Amorphous Iron Oxyhydroxide Research Articles

Arsenic in Playground Soils from Kindergartens and Green Recreational Areas of Bratislava City (Slovakia): Occurrence and Gastric Bioaccessibility.

In this study, playground soils of kindergartens and green recreational zones in Bratislava were investigated for the occurrence and gastric bioaccessibility of arsenic (As) in the < 150μm soil size fraction. Eighty topsoil (0-10cm) samples were collected from playgrounds in kindergartens and green recreational zones throughout the urban area. Bioaccessibility measurements of As were performed using the Simple Bioaccessibility Extraction Test that mimics the human gastric environment, and resulting extracts were analyzed by hydride generation-atomic absorption spectrometry to assess bioaccessible As concentrations in the collected playground soils. Single selective chemical extractions using hydroxylamine hydrochloride-hydrochloric acid and dithionite-citrate-bicarbonate solutions also were used to determine the amount of As associated with amorphous and amorphous/crystalline Fe oxy-hydroxides in soils, respectively. The results showed that the spatial distribution of total As concentrations was related to the historical development of the city, with higher soil concentrations of As found in the old city centre and related urban zones and the lower ones on the outskirts of Bratislava. There was a variation in the values of bioaccessible concentrations and fractions of As, with ranges from 0.40 to 5.60mg/kg and 7.29 to 56.1%, respectively. Correlation and multivariable linear regression analyses revealed that bioaccessible concentrations of As were linearly related to its total concentrations in the soils, whereas dithionite-citrate-bicarbonate extractable Fe (FeDCB) was the main soil property, controlling the bioaccessibility of As. When the amount of FeDCB in the soils increased, As bioaccessibility decreased, confirming an importance of Fe bound to amorphous and crystalline iron oxy-hydroxides to the limitation of As bioaccessibility in urban playground soils of Bratislava. Additionally, single selective extractions showed that As concentrations extracted by hydroxylamine hydrochloride (AsHH) and dithionite-citrate-bicarbonate (AsDCB) were positively correlated with its bioaccessible concentrations (Spearman r = 0.75 and 0.62, respectively; p < 0.001).

Characterization of iron oxide nanoparticle films at the air–water interface in Arctic tundra waters

Massive amounts of organic carbon have accumulated in Arctic permafrost and soils due to anoxic and low temperature conditions that limit aerobic microbial respiration. Alternative electron acceptors are thus required for microbes to degrade organic carbon in these soils. Iron or iron oxides have been recognized to play an important role in carbon cycle processes in Arctic soils, although the exact form and role as an electron acceptor or donor remain poorly understood. Here, Arctic biofilms collected during the summers of 2016 and 2017 from tundra surface waters on the Seward Peninsula of western Alaska were characterized with a suite of microscopic and spectroscopic methods. We hypothesized that these films contain redox-active minerals bound to biological polymers. The major components of the films were found to be iron oxide nanoparticle aggregates associated with extracellular polymeric substances. The observed mineral phases varied between films collected in different years with magnetite (Fe2+Fe23+O4) nanoparticles (<5nm) predominantly identified in the 2016 films, while for films collected in 2017 ferrihydrite-like amorphous iron oxyhydroxides were found. While the exact formation mechanism of these Artic iron oxide films remains to be explored, the presence of magnetite and other iron oxide/oxyhydroxide nanoparticles at the air–water interface may represent a previously unknown source of electron acceptors for continual anaerobic microbial respiration of organic carbon within poorly drained Arctic tundra.

