Biogenic Magnetite Research Articles

Diagenesis and iron paleo-redox proxies: New perspectives from magnetic and iron speciation analyses in the Santa Barbara Basin

Sedimentary redox proxies are usually employed to reconstruct the paleo-redox conditions of bottom water environments, assuming that porewater and bottom water dissolved oxygen concentrations are similar. Using a combination of geochemical and magnetic techniques, we investigate the relationship between iron speciation and mineralogy in recent (~1760–2009 CE) sediments retrieved from the Santa Barbara Basin (SBB) – a modern silled basin with low-oxygen (dissolved O2 < 10 μmol/kg) and sporadically anoxic (no O2 detected) bottom waters. Magnetic analyses reveal that biogenic magnetite is preserved in SBB sulfidic porewaters on at least decadal to centennial time scales. Highly-reactive Fe (oxyhydr)oxides remain preserved despite observed sulfidic porewaters, indicating incomplete pyrite conversion, and producing low Fepy [pyrite Fe]/FeHR ratios. We attribute this observation to restricted porewater reaction kinetics under high sedimentation rates. Our results also reveal non-steady state diagenesis caused by instantaneous depositional events (e.g., turbidites and flood layers). The most reducing water column suggested by Fe speciation coincided with the Macoma layer, where in situ colonization of hypoxia-intolerant bivalve shells argues for the most oxygenated bottom water in the 250 year record. A turbidite potentially introduced fresh unsulfidized FeHR that buffered upward-diffusing sulfide from underlying sediments. Subsequent pyrite precipitation following re-establishment of sulfidic porewaters could have facilitated a “false positive” interpretation. In comparison, redox-sensitive metal enrichments (MoEF, UEF, and ReEF) were not obscured by post-depositional diagenesis and appear to accurately record redox geochemistry at the sediment-water interface.

The Blake Geomagnetic Field Event recorded in a sequence of marine and continental facies outcropping in the coast of Buenos Aires province, Argentina

Different authors have suggested that there is a relationship between Quaternary geomagnetic field events and climate variability. Considering that in a recent paper a detailed stratigraphic study in a section of the coast of Claromecó (Buenos Aires province) indicates Late Pleistocene paleoclimatic changes, a paleomagnetic study was performed in the same stratigraphic succession. The analyzed sedimentary section belongs to “Belgranense” unit that is composed of continental and marine deposits. According to previously published dates and stable isotope results presented in this paper, it is proposed that 6 facies (sedimentary units) of the Claromecó section developed during the interglacial Marine Isotope Stage 5 (MIS 5). These units are presumably coeval with one of the best known geomagnetic field events, the Blake Event, occurred during the MIS 5, between ca. 120 and ca. 115 ka. The studied units from the base to the top are: 1) diagenetic wackestones with clasts of sand, 2) pedogenized loessian deposits, 3) lower marine wackestones, 4) lower tidal channel deposits, 5) upper marine wackestones and 6) upper tidal channel deposits. The section is capped by a continental gravity flow much younger than MIS 5. Different facies record distinct characteristic remanent magnetizations (ChRM) suggesting that these have a not modern origin. Low-field thermomagnetic curves and hysteresis loops were performed for all the sedimentary facies that provide magnetic remanences. Special sediment magnetism experiments were made for the units with reverse and/or oblique reverse components including isothermal remanent magnetization and anhysteretic remanent magnetization to perform the Lowrie-Fuller test. In these units opaque minerals were identified using polished and thin sections together with scanning electron microscopy analysis. According to all the results it is interpreted that the Blake Geomagnetic Field Event was recorded in the pedogenized loessian deposits with magnetite crystals generated during pedogenetic processes, and in extracellular biogenic magnetite crystals in the lower marine wackestones. The reverse and/or oblique reverse ChRM components were recorded before the lower tidal channel deposits, which have normal polarity directions. The Blake Geomagnetic Field Event was recorded in Claromecó during last interglacial MIS 5, however a direct correlation cannot be made between the recorded transitional polarity and a marine transgression corresponding to an important melting of ice sheets during this marine isotope stage. The magnetic components recorded in the studied sequence could be used as a stratigraphic tool to help identify “Belgranense” unit in Argentina or correlative sedimentary facies outcropping in South America.

