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Our understanding of how Fe(II) reacts with Fe(III) oxides has evolved based on evidence for electron transfer at the oxide-water interface and Fe(II)-catalyzed recrystallization. There is, however, some evidence that these, and other processes, such as microbial reduction, cease after continued contact with Fe(II) as the Fe oxide becomes "passivated". Here, we explore the mechanism of oxide passivation by measuring whether exposure to Fe(II) inhibits Fe(II)-goethite electron transfer, and whether this inhibition is reversible. To quantify the extent of electron transfer, we used selective isotope labeling with 57Fe Mössbauer spectroscopy. We provide experimental evidence that pre-exposure to Fe(II) alters the products formed and inhibits the extent of electron transfer between goethite and Fe(II). We demonstrate that the goethite surface can accumulate a passivation layer of sorbed Fe(II) and that further electron transfer between Fe(II) and goethite is inhibited. Importantly, however, electron transfer can be partially restored upon removal of the layer of Fe(II) by extraction or oxidation. Our results suggest that in environments that are commonly subjected to transient geochemical fluctuations, electron transfer between Fe(II) and Fe oxides, and processes linked to it are likely to be relevant beyond just short time scales.

The understanding of phenomena falling outside the Ginzburg-Landau paradigm of phase transitions represents a key challenge in condensed matter physics. A famous class of examples is constituted by the putative deconfined quantum critical points between two symmetry-broken phases in layered quantum magnets, such as pressurised SrCu 2 (BO 3 ) 2 . Experiments find a weak first-order transition, which simulations of relevant microscopic models can reproduce. The origin of this behaviour has been a matter of considerable debate for several years. In this work, we demonstrate that the nature of the deconfined quantum critical point can be best understood in terms of a novel dynamical mechanism, termed Nordic walking. Nordic walking denotes a renormalisation group flow arising from a beta function that is flat over a range of couplings. This gives rise to a logarithmic flow that is faster than the well-known walking behaviour, associated with the annihilation and complexification of fixed points, but still significantly slower than the generic running of couplings. The Nordic-walking mechanism can thus explain weak first-order transitions, but may also play a role in high-energy physics, where it could solve hierarchy problems. We analyse the Wess-Zumino-Witten field theory pertinent to deconfined quantum critical points with a topological term in 2+1 dimensions. To this end, we construct an advanced functional renormalisation group approach based on higher-order regulators. We thereby calculate the beta function directly in 2+1 dimensions and provide evidence for Nordic walking., Competing Interests: Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

As an essential process for the maintenance of cellular homeostasis and function, autophagy is responsible for the lysosome-mediated degradation of damaged proteins and organelles; therefore, dysregulation of autophagy in humans can lead to a variety of diseases. The link between impaired autophagy and disease highlights the need to investigate possible interventions to address dysregulations. One possible intervention is hyperthermia, which is described in this protocol. To investigate these interventions, a method for absolute quantification of autophagosomal compartments is required that allows comparison of autophagosomal activity under different conditions. Existing methods such as western blotting and immunohistochemistry for analysing the location and relative abundance of intracellular proteins associated with autophagy, or transmission electron microscopy (TEM), which are either very time-consuming, expensive, or both, are less suitable for this purpose. The method described in this protocol allows the absolute quantification of autophagosomes per cell in human fibroblasts using the CYTO-ID® Autophagy Detection Kit after heat therapy compared to a control. The Cyto-ID® assay is based on the use of a specific dye that selectively stains autophagic compartments, combined with an additional Hoechst 33342 dye for nuclear staining. The subsequent recognition of these stained compartments by the Cytation Imager enables the software to determine the number of autophagosomes per nucleus in living cells. Additionally, this absolute quantification uses an image-based method, and the protocol is easy to use and not time-consuming. Furthermore, the method is not only suitable for heat therapy but can also be adapted to any other desired therapy or substance. Key features • Absolute quantification of autophagic compartments in living cells. • Optimised protocol for the determination of autophagy in primary human skin fibroblasts. • Allows the testing of active substances and treatments concerning autophagy. • Imaging-based method for the determination of autophagy., Competing Interests: Competing interestsThe authors declare the following financial interests/personal relationships, which may be considered as potential competing interests: Barbara Hochecker reports financial support was provided by “Professor Manfred von Ardenne Forschungsförderungsgesellschaft e.V.”, (©Copyright : © 2024 The Authors; This is an open access article under the CC BY-NC license.)

Transformation of nanocrystalline ferrihydrite to more stable microcrystalline Fe(III) oxides is rapidly accelerated under reducing conditions with aqueous Fe(II) present. While the major steps of Fe(II)-catalyzed ferrihydrite transformation are known, processes in the initial phase that lead to nucleation and the growth of product minerals remain unclear. To track ferrihydrite-Fe(II) interactions during this initial phase, we used Fe isotopes, Mössbauer spectroscopy, and extractions to monitor the structural, magnetic, and isotope composition changes of ferrihydrite within ∼30 min of Fe(II) exposure. We observed rapid isotope mixing between aqueous Fe(II) and ferrihydrite during this initial lag phase. Our findings from Mössbauer spectroscopy indicate that a more magnetically ordered Fe(III) phase initially forms that is distinct from ferrihydrite and bulk crystalline transformation products. The signature of this phase is consistent with the early stage emergence of lepidocrocite-like lamellae observed in previous transmission electron microscopy studies. Its signature is furthermore removed by xylenol extraction of Fe(III), the same approach used to identify a chemically labile form of Fe(III) resulting from Fe(II) contact that is correlated to the ultimate emergence of crystalline product phases detectable by X-ray diffraction. Our work indicates that the mineralogical changes in the initial lag phase of Fh transformation initiated by Fe(II)-Fh electron transfer are critical to understanding ferrihydrite behavior in soils and sediments, particularly with regard to metal uptake and release., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The aim of the study was to investigate the effectiveness of non-invasive and micro-invasive treatments in active enamel carious lesions in high-caries-risk children. Clinical records of children treated in a dental school setting were retrospectively screened for active enamel carious lesions treated non-invasively (topical fluoride applications, oral hygiene instruction, or dietary guidance) or micro-invasively (sealant). The control of active carious lesions was set as the main outcome established by the combination of inactivation and non-progression of the lesions based on Nyvad and ICDAS criteria, respectively. Individual and clinical factors associated with the outcome were analyzed by Poisson regression. The sample consisted of 105 high-caries-risk children with a mean age of 8.3 (± 2.4) years. From a total of 365 active enamel carious lesions, most lesions (84.1%) were active non-cavitated carious lesions (ICDAS scores 1 and 2) and only 15.9% presented localized enamel breakdown (ICDAS score 3). Of these, 72.6% were inactivated and 92.1% did not progress (mean time of 6.5 ± 4.1 months). The prevalence of controlled carious lesions was higher among children older than 6 years (PR:1.43; 95%CI:1.00-2.03; p = 0.04) and in those with better biofilm control (PR:0.99; 95%CI: 0.98-0.99; p = 0.03). Non-operative approaches are effective for controlling active enamel carious lesions. The majority of active enamel carious lesions became inactive and did not progress after treatment. Caries control was associated with older children and better biofilm control.

Predicting the redox behavior of magnetite in reducing soils and sediments is challenging because there is neither agreement among measured potentials nor consensus on which Fe(III) | Fe(II) equilibria are most relevant. Here, we measured open-circuit potentials of stoichiometric magnetite equilibrated over a range of solution conditions. Notably, electron transfer mediators were not necessary to reach equilibrium. For conditions where ferrous hydroxide precipitation was limited, Nernstian behavior was observed with an E H vs pH slope of -179 ± 4 mV and an E H vs Fe(II) aq slope of -54 ± 4 mV. Our estimated E H o of 857 ± 8 mV closely matches a maghemite|aqueous Fe(II) E H o of 855 mV, suggesting that it plays a dominant role in poising the solution potential and that it's theoretical Nernst equation of E H [mV] = 855 - 177 pH - 59 log [Fe 2+ ] may be useful in predicting magnetite redox behavior under these conditions. At higher pH values and without added Fe(II), a distinct shift in potentials was observed, indicating that the dominant Fe(III)|Fe(II) couple(s) poising the potential changed. Our findings, coupled with previous Mössbauer spectroscopy and kinetic data, provide compelling evidence that the maghemite/Fe(II) aq couple accurately predicts the redox behavior of stoichiometric magnetite suspensions in the presence of aqueous Fe(II) between pH values of 6.5 and 8.5.

