Iron Hydroxide Nanoparticles Research Articles

Structure Evolution of Iron (Hydr)oxides under Nanoconfinement and Its Implication for Water Treatment.

In the development of nanoenabled technologies for large-scale water treatment, immobilizing nanosized functional materials into the confined space of suitable substrates is one of the most effective strategies. However, the intrinsic effects of nanoconfinement on the decontamination performance of nanomaterials, particularly in terms of structural modulation, are rarely unveiled. Herein, we investigate the structure evolution and decontamination performance of iron (hydr)oxide nanoparticles, a widely used material for water treatment, when confined in track-etched (TE) membranes with channel sizes varying from 200 to 20 nm. Nanoconfinement drives phase transformation from ferrihydrite to goethite, rather than to hematite occurring in bulk systems, and the increase in the nanoconfinement degree from 200 to 20 nm leads to a significant drop in the fraction of the goethite phase within the aged products (from 41% to 0%). The nanoconfinement configuration is believed to greatly slow down the phase transformation kinetics, thereby preserving the specific adsorption of ferrihydrite toward As(V) even after 20-day aging at 343 K. This study unravels the structure evolution of confined iron hydroxide nanoparticles and provides new insights into the temporospatial effects of nanoconfinement on improving the water decontamination performance.

Sorption of Selenium(IV) and Selenium(VI) onto Iron Oxide/Hydroxide-Based Carbon Materials: Activated Carbon and Carbon Foam

Selenium pollution in water is a worldwide issue. Se(IV) and Se(VI) are mainly found in contaminated water due to their high solubility and mobility; their presence poses a serious risk as they can severely harm human health. Although iron oxide and hydroxide nanoparticles can be efficient candidates for the removal of selenium oxyanions due to their high adsorption capacity, the role of each iron species has not been fully elucidated. Furthermore, iron species are often found to be less effective for Se(VI) than Se(IV). The challenge and novelty of this study was to develop a carbon material impregnated with different iron phases, including oxides (magnetite/hematite) and hydroxides (goethite/lepidocrocite) capable of removing both Se(IV) and Se(VI). Since the phase and morphology of the iron nanoparticles play a significant role in Se adsorption, the study evaluated both characteristics by modifying the impregnation method, which is based on an oxidative hydrolysis with FeSO4 7H2O and CH3COONa, and the type of carbonaceous support (activated carbon or sucrose-based carbon foam). Impregnated activated carbons provide better removal efficiencies (70–80%) than carbon foams (<40%), due to their high surface areas and point zero charges. These results show that the adsorption of Se(VI) is more favorable on magnetic oxides (78%) and hydroxides (71%) than in hematite (<40%). In addition, the activated carbon decorated with magnetite showed a high adsorption capacity for both selenium species, even in alkaline conditions, when the sorbent surface is negatively charged. A mechanism based on the adsorption of inner-sphere complexes was suggested for Se(IV) immobilization, whereas Se(VI) removal occurred through the formation of outer-sphere complexes and redox processes.

Eco-friendly thermosensitive magnetic-molecularly-imprinted polymer adsorbent in dispersive solid-phase microextraction for gas chromatographic determination of organophosphorus pesticides in fruit samples

A thermosensitive magnetic-molecularly-imprinted polymer (TMMIP) was successfully prepared in an aqueous medium. The TMMIP was applied as an effective adsorbent in dispersive solid-phase microextraction for the selective enrichment of five organophosphorus pesticides (OPPs; diazinon, fenitrothion, fenthion, parathion-ethyl, and ethion) before analysis by gas chromatography. The polymerization was performed using mixed-valence iron hydroxide nanoparticles as the magnetic support, N-isopropyl acrylamide as the thermosensitive monomer, ethion as the template, and methacrylic acid as the functional monomer. The adsorption and desorption mechanisms of OPPs depend on their interactions with the adsorbents and solution temperature. Our methodology provides good linearity (0.50–2000 µgL-1), with a correlation determination of R2 > 0.9980, low limit of detection (0.25–0.50 µgL-1), low limit of quantitation (0.50–1.50 μg L−1), and high precision (%RSD < 7%). The developed method demonstrates excellent applicability for accurately and efficiently determining OPP residuals in fruit and vegetable samples with good recoveries (93–117%).

