Uncovering the Size-Dependent Thermal Solid Transformation of Akaganéite.

Investigating the structural evolution and phase transformation of iron oxides is crucial for gaining a deeper understanding of geological changes on diverse planets and preparing oxide materials suitable for industrial applications. In this study, in-situ heating techniques are employed in conjunction with transmission electron microscopy (TEM) observations and ex-situ characterization to thoroughly analyze the thermal solid-phase transformation of akaganéite 1D nanostructures with varying diameters. These findings offer compelling evidence for a size-dependent morphology evolution in akaganéite 1D nanostructures, which can be attributed to the transformation from akaganéite to maghemite (γ-Fe2O3) and subsequent crystal growth. Specifically, it is observed that akaganéite nanorods with a diameter of ∼50 nm transformed into hollow polycrystalline maghemite nanorods, which demonstrated remarkable stability without arresting crystal growth under continuous heating. In contrast, smaller akaganéite nanoneedles or nanowires with a diameter ranging from 20 to 8 nm displayed a propensity for forming single-crystal nanoneedles or nanowires through phase transformation and densification. By manipulating the size of the precursors, a straightforward method is developed for the synthesis of single-crystal and polycrystalline maghemite nanowires through solid-phase transformation. These significant findings provide new insights into the size-dependent structural evolution and phase transformation of iron oxides at the nanoscale.

Fe(III) (oxyhydr)oxide reduction by the thermophilic iron-reducing bacterium Desulfovulcanus ferrireducens.

Some thermophilic bacteria from deep-sea hydrothermal vents grow by dissimilatory iron reduction, but our understanding of their biogenic mineral transformations is nascent. Mineral transformations catalyzed by the thermophilic iron-reducing bacterium Desulfovulcanus ferrireducens during growth at 55°C were examined using synthetic nanophase ferrihydrite, akaganeite, and lepidocrocite separately as terminal electron acceptors. Spectral analyses using visible-near infrared (VNIR), Fourier-transform infrared attenuated total reflectance (FTIR-ATR), and Mössbauer spectroscopies were complemented with x-ray diffraction (XRD) and transmission electron microscopy (TEM) using selected area electron diffraction (SAED) and energy dispersive X-ray (EDX) analyses. The most extensive biogenic mineral transformation occurred with ferrihydrite, which produced a magnetic, visibly dark mineral with spectral features matching cation-deficient magnetite. Desulfovulcanus ferrireducens also grew on akaganeite and lepidocrocite and produced non-magnetic, visibly dark minerals that were poorly soluble in the oxalate solution. Bioreduced mineral products from akaganeite and lepidocrocite reduction were almost entirely absorbed in the VNIR spectroscopy in contrast to both parent minerals and the abiotic controls. However, FTIR-ATR and Mössbauer spectra and XRD analyses of both biogenic minerals were almost identical to the parent and control minerals. The TEM of these biogenic minerals showed the presence of poorly crystalline iron nanospheres (50-200 nm in diameter) of unknown mineralogy that were likely coating the larger parent minerals and were absent from the controls. The study demonstrated that thermophilic bacteria transform different types of Fe(III) (oxyhydr)oxide minerals for growth with varying mineral products. These mineral products are likely formed through dissolution-reprecipitation reactions but are not easily predictable through chemical equilibrium reactions alone.

Understanding the mechanisms of anisotropic dissolution in metal oxides by applying radiolysis simulations to liquid-phase TEM.