Purpose: This in vitro study evaluated the microshear bond strength (μSBS) of a universal adhesive after silver diammine fluoride (SDF) application at different concentrations on carious dentinal lesions in primary teeth., Methods: Flat dentin carious-induced surfaces from 40 primary molars were randomly assigned to four experimental groups: without SDF treatment (control), 12% SDF, 30% SDF, or 38% SDF application. After 14 days of storage in artificial saliva at 37 °C, a universal adhesive system (Scotchbond Universal, 3 M ESPE) was applied in the etch-and-rinse mode and resin composite cylinders were built (0.72 mm 2 ). After 24 h of water storage, the μSBS test was performed and the failure mode was determined. Data were analysed using one-way ANOVA and Tukey's post hoc tests (α = 0.05)., Results: The application of 38% SDF resulted in higher μSBS mean than control and use of 12% SDF (p = 0.006). No significant differences were observed among control, 12% SDF, and 30% SDF. All specimens tested showed adhesive/mixed failure., Conclusion: The use of SDF does not jeopardise the bonding of a universal adhesive applied in the etch-and-rinse mode to carious dentinal lesions in primary teeth, irrespective of the product concentration., (© 2022. The Author(s), under exclusive licence to European Academy of Paediatric Dentistry.)

Abiotic reduction of nitrite (NO 2 - ) by Fe(II) species ( i.e. , chemodenitrification) has been demonstrated in a variety of natural environments and laboratory studies, and is a potentially significant source of atmospheric nitrous oxide (N 2 O) emissions. It is, however, unclear how chemodenitrification rates and N 2 O yields vary among heterogeneous Fe(II) species under similar conditions and whether abiotic reduction competes with biological NO 2 - reduction. Here, we measured rates of NO 2 , pH 7.0, bicarbonate buffer, and 0.1 mM NO - reduction and extents of N 2 O production by several Fe(II) species under consistent, environmentally relevant conditions ( i.e. , pH 7.0, bicarbonate buffer, and 0.1 mM NO 2 - ). Nitrite reduction rates varied significantly among the heterogeneous Fe(II) species with half-lives ( t 1/2 ) ranging from as low as an hour to over two weeks following the trend of goethite/Fe(II) ∼ hematite/Fe(II) ∼ magnetites > maghemite/Fe(II) > sediment/Fe(II). Interestingly, we observed no clear trend of increasing NO 2 - reduction rates with higher magnetite stoichiometry ( x = Fe 2+ /Fe 3+ ). Nitrogen recovery as N 2 O also varied significantly among the Fe species ranging from 21% to 100% recovery. We further probed both chemodenitrification and biological denitrification in the absence and presence of added aqueous Fe(II) with a sediment collected from the floodplain of an agricultural watershed. While abiotic NO 2 - reduction by the sediment + Fe(II) was much slower than the laboratory Fe(II) species, we found near complete mass N balance during chemodenitrification, as well as evidence for both abiotic and biological NO 2 - reduction potentially occurring in the sediment under anoxic conditions. Our results suggest that in redox active sediments and soils both chemodenitrification and biological denitrification are likely to occur simultaneously, and that agricultural watersheds may be significant sources of N 2 O emissions.

Recently, the twist angle between adjacent sheets of stacked van der Waals materials emerged as a new knob to engineer correlated states of matter in two-dimensional heterostructures in a controlled manner, giving rise to emergent phenomena such as superconductivity or correlated insulating states. Here, we use an ab initio based approach to characterize the electronic properties of twisted bilayer MoS 2 . We report that, in marked contrast to twisted bilayer graphene, slightly hole-doped MoS 2 realizes a strongly asymmetric p x -p y Hubbard model on the honeycomb lattice, with two almost entirely dispersionless bands emerging due to destructive interference. The origin of these dispersionless bands, is similar to that of the flat bands in the prototypical Lieb or Kagome lattices and co-exists with the general band flattening at small twist angle due to the moiré interference. We study the collective behavior of twisted bilayer MoS 2 in the presence of interactions, and characterize an array of different magnetic and orbitally-ordered correlated phases, which may be susceptible to quantum fluctuations giving rise to exotic, purely quantum, states of matter., (© 2021. The Author(s).)

Trace metals, such as nickel (Ni), are often found associated with ferrihydrite (Fh) in soil and sediment and have been shown to redistribute during Fe(II)-catalyzed transformation of Fh. Fe(II)-catalyzed transformation of Fh, however, is often inhibited when natural organic matter (NOM) is associated with Fh. To explore whether NOM affects the behavior of Ni during Fe(II)-catalyzed transformation of Fh, we tracked Ni distribution, Fe atom exchange, and mineral transformation of Fh and Fh coprecipitated with Suwannee River natural organic matter (SRNOM-Fh). As expected, in the absence of Fe(II), Fh and SRNOM-Fh did not transform to secondary Fe minerals after two weeks. We further observed little difference in Ni adsorption on SRNOM-Fh compared to Fh. In the presence of Fe(II), however, we found that Ni associated with SRNOM-Fh was more susceptible to acid extraction than Fh. Specifically, we found almost double the amount of Ni remaining in the Fh after mild extraction compared to SRNOM-Fh. XRD showed that Fh transformed to goethite and magnetite whereas SRNOM-Fh did not transform despite 57 Fe isotope tracer experiments confirmed that SRNOM-Fh underwent extensive atom exchange with aqueous Fe(II). Our findings suggest that Fe atom exchange may not be sufficient for obvious Ni stabilization and that transformation to secondary minerals may be necessary for Ni stabilization to occur., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This in vitro study aimed to evaluate the effect of a silane-containing universal adhesive used with or without a silane agent on the repair bond strength between aged and new composites. Forty nanohybrid composite resin blocks were stored in distilled water for 14 d and thermo-cycled. Sandpaper ground, etched, and rinsed speciments were randomly assigned into four experimental groups: silane + two-step etch-and-rinse adhesive system, two-step etch-and-rinse adhesive system, silane + silane-containing universal adhesive system, and silane-containing universal adhesive system. Blocks were repaired using the same composite. After 24 h of water storage, the blocks were sectioned and bonded sticks were submitted to microtensile testing. Ten unaged, non-repaired composite blocks were used as a reference group to evaluate the cohesive strength of the composite. Two-way ANOVA and Tukey's tests were used to analyze average µTBS. One-way ANOVA and Dunnet post-hoc tests were used to compare the cohesive strength values and bond strength obtained in the repaired groups (α = 0.05). The µTBS values were higher for the silane-containing universal adhesive compared to the two-step etch-and-rinse adhesive system (p = 0.002). Silane application improved the repair bond strength (p = 0.03). The repair bond strength ranged from 39.3 to 65.8% of the cohesive strength of the reference group. Using universal silane-containing adhesive improved the repair bond strength of composite resin compared to two-step etch-and-rinse adhesive. However, it still required prior application of a silane agent for best direct composite resin repair outcomes.