Дезактивація рідких радіоактивних відходів Чорнобильської зони відчуження: шляхи вирішення

The purpose of the study: on the basis of information analysis of modern approaches and experimental studies, to develop effective methods of decontamination of radioactively contaminated waters of the Chernobyl Exclusion Zone. Research materials and methods. The object of our research was liquid radioactive waste stored in the sumps of one of the decontamination points for equipment and vehicles (PuSO) - the "Dibrova" facility. Modern research methods are applied - scanning electron microscopy, X-ray diffractometry, laser sedimentography. The mass fraction of cesium, strontium, cobalt, and manganese was determined by the atomic absorption method using an AA-8500 atomic absorption spectrophotometer (Nippon Jarrell Ash Co Ltd, Japan). The results. The effectiveness of the proposed sorbents based on nickel-potassium ferrocyanide-modified iron oxide micro- and nanotubes and iron (III) hydroxide nanoparticles, the size of which is mainly 1-100 μm, is shown. The choice of decontamination algorithm depends on the composition of liquid radioactive waste to be cleaned. To increase the degree of strontium extraction while maintaining the high efficiency of cesium and transition metal extraction, it is advisable to apply preliminary plasma chemical treatment followed by the use of sorbents based on iron oxides/hydroxides modified by ferrocyanides. Conclusions. The possibility and expediency of using the proposed method for the decontamination of liquid radioactive waste accumulated in the Chernobyl exclusion zone and for the current control of the condition of the storage sites of accumulated radioactive waste and radiation monitoring are shown.

Unveiling the role of defects in iron oxyhydroxide for oxygen evolution

Development of earth-abundant and robust oxygen evolution reaction (OER) catalysts is imperative for cost-effective hydrogen production via water electrolysis. Herein, we report ultrafine iron (oxy)hydroxide nanoparticles with average particle size of 2.6 nm and abundant surface defects homogeneously supported on oleum-treated graphite (FeOx(n)@HG-T), providing abundant active sites for the OER. The optimal FeOx(0.03)@HG-110 exhibits high electrocatalytic OER activity and excellent stability. Electrochemical testing results and theoretical calculations reveal that the outstanding OER activity of FeOx(0.03)@HG-110 is due to its stronger charge transfer ability and lower OER energy barrier than defect-free FeOx nanoparticles. This work demonstrates that the OER performance of oxyhydroxide-based electrocatalysts can be improved by surface defect engineering.

Effect of Mn2+/Zn2+/Fe3+ Oxy(Hydroxide) Nanoparticles Doping onto Mg-Al-LDH on the Phosphate Removal Capacity from Simulated Wastewater.

A parent Mg-Al-LDH was upgraded in its adsorption properties due to the incorporation of tri-metal species oxy(hydroxide) nanoparticles obtaining Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite for the phosphate recovery from simulated urban treated wastewater. The physicochemical properties of the synthesized Mn2+/Zn2+/Fe3+/Mg-Al-LDH make promising for real application without being environmentally harmful. The performance of Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was evaluated through batch adsorption assays. The support of iron, manganese, and zinc (oxy)hydroxide nanoparticles onto the parent Mg-Al-LDH structure was performed by precipitation, isomorphic substitution, and complexation reactions. The main improvement of the Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was the highest phosphate adsorption capacity (82.3 mg∙g−1) in comparison to the parent Mg-Al-LDH (65.3 mg∙g−1), in a broad range of concentrations and the effective phosphate adsorption at neutral pH (7.5) near to the real wastewater effluents conditions in comparison to the conventional limitations of other adsorbents. The effectiveness of Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was higher than the conventional metal LDHs materials synthesized in a single co-precipitation step. The phosphate adsorption onto Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was described to be governed by both physical and chemical interactions. The support of Mn2+/Zn2+/Fe3+ oxy(hydroxide) nanoparticles over the parent Mg-Al-LDH was a determinant for the improvement of the phosphate adsorption that was governed by complexation, hydrogen bonding, precipitation, and anion exchange. The intra-particular diffusion also described well the phosphate adsorption onto the Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite. Three specific stages of adsorption were determined during the phosphate immobilization with an initial fast rate, followed by the diffusion through the internal pores and the final equilibrium stage, reaching 80% of removal and the equilibrium within 1 h. The Mn2+/Zn2+/Fe3+/Mg-Al-LDH was strongly selective towards phosphate adsorption in presence of competing ions reducing the adsorption capacity at 20%. The Mn2+/Zn2+/Fe3+/Mg-Al-LDH has limited reusability, only 51% of the adsorbed phosphate could be recovered in the second cycle of the adsorption-desorption process. Around 14% of phosphate was loosely-bond to Mn2+/Zn2+/Fe3+/Mg-Al-LDH which brings the opportunity to be a new source of phosphorus. The use of eluted concentrates and the final disposal of the exhausted adsorbent for soil amendment applications can be an integral nutrient system (P, Mn, Zn, Fe) for agriculture purposes.