Paleoenvironmental signature of the Selandian-Thanetian Transition Event (STTE) and Early Late Paleocene Event (ELPE) in the Contessa Road section (western Neo-Tethys)

Sedimentary records of the Early Cenozoic indicate a series of events with climatic and carbon cycle variability known as hyperthermals. A ~350-kyr-long event of environmental disruption during the Paleocene, not described before and here named Selandian–Thanetian Transition Event (STTE), has been recognized and well constrained in the western Tethys Contessa Road section (Gubbio, Italy) through high-resolution biostratigraphic, geochemical, and rock-magnetic data. The STTE exhibits peculiar stressed ecological responses among calcareous nannofossils and foraminifera, which highlight marked environmental perturbation affecting the biosphere. The environmental instability is not confined within the photic zone but extends to the seafloor leading to little more trophic conditions of the sea surface waters with an enhanced, but of short measure, nutrient availability on the seafloor conditions and marked rise of lysocline. Magnetic Susceptibly (MS) is dominantly controlled by the balance between carbonate productivity and detrital supply, as evidenced by the strong correlation between MS and CaCO3 (%) (r2 = −0.72). However, we also document two components in the isothermal remanent magnetization (IRM) and first-order reversal curves (FORC) diagrams that prove the occurrence of biogenic magnetite throughout the STTE. Systematic variations in bio-geochemical and magnetic parameters show the relative abundance of carbonate production (or inversely dissolution of carbonate) versus detrital supply during the STTE, which induced higher populations of magnetotactic bacteria through increased terrigenous input and, therefore, increased nutrient supply. Noteworthy, the uppermost part of the STTE includes the equivalent of the suspected hyperthermal, short-lived Early Late Paleocene Event (ELPE). The ELPE event shows an episode of increase in magnetic properties of the sediments, including an increase in magnetofossil concentration, as indicated by IRM components and FORC diagrams. The comparison of biotic and abiotic records throughout the STTE at Contessa Road section with available data across the ELPE from former investigated ocean and land-based sites provides lines of evidence that this latter event might be indeed only the terminal part of a long-lasting environmental change than hitherto supposed.

Diagenetic Fate of Biogenic Soft and Hard Magnetite in Chemically Stratified Sedimentary Environments of Mamanguá Ría, Brazil

AbstractMagnetotactic bacteria (MTB) synthesize magnetite and greigite crystals under low oxygen conditions in the water column or uppermost sediment (greigite‐producing bacteria are found below the oxic‐anoxic transition). Dissolved iron and oxygen contents in local environments are known to be limiting factors for the production and preservation of biogenic magnetite. Understanding the processes that link MTB to their living environments is fundamental to reconstructing past chemical variations in the water column and sediment, and for using the magnetic properties of biogenic magnetite as environmental proxy indicators. Previous studies have suggested that the frequently identified biogenic soft (BS) and biogenic hard (BH) magnetite types are associated with equant and more elongated morphologies, respectively, and that their abundance varies in accordance with sedimentary oxygen content, where MTB that produce the BH component live in less oxygenated environments. We test this hypothesis in a high‐resolution integrated environmental magnetic and geochemical study of surface sediments from Mamanguá Ría, SE Brazil. Based on magnetic and pore water profiles, we demonstrate that both the BS and BH components occur within microaerobic environments and that as sediment oxygen content decreases with depth, the BS component disappears before the BH component. With continued burial into the sulfidic diagenetic zone, both components undergo progressive dissolution, but the BH component is more resistant to dissolution than the BS component. Our observations confirm previous inferences about the relative stability of these phases and provide a firmer basis for use of these two types of biogenic magnetite as paleoenvironmental proxies.