For decades, there has been evidence that Fe-containing minerals might contribute to abiotic degradation of chlorinated ethene (CE) plumes. Here, we evaluated whether Fe(II) in clay minerals reduces tetrachloroethene (PCE) and trichloroethene (TCE). We found that structural Fe(II) in both low (SWy-2) and high (NAu-1) Fe clay minerals did not reduce PCE or TCE under anoxic conditions. There was also no reduction of PCE or TCE after adding 5 mM dissolved Fe(II) to the clay mineral suspensions. In the presence of high Fe(II) concentrations (20 mM), however, PCE and TCE reduction products were observed in the presence of low Fe-content clay mineral SWy-2. Mössbauer spectroscopy results indicate that a mixed-valent Fe(II)-Fe(III) precipitate formed in the reactive SWy-2 suspensions. In contrast, in suspensions containing 20 mM Fe(II) alone or Fe-free clay mineral (Syn-1), we observed a purely Fe(II)-containing precipitate (Fe(OH) 2 ) and also PCE and TCE reduction products. Interestingly, the amount of CE products decreased in the order of Fe-free clay mineral Syn-1 > Fe(OH) 2 > low Fe-content clay mineral SWy-2, suggesting that clay mineral Fe controlled the formation of the reactive mineral phase. Additional experiments with hexachloroethane (HCA) revealed that faster HCA reduction occurred with decreasing clay mineral Fe content. Kinetic modeling yielded invariable second-order rate constants and increasing concentrations of reactive Fe(II) as the Fe(II)/Fe(total) content of the precipitates increased. Our data suggest that clay mineral Fe(III) is a sink for electrons from added Fe(II) that otherwise might have reduced the CEs. Furthermore, our findings are consistent with the hypothesis that active precipitation of Fe(II)-containing reactive mineral intermediates (RMI) may be important to CE reduction and suggest that RMI formation depends on clay mineral presence and Fe content.

In the present work, we report the antioxidant, antimicrobial and cytotoxic activities of quercetin-capped gold nanoparticles (AuNPsQct). The synthesis of AuNPsQct was confirmed by UV-Vis spectroscopy, FTIR and transmission electron microscopy (TEM) analyses. The FTIR spectrum showed the integrity of the quercetin molecules on the nanoparticle surface. The TEM images showed sizes less than 100 nm and a slight spherical shape. The electrostatic stability was confirmed by the zeta potential method. The antioxidant activity of quercetin, evaluated by DPPH, ABTS and nitric oxide free radical scavenging methods, was preserved in the gold nanoparticles, furthermore quercetin-capped gold nanoparticles (IR 50 0.37 µg/mL) demonstrated a higher antioxidant activity than free quercetin (IR 50 0.57 µg/mL) by nitric oxide free radical scavenging method. Strong antifungal activity was observed for Aspergillus fumigatus with concentrations ranging from 0.1 to 0.5 mg/mL. The nanoparticles with quercetin did not exhibit cytotoxicity to human fibroblasts (L929 cells). In conclusion, these results suggest that AuNPsQct, produced by cost-effective method, can act as a promising candidate for different medical applications., (© 2019 Production and hosting by Elsevier B.V. on behalf of King Saud University.)

Surface defects have been shown to facilitate electron transfer between Fe(II) and goethite (α-FeOOH) in abiotic systems. It is unclear, however, whether defects also facilitate microbial goethite reduction in anoxic environments where electron transfer between cells and Fe(III) minerals is the limiting factor. Here, we used stable Fe isotopes to differentiate microbial reduction of goethite synthesized by hydrolysis from reduction of goethite that was further hydrothermally treated to remove surface defects. The goethites were reduced by Geobacter sulfurreducens in the presence of an external electron shuttle, and we used ICP-MS to distinguish Fe(II) produced from the reduction of the two types of goethite. When reduced separately, goethite with more defects has an initial rate of Fe(III) reduction about 2-fold higher than goethite containing fewer defects. However, when reduced together, the initial rate of reduction is 6-fold higher for goethite with more defects. Our results suggest that there is a suppression of the reduction of goethite with fewer defects in favor of the reduction of minerals with more defects. In the environment, minerals are likely to contain defects and our data demonstrates that even small changes at the surface of iron minerals may change their bioavailability and determine which minerals will be reduced.

This study was undertaken to investigate the in vitro wound healing effects and the anti-inflammatory and antioxidant activities of terpinolene and α-phellandrene. The in vitro stimulatory effects on the proliferation and migration of fibroblasts were assessed using the scratch assay. The anti-inflammatory activity was evaluated using cell-based assays by investigating their influence on nitric oxide (NO), superoxide anion (O 2 •- ), tumour necrosis factor-alpha (TNF-α) and interleukin 6 (IL-6) production and using the TNF-α-induced nuclear factor kappa (NF-κB) assay. Antioxidant activity was determined by the ABTS cation radical scavenging capacity, ferric reducing/antioxidant potential (FRAP), and NO free radical scavenging assays. Terpinolene and α-phellandrene significantly increased the migration and proliferation of fibroblasts and suppressed the pro-inflammatory cytokines IL-6 and TNF-α in a dose-dependent manner. Terpinolene and α-phellandrene at a concentration of 100 μM significantly inhibited NO production (41.3 and 63.8%, respectively) in a macrophage cell-culture-based assay, and resulted in reductions in O 2 •- production of 82.1 ± 3.5% and 70.6 ± 4.3%, respectively. Moreover, these monoterpenes were verified to suppress NF-κB activity. In summary, terpinolene and α-phellandrene may contribute to broadening clinical options in the treatment of wounds by attenuating inflammation and oxidative stress in vitro., (Copyright © 2019. Published by Elsevier Ltd.)

Vegetable oils have been used for a plethora of health benefits by their incorporation in foods, cosmetics, and pharmaceutical products, especially those intended for skin care. This study aimed to investigate the cutaneous benefits of a vegetable oil blend (VOB) formulation and its fatty acid composition. The anti-inflammatory activity was studied in macrophages of RAW 264.7 cells by investigating the release of nitric oxide (NO), superoxide anion generation (O2-), tumor necrosis factor-alpha (TNF-α), and interleukin 6 (IL-6). ABTS cation radical scavenging capacity assay, ferric reducing antioxidant potential (FRAP), 2,2-diphenyl-1-picrylhydrazyl (DPPH), and NO free radical scavenging assays were used to evaluate the antioxidant activity. VOB was tested for its ability to stimulate fibroblast proliferation and migration using the scratch assay, and antibacterial activity by the microdilution test. The fatty acid profile of a freshly prepared VOB formulation was determined by gas chromatography before and after accelerated stability testing. Chemical composition of VOB revealed the presence of oleic acid (C18:1n-9; 63.3%), linoleic acid (C18:2n-6; 4.7%), and linolenic acid (C18:3n-6; 5.1%) as major mono- and polyunsaturated fatty acids. No changes in the organoleptic characteristics and fatty acid composition were observed after the accelerated stability test. VOB 100 µg/mL reduced the healing time by increasing the total number of cells in the wounded area by 43.0±5.1% compared to the negative control group. VOB also suppressed the pro-inflammatory TNF-α and IL-6 cytokines, and NO and O2- production in lipopolysaccharide-stimulated macrophage cells. In conclusion, the VOB formulation contributed to the improvement of current therapeutic strategies for cutaneous applications in skin care.