Facile and Green Fabrication of Superhydrophobic Polyacrylonitrile Nonwoven Fabric with Iron Hydroxide Nanoparticles for Efficient Oil/Water Separation

Facile and Green Fabrication of Superhydrophobic Polyacrylonitrile Nonwoven Fabric with Iron Hydroxide Nanoparticles for Efficient Oil/Water Separation

Mössbauer spectroscopic investigations on iron oxides and modified nanostructures: A review.

Pure and doped iron oxide and hydroxide nanoparticles are highly potential materials for biological, environment, energy and other technological applications. On demand of the applications, single phase as well as multiple phase of different polymorphs or composites of iron oxides with compatible materials for example, zeolite, SiO2, or Au are prepared. The properties of the as-synthesized nanoparticles are predominantly dictated by the local structure and the distribution of the cations. Mössbauer spectroscopy is a perfect and efficient characterization technique to investigate the local structure of the Mössbauer-active element such as Fe, Au, and Sn. In the present review, the local structure transformation on the optimization of the magnetite coexisted with iron hydroxides, spin dynamics of the bare, caped, core–shell and the composites of iron oxide nanoparticles (IONPs), dipole–dipole interactions and the diffusion of IONPs were discussed, based on the findings using Mössbauer spectroscopy.Graphical abstract

Simultaneous removal of silica and TOC from steam assisted gravity drainage (SAGD) produced water using iron-hydroxide-coated walnut shell filter media

Extracting Alberta’s bitumen by SAGD requires a growing supply of steam, which is mainly generated from recycled produced water (PW). Traditionally, a warm lime softener (WLS), followed by walnut shell filter (WSF) and weak acid cation exchange (WAC) units have been employed to minimize the concentrations of silica, TOC, and hardness from PW. In this study, we enhanced TOC and silica removal in a WSF unit by modifying the surface of the walnut shell media. The walnut shells were modified by anchoring low mass percentages (e.g., < 5 wt%) of iron(hydroxide) nanoparticles under moderate hydrolysis conditions. The nanoparticle-anchored walnut shell particles (WS-NPs) were fully characterized, and their ability to remove TOC and silica was tested using batch and column experiments. In the batch tests, up to 85 % of silica and TOC was removed. In the column tests, which mimicked industrial operations, WS-NPs significantly improved the breakthrough behavior without reaching pressure drop limitations. The column breakthrough behaviors were successfully described by a dimensionless advection-axial dispersion model. The model accurately captured the commercial breakthrough behavior, indicating the possibility of scaling up the filter using a combined unit that removes silica and TOC simultaneously without using WLS and WAC.

Potential of Gum Arabic Functionalized Iron Hydroxide Nanoparticles Embedded Cellulose Paper for Packaging of Paneer

Recently, the interest of scientists has turned towards eco-friendly metal nanoparticles due to their distinctive physicochemical properties that have been used in several biochemical and food applications, including drug and bioactive component delivery, sensing of food pathogenic bacteria, imaging techniques, and theranostics. Therefore, this study aimed to fabricate gum arabic stabilized iron hydroxide nanoparticles (IHNPs) using the co-precipitation process and to develop nanoparticles decorated antimicrobial cellulose paper. The agglomeration of IHNPs is a major concern, therefore, the varied concentration (0.25–2.0%) of gum arabic was used to functionalize and stabilize the nanoparticles, and based on UV-visible spectroscopy and particle size analysis, 1% gum arabic concentration was screened out. Scanning electron microscopy displayed polygonal disc shapes of IHNPs that had sides of approximately equal lengths. Energy dispersive spectroscopy was used to determine the purity of the IHNPs and results illustrated the elemental iron peak at 0.8 keV and 6.34 keV. For thermal stability, differential scanning calorimetry (DSC) was employed, and the glass transition temperature was observed at 138.50 °C with 138.31 °C onset and 147.14 °C endset temperature, respectively. Functionalized IHNPs showed a significantly (p < 0.05) higher zone of inhibition against S. aureus (29.63 mm) than that of E. coli and were found to be non-toxic to Caco-2 cells during cell viability assay. Time-kill kinetics showed that cellulose paper embedded with nanoparticles possessed excellent antibacterial activity against S. aureus. To explore the food application of developed cellulose paper, citric acid coagulated dairy product (Paneer), similar to cottage cheese was formulated, and it was evaluated for its microbial shelf life. The unwrapped sample showed higher microbial load during the fourth day of the storage. However, both wrapped samples were acceptable till the 10th of storage.