Enhanced As (V) Removal from Aqueous Solution by Biochar Prepared from Iron-Impregnated Corn Straw

Fe-loaded adsorbents have received increasing attention for the removal of arsenic in contaminated water or soil. In this study, Fe-loaded biochar was prepared from iron-impregnated corn straw under a pyrolysis temperature of 600°C. The ratio of crystalline Fe oxides including magnetite and natrojarosite to amorphous iron oxyhydroxide in the composite was approximately 2 : 3. Consisting of 24.17% Fe and 27.76% O, the composite exhibited a high adsorption capacity of 14.77 mg g−1 despite low surface areas (4.81 m2 g−1). The pH range of 2.0–8.0 was optimal for arsenate removal and the adsorption process followed the Langmuir isotherms closely. In addition, pseudo-second-order kinetics best fit the As removal data. Fe oxide constituted a major As-adsorbing sink. Based on the X-ray diffraction spectra, saturation indices, and selective chemical extraction, the data suggested three main mechanisms for arsenate removal: sorption of arsenate, strong inner-sphere surface complexes with amorphous iron oxyhydroxide, and partial occlusion of arsenate into the crystalline Fe oxides or carbonized phase. The results indicated that the application of biochar prepared from iron-impregnated corn straw can be an efficient method for the remediation of arsenic contaminated water or soil.

The Formation of Silicate-Stabilized Passivating Layers on Pyrite for Reduced Acid Rock Drainage.

Acid and metalliferous release occurring when sulfide (principally pyrite)-containing rock from mining activities and from natural environments is exposed to the elements is acknowledged as a major environmental problem. Acid rock drainage (ARD) management is both challenging and costly for operating and legacy mine sites. Current technological solutions are expensive and focused on treating ARD on release rather than preventing it at source. We describe here a viable, practical mechanism for reduced ARD through the formation of silicate-stabilized iron oxyhydroxide surface layers. Without silicate, oxidized pyrite particles form an overlayer of crystalline goethite or lepidocrocite with porous structure. With silicate addition, a smooth, continuous, coherent and apparently amorphous iron oxyhydroxide surface layer is observed, with consequent pyrite dissolution rates reduced by more than 90% at neutral pH. Silicate is structurally incorporated within this layer and inhibits the phase transformation from amorphous iron (oxy)hydroxide to goethite, resulting in pyrite surface passivation. This is confirmed by computational simulation, suggesting that silicate-doping of a pseudoamorphous iron oxyhydroxide (ferrihydrite structure) is thermodynamically more stable than the equivalent undoped structure. This mechanism and its controlling factors are described. As a consequence of the greatly reduced acid generation rate, neutralization from on-site available reactive silicate minerals may be used to maintain neutral pH, after initial limestone addition to achieve neutral pH, thus maintaining the integrity of these layers for effective ARD management.

Constructing the novel ultrafine amorphous iron oxyhydroxide/g-C3N4 nanosheets heterojunctions for highly improved photocatalytic performance

Ultrafine particles, more heterojunction interfaces and amorphous materials can effectively enhance the photocatalytic activity of photocatalysts. In this work, a facile in-situ precipitation method was developed to prepare ultrafine amorphous iron oxyhydroxide/ultrathin g-C3N4 nanosheets heterojunction composites. The amorphous iron oxyhydroxide possessed an ultrafine particle size and a wide range of visible light absorption. In this process, the ultrafine particles not only shortened the diffusion distance of photogenerated carriers, but also facilitated the formation of more heterojunctions with ultrathin g-C3N4 nanosheets. The photocatalytic activities were evaluated using rhodamine B, methylene blue, and methyl orange as pollution models under visible light irradiation. Notably, the optimal photocatalytic activity of a-FeOOH/CNNS-800 composite is ~17.8 times higher than that of CNNS towards the degradation of rhodamine B under visible light. The outstanding photocatalytic activities were ascribed to the narrower band gap, the enhanced visible light absorbance, abundant heterojunction interfaces, and the effective separation of the photogenerated charges driven by the matched band edge in the heterostructures. We trusted that the facile and easy-to-extend synthesis method can be further expanded to synthesize other ultrafine semiconductors coupled with g-C3N4 for enhancing the photocatalytic activities.