Synthesis of copper catalysts for click chemistry from distillery wastewater using magnetically recoverable bionanoparticles

Biogenic magnetite nanoparticles were employed to recover copper from whisky distillery wastewaters, generating an efficient and reusable click chemistry catalyst.

Biogenic magnetite nanoparticles: A potent and environmentally benign agent for efficient removal of azo dyes and phenolic contaminants from water.

A comprehensive study was conducted toward the green and facile synthesis of biocompatible magnetite nanoparticles for the efficient removal of organic contaminants from water. The nanoparticles were synthesized using a modified co-precipitation method and functionalized by the taxane diterpenoids extracted from Taxus baccata L., and fully characterized using UV-vis spectroscopy, SEM, FTIR, VSM, and XRD. The synthesized monodisperse magnetite nanoparticles, with a narrow size distribution of less than 50 nm, displayed significant and stable magnetic activity without surface oxidation after several months. The batch experiments clearly indicated the efficient iron-catalyzed removal of Nile blue, methylene blue, methylene orange, and 4-nitrophenol for several cycles without significant loss of catalytic activity. The relevant kinetic data of the dyes removal reactions were fitted to a pseudo-first order model. Moreover, in vitro MTT assay revealed high biocompatibility of the nanoparticles with no significant toxicity on different human cell lines. The overall results indicated high potential of green synthesized, biocompatible magnetite nanoparticles for the environmental applications especially wastewater remediation.

Ferromagnetic Resonance Spectroscopy and Rock Magnetic Characterization of Fossil Coral Skeletons in Ishigaki Islands, Japan

Skeletons of hermatypic corals (e.g., Porites) might have enormous potential as a high-resolution paleomagnetic recorder owing to their rapid and continuous growth over hundreds of years at a rate of up to 2 cm/year, although typical corals show an extremely weak intensity of remanence and low stability. We found that coral tsunami boulders with negligible amounts of calcite on Ishigaki Island show a measurable intensity of remanence; thus, we attempted to characterize the magnetic assemblages in this coral skeleton to determine whether it is of biogenic or detrital magnetite using first-order reversal curve (FORC) measurements, ferromagnetic resonance (FMR) spectroscopy, and petrological observations through field-emission type scanning electron microscope (FE-SEM) with an acid treatment. The FMR derivative spectra of coral skeleton samples represent multiple derivative maxima and extended low-field absorption, indicating the presence of intact biogenic magnetite chains. FORC diagrams represent a “central ridge” signature with a vertical spread. These FMR and FORC features indicate the magnetization of these coral skeletons that are mainly created using intact biogenic magnetites and mixtures of grains from collapsed biogenic magnetites, pseudo-single domain grains, and multi-domain grains such as detrital magnetite. FE-SEM observations confirm the presence of a chain-like structure of iron oxides corresponding to the features of biogenic magnetite. Therefore, the magnetic mineral assemblage in coralline boulders from Ishigaki Island consists of dominant biogenic-origin single-domain magnetite and a trace amount of detrital component, indicating that fossil coral skeletons in Ishigaki Island have potential for utilization in paleomagnetic studies.

Palaeo- and rock magnetic investigations of Late Quaternary sediments from the Upper Congo deep-sea fan: on the difficulty in obtaining palaeomagnetic secular variation records from low latitudes