M\xf6ssbauer study of iron gall inks on historical documents

Iron gall ink was used in the Western world as a permanent writing material already in late Roman times and throughout the Middle Ages, until it became obsolete in the twentieth century. There is much interest in experimental methods to determine the state of the ink and its degradation products on historical documents. Mössbauer spectroscopy with 57Fe is such a method, and it has the particular advantage to be sensitive to the chemical bonding of iron, but this method has only rarely been applied to historical documents. In this paper we present Mössbauer data for two damaged documents from a Library in Granada and a handwritten German book from the eighteenth century. In addition to the inked parts of the manuscripts, ink-free parts were studied to determine the amount and chemical state of the iron in the papers. These new results are discussed in the context of previously published Mössbauer data. In one of the investigated documents Fe(II)-oxalate, FeC2O4·2H2O, was observed. The assignment of the various Fe3+ sites in the different documents is rather difficult and often there is a superposition of various species. Known forms of iron gallate are definitely not present on the inked papers. The observed ferric species can be remains of Fe3+ polyphenol complexes of the ink, complexes of Fe3+ with degradation products of the cellulose of the paper or gum arabic, or very small iron oxide or hydroxide nanoparticles.

Foliar Application of Humic-Stabilized Nanoferrihydrite Resulted in an Increase in the Content of Iron in Wheat Leaves

The objective of this study was to synthesize iron (hydr)oxide nanoparticles (IONPs) stabilized by humic substances, and to estimate the feasibility of their use for foliar application on iron deficient plants. The IONPs were synthesized by rapid hydrolysis of iron(III) nitrate in a solution of potassium humate. The iron speciation and nanoparticle morphologies were characterized using X-ray diffraction, transmission electron microscopy, and Mössbauer spectroscopy. The obtained sample of IONPs was applied at concentrations of 1- and 10-mM Fe, and 0.2% urea was used as an adjuvant. Wheat plants (Triticum aestivum L. cv. L15) were used for the iron uptake test. For both of the concentrations tested, spraying the nanoparticles resulted in a 70–75% higher iron content in wheat leaves compared to ferric ammonium salt of ethylenediaminetetraacetic acid (Fe-EDTA). The synergistic effect of humic substances acting as a surfactant seemed to promote an increase in the iron uptake of the ferrihydrite nanoparticles compared to the aqueous Fe-EDTA solution used in this study. We concluded that humic-stabilized IONPs are much better suited to foliar application as compared to soil amendment when applied as a source of iron for plants. This is because humic substances act as a capping agent for nanoparticles and the surfactants enhance iron penetration into the leaf.

The efficiency of some microelement compositions in spring wheat cultivation system

The studies were performed on the experimental field of the Research Institute of Agricultural Sciences of the Northern Trans-Urals - a branch of the Tyumen Scientific Center of the SB RAS in 2019. In the experiment, studies were carried out on the use of biogenic iron hydroxide nanoparticles in various variations on spring wheat for seed treatment before sowing and plants during the growing season in the complex plant protection complex. Records and observations were performed according to standard guidelines adopted in the State variety testing network, crop production and plant protection. The use of biogenic Fe did not affect the initial development of plants and germination. Analysis of seeds for disease damage showed a general infection within 50%, seed treatment with a fungicide disinfectant reduced their infection by 90%, biogenic iron by 34%, which is the threshold for the assessment of PSM. Root diseases caused by helminthosporious and Fusarium infections were suppressed by 71-93% fungicidal protectants and 30-60% by the use of biogenic iron with an increase in plant maturation efficiency. In the conditions of the year of leaf stem diseases the development of septoriosis of the ear and stem prevailed 30-40%, the use of a chemical fungicide had a reception efficiency of 77-82% against the background of fungicidal protectants and the use of compositions in the earing phase and increased by 10% to 89% from treatment in the tillering phase with biogenic iron and biofungicide. Biogenic Fe applied in the tillering phase had a directed effect on the development of the ear increasing its weight by 1.07 g, and resistance to lodging, but there was a decrease in the length of the stem, the development of the leaf blade of the flag leaf by 8.7-12.7%, and the total mass of plants. Increased yield by 9.8-12.4% and gluten content up to 30% contributed to the use of biogenic iron and biofungicide increasing the effectiveness of the chemical fungicide at low rates. The use of biogenic iron is possible in the technology of spring wheat cultivation to reduce the chemical load by regulating the norms of application of the fungicidal direction of the PSM.

