Dissolution of biogenic and synthetic UO2 under varied reducing conditions.
ABSTRACT: The chemical stability of biogenic UO2, a nanoparticulate product of environmental bioremediation, may be impacted by the particles' surface free energy, structural defects, and compositional variability in analogy to abiotic UO(2+x) (0 < or = x < or = 0.25). This study quantifies and compares intrinsic solubility and dissolution rate constants of biogenic nano-UO2 and synthetic bulk UO2.00, taking molecular-scale structure into account. Rates were determined under anoxic conditions as a function of pH and dissolved inorganic carbon in continuous-flow experiments. The dissolution rates of biogenic and synthetic UO2 solids were lowest at near neutral pH and increased with decreasing pH. Similar surface area-normalized rates of biogenic and synthetic UO2 suggest comparable reactive surface site densities. This finding is consistent with the identified structural homology of biogenic UO2 and stoichiometric UO2.00 Compared to carbonate-free anoxic conditions, dissolved inorganic carbon accelerated the dissolution rate of biogenic UO2 by 3 orders of magnitude. This phenomenon suggests continuous surface oxidation of U(IV) to U(VI), with detachment of U(VI) as the rate-determining step in dissolution. Although reducing conditions were maintained throughout the experiments, the UO2 surface can be oxidized by water and radiogenic oxidants. Even in anoxic aquifers, UO2 dissolution may be controlled by surface U(VI) rather than U(IV) phases.
Project description:Uranium (U) is a ubiquitous element in the Earth's crust at ~2 ppm. In anoxic environments, soluble hexavalent uranium (U(VI)) is reduced and immobilized. The underlying reduction mechanism is unknown but likely of critical importance to explain the geochemical behavior of U. Here, we tackle the mechanism of reduction of U(VI) by the mixed-valence iron oxide, magnetite. Through high-end spectroscopic and microscopic tools, we demonstrate that the reduction proceeds first through surface-associated U(VI) to form pentavalent U, U(V). U(V) persists on the surface of magnetite and is further reduced to tetravalent UO2 as nanocrystals (~1-2?nm) with random orientations inside nanowires. Through nanoparticle re-orientation and coalescence, the nanowires collapse into ordered UO2 nanoclusters. This work provides evidence for a transient U nanowire structure that may have implications for uranium isotope fractionation as well as for the molecular-scale understanding of nuclear waste temporal evolution and the reductive remediation of uranium contamination.
Project description:Chrysotile asbestos is a soil pollutant in many countries. It is a carcinogenic mineral, partly due to its surface chemistry. In chrysotile, FeII and FeIII substitute Mg octahedra (Fe), and FeIII substitutes Si tetrahedra (Fe). Fe on fiber surfaces can generate hydroxyl radicals (HO. ) in Fenton reactions, which damage biomolecules. To better understand chrysotile weathering in soils, net Mg and Si dissolution rates over the pH range 3.0-11.5 were determined in the presence and absence of biogenic ligands. Also, HO. generation and Fe bulk speciation of pristine and weathered fibers were examined by EPR and Mössbauer spectroscopy. Dissolution rates were increased by ligands and inversely related to pH with complete inhibition at cement pH (11.5). Surface-exposed Mg layers readily dissolved at low pH, but only after days at neutral pH. On longer timescales, the slow dissolution of Si layers became rate-determining. In the absence of ligands, Fe precipitated as Fenton-inactive Fe phases, whereas Fe (7 % of bulk Fe) remained redox-active throughout two-week experiments and at pH 7.5 generated 50±10 % of the HO. yield of Fe at pristine fiber surfaces. Ligand-promoted dissolution of Fe (and potentially Al) labilized exposed Si layers. This increased Si and Mg dissolution rates and lowered HO. generation to near-background level. It is concluded that Fe surface species control long-term HO. generation and dissolution rates of chrysotile at natural soil pH.