Iron-based redox-active minerals are ubiquitous in soils, sediments, and aquatic systems. Their dissolution is of great importance for microbial impacts on carbon cycling and the biogeochemistry of the lithosphere and hydrosphere. Despite its widespread significance and extensive prior study, the atomic-to-nanoscale mechanisms of dissolution remain poorly understood, particularly the interplay between acidic and reductive processes. Here, we use in situ liquid-phase-transmission electron microscopy (LP-TEM) and simulations of radiolysis to probe and control acidic versus reductive dissolution of akaganeite (ß-FeOOH) nanorods. Informed by crystal structure and surface chemistry, the balance between acidic dissolution at rod tips and reductive dissolution at rod sides was systematically varied using pH buffers, background chloride anions, and electron beam dose. We find that buffers, such as bis-tris, effectively inhibited dissolution by consuming radiolytic acidic and reducing species such as superoxides and aqueous electrons. In contrast, chloride anions simultaneously suppressed dissolution at rod tips by stabilizing structural elements while promoting dissolution at rod sides through surface complexation. Dissolution behaviors were systematically varied by shifting the balance between acidic and reductive attacks. The findings show LP-TEM combined with simulations of radiolysis effects can provide a unique and versatile platform for quantitatively investigating dissolution mechanisms, with implications for understanding metal cycling in natural environments and the development of tailored nanomaterials.

Schwertmannite and akaganéite for adsorption removals of Cr(VI) from aqueous solutions.

Iron hydroxides have received high attention in the treatment of chromium (Cr) polluted wastewater. In this study, the obtained chemical (or biological) pincushion-schwertmannite spheres had a diameter of 2 - 5 µm (0.5-1 µm), and akaganéite rods had a length of 300-500 nm (100-150 nm) at an axial ratio of about 3. The average diameters (µm) of their agglomerated particles in solutions were 20.6-32.5 (only 0.480 for Aka-Chem). Schwertmannites and akaganéites were used to investigate Cr(VI) adsorption behaviors in aqueous solutions by batch experiments, under various reaction times, initial Cr(VI) and adsorbent levels, pH values, temperature and anions of NO3-, Cl-, CO32-, SO42-, and H2PO4-. Adsorption data well fitted to pseudo-second-order rate model (R2 = 0.999), and Langmuir (R2 = 0.954-0.988) and Freundlich (R2 = 0.984-0.996) isothermal models at pH 7.0. Maximum Cr(VI) adsorption capacities were 119/133 for Sch-Chem/Sch-Bio, and 14.6/83.6 for Aka-Chem/Aka-Bio. The H2PO4- than SO42-/CO32- had a stronger effect on Cr(VI) adsorption. Adsorbents with pHZPC of near to 4.0 still had a good Cr(VI) removal ability at pH 3.0-8.0. The possible Cr(VI) adsorption mechanisms by FTIR and XPS results for schwertmannite and akaganéite were electrostatic attractions and ion exchanges between hydroxyl (or sulfate) and chromate ions. The Cr(VI) adsorption of optimal schwertmannite and bioakaganéite was a spontaneous, endothermic and random process at the temperatures of 288-318 K. They had a good regeneration ability for Cr(VI) adsorption, and removal ratios could reach to about 80% of original values (60-70% in aqueous solution with 60 mg/L Cr(VI) and pH7.0, and 35-50% in wastewater with 120 mg/L Cr(VI) and about pH4.0), after three cycles. Herein, schwertmannite/bioakaganéite have a promising application in treatment of acidic/neutral wastewater with chromate.

Cell-shape assemblage and nanostructure of akaganéite bioformed in FeCl2 solutions.

Akaganéite (ß-FeOOH) with a tunnel structure typically occupied by chloride can undergo anion-exchange reactions in aqueous solutions for pollutant removal. In this work, we studied bioformation of akaganéite in FeCl2 solutions with Acidithiobacillus ferrooxidans cells at pH 2.9, during 36-h incubation. The obtained products were analyzed and characterized by XRD, FTIR, EDS, FETEM, and HRTEM. Results showed that in acidic media with pH 2.9, the cells facilitated ferrous biooxidation and ferric precipitation. The resulting ferric precipitates were identified as polycrystalline akaganéite powders and had a morphology of nanospindles with a length of less 100 nm. The correlatively chemical formula for akaganéite collected at 1 h was reckoned as Fe8O8(OH)6.71(Cl)1.29 with 6.6% Cl. It was observed that ferric precipitates along exterior structures of cells or their extruded organic polymers grew and assembled into cellular shape. The evolved cell-shape akaganéite assemblages were twice of cells (about 2 µm) in size. These results could contribute to understanding of laboratorial bioformation of akaganéite and its biomineralization in acidic environments and promoting its practical applications.

