than pristine GR, the Se(VI) could be quickly removed by nFe0@GR without the rebound. Moreover, the nFe0@GR was demonstrated to be effective in immobilizing Se(VI) from simulated groundwater and has a great potential to reduce the risk of Se(VI) re-release into the environment.

Rationally tailored configuration of multifunctional scavengers by encapsulating nanoscale Fe0 and FeS into zeolite imidazole framework–8 with reinforced perrhenate/pertechnetate confinement

In order to probe into the potential application prospects of multifunctional scavengers in remediating nuclear wastewater, we combined versatile functionality of nanoscale Fe0 and FeS with tailorable porosity of zeolitic imidazole frameworks–8 (ZIF–8) to manufacture two multifunctional scavengers for ReO4– confinement i.e., NZVI@ZIF–8 by reduction approach and FeS@ZIF–8 by coprecipitation approach. Batch approaches unveiled that as–manufactured scavengers illustrated an reinforced performance towards ReO4– confinement. The pseudo-second-order model was well simulated with the kinetic of ReO4– confinement. Thermodynamic analysis unraveled that ReO4– confinement was endothermic and spontaneous. The mechanism was explored via characterization alters of structure and composition of NZVI@ZIF–8 and FeS@ZIF–8 before and after ReO4– confinement. Specifically, fourier transform infrared spectrometer (FTIR) and X-ray diffraction (XRD) indicated that NZVI and FeS were successfully encapsulated into ZIF–8, and NZVI@ZIF–8 and FeS@ZIF–8 remained stable after ReO4– confinement. X–ray absorption fine structure (XAFS) unveiled that various Fe mineral phases were formed on the scavenger surfaces under various reaction conditions. X-ray photoelectron spectroscopy (XPS) unraveled existence of Re(VI)/Re(IV) on scavengers surfaces, unveiling ReO4– was initially enriched NZVI@ZIF–8 and FeS@ZIF–8 surfaces with subsequent reduction into Re(VI)/Re(IV). This work proposed an innovative perspective to tailored multifunctional scavengers in nuclear waste management.

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.

Photochemical Origins of Iron Flocculation in Acid Mine Drainage.

Acid mine drainage (AMD) raises a global environmental concern impacting the iron cycle. Although the formation of Fe(III) minerals in AMD-impacted waters has previously been reported to be regulated by biological processes, the role of abiotic processes remains largely unknown. This study first reported that a photochemical reaction coupled with O2 significantly accelerated the formation of Fe(III) flocculates (i.e., schwertmannite) in the AMD, as evidenced by the comparison of samples from contaminated sites across different natural conditions at latitudes 24-29° N. Combined with experimental and modeling results, it is further discovered that the intramolecular oxidation of photogenerated Fe(II) with a five-coordinative pyramidal configuration (i.e., [(H2O)5Fe]2+) by O2 was the key in enhancing the photooxidation of Fe(II) in the simulated AMD. The in situ attenuated total reflectance-Fourier transform infrared spectrometry (ATR-FTIR), UV-vis spectroscopy, solvent substitution, and quantum yield analyses indicated that, acting as a precursor for flocculation, [(H2O)5Fe]2+ likely originated from both the dissolved and colloidal forms of Fe(III) through homogeneous and surface ligand-to-metal charge transfers. Density functional theory calculations and X-ray absorption spectroscopy results further suggested that the specific oxidation pathways of Fe(II) produced the highly reactive iron species and triggered the hydrolysis and formation of transient dihydroxo dimers. The proposed new pathways of Fe cycle are crucial in controlling the mobility of heavy metal anions in acidic waters and enhance the understanding of complicated iron biochemistry that is related to the fate of contaminants and nutrients.