This study investigated the effect of etching with distinct hydrofluoric (HF) acid concentrations on the cyclic load-to-failure (C Lf ) of simplified lithium disilicate glass-ceramic restorations adhesively cemented to a dentin analogue (n = 20): non-etched/control (CTRL), or etched for 20 s with HF acid at 3% (HF3), 5% (HF5), or 10% (HF10). A silane coating was then applied onto the ceramic surfaces. Fatigue tests followed the staircase approach (initial load= 720 N; step-size= 70 N; 500,000 cycles per sample; 20 Hz) using a hemispheric stainless-steel piston (Ø= 40 mm) under water. The C Lf data were analyzed using Dixon and Mood method. Topographic and fractographic analyses were conducted. C Lf (in N) of HF3 (1355 ± 32.0) and HF5 (1335 ± 58.8) groups were the highest and statistically similar; HF10 presented intermediate C Lf (1175 ± 132.9), while the non-etched group had the lowest one (965 ± 145.0). Topographical analysis showed that the higher the HF acid concentration, the more pronounced the topographical changes. All failures (radial cracks) started from the inner surface of the ceramic discs. Topographical changes promoted by intermediate HF acid concentrations (3% and 5%) may improve fatigue performance for adhesively-cemented lithium disilicate restorations., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Here we revisit whether the common mixed-valent Fe mineral, magnetite, is a viable reductant for the abiotic natural attenuation of perchloroethylene (PCE) and trichloroethylene (TCE) in anoxic groundwater plumes. We measured PCE and TCE reduction by stoichiometric magnetite as a function of pH and Fe(ii) concentration. In the absence of added Fe(ii), stoichiometric magnetite does not reduce PCE and TCE over a three month period under anoxic conditions. When Fe(ii) is added to magnetite suspensions, PCE and TCE are reduced under Fe(ii) and pH conditions that appear to be controlled by the solubility of ferrous hydroxide, Fe(OH)2(s). Reduction rates are slow with only 1 to 30% carbon products (primarily acetylene) accumulating over several months. We conducted a similar set of experiments with Fe(OH)2(s) alone and found that, compared to in the presence of magnetite, Fe(OH)2(s) reduces PCE and TCE only at Fe(ii) concentrations that are too high (≥13 mM, 726 mg L-1) to be representative of natural aquifer conditions. Our results suggest that magnetite present in aquifer sediments alone is unlikely to reduce PCE and TCE sufficiently fast to contribute to natural attenuation of PCE and TCE. The lack of compelling evidence for PCE and TCE reduction by magnetite raises important questions regarding the current application of using magnetic susceptibility as a potential indicator for abiotic natural attenuation. Dynamic conditions and high Fe(ii) concentrations that favor active precipitation of minerals, such as Fe(OH)2(s) in the presence of magnetite (or other Fe minerals), however, may lead to PCE and TCE reduction that could help attenuate PCE and TCE plumes.

Ferrihydrite is a common Fe mineral in soils and sediments that rapidly transforms to secondary minerals in the presence of Fe(II). Both the rate and products of Fe(II)-catalyzed ferrihydrite transformation have been shown to be significantly influenced by natural organic matter (NOM). Here, we used enriched Fe isotope experiments and 57 Fe Mössbauer spectroscopy to track the formation of secondary minerals, as well as electron transfer and Fe mixing between aqueous Fe(II) and ferrihydrite coprecipitated with several types of NOM. Ferrihydrite coprecipitated with humic acids transformed primarily to goethite after reaction with Fe(II). In contrast, ferrihydrite coprecipitated with fulvic acids and Suwannee River NOM (SRNOM) resulted in no measurable formation of secondary minerals. Despite no secondary mineral transformation, Mössbauer spectra indicated electron transfer still occurred between Fe(II) and ferrihydrite coprecipitated with fulvic acid and SRNOM. In addition, isotope tracer experiments revealed that a significant fraction of structural Fe in the ferrihydrite mixed with the aqueous phase Fe(II) (∼85%). After reaction with Fe(II), Mössbauer spectroscopy indicated some subtle changes in the crystallinity, particle size, or particle interactions in the coprecipitate. Our observations suggest that ferrihydrite coprecipitated with fulvic acid and SRNOM remains a highly dynamic phase even without ferrihydrite transformation.

Objectives: To evaluate the effect of different glass-ceramic surface treatments and aging on the fatigue failure load of a lithium disilicate glass-ceramic adhesively cemented to a dentin analogue material., Methods: One hundred and twenty (120) disc-shaped lithium disilicate specimens (Ø=10mm, thickness=1.5mm) were produced and randomly allocated (n=20) into 6 groups, considering 2 study factors: "surface treatment" in 3 levels (SIL-silane application only; HF5+SIL-5% hydrofluoric acid etching and silane application; ME&P-etching with an one-step ceramic primer), and "storage" in 2 levels (baseline-storage for 7 days; aging-storage for 90 days+12,000 thermal cycles). Ceramic discs were adhesively cemented to discs of a dentin analogue material (Ø=10mm, thickness=2.0mm) following the manufacturers' instructions. The fatigue failure load was determined by the staircase approach (250,000 cycles; 20Hz; initial load=1050N [∼70% of mean load-to-failure]; step size=52.5N [5% of initial load]). Micro-morphologic, fractographic, and atomic force microscope analysis were also performed. Fatigue failure load data were evaluated by one-way ANOVA, Bonferroni and t-tests for independent samples., Results: HF5+SIL presented higher fatigue failure load in both conditions (baseline and aging); ME&P presented intermediary mean values, while the SIL group presented the worst performance. All groups had a statistically significant decrease in the fatigue performance after aging., Significance: Hydrofluoric acid followed by silane application showed the best fatigue performance for an adhesively-cemented lithium disilicate ceramic. Aging negatively influenced the fatigue performance for all tested groups., (Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.)

Despite substantial experimental evidence for Fe(II)-Fe(III) oxide electron transfer, computational chemistry calculations suggest that oxidation of sorbed Fe(II) by goethite is kinetically inhibited on structurally perfect surfaces. We used a combination of 57 Fe Mössbauer spectroscopy, synchrotron X-ray absorption and magnetic circular dichroism (XAS/XMCD) spectroscopies to investigate whether Fe(II)-goethite electron transfer is influenced by defects. Specifically, Fe L-edge and O K-edge XAS indicates that the outermost few Angstroms of goethite synthesized by low temperature Fe(III) hydrolysis is iron deficient relative to oxygen, suggesting the presence of defects from Fe vacancies. This nonstoichiometric goethite undergoes facile Fe(II)-Fe(III) oxide electron transfer, depositing additional goethite consistent with experimental precedent. Hydrothermal treatment of this goethite, however, appears to remove defects, decrease the amount of Fe(II) oxidation, and change the composition of the oxidation product. When hydrothermally treated goethite was ground, surface defect characteristics as well as the extent of electron transfer were largely restored. Our findings suggest that surface defects play a commanding role in Fe(II)-goethite redox interaction, as predicted by computational chemistry. Moreover, it suggests that, in the environment, the extent of this interaction will vary depending on diagenetic history, local redox conditions, as well as being subject to regeneration via seasonal fluctuations.

Iron (Fe) and manganese (Mn) are the two most common redox-active elements in the Earth's crust and are well known to influence mineral formation and dissolution, trace metal sequestration, and contaminant transformations in soils and sediments. Here, we characterized the reaction of aqueous Fe(II) with pyrolusite (β-MnO 2 ) using electron microscopy, X-ray diffraction, aqueous Fe and Mn analyses, and 57 Fe Mössbauer spectroscopy. We reacted pyrolusite solids repeatedly with 3 mM Fe(II) at pH 7.5 to evaluate whether electron transfer occurs and to track the evolving reactivity of the Mn/Fe solids. We used Fe isotopes (56 and 57) in conjunction with 57 Fe Mössbauer spectroscopy to isolate oxidation of Fe(II) by Fe(III) precipitates or pyrolusite. Using these complementary techniques, we determined that Fe(II) is initially oxidized by pyrolusite and that lepidocrocite is the dominant Fe oxidation product. Additional Fe(II) exposures result in an increasing proportion of magnetite on the pyrolusite surface. Over a series of nine 3 mM Fe(II) additions, Fe(II) continued to be oxidized by the Mn/Fe particles suggesting that Mn/Fe phases are not fully passivated and remain redox active even after extensive surface coverage by Fe(III) oxides. Interestingly, the initial Fe(III) oxide precipitates became further reduced as Fe(II) was added and additional Mn was released into solution suggesting that both the Fe oxide coating and underlying Mn phase continue to participate in redox reactions when freshly exposed to Fe(II). Our findings indicate that Fe and Mn chemistry is influenced by sustained reactions of Fe(II) with Mn/Fe oxides.