As(III, V) Uptake from Nanostructured Iron Oxides and Oxyhydroxides: The Complex Interplay between Sorbent Surface Chemistry and Arsenic Equilibria.

Iron oxides/oxyhydroxides, namely maghemite, iron oxide-silica composite, akaganeite, and ferrihydrite, are studied for AsV and AsIII removal from water in the pH range 2-8. All sorbents were characterized for their structural, morphological, textural, and surface charge properties. The same experimental conditions for the batch tests permitted a direct comparison among the sorbents, particularly between the oxyhydroxides, known to be among the most promising As-removers but hardly compared in the literature. The tests revealed akaganeite to perform better in the whole pH range for AsV (max 89 mg g-1 at pH0 3) but to be also efficient toward AsIII (max 91 mg g-1 at pH0 3-8), for which the best sorbent was ferrihydrite (max 144 mg g-1 at pH0 8). Moreover, the study of the sorbents' surface chemistry under contact with arsenic and arsenic-free solutions allowed the understanding of its role in the arsenic uptake through electrophoretic light scattering and pH measurements. Indeed, the sorbent's ability to modify the starting pH was a crucial step in determining the removal of performances. The AsV initial concentration, contact time, ionic strength, and presence of competitors were also studied for akaganeite, the most promising remover, at pH0 3 and 8 to deepen the uptake mechanism.

Artificial neural network modeling for Congo red adsorption on microwave-synthesized akaganeite nanoparticles: optimization, kinetics, mechanism, and thermodynamics.

This work aims to synthesize akaganeite nanoparticles (AKNPs) by using microwave and use them to adsorb Congo red dye (CR) from the aqueous solution. The AKNPs with an average particle size of about 50 nm in width and 100 nm in length could be fabricated in 20 min. The effects of pH, CR initial concentration, adsorption time, and adsorbent dosage on the adsorption process were investigated and the artificial neural network (ANN) was used to analyze the adsorption data. The various ANN structures were examined in training the data to find the optimal model. The structure with training function, TRAINLM; adaptation learning function, LARNGDM; transfer function, LOGSIG (in hidden layer) and PURELIN (in output layer); and 10 neutrons in hidden layer having the highest correlation (R2 = 0.996) and the lowest MSE (4.405) is the optimal ANN structure. The consistency between the experimental data and the data predicted by the ANN model showed that the behavior of the adsorption process of CR onto AKNPs under different conditions can be estimated by the ANN model. The adsorption kinetics was studied by fitting the data into pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion models. The results showed that the adsorption kinetics obeyed the pseudo-second-order model and governed by several steps. The adsorption isotherms at the different temperatures were studied by fitting the data to Langmuir, Freundlich, and Temkin isotherm models. The R2 obtained from the Langmuir model was above 0.9 and the highest value in three of four temperatures, suggesting that the adsorption isotherms were the best fit to the Langmuir model and the maximum adsorption capacity was estimated to be more than 150 mg/g. Thermodynamic studies suggested that the adsorption of CR onto AKNPs was a spontaneous and endothermic process and physicochemical adsorption. The obtained results indicated the potential application of microwave-synthesize AKNPs for removing organic dyes from aqueous solutions.

Goethite Nanorods: Synthesis and Investigation of the Size Effect on Their Orientation within a Magnetic Field by SAXS.

Goethite is a naturally anisotropic, antiferromagnetic iron oxide. Following its atomic structure, crystals grow into a fine needle shape that has interesting properties in a magnetic field. The needles align parallel to weak magnetic fields and perpendicular when subjected to high fields. We synthesized goethite nanorods with lengths between 200 nm and 650 nm in a two-step process. In a first step we synthesized precursor particles made of akaganeite (ß-FeOOH) rods from iron(III)chloride. The precursors were then treated in a hydrothermal reactor under alkaline conditions with NaOH and polyvinylpyrrolidone (PVP) to form goethite needles. The aspect ratio was tunable between 8 and 15, based on the conditions during hydrothermal treatment. The orientation of these particles in a magnetic field was investigated by small angle X-ray scattering (SAXS). We observed that the field strength required to trigger a reorientation is dependent on the length and aspect ratio of the particles and could be shifted from 85 mT for the small particles to about 147 mT for the large particles. These particles could provide highly interesting magnetic properties to nanocomposites, that could then be used for sensing applications or membranes.