Petrographic Characterization of the Different Types of Basalts of Harrat Al Fatih, Ablah Area, West Central Arabian Shield, Saudi Arabia

Harrat Al Fatih is located southwest of Ablah area, Assir terrain, southwestern Arabian Shield. It is present as black laterally extended horizontal basaltic sheet just overlying folded strata of the volcano-sedimentary succession of Ablah Formation (green mudstones, dolostones and green and red volcaniclastic red beds). These basalts are rift-related and represent part of the Oligo-Miocene basic volcanics of the western part of Saudi Arabia. The detailed field and microscopic description of these basalts enable the author to classify it into two main types: 1) Grey tuffaceous glassy basalts that present overlying the Ablah Formation. This basalt type is generally soft, bedded and intercalated with grey, green and red tuffaceous mudstones. Microscopically it composed of minute lath-like plagioclase and pyroxene crystals embedded in glassy groundmass. 2) Black olivine-rich basalts which are present in the topmost part of harrat Al Fatih are generally black, hard and contain remarkable reddish brown oxidized olivine spots and some calcite and amorphous quartz domains. Under the microscope, this basalt type is microcrystalline and composed mainly of lamellar twined Ca-plagioclase and colored olivines and pyroxenes. The olivines show different stages of oxidation and formation of amorphous blood red iron-oxyhydroxides and black hematite. The present study revealed the formation of the grey basalts at the initial stages of the volcanic eruption in ephemeral lakes and the second type of basalt was during the consolidation of proper basic magmas at the final stages of the volcanic eruption.

Distribution and hosts of arsenic in a sediment core from the Chianan Plain in SW Taiwan: Implications on arsenic primary source and release mechanisms

High arsenic abundance of 50–700μg/L in the groundwater from the Chianan Plain in southwestern Taiwan is a well-known environmental hazard. The groundwater-associated sediments, however, have not been geochemically characterized, thus hindering a comprehensive understanding of arsenic cycling in this region. In this study, samples collected from a 250m sediment core at the centre of the Chianan Plain were analyzed for arsenic and TOC concentrations (N=158), constituent minerals (N=25), major element abundances (N=105), and sequential arsenic extraction (N=23). The arsenic data show a prevalence of >10mg/kg with higher concentrations of 20–50mg/kg concentrated at 60–80 and 195–210m. Arsenic was extracted mainly as an adsorbate on clay minerals, as a co-precipitate in amorphous iron oxyhydroxide, and as a structural component in clay minerals. Since the sediments consist mainly of quartz, chlorite, and illite, the correlations between arsenic concentration and abundances of K2O and MgO pinpoint illite and chlorite as the major arsenic hosts. The arsenic–total iron correlation reflects the role of chlorite along with the contribution from amorphous iron oxyhydroxide as indicated by arsenic extraction data. Organic matter is not the dominant arsenic host for low TOC content, low arsenic abundance extracted from it, and a relatively low R2 of the arsenic–TOC correlation. The major constituent minerals in the sediments are the same as those of the upriver metapelites, establishing a sink–source relationship. Composition data from two deep groundwater samples near the sediment core show Eh values and As(V)/As(III) ratios of reducing environments and high arsenic, K, Mg, and Fe contents necessary for deriving arsenic from sediments by desorption from clay and dissolution of iron oxyhydroxide. Therefore, groundwater arsenic was mainly derived from groundwater-associated sediments with limited contributions from other sources, such as mud volcanoes.

Molecular Dynamics Simulation Study of the Early Stages of Nucleation of Iron Oxyhydroxide Nanoparticles in Aqueous Solutions.