We report here on results of palaeo- and rock magnetic investigations of two sediment cores from the Upper Congo deep-sea fan. The sediments have a high organic content and contain a heterogeneous Fe-mineral assemblage with biogenic magnetite and detrital (Ti-)magnetite as the main magnetic carrier minerals. Pyrite, hematite, and Fe-oxyhydroxides were identified by comparing high-temperature magnetic susceptibility curves with those from Fe-minerals of known composition. According to AMS 14C dates, the 6.8 m-long profile spans the last 37 kyr. Sediments older than 20 ka are affected by reductive diagenesis that has led to a loss of the fine-grained magnetic mineral fraction. Sediments younger than 20 ka have stable magnetizations. Characteristic remanent magnetization records of inclination and declination were obtained for each core. There is a little agreement between these records, modelled curves, and other sediment records from Equatorial Africa, so no composite record could be established. The cores are not ideal relative palaeointensity recorders and estimates using different normalizers did not yield consistent signals from both cores. Normalization methods used for relative palaeointensity estimation were not developed for sediments that contain large amounts of ultra-fine-grained biogenic magnetite; therefore, the relative palaeointensity estimates should be considered with caution. However, in view of the incoherent picture given by the scarce available palaeointensity information from the region off South-West Africa, the GeoB6517-2 record may provide a tentative relative palaeointensity record for comparison, at least for the past 10 kyr.

Relative Paleointensity and Inclination Anomaly Over the Last 8 Myr Obtained From the Integrated Ocean Drilling Program Site U1335 Sediments in the Eastern Equatorial Pacific

AbstractFor understanding the fundamentals of the geodynamo such as the relation between paleointensity and polarity length and time‐averaged field (TAF) structure, continuous records of relative paleointensity (RPI) and inclination anomaly (ΔI) are desired; however, available records older than ~3 Ma are still very limited in time and space. We conducted a paleomagnetic study of the Integrated Ocean Drilling Program Site U1335 sediments in the eastern equatorial Pacific to obtain continuous RPI and ΔI records since ~8 Ma. Slow deposition, ~8.4 m/Myr or less, limits the resolution of the records but did allow for determination of long‐term variations. Rock‐magnetic measurements showed that biogenic magnetite dominates the magnetic mineral assemblages, and the proportion of biogenic to terrigenous magnetic minerals increases prior to ~4 Ma. The average paleointensity between ~4 and 8 Ma is approximately 30% lower than that from 0 to ~4 Ma. The apparent reduction of RPI at ~4 Ma reaches approximately ~50%, but ~20% of this is estimated to be artificial, induced by the increase in the proportion of biogenic magnetite. No relation between paleointensity and polarity length is recognized for the last ~8 Myr. The magnitude of ΔI is slightly larger during reversed polarity chrons (4.43° ± 1.47°) than normal polarity chrons (−0.69° ± 2.98°) over the last ~5 Myr, which agrees with the available TAF models of this time span. Prior to ~6 Ma, the sign of ΔI during the normal chrons might have switched to positive, and ΔI during reversed chrons might have been slightly larger than that after ~5 Ma.

An Integrated Study of the Eolian Dust in Pelagic Sediments From the North Pacific Ocean Based on Environmental Magnetism, Transmission Electron Microscopy, and Diffuse Reflectance Spectroscopy

AbstractEolian dust is a major terrigenous component in North Pacific Ocean pelagic sediments and is an important recorder of Asian terrestrial environmental evolution and Northern Hemisphere atmospheric circulation. In order to extract and quantify wind‐borne mineral signals and develop a reliable eolian dust proxy for pelagic sediments, we investigated sediments from Ocean Drilling Program Hole 885A, North Pacific Ocean, by integrating results from environmental magnetism, transmission electron microscopy, and diffuse reflectance spectroscopy (DRS). Our results indicate that ferrimagnetic and antiferromagnetic minerals coexist in the sediments. The former includes biogenic magnetite, nano‐sized single domain (titano) magnetite inclusions embedded in silicate hosts, submicron vortex state magnetite, and ultrafine superparamagnetic maghemite. The latter includes hematite and goethite. Our results indicate that magnetic properties can be used to determine an overall trend of increased eolian dust inputs, with additional significant influence from biogenic and volcanogenic components. In contrast, a newly proposed parameter RelHm+Gt (combined hematite and goethite concentration) obtained from DRS measurements extracts precisely the eolian signal and precludes other components. Our DRS results indicate that hematite/goethite and siliceous fractions deposited at Hole 885A were jointly delivered to the North Pacific Ocean from Asian dust sources. Therefore, we suggest that RelHm+Gt is a reliable eolian dust proxy for pelagic sediments in this region.