A Novel "Microbial Bait" Technique for Capturing Fe(III)-Reducing Bacteria.

Microbial reduction of Fe(III) is a key geochemical process in anoxic environments, controlling the degradation of organics and the mobility of metals and radionuclides. To further understand these processes, it is vital to develop a reliable means of capturing Fe(III)-reducing microorganisms from the field for analysis and lab-based investigations. In this study, a novel method of capturing Fe(III)-reducing bacteria using Fe(III)-coated pumice "microbe-baits" was demonstrated. The methodology involved the coating of pumice (approximately diameter 4 to 6 mm) with a bioavailable Fe(III) mineral (akaganeite), and was verified by deployment into a freshwater spring for 2 months. On retrieval, the coated pumice baits were incubated in a series of lab-based microcosms, amended with and without electron donors (lactate and acetate), and incubated at 20°C for 8 weeks. 16S rRNA gene sequencing using the Illumina MiSeq platform showed that the Fe(III)-coated pumice baits, when incubated in the presence of lactate and acetate, enriched for Deltaproteobacteria (relative abundance of 52% of the sequences detected corresponded to Geobacter species and 24% to Desulfovibrio species). In the absence of added electron donors, Betaproteobacteria were the most abundant class detected, most heavily represented by a close relative to Rhodoferax ferrireducens (15% of species detected), that most likely used organic matter sequestered from the spring waters to support Fe(III) reduction. In addition, TEM-EDS analysis of the Fe(III)-coated pumice slurries amended with electron donors revealed that a biogenic Fe(II) mineral, magnetite, was formed at the end of the incubation period. These results demonstrate that Fe(III)-coated pumice "microbe baits" can potentially help target metal-reducing bacteria for culture-dependent studies, to further our understanding of the nano-scale microbe-mineral interactions in aquifers.

Akaganeite nanorices deposited muscovite mica surfaces as sunlight active green photocatalyst.

Thin films of akaganeite [FeO(OH)] nanorices deposited muscovite mica (ANPM) surfaces are synthesized using the facile urea assisted controlled self-assembly technique. The synthesized materials are characterized using scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy, atomic force microscopy, X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). The prepared nanorices on mica surfaces show average particle length and width of 200 and 50 nm, respectively. Synthesized material acts as an efficient photocatalyst under UV and sunlight conditions as demonstrated by the degradation of standard methylene blue (MB) solution. The MB degradation efficiencies of the catalyst under exposure to 180 min sunlight and UV are 89% and 87.5%, respectively, which shows that the catalyst is more highly active under sunlight than under UV light. Therefore, the synthesized material is a potential green photocatalyst in efficient treatment of industrial dye effluents under direct sunlight.

Determination of iron species, including biomineralized jarosite, in the iron-hyperaccumulator moss Scopelophila ligulata by Mössbauer, X-ray diffraction, and elemental analyses.

Scopelophila ligulata is an Fe-hyperaccumulator moss growing in acidic environments, but the mechanism of Fe accumulation remains unknown. To understand the mechanism, we determined Fe species in S. ligulata samples. The moss samples were collected from four sites in Japan. The concentrations of Fe, P, S, Cl, and K in them were measured by induced coupled plasma mass spectrometry. Fe species in some of them were determined by Mössbauer spectroscopy and were confirmed by X-ray diffraction analysis. Fe species in S. ligulata samples were determined to be jarosite, ferritin, high-spin Fe(II) species, and akaganeite. To our knowledge, this is the first report on the biomineralization of jarosite in mosses. This result, combined with the fact that bacteria, a fungus, and a grass mineralize jarosite, suggests that its biomineralization is a common characteristic in a wide variety of living organisms. These findings indicate that the biomineralization of jarosite occurs not only in the region-specific species but in species adapted to a low-pH and metal-contaminated environment in different regions, provide a better understanding of the mechanism of Fe accumulation in the Fe-hyperaccumulator moss S. ligulata, and offer new insights into the biomineralization of jarosite.