Nucleation is a fundamental step in crystal growth. Of environmental and materials relevance are reactions that lead to nucleation of iron oxyhydroxides in aqueous solutions. These reactions are difficult to study experimentally due to their rapid kinetics. Here, we used classical molecular dynamics simulations to investigate nucleation of iron hydroxide/oxyhydroxide nanoparticles in aqueous solutions. Results show that in a solution containing ferric ions and hydroxyl groups, iron-hydroxyl molecular clusters form by merging ferric monomers, dimers, and other oligomers, driven by strong affinity of ferric ions to hydroxyls. When deprotonation reactions are not considered in the simulations, these clusters aggregate to form small iron hydroxide nanocrystals with a six-membered ring-like layered structure allomeric to gibbsite. By comparison, in a solution containing iron chloride and sodium hydroxide, the presence of chlorine drives cluster assembly along a different direction to form long molecular chains (rather than rings) composed of Fe-O octahedra linked by edge sharing. Further, in chlorine-free solutions, when deprotonation reactions are considered, the simulations predict ultimate formation of amorphous iron oxyhydroxide nanoparticles with local atomic structure similar to that of ferrihydrite nanoparticles. Overall, our simulation results reveal that nucleation of iron oxyhydroxide nanoparticles proceeds via a cluster aggregation-based nonclassical pathway.

Lithium Storage Properties of a Bioinspired 2-Line Ferrihydrite: A Silicon-Doped, Nanometric, and Amorphous Iron Oxyhydroxide.

Inspired by a nanometric iron-based oxide material of bacterial origin, silicon (Si)-doped iron oxyhydroxide nanoparticles or 2-line ferrihydrites (2Fhs) were prepared and their lithium (Li) storage properties were investigated. The structures of the Si-doped 2Fhs strongly depended on the Si molar ratio [x = Si/(Fe + Si)] whose long-range atomic ordering gradually vanished as the Si molar ratio increased, with a structural change from nanocrystalline to amorphous at x = 0.30. The most striking properties were observed for the sample with x = 0.30. Over the voltage range of 1.5-4.0 V at a current rate of 500 mA/g, this material exhibited a relatively high reversible capacity of ∼100 mAh/g, which was four times greater than that of the Si-free 2Fh and indicated a good rate capability and cyclability. The large capacity and good rate and cycle performances are presumably because of the amorphous structure and the strong and stabilizing covalent Si-O bonds, respectively. The minor amount of Si(4+) in the structure of the iron oxyhydroxides is considered to improve the electrochemical properties. Use of more appropriate doping elements and fabrication of more appropriate nanostructures could drastically improve the Li storage properties of the developed bioinspired material.

Critical metals in manganese nodules from the Cook Islands EEZ, abundances and distributions

The Cook Islands (CIs) Exclusive Economic Zone (EEZ) encompasses 1,977,000km2 and includes the Penrhyn and Samoa basins abyssal plains where manganese nodules flourish due to the availability of prolific nucleus material, slow sedimentation rates, and strong bottom currents. A group of CIs nodules was analyzed for mineralogical and chemical composition, which include many critical metals not before analyzed for CIs nodules. These nodules have varying sizes and nuclei material; however all are composed predominantly of δ-MnO2 and X-ray amorphous iron oxyhydroxide. The mineralogy, Fe/Mn ratios, rare earth element contents, and slow growth rates (mean 1.9mm/106years) reflect formation primarily by hydrogenetic precipitation. The paucity of diagenetic input can be explained by low primary productivity at the surface and resultant low organic matter content in seafloor sediment, producing oxic seafloor and sub-seafloor environments. The nodules contain high mean contents of Co (0.41%), Ni (0.38%), Ti (1.20%), and total rare earth elements plus yttrium (REY; 0.167%), and also high contents of Mo, Nb, V, W, and Zr.Compiled data from a series of four cruises by the Japan International Cooperation Agency and the Mining agency of Japan from 1985 to 2000 were used to generate a map that defines the statistical distribution of nodule abundance throughout the EEZ, except the Manihiki Plateau. The abundance distribution map shows a belt of high nodule abundance (19–45kg/m2) that starts in the southeast corner of the EEZ, runs northwest, and also bifurcates into a SW trending branch. Small, isolated areas contain abundances of nodules of up to 58kg/m2. Six ~20,000km2 areas of particularly high abundance were chosen to represent potential exploration areas, and maps for metal concentration were generated to visualize metal distribution and to extrapolate estimated metal tonnages within the six sites and the EEZ as a whole. Grades for Mn, Cu, and Ni are low in CIs nodules in areas of high abundance; however, Ti, Co, and REY show high contents where nodule abundances are high. Of the six areas identified to represent a range of metal contents, one at the northern end of the N-S abundance main belt optimizes the most metals and would yield the highest dry metric tons for Mn (61,002,292), Ni (1,247,834), Mo (186,166), V (356,247), W (30,215), and Zr (195,323). When compared with the Clarion–Clipperton Zone, the CIs nodules show higher nodule abundances (>25kg/m2 over ~123,844km2), and are more enriched in the green-tech, high-tech, and energy metals Co, Ti, Te, Nb, REY, Pt, and Zr. The CIs EEZ shows a significant resource potential for these critical metals due to their high prices, high demand, and the high nodule abundance, which will allow for a smaller footprint for a 20-year mine site and therefore smaller environmental impact.

