Two-line Ferrihydrite Research Articles

New Iron(III)-Containing Composite of Salinomycinic Acid with Antitumor Activity—Synthesis and Characterization

In this study we demonstrated for the first time synthetic procedures for composites of salinomycin (SalH) and two-line ferrihydrite. The products were characterized by various methods such as elemental analysis, attenuated total reflectance–Fourier-transform spectroscopy (ATR-FTIR), electron paramagnetic resonance spectroscopy (EPR), powder X-ray diffraction analysis (XRD), electrospray-ionization mass spectrometry (ESI-MS), thermogravimetric analysis with differential thermal analysis (DTA) and mass spectrometry (TG-DTA/MS). The EPR spectra of the isolated compounds consisted of signals associated with both isolated Fe3+ ions and magnetically coupled Fe3+ ions. Powder XRD analyses of the isolated products showed two intense and broad peaks at 9° and 15° 2Θ, corresponding to salinomycinic acid. Broad peaks with very low intensity around 35°, assigned to two-line ferrihydrite, were also registered. Based on the experimental results, we concluded that salinomycin sodium reacted with Fe(III) chloride to form composites consisting of two-line ferrihydrite and salinomycinic acid. One of the composites exerted pronounced antitumor activity in the sub-micromolar concentration range against human cervical cancer (HeLa), non-small-cell lung cancer (A549), colon cancer (SW480), and ovarian teratocarcinoma (CH1/PA1) cells.

Microbial removal of uranyl from aqueous solution by Leifsonia sp. in the presence of different forms of iron oxides

Immobilization of uranyl by indigenous microorganisms has been proposed as an economic and clean in-situ approach for removal of uranium, but the potential mechanisms of the process and the stability of precipitated uranium in the presence of widespread Fe(III) (hydr)oxides remain elusive. The potential of iron to serve as a reductant and/or an oxidant of uranium indicates that bioemediation strategies which mainly rely on the reduction of highly soluble U(VI) to poorly soluble U(IV) minerals to retard uranium transport in groundwater may be enhanced or hindered under different environmental conditions. This study purposes to determine the effect of ubiquitous Fe(III) (hydr)oxides (two-line ferrihydrite, hematite and goethite) on the removal of U(VI) by Leifsonia sp. isolated from an acidic tailings pond in China. The removal mechanism was elucidated via SEM-EDS, XPS and Mössbauer. The results show that the removal of U(VI) was retarded by Fe(III) (hydr)oxides when the initial concentration of U(VI) was 10 mg/L, pH was 6, temperature was 25 °C. Particularly, the retardatory effect of hematite on U(VI) removal was blindingly obvious. Also, it is worth noting that the U(VI) in the precipitate slow-released in the Fe(III) (hydrodr) oxide treatment groups, accompanied by an increase in Fe(II) concentration. SEM-EDS results demonstrated that the ferrihydrite converted to goethite may be the reason for U(VI) release in the process of 15 days culture. Mössbauer spectra fitting results further imply that the metastable iron oxides were transformed into stable Fe3O4 state. XPS measurements results showed that uranium product is most likely a mixture of Iron-U(IV) and Iron-U(VI), which indicated that the hexavalent uranium was converted into tetravalent uranium. These observations imply that the stability of the uranium in groundwater may be impacted on the prevailing environmental conditions, especially the solid-phase Fe(III) (hydr)oxide in groundwater or sediment.

Effects of carbonate on ferrihydrite transformation in alkaline media.