Marine Fe cycling linked to dynamic redox variability, biological activity and post-depositional mineralization in the 1.1 Ga Mesoproterozoic Taoudeni Basin, Mauritania

The concentration of redox sensitive trace metals (RSTEs) and their isotopic composition preserved in Precambrian marine sediments, are critical for the reconstruction of ocean–atmosphere oxygenation history. Particularly, the concentration of Fe, its redox speciation, and isotopic distribution, have gained widespread use for inferring the biogeochemical processes that controlled Fe cycling in Precambrian oceans linked to the reconstruction of Earth surface redox budget. However, questions remain about the biotic and abiotic processes involved in Fe cycling in these ancient oceans, including the impact of post-depositional alterative processes on the reliability of the Fe redox proxy. Here we present a multi-proxy mineralogical and geochemical study of the ∼1.1 Ga Atar and El Mreiti strata of the Taoudeni Basin in Mauritania, to better constrain pathways involved in Fe cycling, linked to Fe mineralogy, redox speciation, isotopic ratios during this time and metamorphism. We compare unmetamorphosed sedimentary deposits with facies metamorphosed by dolerite sill intrusion. The results reveal the occurrence of diagenetic Fe minerals in the basal unmetamorphosed samples associated with light δ56Fe signatures, reflecting dominant anoxic conditions that promoted microbial dissimilatory Fe reduction. Notably, δ56Fe composition of these rocks reveal several fluctuations in evolving seawater redox state from oxic to anoxic/sulfidic conditions associated with changes in sea level stand and periods of full bottom water oxygenation and redox stratification. Overall, Ce anomalies suggest a general up sequence increase in seawater oxygen content. Metamorphosed rocks display heterogeneous δ56Fe distribution, consisting of light and heavy signatures associated with secondary Fe-bearing minerals produced by metamorphic and metasomatic overprinting of carbonated rocks by hot circulating fluids. The results thus indicate metamorphic overprinting of primary seawater δ56Fe promoted by increased mobility of reactive Fe during post-depositional metamorphic transformation. They show that post-depositional metamorphic/metasomatic overprinting complicates direct reconstruction of seawater biogeochemical Fe cycling and redox state using δ56Fe systematics.

Multiple effects of iron oxides on the adsorption and oxidation of dissolved organic matter by manganese oxides

Adsorptive fractionation and oxidation of dissolved organic matter (DOM) on manganese (Mn) oxide surfaces alter the molecular composition and stability of DOM, but the impact of iron (Fe) oxides on the coupled adsorption-oxidation processes of DOM by Mn oxides is largely unknown. In this study, the underlying mechanisms of molecular transformation of DOM on birnessite (Bir) in the presence of ferrihydrite (Fh), with varying Fh/Bir mass ratios, were investigated at both molecular levels and microscopic scales with a suite of characterization techniques, including Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and spherical aberration corrected scanning transmission electron microscopy (Cs-STEM). We found that higher Fh/Bir mass ratio impeded the adsorption of DOM by birnessite and the reductive dissolution of birnessite to release dissolved Mn, and the impediment on the reductive dissolution of birnessite was proportional to Fh/Bir mass ratio. Overall, during the interactions of DOM with ferrihydrite and birnessite, phenolic compounds were preferentially adsorbed by Fe and Mn minerals, and compounds with higher oxygen contents and polymeric substances were formed. FT-ICR-MS analysis further suggested that higher Fh/Bir mass ratio inhibited the occurrence of aromatic ring-opening and carboxylation of substituted groups on aromatic rings, but promoted polymerization of phenolic compounds. Cs-STEM analysis revealed that DOM distributions on ferrihydrite, birnessite, and their mixtures were regulated by their microscopic structures and reactivity. Compared with aromatic carbon (C), carboxylic and phenolic C were more likely to associate with birnessite. Our results highlighted the significance of organo-mineral associations with the mixed minerals in regulating the distribution and reactivity of organic C. This study has provided molecular evidences for molecular transformation of DOM mediated by both Mn and Fe oxides, which contributed to advancing our understanding on coupled reactions of organic C at the mineral–water interfaces in the environment.