Recovery of Gold and Silver and Removal of Copper, Zinc and Lead Ions in Pregnant and Barren Cyanide Solutions

Over the past decade the concern about toxic metals in freshwater has increased. Environmental laws such as the Clean Water Act have forced industries that produce metal containing wastewater to treat their wastewater prior to discharge. The purpose of this study was to investigate the use of a novel method for the minimization of heavy metals in the wastewater from the mining industry. A very promising electrochemical treatment technique that does not require chemical additions is electrocoagulation (EC) and sulphide precipitation. The present study has been done for the recovery of gold and silver contained in pregnant solution from the cyanidation process using the electrocoagulation technology with iron electrodes; that is a developed alternative technology for the Merril-Crowe process. The average gold and silver content in pregnant solution was 4.27 and 283 ppm respectively and the recoveries were 92% for gold and 95% for silver, with optimum operating parameters of pH 10, residence time of 20 minutes and addition of sodium chloride of 4 gr/L. The results of precipitation process show that the elimination of lead, zinc, cooper and iron ions from the barren solution was successful, with optimum operating parameters of pH 3 and residence time of 15 minutes, and the recoveries were 99% of these ions. Finally the characterization of the solid products of gold and silver formed during the EC process with Scanning Electronic Microscope was performed. Results suggest that magnetite particles and amorphous iron oxyhydroxides (lepidocrocite) were present.

High-intensity ultrasonication as a way to prepare graphene/amorphous iron oxyhydroxide hybrid electrode with high capacity in lithium battery

The preparation of graphene/iron oxyhydroxide hybrid electrode material with very homogeneous distribution and close contact of graphene and amorphous iron oxyhydroxide nanoparticles has been achieved by using high-intensity ultrasonication. Due to the negative charge of the graphene surface, iron ions are attracted toward the surface of dispersed graphene, according to the zeta potential measurements. The anchoring of the FeO(OH) particles to the graphene layers has been revealed by using mainly TEM, XPS and EPR. TEM observations show that the size of the iron oxide particles is about 4nm. The ultrasonication treatment is the key parameter to achieve small particle size in these graphene/iron oxyhydroxide hybrid materials. The electrochemical behavior of composite graphene/amorphous iron oxyhydroxide prepared by using high-intensity ultrasonication is outstanding in terms of gravimetric capacity and cycling stability, particularly when metallic foam is used as both the substrate and current collector. The XRD-amorphous character of iron oxyhydroxide in the hybrid electrode material and the small particle size contribute to achieve the improved electrochemical performance.

Speciation and multivariable analyses of geogenic cadmium in soils at Le Gurnigel, Swiss Jura Mountains