Co-transport of U(VI) and akaganéite colloids in water-saturated porous media: Role of U(VI) concentration, pH and ionic strength.

Remediating uranium contamination becomes a worldwide interest because of increasing uranium release from mining activities. Due to ubiquitous presence of pyrite and the application of iron-based technology, colloidal iron oxy-hydroxides such as akaganéite colloid (AKC) extensively exist in uranium polluted water at uranium tailing sites. In this context, we studied individual and co-transport of U(VI) and AKC in water-saturated sand columns at 50 mg/L AKC and environmentally relevant U(VI) concentrations (5.0 × 10-7 ∼ 5.0 × 10-5 M). It was found that, in addition to the impact of pH and ionic strength, whether AKC facilitated U(VI) transport depended on U(VI) concentration as well. The presence of AKC facilitated U(VI) transport at relatively low U(VI) concentration (5.0 × 10-7 ∼ 5.0 × 10-6 M), which was due to the strong adsorption of U(VI) on AKC and faster transport of AKC than that U(VI) as observed in their individual transport experiments. At relatively high U(VI) concentrations (5.0 × 10-5 M), however, AKC impeded U(VI) transport because U(VI) of high concentration decreased AKC colloidal stability and increased AKC aggregation and attachment. Thus, U(VI) and AKC co-transport was even blocked completely at relatively high pH and ionic strength. The mechanisms behind the co-transport of U(VI) and AKC were also confirmed by assessing the evolutions of aqueous pH and AKC zeta potential and particle size distribution in the column effluents. A two-site non-equilibrium model and a two-site kinetic attachment/detachment model well-described the breakthrough curves of U(VI) and AKC, respectively. Knowledge generated from this study provides a thorough understanding of uranium transport in the absence/presence of AKC, and brings new insights into the influence of contaminant concentration on co-transport in the presence of colloids.

Spectral and morphological characteristics of synthetic nanophase iron (oxyhydr)oxides.

Nanophase iron (oxyhydr)oxides are ubiquitous on Earth, globally distributed on Mars, and likely present on numerous other rocky solar system bodies. They are often structurally and, therefore, spectrally distinct from iron (oxyhydr)oxide bulk phases. Because their spectra vary with grain size, they can be difficult to identify or distinguish unless multiple analysis techniques are used in tandem. Yet, most literature reports fail to use multiple techniques or adequately parameterize sample morphology, making it difficult to understand how morphology affects spectral characteristics across techniques. Here, we present transmission electron microscopy, Raman, visible and near-infrared, and mid-infrared attenuated total reflectance data on synthetic, nanophase akaganéite, lepidocrocite, goethite, hematite, ferrihydrite, magnetite, and maghemite. Feature positions are tabulated and compared to those for bulk (oxyhydr)oxides and other nanophase iron (oxyhydr)oxides from the literature. The utility and limitations of each technique in analyzing nanophase iron (oxyhydr)oxides are discussed. Raman, mid-infrared, and visible near-infrared spectra show broadening, loss of some spectral features, and shifted positions compared to bulk phases. Raman and mid-infrared spectroscopies are useful in identifying and distinguishing akaganéite, lepidocrocite, goethite, and hematite, though ferrihydrite, magnetite, and maghemite have overlapped band positions. Visible near-infrared spectroscopy can identify and distinguish among ferrihydrite, magnetite, and maghemite in pure spectra, though akaganéite, lepidocrocite, and goethite can have overlapping bands. It is clear from this work that further understanding of variable spectral features in nanophase iron (oxyhydr)oxides must await additional studies to robustly assess effects of morphology. This study establishes a template for future work.

Synthetic Iron Oxides for Adsorptive Removal of Arsenic.