Project description:The combined effects of anthropogenic and biological CO2 inputs may lead to more rapid acidification in coastal waters compared to the open ocean. It is less clear, however, how redox reactions would contribute to acidification. Here we report estuarine acidification dynamics based on oxygen, hydrogen sulfide (H2S), pH, dissolved inorganic carbon and total alkalinity data from the Chesapeake Bay, where anthropogenic nutrient inputs have led to eutrophication, hypoxia and anoxia, and low pH. We show that a pH minimum occurs in mid-depths where acids are generated as a result of H2S oxidation in waters mixed upward from the anoxic depths. Our analyses also suggest a large synergistic effect from river-ocean mixing, global and local atmospheric CO2 uptake, and CO2 and acid production from respiration and other redox reactions. Together they lead to a poor acid buffering capacity, severe acidification and increased carbonate mineral dissolution in the USA's largest estuary.The potential contribution of redox reactions to acidification in coastal waters is unclear. Here, using measurements from the Chesapeake Bay, the authors show that pH minimum occurs at mid-depths where acids are produced via hydrogen sulfide oxidation in waters mixed upward from anoxic depths.
Project description:The highly efficient removal of uranium from mine tailings effluent, radioactive wastewater and enrichment from seawater is of great significance for the development of nuclear industry. In this work, we prepared an efficient U(VI) adsorbent by EDTA modified sugarcane bagasse (MESB) with a simple process. The prepared adsorbent preserves high adsorptive capacity for UO22+ (pH 3.0) and uranyl complexes, such as UO2(OH)+, (UO2)2(OH)22+ and (UO2)3(OH)5+ (pH 4.0 and pH 5.0) and good repeatability in acidic environment. The maximum adsorption capacity for U(VI) at pH 3.0, 4.0 and 5.0 is 578.0, 925.9 and 1394.1?mg/g and the adsorption capacity loss is only 7% after five cycles. With the pH from 3.0 to 5.0, the inhibitive effects of Na+ and K+ decreased but increased of Mg2+ and Ca2+. MESB also exhibits good adsorption for [UO2(CO3)3]4- at pH 8.3 from 10?mg/L to 3.3??g/L. Moreover, MESB could effectively extract U(VI) from simulated seawater in the presence of other metals ions. This work provided a general and efficient uranyl enriched material for nuclear industry.
Project description:Acidification of airborne dust particles can dramatically increase the amount of bioavailable phosphorus (P) deposited on the surface ocean. Experiments were conducted to simulate atmospheric processes and determine the dissolution behavior of P compounds in dust and dust precursor soils. Acid dissolution occurs rapidly (seconds to minutes) and is controlled by the amount of H+ ions present. For H+ < 10-4 mol/g of dust, 1-10% of the total P is dissolved, largely as a result of dissolution of surface-bound forms. At H+ > 10-4 mol/g of dust, the amount of P (and calcium) released has a direct proportionality to the amount of H+ consumed until all inorganic P minerals are exhausted and the final pH remains acidic. Once dissolved, P will stay in solution due to slow precipitation kinetics. Dissolution of apatite-P (Ap-P), the major mineral phase in dust (79-96%), occurs whether calcium carbonate (calcite) is present or not, although the increase in dissolved P is greater if calcite is absent or if the particles are externally mixed. The system was modeled adequately as a simple mixture of Ap-P and calcite. P dissolves readily by acid processes in the atmosphere in contrast to iron, which dissolves more slowly and is subject to reprecipitation at cloud water pH. We show that acidification can increase bioavailable P deposition over large areas of the globe, and may explain much of the previously observed patterns of variability in leachable P in oceanic areas where primary productivity is limited by this nutrient (e.g., Mediterranean).
Project description:Coccoliths are micrometer scale shields made from 20 to 60 individual calcite (CaCO(3)) crystals that are produced by some species of algae. Currently, coccoliths serve as an important sink in the global carbon cycle, but decreasing ocean pH challenges their stability. Chalk deposits, the fossil remains of ancient algae, have remained remarkably unchanged by diagenesis, the process that converts sediment to rock. Even after 60 million years, the fossil coccolith crystals are still tiny (< 1 ?m), compared with inorganically produced calcite, where one day old crystals can be 10 times larger, which raises the question if the biogenic nature of coccolith calcite gives it different properties than inorganic calcite? And if so, can these properties protect coccoliths in CO(2) challenged oceans? Here we describe a new method for tracking dissolution of individual specimens, at picogram (10(-12) g) resolution. The results show that the behavior of modern and fossil coccoliths is similar and both are more stable than inorganic calcite. Organic material associated with the biogenic calcite provides the explanation. However, ancient and modern coccoliths, that resist dissolution in Ca-free artificial seawater at pH > 8, all dissolve when pH is 7.8 or lower. Ocean pH is predicted to fall below 7.8 by the year 2100, in response to rising CO(2) levels. Our results imply that at these conditions the advantages offered by the biogenic nature of calcite will disappear putting coccoliths on algae and in the calcareous bottom sediments at risk.