Mineralogical and geochemical analyses were performed on six closely spaced (within a perimeter of 300m) soil profiles, which are naturally enriched in cadmium (Cd) at Le Gurnigel, Swiss Jura Mountains. The soils consist of Cambisols and Cambic Luvisols, the latter including an important allochthonous, aeolian fraction (loess). All soils are associated with bedrock composed of middle Jurassic (Bajocian) oolithic carbonate — a lithology, which has been identified as a source of geogenic Cd. Cd concentrations generally increase down the analyzed soil profiles, showing maxima (up to 16.3mg·kg−1) near the soil–bedrock interface. A sequential extraction analysis suggests that most Cd resides in the carbonate and organic fractions of topsoils, whereas the amorphous iron and manganese oxyhydroxide fraction become the most important Cd-bearing phase in the middle and deeper parts of the soils. A principal component analysis shows that Cd, Zn and Cr are positively correlated with comparable distributions in the soil profiles suggesting a common bearing phase such as Fe oxyhydroxides for these three elements. A complex transfer pattern of Cd is proposed for the analyzed soil profiles, which starts with the release of Cd from the underlying bedrock, and its transfer into oxide, hydroxide, carbonate and organic phases. Additionally, the lateral advection of Cd-rich soils on top of these soils adds Cd to them, which is transferred from the topsoil towards the deeper horizons by biological and pedological processes. The amount of readily exchangeable and therefore potentially bioavailable Cd is low in these soils (on average 0.2mg·kg−1), provided that the pH remains above 5. Under stronger acidic conditions the concentration of bioavailable Cd may increase in the topsoils of thin Cambisols (3.0mg·kg−1) and Cambic Luvisols (1.2mg·kg−1). Under stronger acidic (pH<4.5) and oxidizing conditions, Cd bound to organic matter may be mobilized in addition, and the bioavailability of Cd would range between 3.3 and 5.4mg·kg−1 in Cambisols and reach up to 1.7mg·kg−1 in Cambic Luvisols.

Electrochemically Induced Oxidative Precipitation of Fe(II) for As(III) Oxidation and Removal in Synthetic Groundwater

Mobilization of Arsenic in groundwater is primarily induced by reductive dissolution of As-rich Fe(III) oxyhydroxides under anoxic conditions. Creating a well-controlled artificial environment that favors oxidative precipitation of Fe(II) and subsequent oxidation and uptake of aqueous As can serve as a remediation strategy. We reported a proof of concept study of a novel iron-based dual anode system for As(III) oxidation and removal in synthetic groundwater. An iron anode was used to produce Fe(II) under iron-deficient conditions, and another inert anode was used to generate O2 for oxidative precipitation of Fe(II). For 30 min's treatment, 6.67 μM (500 μg/L) of As(III) was completely oxidized and removed from the solution during the oxidative precipitation process when a total current of 60 mA was equally partitioned between the two anodes. The current on the inert anode determined the rate of O2 generation and was linearly related to the rates of Fe(II) oxidation and of As oxidation and removal, suggesting that the process could be manipulated electrochemically. The composition of Fe precipitates transformed from carbonate green rust to amorphous iron oxyhydroxide as the inert anode current increased. A conceptual model was proposed for the in situ application of the electrochemically induced oxidative precipitation process for As(III) remediation.

Removal of phosphorus from wastewaters using ferrous salts – A pilot scale membrane bioreactor study

A pilot scale membrane bioreactor (3.7 m3/day capacity), configured for alternate point ferrous sulphate addition, was evaluated in a fourteen month trial to comply with an effluent discharge requirement of less than 0.15 mg-P/L at the 50th percentile and less than 0.30 mg-P/L at the 90th percentile. Ferrous sulphate was added at a molar ratio (Fe(II):PO4) of 2.99 in the filtration chamber for 85 days and 2.60 in the primary anoxic zone for 111 days. Addition of ferrous salts to the anoxic zone achieved a final effluent phosphorous concentration (mg-P/L) of <0.05 (29%), <0.15 (77%) and <0.30 (95%), while addition of ferrous salts in the filtration zone achieved <0.05 (18%), <0.15 (63%) and <0.30 (95%). Analysis of the concentration of iron(II) in the supernatant indicated that phosphorus was mainly removed via adsorption to amorphous iron oxyhydroxides particles in both dosing scenarios. However, analysis of residence time distribution (RTD) data of the reactor indicated that severe short-circuiting from the dosing point to the membrane outlet could occur when the ferrous salts were added to the membrane zone while the reactor behaved close to a completely mixed reactor when dosing to the primary anoxic zone, resulting in improved phosphorus removal. The addition of ferrous salt was also found to delay the onset of severe increase in trans-membrane pressure as a result of the removal of macro-molecules. However, detailed analysis of the form and concentration of iron species in the supernatant and permeate indicated that the presence of fine iron particles resulted in a higher fouling rate when Fe(II) was added to the membrane zone rather than the primary anoxic zone and could cause more severe irreversible fouling in long-term operation.