Removal of Cr (III) and Ni (II) from tannery effluent using calcium carbonate coated bacterial magnetosomes

Heavy metal contamination of surface water bodies and ground water has been a major problem around the world. Calcium-based adsorbents are effective but cannot be separated easily after the treatment. Magnetosomes are biogenic magnetite synthesised as highly ordered chain-like structures by magnetotactic bacteria. In this study, we have prepared magnetically controlled calcite microcrystals using magnetosomes for the adsorption experiment. The ability of magnetic calcite as adsorbent was investigated for the removal of Cr (III) and Ni (II) ions from synthetic solution. Critical parameters, such as the effect of pH, temperature, contact time, initial ion concentration, and adsorbent dose, were optimised in comparison with calcite, magnetosomes, and activated carbon for maximum metal ion removal. The study showed that equilibrium was established in 1 h for both Cr (III) and Ni (II) at a pH of 6.0 and 8.0, respectively. The adsorption process follows pseudo-second-order reaction kinetics, along with Langmuir and Freundlich adsorption isotherms. The thermodynamics of adsorption of both metal ions on magnetic calcite showed that the adsorption was spontaneous and endothermic in nature. Magnetically controlled calcite crystals successfully removed Cr (III) and Ni (II) from collected tannery effluent and separated from the solution by applying magnetic field. Maximum removal of chromium and nickel (94 and 84%) by magnetic calcite is similar to calcite crystals but higher than magnetosomes and activated carbon. The results indicated that magnetic calcite could be used as an alternative adsorbent for removing heavy metals from tannery effluent.

Fingerprints of partial oxidation of biogenic magnetite from cultivated and natural marine magnetotactic bacteria using synchrotron radiation.

Magnetotactic bacteria are a multi-phyletic group of bacteria that synthesize membrane-bound magnetic minerals. Understanding the preservation of these minerals in various environments (e.g., with varying oxygen concentrations and iron supply) is important for understanding their role as carriers of primary magnetizations in sediments and sedimentary rocks. Here we present X-ray near edge structure (XANES) spectra for Fe in magnetotactic bacteria samples from recent sediments to assess surface oxidation and crystal structure changes in bacterial magnetite during early burial. Our results are compared with a XANES spectrum of cultivated Magnetofaba australis samples, and with magnetic properties, and indicate that oxidation of magnetite to maghemite increases with depth in the sediment due to longer exposure tomolecular oxygen. These results are relevant tounderstanding magnetic signatures carried by magnetofossils in oxic sediments and sedimentary rocks of different ages.

Effects of Aging on Transformation of Biogenic Magnetite Nanoparticles

This study examined the microbial synthesis of magnetite and Pd/Zn-substituted magnetite using metal-reducing bacteria (Clostridium sp.), and the mineralogical characteristics of various types of magnetite formed initially and transformed minerals aged for 5 years. XRD, SXRD, and TEM-EDS analyses were used to characterize the mineralogy, crystal structure, chemistry, shape, and size distribution of the magnetites and transformed minerals. The metal-reducing bacteria reduced akaganeite and Pd/Zn-akaganeite to magnetite and Pd/Zn-substituted magnetite using glucose as an electron donor, respectively. Metal substitution of Pd and Zn within the magnetite structure resulted in a decrease in the unit-cell parameter of the magnetite crystals. After 5 years, the biogenic magnetite showed changes in unit-cell parameters and transformation to siderite during prolonged cultivation under anaerobic conditions. These results indicate that long-term aging may affect the mineralogical transformation and alter the nano-sized crystal structure.

Nanoscale synchrotron X-ray speciation of iron and calcium compounds in amyloid plaque cores from Alzheimer's disease subjects.