Exposure to As in groundwater negatively impacts millions of people around the globe, and As mobility in groundwater is often controlled by Fe mineral dissolution and precipitation. Additionally, trace elements can be released from and incorporated into the structure of Fe oxides in the presence of dissolved Fe(ii). The potential for As to redistribute between sorbed on the magnetite surface and incorporated in the magnetite structure, however, remains unclear. In this study, we use selective chemical extraction and X-ray absorption spectroscopy (XAS) to distinguish magnetite-sorbed and incorporated As(v) and to provide evidence for As(v) incorporation during magnetite precipitation. While As in the As-magnetite coprecipitates did not redistribute between sorbed and incorporated over a 4 month period, a small, but measurable increase in incorporated As(v) of up to 13% was observed for sorbed As(v). We suggest that Fe(ii)-catalyzed recrystallization of magnetite did not significantly influence the redistribution of sorbed As(v) because the extent of Fe atom exchange was small (∼10%). In addition, the extent of As redistribution was the same in the absence and presence of added aqueous Fe(ii), suggesting that aqueous Fe(ii) had, overall, a minor effect on As redistribution for both coprecipitated and sorbed As(v). Our results suggest that coprecipitation of As(v) with magnetite and redistribution of As(v) sorbed on magnetite are potential pathways for irreversible As(v) uptake and sequestration. These pathways are likely to play a significant role in controlling As mobility in natural systems, during human-induced redox cycling of groundwater such as aquifer storage and recovery, as well as in iron oxide-based As removal systems.

Background: Occlusal sealants are an effective method for caries prevention, although the effectiveness of different application strategies has not been established yet., Aim: This systematic review compared the retention rate of sealants placed on occlusal surfaces following the use of self-etch adhesive systems and traditional acid etching, with or without the application of adhesive system., Design: Literature searching was carried out until June 2015 in PubMed/MEDLINE, CENTRAL, and ClinicalTrials databases selecting randomized clinical trials that evaluated self-etch adhesive systems associated with pit and fissure sealants in primary or permanent molars comprising retention as outcome. From 683 potentially eligible studies, 10 were selected for full-text analysis and 5 were included in the meta-analysis. Two reviewers independently selected the studies, extracted the data, and assessed the bias risk. Pooled-effect estimates were obtained by comparing the retention failure rate between groups (self-etch systems vs acid etching with or without adhesive systems)., Results: Significant difference was found between groups, favoring the control group (prior acid etching) (P < 0.05), which showed lower failure rate in the retention of occlusal sealants. High heterogeneity was found on the meta-analysis. Most trials showed good evidence strength., Conclusions: Occlusal sealants applied with self-etch systems show lower retention throughout time than sealants applied in the conventional approach, regardless of the use of adhesive systems., (© 2015 BSPD, IAPD and John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Manganese is biogeochemically cycled between aqueous Mn(II) and Mn(IV) oxides. Aqueous Mn(II) often coexists with Mn(IV) oxides, and redox reactions between the two (e.g., comproportionation) are well known to result in the formation of Mn(III) minerals. It is unknown, however, whether aqueous Mn(II) exchanges with structural Mn(III) in manganese oxides in the absence of any mineral transformation (similar to what has been reported for aqueous Fe(II) and some Fe(III) minerals). To probe whether atoms exchange between a Mn(III) oxide and water, we use a (17)O tracer to measure oxygen isotope exchange between structural oxygen in manganite (γ-MnOOH) and water. In the absence of aqueous Mn(II), about 18% of the oxygen atoms in manganite exchange with the aqueous phase, which is close to the estimated surface oxygen atoms (∼11%). In the presence of aqueous Mn(II), an additional 10% (for a total of 28%) of the oxygen atoms exchange with water, suggesting that some of the bulk manganite mineral (i.e., beyond surface) is exchanging with the fluid. Exchange of manganite oxygen with water occurs without any observable change in mineral phase and appears to be independent of the rapid Mn(II) sorption kinetics. These experiments suggest that Mn(II) catalyzes manganese oxide recrystallization and illustrate a new pathway by which these ubiquitous minerals interact with their surrounding fluid.

We use the functional renormalization group and the [Formula: see text]-expansion concertedly to explore multicritical universality classes for coupled [Formula: see text] vector-field models in three Euclidean dimensions. Exploiting the complementary strengths of these two methods we show how to make progress in theories with large numbers of interactions, and a large number of possible symmetry-breaking patterns. For the three- and four-field models we find a new fixed point that arises from the mutual interaction between different field sectors, and we establish the absence of infrared-stable fixed-point solutions for the regime of small [Formula: see text]. Moreover, we explore these systems as toy models for theories that are both asymptotically safe and infrared complete. In particular, we show that these models exhibit complete renormalization group trajectories that begin and end at nontrivial fixed points.

Aqueous Fe(II) has been shown to exchange with structural Fe(III) in goethite without any significant phase transformation. It remains unclear, however, whether aqueous Fe(II) undergoes similar exchange reactions with structural Fe(III) in hematite, a ubiquitous iron oxide mineral. Here, we use an enriched (57)Fe tracer to show that aqueous Fe(II) exchanges with structural Fe(III) in hematite at room temperature, and that the amount of exchange is influenced by particle size, pH, and Fe(II) concentration. Reaction of 80 nm-hematite (27 m(2) g(-1)) with aqueous Fe(II) at pH 7.0 for 30 days results in ∼5% of its structural Fe(III) atoms exchanging with Fe(II) in solution, which equates to about one surface iron layer. Smaller, 50 nm-hematite particles (54 m(2) g(-1)) undergo about 25% exchange (∼3× surface iron) with aqueous Fe(II), demonstrating that structural Fe(III) in hematite is accessible to the fluid in the presence of Fe(II). The extent of exchange in hematite increases with pH up to 7.5 and then begins to decrease as the pH progresses to 8.0, likely due to surface site saturation by sorbed Fe(II). Similarly, when we vary the initial amount of added Fe(II), we observe decreasing amounts of exchange when aqueous Fe(II) is increased beyond surface saturation. This work shows that Fe(II) can catalyze iron atom exchange between bulk hematite and aqueous Fe(II), despite hematite being the most thermodynamically stable iron oxide.

Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

We study models with three coupled vector fields characterized by O(N&#95;{1})⊕O(N&#95;{2})⊕O(N&#95;{3}) symmetry. Using the nonperturbative functional renormalization group, we derive β functions for the couplings and anomalous dimensions in d dimensions. Specializing to the case of three dimensions, we explore interacting fixed points that generalize the O(N) Wilson-Fisher fixed point. We find a symmetry-enhanced isotropic fixed point, a large class of fixed points with partial symmetry enhancement, as well as partially and fully decoupled fixed-point solutions. We discuss their stability properties for all values of N&#95;{1},N&#95;{2}, and N&#95;{3}, emphasizing important differences to the related two-field models. For small numbers of field components, we find no stable fixed-point solutions, and we argue that this can be attributed to the presence of a large class of possible (mixed) couplings in the three-field and multifield models. Furthermore, we contrast different mechanisms for stability interchange between fixed points in the case of the two- and three-field models, which generically proceed through fixed-point collisions.