Key parameters controlling arsenic dynamics in coastal sediments: An analytical and modeling approach

The coupling of analytical tools and modeling approaches allowed the identification of the key parameters controlling arsenic (As) dynamics in anoxic marine sediments. Eh, pH, dissolved/particulate As, Fe, Mn, S, P, and organic/inorganic C were determined in sedimentary porewaters and in the sediments itself at 3 geochemically contrasting stations and at different seasons, in the heavily contaminated, semi-closed Toulon bay (NW Mediterranean Sea). Elemental analysis and selective extractions allowed the identification of As distribution in the studied sediments. Organic matter (OM) quality was characterized by fluorescence measurements. A 1D steady-state modeling (PROFILE) was used to estimate depth reaction intervals and reaction rates by fitting the measured element profiles. Thermodynamic simulation (PHREEQC) was also performed to calculate the chemical speciation and simulate the dissolved/particulate As fractionation. This work demonstrated the consistency of the additive speciation/adsorption modeling to simulate As profiles in marine porewaters while considering the different sedimentary phases and the species that could potentially act as competitors (e.g. CO32−, PO43−, …). By taking into account the presence of OM and appropriately adjusting its reactivity toward As, the simulated dissolved As profiles consistently fitted the measured one. This As–OM reactivity is related to the organic matter quality, determined by fluorescence measurements.In all samples, As dynamics in the subsurface sediments was shown to be strongly linked to the iron cycling, especially to amorphous iron oxyhydroxide, through diagenesis reactions. The Fe/As ratio involved in the diagenesis processes (determined both experimentally and from the PHREEQC simulation of the dissolved As profiles without organic matter interaction) was close to ~210. Higher ratio was predicted by the simulation when considering the As–organic matter interaction. A similar observation was found for other mineral phases in sulfidic sediments (sulfide, clays …). The decreased affinity of As for inorganic minerals could be due to a competition between organic/inorganic phases or to a ternary arsenic–OM–inorganic phase association, as recently suggested in the literature. Trials provided OM–As stability constant values in these samples, ranging (in log10) from 2 to 3.2 for particulate OM and from 2 to 4.7 for dissolved OM. Therefore, organic matter was clearly shown to play a role in As dynamics in sediments or porewater (and thus potentially in other natural samples), even in the presence of inorganic phases. OM, thus, should be added in databases and taken into account in future simulations.

Characterization of biogenic iron oxides collected by the newly designed liquid culture method using diffusion chambers

We designed a new culture method for neutrophilic iron-oxidizing bacteria using liquid medium (i) to study the formation and mineralogical characteristics of biogenic iron oxides (BIOS) and (ii) to apply BIOS to various scientific and engineering applications. An iron-oxidizing bacterium, Mariprofundus ferrooxydans PV-1(T) (ATCC, BAA-1020), was cultured using a set of diffusion chambers to prepare a broad anoxic-oxic interface, upon which BIOS formation is typically observed in natural environments. Iron oxide precipitates were generated in parallel with bacterial growth. A scanning electron microscopy analysis indicated that the morphological features of the iron oxide precipitates in the medium (in vitro BIOS) were similar to those of BIOS collected from natural deep-sea hydrothermal environments in the Northwest Eifuku Seamount field in the northern Mariana Arc (in situ BIOS). Further chemical speciation of both the in vitro and in situ BIOS was examined with X-ray absorption fine structure (XAFS). A bulk XAFS analysis showed that the minerals in both BIOS were mainly ferrihydrite and oligomeric stages of amorphous iron oxyhydroxides with edge-sharing octahedral linkages. The amount of in vitro BIOS produced with the diffusion-chamber method was greater than those produced previously with other culture methods, such as gel-stabilized gradient and batch liquid culture methods. The larger yields of BIOS produced with the new culture method will allow us to clarify in the future the mineralization mechanisms during bacterial growth and to examine the physicochemical properties of BIOS, such as their adsorption to and coprecipitation with various elements and substances.