Removal of arsenic from water reservoirs is the issue of great concern in many places around the globe. As adsorption is one of the most efficient techniques for treatment of As-containing media, thus the present study concerns application of iron oxides-hydroxides (akaganeite) as adsorbents for removal of this harmful metal from aqueous solution. Two types of akaganeite were tested: synthetic one (A) and the same modified using hexadecyltrimethylammonium bromide (AM). Removal of As was tested in batch studies in function of pH, adsorbent dosage, contact time, and initial arsenic concentration. The adsorption isotherms obey Langmuir mathematical model. Adsorption kinetics complies with pseudo-second-order kinetic model, and the constant rates were defined as 2.07 × 10-3and 0.92 × 10-3 g mg-1 min-1 for the samples (A) and (AM), respectively. The difference was caused by significant decrease in adsorption rate in initial state of the process carried out for the sample AM. The maximum adsorption capacity achieved for (A) and (AM) akaganeite taken from Langmuir isotherm was 148.7 and 170.9 mg g-1, respectively. The results suggest that iron oxides-hydroxides can be used for As removal from aqueous solutions.

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.

The impact of aqueous washing on the ability of ßFeOOH to corrode iron.

Controlling the corrosion of historical and archaeological ferrous metal objects presents a significant challenge to conservators. Chloride is a major corrosion accelerator in coastal areas for historic ferrous metal structures and for the many chloride-containing archaeological objects within museums. Corrosion reactions involve the formation of akaganéite (ßFeOOH) which incorporates chloride within its crystal structure and adsorbs it onto its surface. The mobility of the surface-adsorbed chloride in aqueous systems and atmospheric moisture means ßFeOOH can itself cause iron to corrode. The extraction of chloride from ßFeOOH by aqueous Soxhlet hot wash and aqueous room temperature washing is measured. The impact of this washing on the ability of ßFeOOH to corrode iron is quantitatively investigated by determining the oxygen consumption of unwashed, Soxhlet-washed and room temperature-washed samples of ßFeOOH mixed with iron powder and exposed to 80 % relative humidity. This acts as a proxy measurement for the corrosion rate of iron. The results are discussed relative to climatic factors for outdoor heritage objects and the treatment of archaeological iron in museums. Delivering better understanding of the properties of ßFeOOH supports the development of evidence-based treatments and management procedures in heritage conservation.

Study of corrosion in archaeological gilded irons by Raman imaging and a coupled scanning electron microscope-Raman system.

In this work, analytical and chemical imaging tools have been applied to the study of a gilded spur found in the medieval necropolis of Erenozar (Bizkaia, Spain). As a first step, a lot of portable equipment has been used to study the object in a non-invasive way. The hand-held energy-dispersive X-ray fluorescence equipment allowed us to characterize the artefact as a rare example of an iron matrix item decorated by means of a fire gilding technique. On the other hand, the use of a portable Raman system helped us to detect the main degradation compounds affecting the spur. Afterwards, further information was acquired in the laboratory by analysing detached fragments. The molecular images obtained using confocal Raman microscopy permitted us to characterize the stratigraphic succession of iron corrosions. Furthermore, the combined use of this technique with a scanning electron microscope (SEM) was achieved owing to the use of a structural and chemical analyser interface. In this way, the molecular characterization, enhanced by the magnification feature of the SEM, allowed us to identify several micrometric degradation compounds. Finally, the effectiveness of one of the most used desalination baths (NaOH) was evaluated by comparing its effects with those provided by a reference bath (MilliQ). The comparison proved that basic treatment avoided any side effects on the spur decorated by fire gilding, compensating for the lack of bibliographic documentation in this field.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.

Microwave-ultrasound assisted synthesis of ß-FeOOH and its catalytic property in a photo-Fenton-like process.

