Reactivity of Uranium and Ferrous Iron with Natural Iron Oxyhydroxides.

Determining key reaction pathways involving uranium and iron oxyhydroxides under oxic and anoxic conditions is essential for understanding uranium mobility as well as other iron oxyhydroxide mediated processes, particularly near redox boundaries where redox conditions change rapidly in time and space. Here we examine the reactivity of a ferrihydrite-rich sediment from a surface seep adjacent to a redox boundary at the Rifle, Colorado field site. Iron(II)-sediment incubation experiments indicate that the natural ferrihydrite fraction of the sediment is not susceptible to reductive transformation under conditions that trigger significant mineralogical transformations of synthetic ferrihydrite. No measurable Fe(II)-promoted transformation was observed when the Rifle sediment was exposed to 30 mM Fe(II) for up to 2 weeks. Incubation of the Rifle sediment with 3 mM Fe(II) and 0.2 mM U(VI) for 15 days shows no measurable incorporation of U(VI) into the mineral structure or reduction of U(VI) to U(IV). Results indicate a significantly decreased reactivity of naturally occurring Fe oxyhydroxides as compared to synthetic minerals, likely due to the association of impurities (e.g., Si, organic matter), with implications for the mobility and bioavailability of uranium and other associated species in field environments.

Influence of chelating agents on biogenic uraninite reoxidation by Fe(III) (Hydr)oxides.

Microbially mediated reduction of soluble U(VI) to U(IV) with subsequent precipitation of uraninite, UO(2(S)), has been proposed as a method for limiting uranium (U) migration. However, microbially reduced UO(2) may be susceptible to reoxidation by environmental factors, with Fe(III) (hydr)oxides playing a significant role. Little is known about the role that organic compounds such as Fe(III) chelators play in the stability of reduced U. Here, we investigate the impact of citrate, DFB, EDTA, and NTA on biogenic UO(2) reoxidation with ferrihydrite, goethite, and hematite. Experiments were conducted in anaerobic batch systems in PIPES buffer (10 mM, pH 7) with bicarbonate for approximately 80 days. Results showed EDTA accelerated UO(2) reoxidation the most at an initial rate of 9.5 µM day(-1) with ferrihydrite, 8.6 µM day(-1) with goethite, and 8.8 µM day(-1) with hematite. NTA accelerated UO(2) reoxidation with ferrihydrite at a rate of 4.8 µM day(-1); rates were less with goethite and hematite (0.66 and 0.71 µM day(-1), respectively). Citrate increased UO(2) reoxidation with ferrihydrite at a rate of 1.8 µM day(-1), but did not increase the extent of reaction with goethite or hematite, with no reoxidation in this case. In all cases, bicarbonate increased the rate and extent of UO(2) reoxidation with ferrihydrite in the presence and absence of chelators. The highest rate of UO(2) reoxidation occurred when the chelator promoted both UO(2) and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO(2) dissolution did not occur, UO(2) reoxidation likely proceeded through an aqueous Fe(III) intermediate with lower reoxidation rates observed. Reaction modeling suggests that strong Fe(II) chelators promote reoxidation whereas strong Fe(III) chelators impede it. These results indicate that chelators found in U contaminated sites may play a significant role in mobilizing U, potentially affecting bioremediation efforts.

Detection of biological uranium reduction using magnetic resonance.

The conversion of soluble uranyl ions (UO2²âº) by bacterial reduction to sparingly soluble uraninite (UO2(s)) is being studied as a way of immobilizing subsurface uranium contamination. Under anaerobic conditions, several known types of bacteria including iron and sulfate reducing bacteria have been shown to reduce U (VI) to U (IV). Experiments using a suspension of uraninite (UO2(s)) particles produced by Shewanella putrefaciens CN32 bacteria show a dependence of both longitudinal (T1) and transverse (T2) magnetic resonance (MR) relaxation times on the oxidation state and solubility of the uranium. Gradient echo and spin echo MR images were compared to quantify the effect caused by the magnetic field fluctuations (T*2) of the uraninite particles and soluble uranyl ions. Since the precipitate studied was suspended in liquid water, the effects of concentration and particle aggregation were explored. A suspension of uraninite particles was injected into a polysaccharide gel, which simulates the precipitation environment of uraninite in the extracellular biofilm matrix. A reduction in the T2 of the gel surrounding the particles was observed. Tests done in situ using three bioreactors under different mixing conditions, continuously stirred, intermittently stirred, and not stirred, showed a quantifiable T2 magnetic relaxation effect over the extent of the reaction.

A low-input strategy for chromium removal from industrial stormwater using peat sorbent.