Altered metabolism of biometals in the brain is a key feature of Alzheimer's disease, and biometal interactions with amyloid-β are linked to amyloid plaque formation. Iron-rich aggregates, including evidence for the mixed-valence iron oxide magnetite, are associated with amyloid plaques. To test the hypothesis that increased chemical reduction of iron, as observed in vitro in the presence of aggregating amyloid-β, may occur at sites of amyloid plaque formation in the human brain, the nanoscale distribution and physicochemical states of biometals, particularly iron, were characterised in isolated amyloid plaque cores from human Alzheimer's disease cases using synchrotron X-ray spectromicroscopy. In situ X-ray magnetic circular dichroism revealed the presence of magnetite: a finding supported by ptychographic observation of an iron oxide crystal with the morphology of biogenic magnetite. The exceptional sensitivity and specificity of X-ray spectromicroscopy, combining chemical and magnetic probes, allowed enhanced differentiation of the iron oxides phases present. This facilitated the discovery and speciation of ferrous-rich phases and lower oxidation state phases resembling zero-valent iron as well as magnetite. Sequestered calcium was discovered in two distinct mineral forms suggesting a dynamic process of amyloid plaque calcification in vivo. The range of iron oxidation states present and the direct observation of biogenic magnetite provide unparalleled support for the hypothesis that chemical reduction of iron arises in conjunction with the formation of amyloid plaques. These new findings raise challenging questions about the relative impacts of amyloid-β aggregation, plaque formation, and disrupted metal homeostasis on the oxidative burden observed in Alzheimer's disease.

Reduction of Hg(II) to Hg(0) by Biogenic Magnetite from two Magnetotactic Bacteria

ABSTRACTUnderstanding the biogeochemical cycle of the highly toxic element mercury (Hg) is necessary to predict its fate and transport. In this study, we determined that biogenic magnetite isolated from Magnetospirillum gryphiswaldense MSR-1 and Magnetospirillum magnetotacticum MS-1 was capable of reducing inorganic mercury [Hg(II)] to elemental mercury [Hg(0)]. These two magnetotactic bacteria (MTB) lacked mercuric resistance operons in the genomes. However, they revealed high resistance to Hg(II) under atmospheric conditions and an even higher resistance under microaerobic conditions (1% O2 and 99% N2). Neither strain reduced Hg(II) to Hg(0) under atmospheric conditions. However, a slow rate (0.05–0.21 µM·d−1) of Hg(II) loss occurred from late log phase to stationary phase in two MTBs' culture media under microaerobic conditions. Increased Hg(II) entered both cells under microaerobic conditions relative to atmospheric conditions. The majority of Hg(II) was still blocked by the cell membrane. Hg(II) reduction was more effective when biogenic magnetite was extracted out, with or without the magnetosome membrane envelope. When magnetosome membrane was present, 8.55–13.53% of 250 nM Hg(II) was reduced to Hg(0) by 250 mg/L biogenic magnetite suspension within 2 hours. This ratio increased to 55.07–64.70% while magnetosome membrane was removed. We concluded that two MTBs contributed to the reduction of Hg(II) to Hg(0) at a slow rate in vivo. Such reduction was more favorable to occur when biogenic magnetite is released from dead cells. It proposed a new biotic pathway for the formation of Hg(0) in aquatic systems.

Reduction of Hg(II) to Hg(0) by biogenic magnetite from two magnetotactic bacteria

Understanding the biogeochemical cycle of the highly toxic element mercury (Hg) is necessary to predict its fate and transport. In this study, we determined that biogenic magnetite isolated from Ma...