Results from enriched (57)Fe isotope tracer experiments have shown that atom exchange can occur between structural Fe in Fe(III) oxides and aqueous Fe(II) with no formation of secondary minerals or change in particle size or shape. Here we derive a mass balance model to quantify the extent of Fe atom exchange between goethite and aqueous Fe(II) that accounts for different Fe pool sizes. We use this model to reinterpret our previous work and to quantify the influence of particle size and pH on extent of goethite exchange with aqueous Fe(II). Consistent with our previous interpretation, substantial exchange of goethite occurred at pH 7.5 (≈ 90%) and we observed little effect of particle size between nanogoethite (average size of 81 × 11 nm; ≈ 110 m(2)/g) and microgoethite (average size of 590 × 42 nm; ≈ 40 m(2)/g). Despite ≈ 90% of the bulk goethite exchanging at pH 7.5, we found no change in mineral phase, average particle size, crystallinity, or reactivity after reaction with aqueous Fe(II). At a lower pH of 5.0, no net sorption of Fe(II) was observed and significantly less exchange occurred accounting for less than the estimated proportion of surface Fe atoms in the particles. Particle size appears to influence the amount of exchange at pH 5.0 and we suggest that aggregation and surface area may play a role. Results from sequential chemical extractions indicate that (57)Fe accumulates in extracted Fe(III) goethite components. Isotopic compositions of the extracts indicate that a gradient of (57)Fe develops within the goethite with more accumulation of (57)Fe occurring in the more easily extracted Fe(III) that may be nearer to the surface.

We employ the nonperturbative functional renormalization group to study models with an O(N(1) ⊕O(N)(2)) symmetry. Here different fixed points exist in three dimensions, corresponding to bicritical and tetracritical behavior induced by the competition of two order parameters. We discuss the critical behavior of the symmetry-enhanced isotropic, the decoupled and the biconical fixed point, and analyze their stability in the N(1),N(2) plane. We study the fate of nontrivial fixed points during the transition from three to four dimensions, finding evidence for a triviality problem for coupled two-scalar models in high-energy physics. We also point out the possibility of noncanonical critical exponents at semi-Gaussian fixed points and show the emergence of Goldstone modes from discrete symmetries.

Natural Fe(III) oxides typically contain a range of trace elements including P. Although solution phase and adsorbed P (as phosphate) have been shown to impact the bioreduction of Fe(III) oxides and the formation of "biogenic" secondary minerals, little is known about the potential effects of occluded/incorporated phosphate. We have examined the bioreduction of Fe(III) oxides (lepidocrocite (γ-FeOOH) and maghemite (γ-Fe2O3)) containing 0-3 mass% P as "bound" (a term we use to include both adsorbed and occluded/incorporated) phosphate. Kinetic dissolution studies showed congruent release of Fe and P, suggesting that the phosphate in these materials was incorporated within the particles; however, 53% or 86% of the total phosphate associated with the lepidocrocites containing 0.7 or 3 mass% P, respectively, was extracted with 0.1 M NaOH and can be considered to be adsorbed, both to exterior surfaces and within micropores. In the absence of phosphate, lepidocrocite was rapidly reduced to magnetite by Shewanella putrefaciens CN32, and over time the magnetite was partially transformed to ferrous hydroxy carbonate (FHC). The presence of 0.2-0.7 mass% P significantly inhibited the initial reduction of lepidocrocite but ultimately resulted in greater Fe(II) production and the formation of carbonate green rust. The bioreduction of maghemite with and without bound phosphate resulted in solid-state conversion to magnetite, with subsequent formation of FHC. We also examined the potential redox cycling of green rust under alternating Fe(III)-reducing and oxic conditions. Oxidation of biogenic green rust by O2 resulted in conversion to ferric green rust, which was readily reduced back to green rust by S. putrefaciens CN32. These results indicate the potential for cycling of green rust between reduced and oxidized forms under redox dynamics similar to those encountered in environments that alternate between iron-reducing and oxic conditions, and they are consistent with the identification of green rust in soils/sediments with seasonal redox cycling.

Abiotic reduction of inorganic mercury by natural organic matter and native soils is well-known, and recently there is evidence that reduced iron (Fe) species, such as magnetite, green rust, and Fe sulfides, can also reduce Hg(II). Here, we evaluated the reduction of Hg(II) by magnetites with varying Fe(II) content in both the absence and presence of chloride. Specifically, we evaluated whether magnetite stoichiometry (x = Fe(II)/Fe(III)) influences the rate of Hg(II) reduction and formation of products. In the absence of chloride, reduction of Hg(II) to Hg(0) is observed over a range of magnetite stoichiometries (0.29 < x < 0.50) in purged headspace reactors and unpurged low headspace reactors, as evidenced by Hg recovery in a volatile product trap solution and Hg L(III)-edge X-ray absorption near edge spectroscopy (XANES). In the presence of chloride, however, XANES spectra indicate the formation of a metastable Hg(I) calomel species (Hg2Cl2) from the reduction of Hg(II). Interestingly, Hg(I) species are only observed for the more oxidized magnetite particles that contain lower Fe(II) content (x < 0.42). For the more reduced magnetite particles (x ≥ 0.42), Hg(II) is reduced to Hg(0) even in the presence of high chloride concentrations. As previously observed for nitroaromatic compounds and uranium, magnetite stoichiometry appears to influence the rate of Hg(II) reduction (both in the presence and absence of chloride) confirming that it is important to consider magnetite stoichiometry when assessing the fate of contaminants in Fe-rich subsurface environments.

Despite the importance of Fe redox cycling in clay minerals, the mechanism and location of electron transfer remain unclear. More specifically, there is some controversy whether electron transfer can occur through both basal and edge surfaces. Here we used Mössbauer spectroscopy combined with selective chemical extractions to study electron transfer from Fe(II) sorbed to basal planes and edge OH-groups of clay mineral NAu-1. Fe(II) sorbed predominantly to basal planes at pH values below 6.0 and to edge OH-groups at pH value 7.5. Significant electron transfer occurred from edge OH-group bound Fe(II) at pH 7.5, whereas electron transfer from basal plane-sorbed Fe(II) to structural Fe(III) in clay mineral NAu-1 at pH 4.0 and 6.0 occurred but to a much lower extent than from edge-bound Fe(II). Mössbauer hyperfine parameters for Fe(II)-reacted NAu-1 at pH 7.5 were consistent with structural Fe(II), whereas values found at pH 4.0 and 6.0 were indicative of binding environments similar to basal plane-sorbed Fe(II). Reference experiments with Fe-free synthetic montmorillonite SYn-1 provided supporting evidence for the assignment of the hyperfine parameters to Fe(II) bound to basal planes and edge OH-groups. Our findings demonstrate that electron transfer to structural Fe in clay minerals can occur from Fe(II) sorbed to both basal planes and edge OH-groups. These findings require us to reassess the mechanisms of abiotic and microbial Fe reduction in clay minerals as well as the importance of Fe-bearing clay minerals as a renewable source of redox equivalents in subsurface environments.

Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe2+-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe2+-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe2+-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe2+-catalysed iron oxide recrystallization.

The reaction between magnetite and aqueous Fe(2+) has been extensively studied due to its role in contaminant reduction, trace-metal sequestration, and microbial respiration. Previous work has demonstrated that the reaction of Fe(2+) with magnetite (Fe(3)O(4)) results in the structural incorporation of Fe(2+) and an increase in the bulk Fe(2+) content of magnetite. It is unclear, however, whether significant Fe atom exchange occurs between magnetite and aqueous Fe(2+), as has been observed for other Fe oxides. Here, we measured the extent of Fe atom exchange between aqueous Fe(2+) and magnetite by reacting isotopically "normal" magnetite with (57)Fe-enriched aqueous Fe(2+). The extent of Fe atom exchange between magnetite and aqueous Fe(2+) was significant (54-71%), and went well beyond the amount of Fe atoms found at the near surface. Mössbauer spectroscopy of magnetite reacted with (56)Fe(2+) indicate that no preferential exchange of octahedral or tetrahedral sites occurred. Exchange experiments conducted with Co-ferrite (Co(2+)Fe(2)(3+)O(4)) showed little impact of Co substitution on the rate or extent of atom exchange. Bulk electron conduction, as previously invoked to explain Fe atom exchange in goethite, is a possible mechanism, but if it is occurring, conduction does not appear to be the rate-limiting step. The lack of significant impact of Co substitution on the kinetics of Fe atom exchange, and the relatively high diffusion coefficients reported for magnetite suggest that for magnetite, unlike goethite, Fe atom diffusion is a plausible mechanism to explain the rapid rates of Fe atom exchange in magnetite.