Iron cycling and isotopic fractionation in a ferruginous, seasonally ice-covered lake

Ferruginous conditions, defined by anoxia and abundant dissolved ferrous iron (Fe2+aq), dominated the Precambrian oceans but are essentially non-existent in a modern, oxygenated world. Ferruginous meromictic lakes represent natural laboratories to ground truth our understanding of the stable Fe isotope proxy, which has been used extensively in interpreting the origins of Fe-rich sedimentary rocks like iron formations (IFs) and the interactions of early life with high-Fe2+aq conditions. Here we report comprehensive geochemical and Fe isotopic analyses of samples collected in May and August 2022, and March 2023, from Deming Lake, Minnesota, a ferruginous meromictic lake that undergoes surface freezing in winter and never becomes euxinic. Through chemical and Fe isotopic analyses of different putative Fe sources to Deming Lake; including eolian input trapped in winter ice cover, nearby bogs, and regional groundwaters sampled at surface springs; we find that a groundwater source provides the best chemical and Fe isotopic match for Deming Lake and can support Fe2+aq-rich waters at depth that maintain a permanent chemocline at ∼12 m. The ice-free Deming Lake water column can be split into three layers dominated by distinct Fe cycling regimes. Layer (I) extends from the lake surface to the base of the oxycline at ∼6 m, and its Fe cycling is dominated by isotopically light Fe uptake into biomass, likely from stabilized dissolved Fe3+, with variable eolian lithogenic influences. Layer (II) extends between the oxycline and the chemocline at ∼12 m and is dominated by partial Fe2+aq oxidation on approach to the oxycline, with the formation of variably isotopically heavy Fe3+-bearing particles. Layer (III) underlies the chemocline and is defined by Fe2+ phosphate (vivianite) and carbonate saturation and precipitation under anoxic, Fe2+aq-rich conditions with little Fe isotopic fractionation. The ice-covered winter water column features more homogenous Fe chemistry above the chemocline, which we attribute to seasonal homogenization of Layers (I) and (II), with suppressed ferric particle formation. Authigenic Fe minerals with non-crustal (light) Fe isotopic compositions only appreciably accumulate in sediments in Deming Lake underlying the chemocline. All sediments deposited above 12 m appear crustal in their Fe isotopic, Mn/Fe, and Fe/Al ratios, likely revealing efficient reductive dissolution of Fe3+-bearing lake precipitates and remineralization of Fe-bearing biomass. We find limited fractionation of Fe isotopes in the ice-covered water column and suggest this provides evidence that substantial delivery of oxidants is required to generate highly fractionated Fe isotopic compositions in Sturtian Snowball era IFs. By comparing Fe isotopic and Mn/Fe fractionation trends in the different Deming Lake layers, we also suggest that correlations between these two parameters in giant early Paleoproterozoic IFs requires the simultaneous deposition of multiple authigenic phases on the ancient seafloor. Finally, high-precision triple Fe isotopic analyses of dissolved Fe impacted by extensive oxidation near the Deming Lake oxycline reveal that the slope of the mass fractionation law for natural, O2-mediated Fe2+aq oxidation is identical to those previously defined for both UV photo-oxidation, and for an array of highly fractionated Paleoproterozoic IFs.

Iron minerals enhance Fe(II)-mediated abiotic As(III) oxidation

The abiotic oxidation of As(III) is simultaneously mediated by the oxidation of Fe(II) in microaerobic environment, but the role of Fe minerals in the Fe(II)-mediated As(III) oxidation have been neglected. This work mimicked the microaerobic environment and examined the mechanisms of Fe(II) mediated the As(III) oxidation in the presence of Fe minerals using a variety of iron minerals (lepidocrocite, goethite, etc.). The results indicated the Fe(II) and As(III) oxidation rate were improved with Fe minerals, while As(III) oxidation efficiency increased by 1.3–1.8 times in comparison to that without minerals. Fe(II) mediated the As(III) oxidation happened on Fe minerals surface in the presence of Fe minerals. The As(III) oxidation efficiency increased with increasing Fe mineral concentrations (from 0.5 to 2 g L−1) but decreased with increasing pH values. Reactive oxygen species (ROS) that play a crucial role in As(III) oxidation were Fe(IV) and ·O2−, accounting for 42.7%–47.9% and 24.1%–29.8%, respectively. The Fe minerals facilitated the oxidation of As(III) by ROS and stimulated the release of ROS through the adsorbed-Fe(II) oxidation, both of which favored As(III) oxidation. This work highlighted the potential mechanisms of Fe minerals in promoting Fe(II) mediated the As(III) oxidation in microaerobic environment, especially in terms of As(III) oxidation efficiency, shedding a valuable insight on optimization of arsenic contaminated wastewater treatment processes.