Deccan volcanism induced high-stress environment during the Cretaceous–Paleogene transition at Zumaia, Spain: Evidence from magnetic, mineralogical and biostratigraphic records

We conducted detailed rock magnetic, mineralogical and geochemical (mercury) analyses spanning the Cretaceous–Paleogene boundary (KPB) at Zumaia, Spain, to unravel the signature of Deccan-induced climate and environmental changes in the marine sedimentary record. Our biostratigraphic results show that Zumaia is not complete, and lacks the typical boundary clay, zone P0 and the base of zone P1a(1) in the basal Danian. Presence of an unusual ∼1m-thick interval spanning the KPB is characterized by very low detrital magnetite and magnetosome (biogenic magnetite) contents and by the occurrence of akaganéite, a very rare mineral on Earth in oxidizing, acidic and hyper-chlorinated environments compatible with volcanic settings. These benchmarks correlate with higher abundance of the opportunist Guembelitria cretacea species. Detrital magnetite depletion is not linked to significant lithological changes, suggesting that iron oxide dissolution by acidification is the most probable explanation. The concomitant decrease in magnetosomes, produced by magnetotactic bacteria at the anoxic–oxic boundary, is interpreted as the result of changes in seawater chemistry induced by surficial ocean acidification. Mercury peaks up to 20–50 ppb are common during the last 100 kyr of the Maastrichtian (zone CF1) but only one significant anomaly is present in the early Danian, which is likely due to the missing interval. Absence of correlation between mercury content (R2 = 0.009) and total organic carbon (R2 = 0.006) suggest that the former originated from the Deccan Traps eruptions. No clear relation between the stratigraphic position of the mercury peaks and the magnetite-depleted interval is observed, although the frequency of the mercury peaks tends to increase close to the KPg boundary. In contrast to Bidart (France) and Gubbio (Italy), where magnetite depletion and akaganéite feature within a ∼50cm-thick interval located 5 cm below the KPg boundary, the same benchmarks are observed in a 1m-thick interval encompassing the KPg boundary at Zumaia. Results reinforce the synchronism of the major eruptions of the Deccan Traps Magmatic Province with the Cretaceous–Paleogene (KPg) mass extinction and provide new clues to better correlate the Deccan imprint of the global sedimentary record.

Interactions between magnetite and humic substances: redox reactions and dissolution processes

Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe3O4) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.

Current and future microbiological strategies to remove As and Cd from drinking water.

Current and future microbiological strategies to remove As and Cd from drinking water.

Use of Bacteria To Stabilize Archaeological Iron.

Iron artifacts are common among the findings of archaeological excavations. The corrosion layer formed on these objects requires stabilization after their recovery, without which the destruction of the item due to physicochemical damage is likely. Current technologies for stabilizing the corrosion layer are lengthy and generate hazardous waste products. Therefore, there is a pressing need for an alternative method for stabilizing the corrosion layer on iron objects. The aim of this study was to evaluate an alternative conservation-restoration method using bacteria. For this, anaerobic iron reduction leading to the formation of stable iron minerals in the presence of chlorine was investigated for two strains of Desulfitobacterium hafniense (strains TCE1 and LBE). Iron reduction was observed for soluble Fe(III) phases as well as for akaganeite, the most troublesome iron compound in the corrosion layer of archaeological iron objects. In terms of biogenic mineral production, differential efficiencies were observed in assays performed on corroded iron coupons. Strain TCE1 produced a homogeneous layer of vivianite covering 80% of the corroded surface, while on the coupons treated with strain LBE, only 10% of the surface was covered by the same mineral. Finally, an attempt to reduce iron on archaeological objects was performed with strain TCE1, which led to the formation of both biogenic vivianite and magnetite on the surface of the artifacts. These results demonstrate the potential of this biological treatment for stabilizing archaeological iron as a promising alternative to traditional conservation-restoration methods.IMPORTANCE Since the Iron Age, iron has been a fundamental material for the building of objects used in everyday life. However, due to its reactivity, iron can be easily corroded, and the physical stability of the object built is at risk. This is particularly true for archaeological objects on which a potentially unstable corrosion layer is formed during the time the object is buried. After excavation, changes in environmental conditions (e.g., higher oxygen concentration or lower humidity) alter the stability of the corrosion layer and can lead to the total destruction of the object. In this study, we demonstrate the feasibility of an innovative treatment based on bacterial iron reduction and biogenic mineral formation to stabilize the corrosion layer and protect these objects.