Iron-containing oxide nanoparticles are of great interest from a number of technological perspectives and they are also present in the natural environment. Although recent evidence suggests that particle size plays an important role in the dissolution of metal oxides, a detailed fundamental understanding of the influence of particle size is just beginning to emerge. In the current study, we investigate whether nanoscale size-effects are observed for the dissolution of iron oxyhydroxide under different conditions. The dissolution of two particle sizes of goethite, α-FeOOH in the nanoscale and microscale size regimes (herein referred to as nanorods and microrods), in aqueous suspensions at pH 2 is investigated. It is shown here that in the presence of nitrate, nanorods shows greater dissolution on both a per mass and per surface area basis relative to microrods, in agreement with earlier studies. In the presence of carbonate and phosphate, however, dissolution of α-FeOOH nanorods at pH 2 is significantly inhibited, despite the fact that these anions result in a three- to fivefold enhancement of the dissolution of microrods relative to the nitrate anion. Light scattering techniques and electron microscopy show that nanorod suspensions are less stable compared to microrod suspensions resulting in nanorod aggregation under conditions where microrods stay more dispersed. Furthermore, spectroscopic studies using ATR-FTIR spectroscopy show distinct differences in phosphate and carbonate adsorption on nanorods compared to microrods. These results demonstrate that aggregation and the details of surface adsorption are important in the dissolution behavior of nanoscale materials., (Copyright © 2012 Elsevier Inc. All rights reserved.)

The reaction of Fe(II) with Fe(III) oxides and hydroxides is complex and includes sorption of Fe(II) to the oxide, electron transfer between sorbed Fe(II) and structural Fe(III), reductive dissolution coupled to Fe atom exchange, and, in some cases mineral phase transformation. Much of the work investigating electron transfer and atom exchange between aqueous Fe(II) and Fe(III) oxides has been done under relatively simple aqueous conditions in organic buffers to control pH and background electrolytes to control ionic strength. Here, we investigate whether electron transfer is influenced by cation substitution of Al(III) in goethite and the presence of anions such as phosphate, carbonate, silicate, and natural organic matter. Results from (57)Fe Mössbauer spectroscopy indicate that both Al-substitution (up to 9%) and the presence of common anions (PO(4)(3-), CO(3)(2-), SiO(4)(4-), and humic acid) does not inhibit electron transfer between aqueous Fe(II) and Fe(III) in goethite under the conditions we studied. In contrast, sorption of a long-chain phospholipid completely shuts down electron transfer. Using an enriched isotope tracer method, we found that Al-substitution in goethite (10%), does, however, significantly decrease the extent of atom exchange between Fe(II) and goethite (from 43 to 12%) over a month's time. Phosphate, somewhat surprisingly, appears to have little effect on the rate and extent of atom exchange between aqueous Fe(II) and goethite. Our results show that electron transfer between aqueous Fe(II) and solid Fe(III) in goethite can occur under wide range of geochemical conditions, but that the extent of redox-driven Fe atom exchange may be dependent on the presence of substituting cations such as Al.

Using a combination of quantum Monte Carlo simulations, functional renormalization group calculations and mean-field theory, we study the Hubbard model on the Bernal-stacked honeycomb bilayer at half-filling as a model system for bilayer graphene. The free bands consisting of two Fermi points with quadratic dispersions lead to a finite density of states at the Fermi level, which triggers an antiferromagnetic instability that spontaneously breaks sublattice and spin rotational symmetry once local Coulomb repulsions are introduced. Our results reveal an inhomogeneous participation of the spin moments in the ordered ground state, with enhanced moments at the threefold coordinated sites. Furthermore, we find the antiferromagnetic ground state to be robust with respect to enhanced interlayer couplings and extended Coulomb interactions.

Aqueous Fe(II) reacts with Fe(III) oxides by coupled electron transfer and atom exchange (ETAE) resulting in mineral recrystallization, contaminant reduction, and trace element cycling. Previous studies of Fe(II)-Fe(III) ETAE have explored the reactivity of either pure iron oxide phases or those containing small quantities of soluble trace elements. Naturally occurring iron oxides, however, contain substantial quantities of insoluble impurities (e.g., Al) which are known to affect the chemical properties of such minerals. Here we explore the effect of Al(III), Cr(III), and Sn(IV) substitution (1-8 mol %) on trace element release from Ni(II)-substituted goethite and Zn(II)-substituted hematite during reaction with aqueous Fe(II). Fe(II)-activated trace element release is substantially inhibited from both minerals when an insoluble element is cosubstituted into the structure, and the total amount of release decreases exponentially with increasing cosubstituent. The limited changes in surface composition that occur following reaction with Fe(II) indicate that Al, Cr, and Sn do not exsolve from the structure and that Ni and Zn released to solution originate primarily from the bulk rather than the particle exterior (upper ~3 nm). Incorporation of Al into goethite substantially decreases the amount of iron atom exchange with aqueous Fe(II) and, consequently, the amount of Ni release from the structure. This implies that trace element release inhibition caused by substituting insoluble elements results from a decrease in the amount of mineral recrystallization. These results suggest that naturally occurring iron oxides containing insoluble elements are less susceptible to Fe(II)-activated recrystallization and exhibit a greater retention of trace elements and contaminants than pure mineral phases.

Anthropogenic coal fly ash (FA) aerosol may represent a significant source of bioavailable iron in the open ocean. Few measurements have been made that compare the solubility of atmospheric iron from anthropogenic aerosols and other sources. We report here an investigation of iron dissolution for three FA samples in acidic aqueous solutions and compare the solubilities with that of Arizona test dust (AZTD), a reference material for mineral dust. The effects of pH, simulated cloud processing, and solar radiation on iron solubility have been explored. Similar to previously reported results on mineral dust, iron in aluminosilicate phases provides the predominant component of dissolved iron. Iron solubility of FA is substantially higher than of the crystalline minerals comprising AZTD. Simulated atmospheric processing elevates iron solubility due to significant changes in the morphology of aluminosilicate glass, a dominant material in FA particles. Iron is continuously released into the aqueous solution as FA particles break up into smaller fragments. These results suggest that the assessment of dissolved atmospheric iron deposition fluxes and their effect on the biogeochemistry at the ocean surface should be constrained by the source, environmental pH, iron speciation, and solar radiation.

Hexavalent uranium (U(VI)) can be reduced enzymatically by various microbes and abiotically by Fe(2+)-bearing minerals, including magnetite, of interest because of its formation from Fe(3+) (oxy)hydroxides via dissimilatory iron reduction. Magnetite is also a corrosion product of iron metal in suboxic and anoxic conditions and is likely to form during corrosion of steel waste containers holding uranium-containing spent nuclear fuel. Previous work indicated discrepancies in the extent of U(VI) reduction by magnetite. Here, we demonstrate that the stoichiometry (the bulk Fe(2+)/Fe(3+) ratio, x) of magnetite can, in part, explain the observed discrepancies. In our studies, magnetite stoichiometry significantly influenced the extent of U(VI) reduction by magnetite. Stoichiometric and partially oxidized magnetites with x ≥ 0.38 reduced U(VI) to U(IV) in UO(2) (uraninite) nanoparticles, whereas with more oxidized magnetites (x < 0.38) and maghemite (x = 0), sorbed U(VI) was the dominant phase observed. Furthermore, as with our chemically synthesized magnetites (x ≥ 0.38), nanoparticulate UO(2) was formed from reduction of U(VI) in a heat-killed suspension of biogenic magnetite (x = 0.43). X-ray absorption and Mössbauer spectroscopy results indicate that reduction of U(VI) to U(IV) is coupled to oxidation of Fe(2+) in magnetite. The addition of aqueous Fe(2+) to suspensions of oxidized magnetite resulted in reduction of U(VI) to UO(2), consistent with our previous finding that Fe(2+) taken up from solution increased the magnetite stoichiometry. Our results suggest that magnetite stoichiometry and the ability of aqueous Fe(2+) to recharge magnetite are important factors in reduction of U(VI) in the subsurface.