Konvencionalni i napredni adjuvansi u formulacijama vakcina - mineralni adsorbenti, nanočestični nosači i sistemi tipa mikroigala

In the era of modern vaccinology, limited immunogenicity of the most commonly used antigens has enforced the use of various adjuvants in vaccine formulations to achieve desired immune response. Aluminum-containing adjuvants have been, historically, the most widely used mineral immunostimulants, generally regarded as safe to use in human vaccines. The great academic progress in inorganic (nano)materials synthesis, structure control and functionalization design has led to a growing interest in innovative adjuvants such as clays, mesoporous silica nanoparticles, zinc oxide, iron oxide and iron hydroxide nanoparticles, etc. On the other hand, there has been an intention to use specific nanoparticulated antigen delivery systems, such as nanoemulsions, in order to protect antigens from premature proteolytic degradation and/or to improve antigen immunogenicity by facilitating antigen uptake and processing by antigen presenting cells. Simultaneously, numerous research efforts have been focused on the development of innovative technologies for antigen delivery into the skin (such as microneedles), with the aim to improve vaccine efficacy alongside with enhanced patient adherence, particularly in children population (noninvasive or minimally invasive administration). Therefore, this review deals with each of these approaches in more detail, with the special emphasis on examples of their use in vaccine formulations as well as on the factors influencing their efficacy and safety.

Features of the terahertz spectra of iron oxide nanoparticles in a silicon dioxide shell and of iron oxide and hydroxide nanoparticles

New methods have been developed for noninvasive monitoring of pathological processes in a living organism by means of terahertz spectroscopy and visualization using contrast agents based on magnetic nanoparticles. The nanoparticles must possess good magnetic characteristics, must be nontoxic and stable against aggregation, and must exhibit chemical stability; therefore, they are enclosed in a biologically inert shell. This paper discusses the spectral features of iron oxide nanoparticles in a biologically inert shell consisting of silicon dioxide and nanoparticles of iron oxide and hydroxide in the terahertz frequency range. It is shown that the crystalline phase of iron oxide can be identified for both types of nanoparticles by means of terahertz spectroscopy.

Pre-coating of outside-inside capillary UF membranes with iron hydroxide particles to limit non-backwashable fouling during seawater algal blooms

AbstractThis research is structured on two hypotheses in which the first one is that pre-coating method using iron hydroxide particles in combination with ultrafiltration (UF) is able to control the non-backwashable (nBW) fouling in outside-inside UF membrane system caused by transparent exopolymer particles produced by marine algae species, Chaetoceros affinis. The initial assumption is that the success of the pre-coating method strongly depends on the uniform coverage of pre-coat material along the membrane surface that forms a protective layer. The second hypothesis is based on the presumption that a sequestering agent can avoid the growth of the iron hydroxide nanoparticles over time. Pre-coating experiments were performed with 6, 1, and 0.15 mg Fe3+/L coagulant equivalent dose to synthetic seawater spiked with algal organic matter to assess its effect to membrane backwashability, especially the nBW fouling development. The results showed that all of the applied dosages for pre-coating were able to re...

Effect of Humic Substances and Silicon Ions on Stability of Iron Hydroxide (III) Nanoparticles

The paper reports on experimental modeling of the colloid system composition in natural groundwater. It is shown that the stability of iron hydroxide nanoparticles relates to the presence of silica and humic substances. It was found out the molar ratio of iron/silicon/organic substance is equal to 1/7/2, where stable iron (III) hydroxide nanoparticles form. The iron hydroxide nanoparticle size ranging from 30 to 600 nm was determined. It characterizes the steady state of the colloidal system.

Water Oxidation Catalysis with Nonheme Iron Complexes under Acidic and Basic Conditions: Homogeneous or Heterogeneous?