Alkaline media widely exist in natural and engineered systems such as semiarid/arid areas, radioactive waste sites, and mine tailings. In these settings, the commonly occurring iron (oxyhydr)oxides differed in their ability to influence the fate of nutrients and contaminants. Due to the substantially increased atmospheric carbon dioxide (CO2) concentration, carbonate stands to increase in these media. However, how increasing carbonate affects the transformation of poorly crystalline iron (oxyhydr)oxides (e.g., two-line ferrihydrite) under alkaline conditions still remains unclear. Here, kinetics of ferrihydrite transformation were evaluated at pH ∼10 as a function of [carbonate] = 0-286 mM using synchrotron-based X-ray and vibrational spectroscopic techniques. The results showed that carbonate slowed down ferrihydrite transformation slightly and suppressed goethite formation, but promoted hematite formation regardless of its concentration. At low carbonate concentration (11.42 mM), the effect of carbonate on product formation was obvious due to the weak inner-sphere complex; however, at high carbonate concentration (80-286 mM), the effect was retarded because of the adsorption equilibrium of carbonate as well as the initial carbonate adsorption followed by desorption. Moreover, carbonate modified the morphology of hematite from rhombic to ellipsoidal to honeycomb and goethite from rod-like to needle-like to spindle-like due to the inner-sphere adsorption-desorption of carbonate and adsorption of hydroxyl ions on reactive sites of iron (oxyhydr)oxides in alkaline media. The results suggest that the concurrently increasing carbonate with enhanced atmospheric CO2 could control the transformation and occurrence of iron (oxyhydr)oxides in natural and engineered environments and have important implications for the biogeochemical cycles of iron and carbon.

Mineralogical characteristics of root iron plaque and its functional mechanism for regulating Cr phytoextraction of hyperaccumulator Leersia hexandra Swartz

Leersia hexandra Swartz (L. hexandra) is a promising hyperaccumulator for Cr pollution remediation, but whether its Cr phytoextraction is subject to the root surface-attached iron plaque (IP) remains unclear. In this research, the natural and artificial IPs were proven to be comprised of small amounts of exchangeable Fe as well as carbonate Fe, and dominantly Fe minerals involving amorphous two-line ferrihydrite (Fh), poorly crystalline lepidocrocite (Le) and highly crystalline goethite (Go). The Fe content in the artificial IPs augmented with increasing induced Fe(II) concentration, and the 50 mg/L Fe(II) led to the identical Fe content and different component proportions of artificial IP (Fe50) and natural IP. Fh was consisted of highly aggregated nanoparticles, and the aging of Fh caused its phase conversion to rod-like Le and Go. The Cr(VI) adsorption results of Fe minerals corroborated the coordination of Cr(VI) onto the Fh surface and the significantly greater equilibrium Cr(VI) adsorption amount of Fh over Le and Go. The greatest Cr(VI) reduction capacity of Fh among three Fe minerals was found to be related to its most abundant surface-adsorbed Fe(II) content. The results of hydroponic experiment of L. hexandra showed that the presence of IP facilitated the Cr(VI) removal by L. hexandra during the cultivation period of 10–45 days, and consequently, compared to the Fe0 group (without IP), around 60% of increase in the Cr accumulation of shoots was achieved by Fe50 group. The findings of this work are conductive to furthering our understanding of IP-regulated Cr phytoextraction of L. hexandra.

Coagulation removal of nickel (II) ions by ferric chloride: Efficiency and mechanism.

Removal of heavy metal ions, in particular, divalent nickel ions from natural and wastewater, is of great importance for the environment. Nickel (II) ions are very toxic and provoke many diseases. The purpose of this work was to study the possibility of removing toxic nickel (II) ions from polluted water using an iron (III) chloride (FeCl3) coagulant. It is shown that the removal of nickel ions from aqueous solution by iron (III) hydroxide precipitate formed during the coagulation process at pH7 and 8 is described with satisfactory accuracy by the classical adsorption isotherms of Freundlich, Langmuir, and Dubinin-Radushkevich. The studies performed with the use of X-ray powder diffraction and thermal analyses, IR, Raman, and Mössbauer spectroscopy have shown that the uptake of nickel ions by iron (III) hydroxide precipitate is due to simple physical adsorption and is not accompanied by the formation of mixed iron and nickel compounds. No alloying of the formed iron (III) hydroxide precipitate with nickel ions takes place either. The formed iron (III) hydroxide precipitate is a two-line ferrihydrite having the gross formula Fe2 O3 × 3H2 O. Its sorption capacity for nickel ions is almost an order of magnitude higher than that of some mineral and carbon sorbents, and at pH7 and 8, it is 60.5 and 141.9mg/g, respectively. PRACTITIONER POINTS: Coagulant FeCl3 cleans contaminated solutions from Ni(II) ions. Iron (III) hydroxide precipitated at pH 7 and 8 is a two-line ferrihydrite Fe2 O3 × 3H2 O. Removing of Ni(II) ions is described by classical adsorption isotherms. The most complete removal of Ni(II) ions occurs at pH = 8.