Thermodynamic Study for Arsenic Removal from Freshwater by Using Electrocoagulation Process

Insert Industrial treatment of mineral-processing and non-ferrous metal-smelting acid wastewater effluents is becoming an enormous worldwide problem. In Mexico, heavy metalscontaminated natural waters, including freshwater, surface water and ground water, are a significant problem as some of these compounds are known as toxic, mutagenic, and carcinogenic. A very promising electrochemical treatment technique that does not require chemical additions to remove arsenic is electrocoagulation (EC) with air injection. The proposed electrochemical process is efficient because used low cost iron electrodes and promising in industrial application. Theoretical the purpose of this research was to investigate the thermodynamic of arsenic adsorption on iron species using the Langmuir’s Isotherm. Also, thermodynamic parameters such as , and were calculated and the adsorption process was found to be exothermic and spontaneous. X-ray Diffraction and Scanning Electron Microscopy, were used to characterize the solid products formed during EC. The results of this study suggest that magnetite particles and amorphous iron oxyhydroxides are present in the examined EC products and this study indicate that arsenic can be successfully adsorbed on iron species by electrocoagulation process. Field pilot-scale study demonstrated the removal of As(III)/As(V) with an efficiency of more than 99% from both wastewater and wells.

Recovery of Silver from Cyanide Solutions Using Electrochemical Process Like Alternative for Merrill-Crowe Process

The conventional processes for recovery of silver from cyanide leach solutions are the carbon adsorption, the Merrill-Crowe zinc dust cementation, the Ion Exchange, and Solvent Extraction processes; among other available options for recovery of precious metals from cyanide solutions, Electrocoagulation (EC) is a very promising electrochemical process that does not require high concentrations of silver in cyanide solutions to yield excellent results and neither pretreatment of cyanide solutions like Merrill-Crowe process (deoxygenating and clarification). The present study has been done for the recovery of silver contained in pregnant solution from the cyanidation process using the electrocoagulation technology with iron electrodes, and therefore develops an alternative technology for Merril-Crowe process. The average silver content in pregnant solution was of 52 ppm, recovery was obtained of 99% of silver, with this optimum operating parameters, pH = 8, residence time = 20 minutes and conductivity by addition of sodium chloride = 4 grs/L. Finally the characterization of the solid products formed during the EC process with X-ray Diffraction and Scanning Electronic Microscope was performed, results suggest that magnetite particles and amorphous iron oxyhydroxides are present (Lepidocrocite).

Amorphous Iron Oxyhydroxide Nanosheets: Synthesis, Li Storage, and Conversion Reaction Kinetics

We present a facile approach to synthesize amorphous iron oxyhydroxide nanosheet from the surfactant-assisted oxidation of iron sulfide nanosheet. The amorphous iron oxyhydroxide nanosheet is porous and has a high surface area of 223 m2 g–1. The lithium storage properties of the amorphous iron oxyhydroxide are characterized: it is a conversion-reaction electrode material, and it demonstrates superior rate capabilities (e.g., discharge capacities as high as 642 mAh g–1 are delivered at a current density of 2 C). The impedance spectroscopy analysis identifies a RC series subcircuit originated by the conversion-reaction process. Investigation of the conversion-reaction kinetics through the RC subcircuit time constant reproduces the hysteresis in the discharge/charge voltage profile. Hysteresis is then connected to underlying thermodynamics of the conversion reaction rather than to a kinetic limitation.