Thermal water oxidation by cerium(IV) ammonium nitrate (CAN) was catalyzed by nonheme iron complexes, such as Fe(BQEN)(OTf)2 (1) and Fe(BQCN)(OTf)2 (2) (BQEN = N,N'-dimethyl-N,N'-bis(8-quinolyl)ethane-1,2-diamine, BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)cyclohexanediamine, OTf = CF3SO3(-)) in a nonbuffered aqueous solution; turnover numbers of 80 ± 10 and 20 ± 5 were obtained in the O2 evolution reaction by 1 and 2, respectively. The ligand dissociation of the iron complexes was observed under acidic conditions, and the dissociated ligands were oxidized by CAN to yield CO2. We also observed that 1 was converted to an iron(IV)-oxo complex during the water oxidation in competition with the ligand oxidation. In addition, oxygen exchange between the iron(IV)-oxo complex and H2(18)O was found to occur at a much faster rate than the oxygen evolution. These results indicate that the iron complexes act as the true homogeneous catalyst for water oxidation by CAN at low pHs. In contrast, light-driven water oxidation using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and S2O8(2-) as a sacrificial electron acceptor was catalyzed by iron hydroxide nanoparticles derived from the iron complexes under basic conditions as the result of the ligand dissociation. In a buffer solution (initial pH 9.0) formation of the iron hydroxide nanoparticles with a size of around 100 nm at the end of the reaction was monitored by dynamic light scattering (DLS) in situ and characterized by X-ray photoelectron spectra (XPS) and transmission electron microscope (TEM) measurements. We thus conclude that the water oxidation by CAN was catalyzed by short-lived homogeneous iron complexes under acidic conditions, whereas iron hydroxide nanoparticles derived from iron complexes act as a heterogeneous catalyst in the light-driven water oxidation reaction under basic conditions.

The influence of pH on iron speciation in podzol extracts: Iron complexes with natural organic matter, and iron mineral nanoparticles

The quantities of natural organic matter (NOM) and associated iron (Fe) in soil extracts are known to increase with increasing extractant pH. However, it was unclear how the extraction pH affects Fe speciation for particles below 30nm. We used flow field-flow fractionation (FlowFFF) and transmission electron microscopy (TEM) to investigate the association of Fe and trace elements with NOM and nanoparticulate iron (oxy)hydroxides in podzol extracts.For extracts prepared at the native soil pH (~4), and within a 1–30nm size range, Fe was associated with NOM. In extracts with a pH≥7 from the E and B soil horizons, Fe was associated with NOM as well as with iron (oxy)hydroxide nanoparticles with a size of approximately 10nm. The iron (oxy)hydroxide nanoparticles may have either formed within the soil extracts in response to the increase in pH, or they were mobilized from the soil. Additionally, pH shift experiments showed that iron (oxy)hydroxides formed when the native soil pH (~4) was increased to 9 following the extraction. The iron (oxy)hydroxide nanoparticles aggregated if the pH was decreased from 9 to 4.The speciation of Fe also influenced trace element speciation: lead was partly associated with the iron (oxy)hydroxides (when present), while copper binding to NOM remained unaffected by the presence of iron (oxy)hydroxide nanoparticles. The results of this study are important for interpreting the representativeness of soil extracts prepared at a pH other than the native soil pH, and for understanding the changes in Fe speciation that occur along a pH gradient.

Formation of Iron(III) (Hydr)oxides on Polyaspartate- and Alginate-Coated Substrates: Effects of Coating Hydrophilicity and Functional Group

To better understand the transport of contaminants in aqueous environments, we need more accurate information about heterogeneous and homogeneous nucleation of iron(III) hydroxide nanoparticles in the presence of organics. We combined synchrotron-based grazing incidence small-angle X-ray scattering (GISAXS) and SAXS and other nanoparticle and substrate surface characterization techniques to observe iron(III) (hydr)oxide [10⁻⁴ M Fe(NO₃)₃ in 10 mM NaNO₃] precipitation on quartz and on polyaspartate- and alginate-coated glass substrates and in solution (pH = 3.7 ± 0.2). Polyaspartate was determined to be the most negatively charged substrate and quartz the least; however, after 2 h, total nanoparticle volume calculations--from GISAXS--indicate that positively charged precipitation on quartz is twice that of alginate and 10 times higher than on polyaspartate, implying that electrostatics do not govern iron(III) (hydr)oxide nucleation. On the basis of contact angle measurements and surface characterization, we concluded that the degree of hydrophilicity may control heterogeneous nucleation on quartz and organic-coated substrates. The arrangement of functional groups at the substrate surface (--OH and --COOH) may also contribute. These results provide new information for elucidating the effects of polymeric organic substrate coatings on the size, volume, and location of nucleating iron hydroxides, which will help predict nanoparticle interactions in natural and engineered systems.