Adsorption Characteristics of Dimethylated Arsenicals on Iron Oxide-Modified Rice Husk Biochar.

In this study, the adsorption characteristics of dimethylated arsenicals to rice husk biochar (BC) and Fe/biochar composite (FeBC) were assessed through isothermal adsorption experiments and X-ray absorption spectroscopy analysis. The maximal adsorption capacities (qm) of inorganic arsenate, calculated using the Langmuir isotherm equation, were 1.28 and 6.32 mg/g for BC and FeBC, respectively. Moreover, dimethylated arsenicals did not adsorb to BC at all, and in the case of FeBC, qm values of dimethylarsinic acid (DMA(V)), dimethylmonothioarsinic acid (DMMTA(V)), and dimethyldithioarsinic acid (DMDTA(V)) were calculated to be 7.08, 0.43, and 0.28 mg/g, respectively. This was due to the formation of iron oxide (i.e., two-line ferrihydrite) on the surface of BC. Linear combination fitting using As K-edge X-ray absorption near edge structure spectra confirmed that all chemical forms of dimethylated arsenicals adsorbed on the two-line ferrihydrite were DMA(V). Thus, FeBC could retain highly mobile and toxic arsenicals such as DMMTA(V) and DMDTA(V)) in the environment, and transform them into DMA(V) with relatively low toxicity.

Hematite Crystallization from a Two-Line Ferrihydrite Suspension

Rational design and synthesis of materials, determination of environmental conditions at the time of mineral formation, and definition of mechanisms in biomineralizing systems all require an understanding of the effect of multiple factors on modulating crystallization pathways. In this study, we investigate the influence of temperature, oxalate additive, aging time, and addition of seed crystals on hematite (α-Fe2O3, Hm) crystallization from a two-line ferrihydrite (Fe2O3·xH2O, Fh) suspension. We also investigate the effect of temperature on the aging of spindle-shaped Hm mesocrystals, which we synthesize through the addition of sodium oxalate. The results show that Hm mesocrystals form in a temperature window of 45 °C−130 °C. Temperatures ≥ 140 °C favor formation of rhombohedral Hm, suggesting classical monomer-by-monomer growth dominates, whereas crystallization by particle attachment (CPA) is dominant between 45 and 90 °C, while the two processes compete in the intermediate temperature range. Aging of mesocrystals in the original solution at 90 °C or 180 °C leads to a slow morphological evolution towards rhombohedral crystals due to Ostwald ripening. Finally, by utilizing rhombohedral Hm and rod-shaped goethite as substrates on which to assemble the mesocrystals, we demonstrate formation of complex heterogeneous structures.