Loss of microbial diversity increases methane emissions and arsenic release in paddy soils

Microorganisms are vital to the emission of greenhouse gases and transforming pollutants in paddy soils. However, the impact of microbial diversity loss on anaerobic methane (CH4) oxidation and arsenic (As) reduction under flooded conditions remains unclear. In this study, we inoculated microbial suspensions into natural As-contaminated paddy soils using a dilution approach (untreated, 10−2, 10−4, 10−6, 10−8 dilutions) to manipulate microbial diversity levels. The results revealed that the 10−4 and 10−6 dilutions resulted in the highest CH4 emissions (97.0 μmol and 102.3 μmol) compared to untreated groups (27.6 μmol). However, anaerobic CH4 oxidation was not observed in 10−4 dilution groups and higher dilutions, suggesting the loss of diversity inhibited the natural reduction of CH4. Moreover, the porewater As concentration in the dilution groups was 1.8–8.2 times greater than in the untreated groups. The loss of microbial diversity promoted the reductive dissolution of iron (Fe) minerals bearing As, leading to increased concentrations of Fe(II) and dissolved organic carbon (DOC), which further enhanced As release (Fe(II), R = 0.9, p < 0.001) (DOC, R = 0.8, p < 0.001) from soil to porewater. However, CH4-dependent As(V) reduction was almost entirely inhibited under diversity loss. The decline in microbial diversity increased the relative abundances of methanogens (e.g., Methanobacterium and Methanomassiliicoccus), Fe(III)/As(V)-reducing bacteria (e.g., Bacillus, Clostridium_sensu_stricto_10, and Geobacter), and the related functional genes (i.e., mcrA and Geo). These findings suggest that microbial diversity is critical for specialized soil processes, highlighting the detrimental effects of biodiversity loss on CH4 emissions and As release in As-contaminated paddies.

Environmental relevance monitoring and assessment of ochreous precipitates, hydrochemistry and water sources from abandoned coal mine drainage

This study investigated the mineralogical and chemical characteristics of ochreous precipitates and mine water samples from abandoned Upper Carboniferous hard coal mines in an extensive former mining area in western Germany. Mine water characteristics have been monitored and assessed using a multi-methodological approach. Thirteen mine water discharge locations were sampled for hydrochemical analysis, with a total of 46 water samples seasonally collected in the whole study area for stable isotopic analyses. Mineralogical composition of 13 ochreous precipitates was identified by a combination of powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FE-SEM/EDS). Results showed that abandoned mine drainage was characterized by circumneutral pH, Eh values ranging from 163 to 269 mV, relatively low concentrations of Fe and Mn, and was dominated by HCO3− > SO42− > Cl− > NO3− and Na+ > Ca2+ > Mg2+ > K+. Goethite and ferrihydrite were the dominant precipitated Fe minerals, with traces of quartz, dolomite, and clay minerals. Some metal and metalloid elements (Mn, Al, Si, and Ti) were found in the ochreous sediments. The role of bacteria in the formation of secondary minerals was assessed with the detection of Leptothrix ochracea. The δ18O and δ2H values of mine water plotted on and close to the GMWL and LMWLs indicated local derivation from meteoric water and represented the annual mean precipitation isotopic composition. Results might help to develop strategies for the management of water resources, contaminated mine water, and public health.