We review the functional renormalization group (RG) approach to the Bardeen-Cooper-Schrieffer to Bose-Einstein condensation (BCS-BEC) crossover for an ultracold gas of fermionic atoms. Formulated in terms of a scale-dependent effective action, the functional RG interpolates continuously between the atomic or molecular microphysics and the macroscopic physics on large length scales. We concentrate on the discussion of the phase diagram as a function of the scattering length and the temperature, which is a paradigm example for the non-perturbative power of the functional RG. A systematic derivative expansion provides for both a description of the many-body physics and its expected universal features as well as an accurate account of the few-body physics and the associated BEC and BCS limits.

Interfacial electron transfer has been shown to occur between sorbed Fe(II) and structural Fe(III) in Fe oxides, but it is unknown whether a similar reaction occurs between sorbed Fe(II) and Fe(III)-bearing clay minerals. Here, we used the isotopic specificity of (57)Fe Mössbauer spectroscopy to demonstrate electron transfer between sorbed Fe(II) and structural Fe(III) in an Fe-bearing smectite clay mineral (NAu-2, nontronite). Mössbauer spectra of NAu-2 reacted with aqueous (56)Fe(II) (which is invisible to (57)Fe Mössbauer spectroscopy) showed direct evidence for reduction of NAu-2 by sorbed Fe(II). Mössbauer spectra using aqueous (57)Fe(II) showed that sorbed Fe(II) is oxidized upon sorption to the clay and pXRD patterns indicate that the oxidation product is lepidocrocite. Spectra collected at different temperatures indicate that reduction of structural Fe(III) by sorbed Fe(II) induces electron delocalization in the clay structure. Our results also imply that interpretation of room temperature and 77 K Mössbauer spectra may significantly underestimate the amount of Fe(II) in Fe-bearing clays. These findings provide compelling evidence for abiotic reduction of Fe-bearing clay minerals by sorbed Fe(II), and require us to reframe our conceptual model for interpreting biological reduction of clay minerals, as well as contaminant reduction by reduced clays.

Microbial reduction of Fe(III) oxides results in the production of Fe(II) and may lead to the subsequent formation of Fe(II)-bearing secondary mineralization products including magnetite, siderite, vivianite, chukanovite (ferrous hydroxy carbonate (FHC)), and green rust; however, the factors controlling the formation of specific Fe(II) phases are often not well-defined. This study examined effects of (i) a range of inorganic oxyanions (arsenate, borate, molybdate, phosphate, silicate, and tungstate), (ii) natural organic matter (citrate, oxalate, microbial extracellular polymeric substances [EPS], and humic substances), and (iii) the type and number of dissimilatory iron-reducing bacteria on the bioreduction of lepidocrocite and formation of Fe(II)-bearing secondary mineralization products. The bioreduction kinetics clustered into two distinct Fe(II) production profiles. "Fast" Fe(II) production kinetics [19-24 mM Fe(II) d(-1)] were accompanied by formation of magnetite and FHC in the unamended control and in systems amended with borate, oxalate, gellan EPS, or Pony Lake fulvic acid or having "low" cell numbers. Systems amended with arsenate, citrate, molybdate, phosphate, silicate, tungstate, EPS from Shewanella putrefaciens CN32, or humic substances derived from terrestrial plant material or with "high" cell numbers exhibited comparatively slow Fe(II) production kinetics [1.8-4.0 mM Fe(II) d(-1)] and the formation of green rust. The results are consistent with a conceptual model whereby competitive sorption of more strongly bound anions blocks access of bacterial cells and reduced electron-shuttling compounds to sites on the iron oxide surface, thereby limiting the rate of bioreduction.

Ferrous iron [Fe(II)] bound to mineral surfaces has been shown to reduce several important groundwater contaminants, but little is known of the nature of the newly formed, insoluble ferric iron [Fe(III)] and whether it influences the heterogeneous contaminant reduction process. To explore how the formation and evolution of the Fe oxidation products influences contaminant reduction, we measured the kinetics of nitrobenzene reduction by Fe(II) sorbed on alpha-Al(2)O(3) while simultaneously characterizing the Fe oxidation product with Mossbauer spectroscopy and electron microscopy. After a brief period of slow kinetics, the onset of nitrobenzene reduction coincided with a change in particle suspension color from white to yellow-ocher due to formation of nanogoethite rods (alpha-FeOOH) from oxidation of sorbed Fe(II). Formation of nanogoethite on the alpha-Al(2)O(3) particles appears to promote the rapid reduction of nitrobenzene. Our results show that nanogoethite crystals can form rapidly by heterogeneous Fe(II) oxidation, and formation of goethite can profoundly influence contaminant reduction rates by Fe(II).

A number of recent studies have shown that iron dissolution in Fe-containing dust aerosol can be linked to source material (mineral or anthropogenic), mineralogy, and iron speciation. All of these factors need to be incorporated into atmospheric chemistry models if these models are to accurately predict the impact of Fe-containing dusts into open ocean waters. In this report, we combine dissolution measurements along with spectroscopy and microscopy to focus on nanoscale size effects in the dissolution of Fe-containing minerals in low-pH environments and the importance of acid type, including HNO(3), H(2)SO(4), and HCl, on dissolution. All of these acids are present in the atmosphere, and dust particles have been shown to be associated with nitrate, sulfate, and/or chloride. These measurements are done under light and dark conditions so as to simulate and distinguish between daytime and nighttime atmospheric chemical processing. Both size (nano- versus micron-sized particles) and anion (nitrate, sulfate, and chloride) are found to play significant roles in the dissolution of alpha-FeOOH under both light and dark conditions. The current study highlights these important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol.

Metal-containing nanorods are of great interest from a number of technological perspectives, and they are also present in the natural environment. Here we show that dissolution, both rate and extent, is greater for rod-shaped alpha-FeOOH particles on the nanoscale at pH 2 relative to microrods. However, when nanorods aggregate, either at lower pH and/or high ionic strength, dissolution is either completely quenched or severely quenched, by orders of magnitude. Furthermore, nanorod suspensions are less stable compared to microrod suspensions, resulting in nanorod aggregation under conditions where microrods stay fairly well dispersed. Although recent evidence suggests that particle size is a controlling factor in the solubility of iron oxides, a fundamental understanding of the influence of particle size is just beginning to emerge. The results presented here not only address some of the complexities of size-dependent dissolution of metal-containing nanorods in solution, they also contribute to our understanding of the factors that can influence Fe-mobilization in the global environment.

The factors controlling rates of contaminant reduction by magnetite (Fe3O4) are poorly understood. Here, we measured the reduction rates of three ArNO2 compounds by magnetite particles ranging from highly oxidized (x = Fe2+/Fe3+ = 0.31) to fully stoichiometric (x = 0.50). Rates of ArNO2 reduction became almost 5 orders of magnitude faster as the particle stoichiometry increased from x = 0.31 to 0.50. To evaluate what was controlling the rate of ArNO2 reduction, we measured apparent 15N kinetic isotope effects ((15)N-AKIE) values for nitrobenzene and magnetite open-circuit potentials (E(OCP)). 15N-AKIE values were greater than unity for all magnetite stoichiometries investigated, indicating that mass transfer processes are not controlling the rate of ArNO2 reduction by magnetite. E(OCP) measurements showed that the E(OCP) for magnetite was linearly related to the stoichiometry, with more stoichiometric magnetite having a lower potential. Based on these results, we propose that conceptual models that incorporate both redox and Fe2+ diffusion processes, rather than those that rely solely on diffusion of Fe2+, are more appropriate for understanding contaminant reduction by magnetite. Our work indicates that particle stoichiometry should be considered when evaluating rates of contaminant reduction by magnetite.