Hematite-goethite ratios at pH 2–13 and 25–170 °C: A time-resolved synchrotron X-ray diffraction study

Iron (oxyhydr)oxides are sensitive indicators of pH, Eh, temperature, microbial activity, and climate conditions in the Critical Zone. The most ubiquitous and environmentally significant iron oxides in most soils are two-line ferrihydrite, goethite, and hematite. Here we present a comprehensive study of the transformation of two-line ferrihydrite to hematite and goethite over a wide range of temperature (25–170 °C) and initial pH (2−13) conditions through ex situ batch and in situ synchrotron X-ray diffraction (XRD) experiments.Within the high time resolution of our experiments, goethite and hematite nucleated nearly simultaneously from ferrihydrite in nearly equal concentrations by mass. Hematite increased in abundance relative to goethite until a steady-state ratio was achieved, and both phases ceased growth on the depletion of ferrihydrite. Higher temperatures and lower water activities favored hematite formation at all pH values studied. In both our batch and our time-resolved, angle-dispersive synchrotron X-ray diffraction experiments, hematite was favored relative to goethite at an initial pH of 3 to 5. In contrast, goethite preferentially formed in neutral (initial pH 7–8) and highly alkaline conditions (initial pH ≥ 11). Surprisingly, mildly alkaline conditions (initial pH 9–11) induced the precipitation of a highly Fe-deficient (Feocc = ~0.80–0.90) variety of hematite known as “hydrohematite” in greater concentrations than goethite. Our results are useful for the application of hematite-goethite ratios as paleoclimate proxies for soil and sediment systems with low pH buffering capacities.

Interference of Phosphate in Adsorption of Arsenate and Arsenite over Confined Metastable Two-Line Ferrihydrite and Magnetite

Contamination of groundwater by arsenic (As(III/V)) is a serious global issue, and phosphate (P(V)) is known to be the biggest interference in adsorption-based remediation methods. The present study is focused on understanding the interaction between phosphate and iron oxides/oxy-hydroxides with two well-known classes of potential adsorbents in the important pH range of 5–9 and the effect of such interactions on the uptake of arsenite and arsenate. Spectroscopic studies such as X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy were used to understand the binding of various oxyanions of phosphorous and arsenic with the iron oxides/oxy-hydroxides, exploring the core levels of P 2p and Fe 2p. Materials used for adsorption experiments were magnetite (MAG) and a nanocomposite, confined metastable two-line ferrihydrite (CM2LF); CM2LF is used for arsenic remediation in the affected states in India. Further, we studied the interference of P(V) in As(III/V) adsorption. The kinetics of adsorption was quantified using ion chromatography (IC), where P(V) alone followed a pseudo-second-order model. In the case of mixed solutions, namely, APmix1 (P(V) + As(III)) and APmix2 (P(V) + As(V)), kinetics data suggested that P(V) or As(III/V) oxyanions partially follow the pseudo-second-order model. Results also confirmed that CM2LF performed better than magnetite (MAG) for As(III/V) uptake in the presence of P(V). As(III) and As(V) species are more competitive than P(V) at neutral pH. A model for the adsorption of P(V) species in water on ferrihydrite particles was developed using density functional theory (DFT). This accounted for phosphate complexation at various pH values. The study is highly useful in developing an affordable solution for sustainable arsenic remediation. Various aspects of sustainability are discussed.

Synthesis and Characterization of Nano Fe and Mn (hydr)oxides to Be Used as Natural Sorbents and Micronutrient Fertilizers

Fe and Mn (hydr)oxides are widely used as contaminant sorbents in water/wastewater systems but their potential use as micronutrient fertilizers is still poorly known. In this research, four nano-metal (hydr)oxides (amorphous Mn oxide (AMO), Fe-Mn binary oxide (FMBO), two-line ferrihydrite (2L-Fh) and goethite) were successfully synthesized and completely characterized (infrared and Mössbauer spectroscopy, X-ray diffraction particle size, specific surface area, point of zero charge). AMO, FMBO and 2L-Fh were introduced to interact with AgNO3 (20.0 µM) and TlNO3 (100.0 µM) diluted solutions for three days to check their potential capability as potential Ag+ and Tl+ adsorbents. AMO and FMBO (4% w/w) were tested as nanofertilizers by arranging a hydroponic bioassay for 35 days on white lupin culture as a Mn-hyperaccumulator plant model. AMO structure was identified as an amorphous mixture of Mn oxides while FMBO was an Fe dopped birnessite. Both materials were efficient in extracting Ag+ and Tl+ although large Mn concentration was released from FMBO to the solutions. AMO and FMBO promoted Fe and Mn nutrition in plants. Synthetic iron chelate (Fe-EDDHA), present in the nutrient dissolution, could be adsorbed onto AMO surface by producing Fe and Mn accumulation in roots and increasing Mn uptake rate without toxicity symptoms. Therefore, AMO and FMBO not only demonstrated their efficiency as adsorbents, but also displayed they would be promising nanomaterials as micronutrient fertilizers.