New strategy to optimize in-situ fenton oxidation for TPH contaminated soil remediation via artificial neural network approach

In-situ remediation of total petroleum hydrocarbon (TPH) contaminated soils via Fenton oxidation is a promising approach. However, determining the proper injection amount of H2O2 and Fe source over the Fenton reaction in the complex geological conditions for in-situ TPH soil remediation remains a daunting challenge. Herein, we introduced a practical and novel approach using soft computational models, a multilayer perception artificial neural network (MPLNN), for predicting the TPH removal performance. In this study, we conducted 48 sets of TPH removal experiments using Fenton oxidation to determine the TPH removal performance of a wide range of different ground conditions and generated 336 data points. As a result, a negative Pearson correlation coefficient was obtained in the Fe injection mass and the natural presence of Fe mineral in the soil, indicating that the excess of Fe could significantly retarded the TPH removal performance in the Fenton reaction. In addition, the MPLNN model with 6-6-1 training using Scaled conjugate gradient backpropagation (SCG) with tangent sigmoid as the transfer function demonstrated a high accuracy for TPH removal prediction with the correlation determination of 0.974 and mean square error value of 0.0259. The optimized MPLNN model achieved less than 20% error for predicting TPH removal performance in actual TPH-contaminated soil via Fenton oxidation. Hence, the proposed MPLNN can be useful in improving the Fenton oxidation of TPH removal performance in-situ soil remediation.

Episodic hydrothermal supply and microbial anaerobic Fe(II) oxidation in early Archean ocean: Insights from precursor mineral compositions of the 3.46 Ga Marble Bar Chert, Pilbara Craton, Western Australia

The 3.46 Ga Marble Bar Chert (MBC) from the Pilbara Craton in Western Australia is known as the oldest chert on Earth. The origin of its Fe minerals was investigated to decipher the geochemistry and redox conditions of the early Archean ocean, as well as to explore the possible microbial contribution to the earliest sedimentary processes on Earth. However, the composition of the precursor minerals in the MBC remains poorly understood, giving rise to controversies on its genesis. Here we performed high-resolution petrographic, laser Raman, Mössbauer, X-ray diffraction, and Mn K-edge X-ray absorption near edge structure spectroscopic studies on two typical types of finely laminated MBC, grey-black chert and red chert. The grey-black chert contains considerable amounts of siderite, carbonaceous materials, and minor phyllosilicates and hematite. By contrast, the red chert contains high hematite and silicates, minor siderite and rare carbonaceous materials. Microcrystals in the cores of chert polyhedral are among the earliest mineral phases without signs of alterations, recrystallisation, erosion or replacement histories. Ferrihydrite, greenalite, siderite, and green rust are possible precursors of Fe-bearing minerals in the MBC. Their respective proportion in each lamina was regulated by pH, Fe(II)-oxidation rate, DIC, and Fe(II) content in the seawater. Approximately half Fe in the MBC primary minerals existed as Fe(III), indicating the existence of indigenous Fe(II)-oxidation in the Paleoarchean seawater. The element Mn in the MBC is primarily Mn(II) coordinated with O, suggesting a reduced depositional environment and hence implying the involvement of anaerobic microbial Fe(II)-oxidation in the formation of the MBC. Collectively, the grey-black laminae with abundant carbonaceous materials reflect limited Fe(II)-oxidation and increased dissolved inorganic carbon content likely due to enhanced hydrothermal CO2 supply, while the red laminae with considerable hematite represent substantial Fe(III)-supply due to rapid indigenous anaerobic Fe(II)-oxidation.

The pH-dependent role of different manganese oxides in the fate of arsenic during microbial reduction of arsenate-bearing goethite

Manganese oxides reduce arsenic (As) toxicity by promoting aqueous-phase As(III) oxidation and immobilization in natural aquatic ecosystems. In anaerobic water-sediment systems, arsenic exists both in a free state in the liquid phase and in an adsorbed state on iron (Fe) minerals. However, the influence of different manganese oxides on the fate of As in this system remains unclear. Therefore, in this study, we constructed an anaerobic microbial As(V) reduction environment and investigated the effects of three different manganese oxides on the fate of both aqueous-phase and goethite-adsorbed As under different pH conditions. The results showed that δ-MnO2 had a superior As(III) oxidation ability in both aqueous and solid phase due not only to the higher SSA, but also to its wrinkled crystalline morphology, less favorable structure for bacterial reduction, structure conducive to ion exchange, and less interference caused by the formation of secondary Fe-minerals compared to α-MnO2 and γ-MnO2. Regarding aqueous-phase As, δ-MnO2, α-MnO2, and γ-MnO2 required an alkaline condition (pH 9) to exhibit their strongest As(III) oxidation and immobilization capability. For goethite-adsorbed As, under microbial-reducing conditions, all manganese oxides had the highest As immobilization effect in neutral pH environments and the strongest As oxidation effect in alkaline environments. This was because at pH 7, Fe(II) and Mn(II) formed hydrated complexes, which was more favorable for As adsorption. At pH 9, the negatively charged state of goethite hindered As adsorption but promoted the adsorption and oxidation of As by the manganese oxides. Our research offers new insights for optimizing As removal from water using various manganese oxides and for controlling the mobilization of As in water-sediment system under different pH conditions.