In this study, nanoparticles of single-phase akaganeite (ß-FeOOH) were synthesized by an ultrasound-microwave assisted method. The synthesis parameters were optimized by means of response surface methodology. X-ray diffractions (XRD), Fourier transform infrared spectrum (FTIR), UV-vis diffused reflection spectra (UV-vis DRS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and specific surface area were used to characterize the as-prepared samples. The catalytic activity of the prepared ß-FeOOH was evaluated in a heterogeneous photo-Fenton-like process using methyl orange as target pollutant. It is found that the reaction temperature and interaction between microwave and ultrasound have a significant influence on the catalytic properties of the prepared ß-FeOOH samples. The ß-FeOOH prepared at microwave power of 400 W, ultrasound power of 200 W, reaction temperature of 70°C and reaction time of 3 h, exhibited considerable catalytic activity in weak alkaline solution and under visible light irradiation, which would be of great promise for the industrial application of this catalyst to oxidize organic pollutants for wastewater treatment.

An integrated bioremediation process for petroleum hydrocarbons removal and odor mitigation from contaminated marine sediment.

This study developed a novel integrated bioremediation process for the removal of petroleum hydrocarbons and the mitigation of odor induced by reduced sulfur from contaminated marine sediment. The bioremediation process consisted of two phases. In Phase I, acetate was dosed into the sediment as co-substrate to facilitate the sulfate reduction process. Meanwhile, akaganeite (ß-FeOOH) was dosed in the surface layer of the sediment to prevent S(2-) release into the overlying seawater. In Phase II, NO3(-) was injected into the sediment as an electron acceptor to facilitate the denitrification process. After 20 weeks of treatment, the sequential integration of the sulfate reduction and denitrification processes led to effective biodegradation of total petroleum hydrocarbons (TPH), in which about 72% of TPH was removed. In Phase I, the release of S(2-) was effectively controlled by the addition of akaganeite. The oxidation of S(2-) by Fe(3+) and the precipitation of S(2-) by Fe(2+) were the main mechanisms for S(2-) removal. In Phase II, the injection of NO3(-) completely inhibited the sulfate reduction process. Most of residual AVS and S(0) were removed within 4 weeks after NO3(-) injection. The 16S rRNA clone library-based analysis revealed a distinct shift of bacterial community structure in the sediment over different treatment phases. The clones affiliated with Desulfobacterales and Desulfuromonadales were the most abundant in Phase I, while the clones related to Thioalkalivibrio sulfidophilus, Thiohalomonas nitratireducens and Sulfurimonas denitrificans predominated in Phase II.

Akaganeite decorated graphene oxide composite for arsenic adsorption/removal and its proconcentration at ultra-trace level.

Carboxylic graphene oxide (GO-COOH) is decorated with akaganeite (ß-FeOOH) to produce a ß-FeOOH@GO-COOH nanocomposite. The nanocomposite acts as an efficient adsorption medium for the uptake of arsenite and arsenate within a wide range of pH 3-10, providing high adsorption capacities of 77.5mgg(-1) for As(III) and 45.7mgg(-1) for As(V), respectively. Adsorption efficiencies of 100% and 97% are achieved for 5 successive operation cycles for the removal of 100µgL(-1) As(V) and As(III) in 5 fresh portions of aqueous solution (1.0mL for each) with 3mg nanocomposite. After 20 successive adsorption cycles, removal efficiency of >80% is still maintained for both arsenate and arsenite. Further, a removal efficiency of >90% is obtained for 1000µgL(-1) As(V) with 3mg ß-FeOOH@GO-COOH for 5 successive adsorption cycles, and the presence of 2000-fold SO4(2-), NO3(-), Cl(-) and Mg(2+) pose no interfering effect. ß-FeOOH@GO-COOH also provides a promising medium for the preconcentration of ultra-trace inorganic arsenic. 1mg of nanocomposite is used to adsorb 0.1-3.00µgL(-1) As(V) in 4.0mL solution, and the retained arsenate is recovered by 400µL of NaOH (2molL(-1), containing 2.0% NaBH4), followed by detection with atomic fluorescence spectrometry. A detection limit of 29ngL(-1) is obtained for arsenate. This procedure is validated by analyzing arsenic in a certified reference material (GBW 09101b) and further applied for arsenic determination in water samples.