The structure of natural biogenic iron (oxyhydr)oxides formed in circumneutral pH environments

Biogenic iron (Fe) (oxyhydr)oxides (BIOS) partially control the cycling of organic matter, nutrients, and pollutants in soils and water via sorption and redox reactions. Although recent studies have shown that the structure of BIOS resembles that of two-line ferrihydrite (2LFh), we lack detailed knowledge of the BIOS local coordination environment and structure required to understand the drivers of BIOS reactivity in redox active environments. Therefore, we used a combination of microscopy, scattering, and spectroscopic methods to elucidate the structure of BIOS sampled from a groundwater seep in North Carolina and compare them to 2LFh. We also simulated the effects of wet-dry cycles by varying sample preparation (e.g., freezing, flash freezing with freeze drying, freezing with freeze drying and oven drying). In general, the results show that both the long- and short-range ordering in BIOS are structurally distinct and notably more disordered than 2LFh. Our structure analysis, which utilized Fe K-edge X-ray absorption spectroscopy, Mössbauer spectroscopy, X-ray diffraction, and pair distribution function analyses, showed that the BIOS samples were more poorly ordered than 2LFh and intimately mixed with organic matter. Furthermore, pair distribution function analyses resulted in coherent scattering domains for the BIOS samples ranging from 12–18 Å, smaller than those of 2LFh (21–27 Å), consistent with reduced ordering. Additionally, Fe L-edge XAS indicated that the local coordination environment of 2LFh samples consisted of minor amounts of tetrahedral Fe(III), whereas BIOS were dominated by octahedral Fe(III), consistent with depletion of the sites due to small domain size and incorporation of impurities (e.g., organic C, Al, Si, P). Within sample sets, the frozen freeze dried and oven dried sample preparation increased the crystallinity of the 2LFh samples when compared to the frozen treatment, whereas the BIOS samples remained more poorly crystalline under all sample preparations. This research shows that BIOS formed in circumneutral pH waters are poorly ordered and more environmentally stable than 2LFh.

Shaping Magnetite by Hydroxyl Group Numbers of Small Molecules.

Despite numerous reports on magnetite formation with the assistance of various additives, the role of hydroxyl group (-OH) numbers in small polyol molecules has not yet been understood well. We selected small molecules containing different -OH numbers, such as ethanol, ethylene glycol, propanetriol, butanetetrol, pentitol, hexanehexol, and cyclohexanehexol, as additives in coprecipitation. By increasing the -OH number in these small polyol molecules, the formation of crystallization was slowed, and the size and shape of magnetite were regulated as well possibly due to the changed complexation strength and the stability of the precursor. The increase in temperature and the Fe2+/Fe3+ ratio can reduce the complexation strength. The nucleation and growth of magnetite proceed possibly through the aggregation of polyol-stabilized amorphous complexes and two-line ferrihydrite with low crystallinity based on the -OH numbers, suggesting a nonclassical pathway. The as-prepared magnetite showed a r2/r1 ratio after in vitro MRI measurement as follows: Fe3O4@He-6OH rod < Fe3O4@Pr-3OH sheet < Fe3O4@Pe-5OH cube. The Fe3O4@He-6OH rod and Fe3O4@Pr-3OH sheet displayed T1-T2 dual modal contrast ability, while the Fe3O4@Pe-5OH cube can be T2-dominated. This research provides a simple but an essential approach for designing MRI contrast agents.