Low-cost and low-input water treatment systems are important for industrial stormwater remediation. Here we examine a flow-through reactor treatment installation where water exceeds the allowable maximum concentration for drinking water in multiple metals (e.g., chromium [Cr], cadmium [Cd], zinc [Zn]) prior to treatment. Specifically, we seek to understand why Cr attenuated in the reactors is not leachable by identifying the specific chemical form of Cr and dominant mechanisms promoting sequestration in the reactors. Total solid-phase Cr concentration in the peat media ranged from 50 to 150 mg/kg after 1 yr of exposure to stormwater to 300 to 900 mg/kg after 3.5 yr. X-ray fluorescence mapping images show Cr, iron (Fe), and Zn spatially correlated over a scale of 10 µm to 5 mm. Chromium rinds form on the edges of peat particles as Cr accumulates. Chromium and Fe K-edge X-ray absorption near edge structure spectroscopy reveal chromium predominately in the 3+ oxidation state with lesser amounts of elemental Cr. We propose the primary means of chromium attenuation in the reactors is precipitation as Cr-Fe hydroxides combined with trivalent Cr adsorption onto peat surfaces.

Effect of uranium(VI) speciation on simultaneous microbial reduction of uranium(VI) and iron(III).

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates whether it will reside in the aqueous or solid phase and thus plays an integral role in the mobility of uranium within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO2(2+) and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO. However, various factors within soils and sediments, such as U(VI) speciation and the presence of competitive electron acceptors, may limit biological reduction of U(VI). Here we examine simultaneous dissimilatory reduction of Fe(III) and U(VI) in batch systems containing dissolved uranyl acetate and ferrihydrite-coated sand. Varying amounts of calcium were added to induce changes in aqueous U(VI) speciation. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% in absence of Ca or ferrihydrite, but only 24% (with ferrihydrite) and 14% (without ferrihydrite) were removed for systems with 0.8 mM Ca. Dissimilatory reduction of Fe(III) and U(VI) proceed through different enzyme pathways within one type of organism. We quantified the rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concecentration (0-0.8 mM). The mathematical construct, implemented with the reactive transport code MIN3P, reveals predominant factors controlling rates and extent of uranium reduction in complex geochemical systems.

Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI).

Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.

An evidence-based resource for the management of comorbidities associated with childhood overweight and obesity.

PURPOSE: Overweight and obesity in children and adolescents is often accompanied by obesity-related comorbidities. An integrative review of the literature was performed to create a comprehensive algorithm to help primary care providers manage the common comorbidities associated with childhood overweight and obesity. DATA SOURCES: The Cumulative Index to Nursing and Allied Health Literature, ProQuest Nursing and Allied Health Source, and PubMed databases were searched. Evidence from 2002 to present was reviewed. Guidelines and algorithms from the American Academy of Pediatrics, National Association of Pediatric Nurse Practitioners, American Heart Association, American Diabetes Association, Centers for Disease Control and Prevention, National Heart, Lung, and Blood Institute, Agency for Healthcare and Research Quality, U.S. Department of Health and Human Services, and the International Diabetes Federation were also reviewed. CONCLUSIONS: Key information was extracted and data sources ranked according to the Polit and Beck evidence hierarchy. Highest level evidence guided the selection and development of recommendations to formulate a comprehensive resource for the recognition and management of pediatric hypertension, sleep apnea, vitamin D deficiency, nonalcoholic fatty liver disease, dyslipidemia, thyroid disease, diabetes mellitus, insulin resistance, metabolic syndrome, and polycystic ovarian syndrome. IMPLICATIONS FOR PRACTICE: The Childhood Overweight and Obesity Comorbidities Resource provides a consistent, convenient point-of-care reference to help primary care providers improve pediatric health outcomes.

Kinetic and mechanistic constraints on the oxidation of biogenic uraninite by ferrihydrite.

The oxidation state of uranium plays a major role in determining uranium mobility in the environment. Under anaerobic conditions, common metal respiring bacteria enzymatically reduce soluble U(VI) to U(IV), resulting in the formation of sparingly soluble UO(2(bio)) (biogenic uraninite). The stability of biologically precipitated uraninite is critical for determining the long-term fate of uranium and is not well characterized within soils and sediments. Here, we demonstrate that biogenic uraninite oxidation by ferrihydrite, an environmentally ubiquitous, disordered Fe(III) (hydr)oxide, appears to proceed through a soluble U(IV) intermediate and results in the concomitant production of Fe(II) and dissolved U(VI). Uraninite oxidation rates are accelerated under conditions that increase its solubility and decrease uraninite surface passivation, which include high bicarbonate concentration and pH values deviating from neutrality. Thus, our results demonstrate that UO(2(bio)) oxidation by Fe(III) (hydr)oxides is controlled by the rate of uraninite dissolution and that this process may limit uranium(IV) sequestration in the presence of Fe(III) (hydr)oxides.

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments.

Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a range of aqueous uranyl species. U(VI) adsorption is directly linked to UO(2)(2+) speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K(d) values decrease from 48 to 17 L kg(-1) for goethite, from 64 to 29 L kg (-1) for Hanford sediments, and from 95 to 51 L kg(-1) for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ( approximately 5) and limited dissolved calcium are optimal for uranium adsorption.

Stability of uranium incorporated into Fe (hydr)oxides under fluctuating redox conditions.

Reaction pathways resulting in uranium-bearing solids that are stable (i.e., having limited solubility) under aerobic and anaerobic conditions will limit dissolved concentrations and migration of this toxin. Here, we examine the sorption mechanism and propensity for release of uranium reacted with Fe (hydr)oxides under cyclic oxidizing and reducing conditions. Upon reaction of ferrihydrite with Fe(II) under conditions where aqueous Ca-UO2-CO3 species predominate (3 mM Ca and 3.8 mM total CO3), dissolved uranium concentrations decrease from 0.16 mM to below detection limit (BDL) after 5-15 d, depending on the Fe(II) concentration. In systems undergoing 3 successive redox cycles (14 d of reduction, followed by 5 d of oxidation) and a pulsed decrease to 0.15 mM total CO3, dissolved uranium concentrations varied depending on the Fe(II) concentration during the initial and subsequent reduction phases. U concentrations resulting during the oxic "rebound" varied inversely with the Fe(II) concentration during the reduction cycle. Uranium removed from solution remains in the oxidized form and is found adsorbed onto and incorporated into the structure of newly formed goethite and magnetite. Our results reveal that the fate of uranium is dependent on anaerobic/ aerobic conditions, aqueous uranium speciation, and the fate of iron.

Incorporation of oxidized uranium into Fe (hydr)oxides during Fe(II) catalyzed remineralization.

The form of solid phase U after Fe(II) induced anaerobic remineralization of ferrihydrite in the presence of aqueous and absorbed U(VI) was investigated under both abiotic batch and biotic flow conditions. Experiments were conducted with synthetic ground waters containing 0.168 mM U(VI), 3.8 mM carbonate, and 3.0 mM Ca2+. In spite of the high solubility of U(VI) under these conditions, appreciable removal of U(VI) from solution was observed in both the abiotic and biotic systems. The majority of the removed U was determined to be substituted as oxidized U (U(VI) or U(V)) into the octahedral position of the goethite and magnetite formed during ferrihydrite remineralization. It is estimated that between 3 and 6% of octahedral Fe(III) centers in the new Fe minerals were occupied by U. This site specific substitution is distinct from the nonspecific U coprecipitation processes in which uranyl compounds, e.g., uranyl hydroxide or carbonate, are entrapped within newly formed Fe oxides. The prevalence of site specific U incorporation under both abiotic and biotic conditions and the fact that the produced solids were shown to be resistant to both extraction (30 mM KHCO3) and oxidation (air for 5 days) suggest the potential importance of sequestration in Fe oxides as a stable and immobile form of U in the environment.

Speciation-dependent microbial reduction of uranium within iron-coated sands.

Transport of uranium within surface and subsurface environments is predicated largely on its redox state. Uranyl reduction may transpire through either biotic (enzymatic) or abiotic pathways; in either case, reduction of U(VI) to U(IV) results in the formation of sparingly soluble UO2 precipitates. Biological reduction of U(VI), while demonstrated as prolific under both laboratory and field conditions, is influenced by competing electron acceptors (such as nitrate, manganese oxides, or iron oxides) and uranyl speciation. Formation of Ca-UO2-CO3 ternary complexes, often the predominate uranyl species in carbonate-bearing soils and sediments, decreases the rate of dissimilatory U(VI) reduction. The combined influence of uranyl speciation within a mineralogical matrix comparable to natural environments and under hydrodynamic conditions, however, remains unresolved. We therefore examined uranyl reduction by Shewanella putrefaciens within packed mineral columns of ferrihydrite-coated quartz sand under conditions conducive or nonconducive to Ca-UO2-CO3 species formation. The results are dramatic. In the absence of Ca, where uranyl carbonato complexes dominate, U(VI) reduction transpires and consumes all of the U(VI) within the influent solution (0.166 mM) over the first 2.5 cm of the flow field for the entirety of the 54 d experiment. Over 2 g of U is deposited during this reaction period, and despite ferrihydrite being a competitive electron acceptor, uranium reduction appears unabated for the duration of our experiments. By contrast, in columns with 4 mM Ca in the influent solution (0.166 mM uranyl), reduction (enzymatic or surface-bound Fe(III) mediated) appears absent and breakthrough occurs within 18 d (at a flow rate of 3 pore volumes per day). Uranyl speciation, and in particular the formation of ternary Ca-UO2-CO3 complexes, has a profound impact on U(VI) reduction and thus transport within anaerobic systems.