Model-Based Analysis of Arsenic Retention by Stimulated Iron Mineral Transformation under Coastal Aquifer Conditions.

A multitude of geochemical processes control the aqueous concentration and transport properties of trace metal contaminants such as arsenic (As) in groundwater environments. Effective As remediation, especially under reducing conditions, has remained a significant challenge. Fe(II) nitrate treatments are a promising option for As immobilization but require optimization to be most effective. Here, we develop a process-based numerical modeling framework to provide an in-depth understanding of the geochemical mechanisms controlling the response of As-contaminated sediments to Fe(II) nitrate treatment. The analyzed data sets included time series from two batch experiments (control vs treatment) and effluent concentrations from a flow-through column experiment. The reaction network incorporates a mixture of homogeneous and heterogeneous reactions affecting Fe redox chemistry. Modeling revealed that the precipitation of the Fe treatment caused a rapid pH decline, which then triggered multiple heterogeneous buffering processes. The model quantifies key processes for effective remediation, including the transfer of aqueous As to adsorbed As and the transformation of Fe minerals, which act as sorption hosts, from amorphous to more stable phases. The developed model provides the basis for predictions of the remedial benefits of Fe(II) nitrate treatments under varying geochemical and hydrogeological conditions, particularly in high-As coastal environments.

Magnetite enhances As immobilization during nitrate reduction and Fe(II) oxidation by Acidovorax sp. strain BoFeN1

Arsenic (As) cycling in groundwater is commonly coupled to the biogeochemical cycling of iron (Fe) and the associated transformation of Fe minerals present. Numerous laboratory studies suggested that Fe minerals can act as nucleation sites for further crystal growth and as catalysts for abiotic Fe(II) oxidation. In view of the widespread existence of magnetite in anoxic environments where As is often dissolved, we firstly exploited magnetite to enhance As immobilization during nitrate-reducing Fe(II) oxidation (NRFO) induced by Acidovorax sp. strain BoFeN1, a mixotrophic nitrate-reducing Fe(II)-oxidizing bacterium that can oxidize Fe(II) through both enzymatic and abiotic pathways. Subsequently, we investigated how magnetite affects NRFO and As immobilization. Results demonstrated a significant increase in As(III) removal efficiency from 75.4 % to 97.2 % with magnetite, attributed to the higher amount of NRFO and As(III) oxidation promoted by magnetite. It was found that magnetite stimulated the production of extracellular polymeric substances (EPS), which could decrease the diffusion of nitrate in the periplasm of bacteria and shield them against encrustation, resulting in a more rapid reduction of nitrate in the system with magnetite than that without magnetite. Meanwhile, Fe(II) was almost completely oxidized in the presence of magnetite during the whole 72 h experiment, while in the absence of magnetite, 47.7 % of Fe(II) remained, indicating that magnetite could obviously accelerate the chemical oxidation of Fe(II) with nitrite (the intermediates of nitrate bioreduction). Furthermore, the formation of labile Fe(III), an intermediate product of electron transfer between Fe(II) and magnetite, was reasonably deduced to be vital for anoxic As(III) oxidation. Additionally, the XPS analysis of the solid phase confirmed the oxidation of 43.8 % of As(III) to As(V). This study helps to understand the biogeochemical cycling of Fe and As in the environment, and provides a cost-effective and environmentally friendly option for in situ remediation of As-contaminated groundwater.