Thermodynamic Impact of Mineral Surfaces on Amino Acid Polymerization: Aspartate Dimerization on Two-Line Ferrihydrite, Anatase, and γ-Alumina

The presence of amino acids in diverse extraterrestrial materials has suggested that amino acids are widespread in our solar system, serving as a common class of components for the chemical evolution of life. However, there are a limited number of parameters available for modeling amino acid polymerization at mineral–water interfaces, although the interfacial conditions inevitably exist on astronomical bodies with surface liquid water. Here, we present a set of extended triple-layer model parameters for aspartate (Asp) and aspartyl-aspartate (AspAsp) adsorptions on two-line ferrihydrite, anatase, and γ-alumina determined based on the experimental adsorption data. By combining the parameters with the reported thermodynamic constants for amino acid polymerization in water, we computationally demonstrate how these minerals impact the AspAsp/Asp equilibrium over a wide range of environmental conditions. It was predicted, for example, that two-line ferrihydrite strongly promotes Asp dimerization, leading to the AspAsp/Asp ratio in the adsorbed state up to 41% even from a low Asp concentration (0.1 mM) at pH 4, which is approximately 5 × 107 times higher than that attainable without mineral (8.5 × 10−6%). Our exemplified approach enables us to screen wide environmental settings for abiotic peptide synthesis from a thermodynamic perspective, thereby narrowing down the geochemical situations to be explored for life’s origin on Earth and Earth-like habitable bodies.

Exploring passivation-based treatments for jarosite from an acid sulfate soil

Jarosite (KFe3(SO4)2(OH)6) is a common secondary reaction product of iron sulfide oxidation and can pose a considerable risk to soil and water quality. The overarching objective of this study was to explore the possibility of employing passivation-based treatments to mitigate the risks associated with jarosite-rich materials by investigating the alteration of pedogenic jarosite to a relatively benign, sparingly-soluble mineral such as goethite or strengite. Samples of jarositic phytotubules (from an acid sulfate soil with sulfuric material) were treated with: (i) alkaline solutions with a view to produce ferric (oxyhydr)oxide; (ii) phosphate solutions with a view to produce ferric phosphate; and (iii) alkaline solutions, followed by phosphate solutions, with a view to produce ferric phosphate. These treatments were conducted at both ambient (25°C) and elevated temperatures (80°C) to explore the effects of temperature on the extent of jarosite alteration. Under alkaline conditions, jarosite readily decomposed to yield poorly-crystalline ferric (oxyhydr)oxides (e.g. two-line ferrihydrite), regardless of temperature. These ferric (oxyhydr)oxides readily reacted with phosphoric acid to yield ferric phosphate; and with monoammonium phosphate (MAP) to yield spheniscidite ((NH4,K)(Fe,Al)2(PO4)2(OH).2H2O). Jarosite reacted with phosphoric acid to produce strengite or phosphosiderite (depending on the reaction temperature) and, to a lesser extent, gengenbachite (KFe3(HPO4)4(H2PO4)2.6H2O). Similarly, jarosite reacted with MAP to produce hydrogen ammonium ferric phosphate (H2(NH4)Fe(PO4)2). The direct alteration of jarosite to ferric phosphate appears to be very limited under ambient conditions. However, this study predominantly focuses on changes to the bulk chemical composition of jarosite. Consequently, further investigation (e.g. SEM analysis) is recommended to explore subtle changes in surface chemistry and the related effects on jarosite reactivity. Column perfusion experiments were also conducted to study the release of key elements during the dissolution of NaOH- and MAP-treated jarosite. The results suggest that these treatments do not considerably lower the risks to soil and water quality posed by jarosite dissolution. The practicality of the treatments is discussed, including the potential negative side effects. Further investigation is required to determine if these, or alternative, passivation treatments could be employed in the field to effectively mitigate the environmental risk associated with jarosite.

Carbonate-Enhanced Transformation of Ferrihydrite to Hematite.

An elevated activity of (bi)carbonate in soils and sediments (pCO2, ∼2%) above current atmospheric CO2 (∼0.04%) could influence the iron cycling in mineral-water interfacial chemistry. However, the impact of (bi)carbonate on mineral transformation is unclear. Here, a model short range-ordered iron oxyhydroxide, two-line ferrihydrite, was used to evaluate the impact of (bi)carbonate on mineral transformation at near-neutral pH using experimental geochemistry, X-ray diffraction, X-ray absorption spectroscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. Results showed that (bi)carbonate promoted the transformation of ferrihydrite to hematite and retarded the goethite formation. As pCO2 increased from 408 to 20,000 ppmv at 40 °C, the transformation efficiency of ferrihydrite increased from 53 to 95%, and the formation of hematite increased from 13 to 76%. During the formation of hematite, a terminal ligand on a Fe(III)O6 octahedral monomer such as a hydroxyl or water was displaced to form Fe(III)O6 octahedral dimers and/or polymers. Because the Fe-O bond of ≡(Fe-O)2-CO is much weaker than that of ≡Fe-O-H, the -O2CO group can be more easily replaced by two terminal -OH groups; the dehydration/rearrangement between Fe(III)O6 octahedral monomers was enhanced under high pCO2. Results suggest that high carbonate activity is an important geochemical parameter controlling the occurrence of hematite in oxic environments and, in turn, iron cycling in the critical zone.

Hematite Nanoparticles from Unexpected Reaction of Ferrihydrite with Concentrated Acids for Biomedical Applications.

The development of synthetic ways to fabricate nanosized materials with a well-defined shape, narrow-sized distribution, and high stability is of great importance to a rapidly developing area of nanotechnology. Here, we report an unusual reaction between amorphous two-line ferrihydrite and concentrated sulfuric or other mineral and organic acids. Instead of the expected dissolution, we observed the formation of new narrow-distributed brick-red nanoparticles (NPs) of hematite. Different acids produce similar nanoparticles according to scanning (SEM) and transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), infrared spectroscopy (FTIR), and energy-dispersive X-ray spectroscopy (EDX). The reaction demonstrates new possibilities for the synthesis of acid-resistant iron oxide nanoparticles and shows a novel pathway for the reaction of iron hydroxide with concentrated acids. The biomedical potential of the fabricated nanoparticles is demonstrated by the functionalization of the particles with polymers, fluorescent labels, and antibodies. Three different applications are demonstrated: i) specific targeting of the red blood cells, e.g., for red blood cell (RBC)-hitchhiking; ii) cancer cell targeting in vitro; iii) infrared ex vivo bioimaging. This novel synthesis route may be useful for the development of iron oxide materials for such specificity-demanding applications such as nanosensors, imaging, and therapy.

Biomimetic System for the Application of Nanomaterials in Fluid Purification: Removal of Arsenic with Ferrihydrite.

The use of nanomaterials has transformed fields such as medicine and electronics. However, aggregation of nanomaterials in aqueous solutions, difficult recovery of spent nano-adsorbents from reactors, and a tremendous pressure loss caused by nano-adsorbents in adsorption columns have prevented the wide-scale use of nano-adsorbents in industrial applications for water purification. An over-reliance on traditional adsorption media for fluid purification practices has slowed innovation in this field. This study serves as a proof of concept for a new approach in utilizing nano-adsorbents in water treatment. A system based on the concept of renal dialysis was used to treat a solution of arsenite using two-line ferrihydrite (Fh) under environmental conditions. The performance was compared to traditional batch studies, and environmental variables pH and Eh were monitored. The system removed 67 and 91% of arsenite at 1.22 and 2.61 g/L Fh loadings, respectively, in comparison to batch experiments that removed 82 and 94% for similar loadings. Operational conditions and the physical design of the vessel limited the extent of removal that could be obtained with the system. Design advantages, shortcomings, and required improvements are discussed.

Effects of Fullerol and Graphene Oxide on the Phase Transformation of Two-Line Ferrihydrite

Two-line ferrihydrite (Fh) is an omnipresent iron oxyhydroxide nanomineral with high surface reactivity and weak crystallinity, and its phase transformation in nature has drawn significant concerns...

Elucidating the biomineralization of low-temperature hydrothermal precipitates with varying Fe, Si contents: Indication from ultrastructure and microbiological analyses

Fe, Si-rich low-temperature hydrothermal precipitates, typical hydrothermal products of low-temperature diffuse flow, have been found widely on the seafloor. It is believed that microorganisms play an important role in the formation of Fe, Si-rich low-temperature precipitates, yet, microbial biomineralization within these precipitates has not been well understood. In this study, we characterized different hydrothermal precipitates collected from the Lau Basin of the western Pacific Ocean, using an integrated mineralogical, geochemical, ultrastructural and microbiological approach. Three types of Fe, Si-rich precipitates were identified: Fe-rich, Fe–Si-rich and Si-rich, consisting of amorphous or poor crystalline minerals, from the two-line ferrihydrite to opal-A. Geochemical indices suggest that the precipitates are typical low-temperature hydrothermal origin, precipitated from mixing, at various extent, of hydrothermal fluid and seawater. All three types of Fe, Si-rich precipitates show abundant and distinctive biogenic ultrastructures, indicating different biomineralization experiences. The Fe-rich precipitates dominantly exhibited the typical Fe-enriched ultrastructures produced by putative iron-oxidizing bacteria (FeOB), suggesting the prevalence of Fe-oxidation catalyzed by FeOB in its formation process. Similar FeOB-catalyzed biomineralization process also happened in Fe–Si-rich precipitates with the abundant occurrence of FeOB-induced ultrastructures. By contrast, the Si-enriched architectures, encompassing mycelium-like networks, became absolutely prevailing within Si-rich precipitates. Based on their indicative morphologies, mycelium-like networks were ascribed as silicified actinobacteria or fungi, suggesting that silicification induced by actinobacteria or fungi dominated the biomineralization process. Microbiological analysis revealed the existence of a series of diverse, heterogeneous microbial populations within different Fe, Si-rich precipitates. However, no putative FeOB lineages were detected in the Fe-rich and Fe–Si-rich precipitates. Taken together, our results indicate that different biomineralization processes induced by different microbial lineages contributed to the formation of the three different types of Fe, Si-rich precipitates and the distinct environmental conditions existed for heterogeneous microorganisms within these different Fe, Si-rich precipitates.

Synthesis of 2D Hexagonal Hematite Nanosheets and the Crystal Growth Mechanism.

Nanostructure engineering of hematite is a promising strategy to overcome its performance limitations as a photodegradation catalyst for organic dyes or toxic organic chemicals. Precise control of exposed facets plays a vital role as an optimization strategy. Although great progress has been made in the synthesis of different crystal morphologies, design principles remain ad hoc, awaiting systematic control of facet expression within a clean synthesis protocol yielding versatile results. Herein, we report a simple method that enables precise morphology control to synthesize 2D hexagonal hematite nanosheets from two-line ferrihydrite. Nanosheet sizes and facet proportions were successfully tuned by changing the pH, the ratio of solvent ethanol to water, and the concentration of FeIII ions. The growth mechanism appears to involve a combination of ferrihydrite solid-state transformation and assembly into hematite, followed by an ion-by-ion growth that perfects the surface terminations. The finding helps to establish a rational basis for the design and optimization of hematite nanostructures.