Project description:The impact on U(VI) adsorbed to lepidocrocite (?-FeOOH) and hematite (?-Fe2O3) was assessed when exposed to aqueous sulfide (S(-II)aq) at pH 8.0. With both minerals, competition between S(-II) and U(VI) for surface sites caused instantaneous release of adsorbed U(VI). Compared to lepidocrocite, consumption of S(-II)aq proceeded slower with hematite, but yielded maximum dissolved U concentrations that were more than 10 times higher, representing about one-third of the initially adsorbed U. Prolonged presence of S(-II)aq in experiments with hematite in combination with a larger release of adsorbed U(VI), enhanced the reduction of U(VI): after 24 h of reaction about 60-70% of U was in the form of U(IV), much higher than the 25% detected in the lepidocrocite suspensions. X-ray absorption spectra indicated that U(IV) in both hematite and lepidocrocite suspensions was not in the form of uraninite (UO2). Upon exposure to oxygen only part of U(IV) reoxidized, suggesting that monomeric U(IV) might have become incorporated in newly formed iron precipitates. Hence, sulfidization of Fe oxides can have diverse consequences for U mobility: in short-term, desorption of U(VI) increases U mobility, while reduction to U(IV) and its possible incorporation in Fe transformation products may lead to long-term U immobilization.
Project description:The distribution and speciation of Zn sorbed to biogenic Mn oxides forming in the hyporheic zone of Pinal Creek, AZ, was investigated using extended X-ray absorption fine structure (EXAFS) and microfocused synchrotron X-ray fluorescence (?SXRF) mapping, and chemical extraction. ?SXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and microfocused EXAFS spectra of Zn in the biogenic Mn oxide coating are indicative of Zn forming triple-corner-sharing inner-sphere complexes over octahedral vacancies in the Mn oxide sheet structure. Zn desorbed in response to the decrease in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in the solid/solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating that desorption is not controlled by dissolution of secondary Zn phases. In summary, these findings support the idea that Zn attenuation in Pinal Creek is largely controlled by sorption to microbial Mn oxides forming in the streambed during hyporheic exchange. Sorption to biogenic Mn oxides is likely an important process of Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present.
Project description:Interactions of a facultative anaerobic bacterial isolate named Paenibacillus sp. JG-TB8 with U(VI) were studied under oxic and anoxic conditions in order to assess the influence of the oxygen-dependent cell metabolism on microbial uranium mobilization and immobilization. We demonstrated that aerobically and anaerobically grown cells of Paenibacillus sp. JG-TB8 accumulate uranium from aqueous solutions under acidic conditions (pH 2 to 6), under oxic and anoxic conditions. A combination of spectroscopic and microscopic methods revealed that the speciation of U(VI) associated with the cells of the strain depend on the pH as well as on the aeration conditions. At pH 2 and pH 3, uranium was exclusively bound by organic phosphate groups provided by cellular components, independently on the aeration conditions. At higher pH values, a part (pH 4.5) or the total amount (pH 6) of the dissolved uranium was precipitated under oxic conditions in a meta-autunite-like uranyl phosphate mineral phase without supplying an additional organic phosphate substrate. In contrast to that, under anoxic conditions no mineral formation was observed at pH 4.5 and pH 6, which was clearly assigned to decreased orthophosphate release by the cells. This in turn was caused by a suppression of the indigenous phosphatase activity of the strain. The results demonstrate that changes in the metabolism of facultative anaerobic microorganisms caused by the presence or absence of oxygen can decisively influence U(VI) biomineralization.
Project description:Under pH 7 - 10 conditions, the mesoporous silica supports proposed for use in water treatment are relatively unstable. In batch experiments conducted in pH 7 solutions, the commonly used support SBA-15 dissolved quickly, releasing approximately 30 mg/L of dissolved silica after 2 hours. In column experiments, more than 45% of an initial mass of 0.25 g SBA-15 dissolved within 2 days when a pH 8.5 solution flowed through the column. In a mixed iron oxide/SBA-15 system, the dissolution of SBA-15 changed the iron oxide reactivity toward H(2)O(2) decomposition, because dissolved silica deposited on iron oxide surface and changed its catalytic active sites. As with SBA-15, other mesoporous silica materials including HMS, MCM-41, four types of functionalized SBA-15, and two types of metal oxide-containing SBA-15 also dissolved under circumneutral pH solutions. The dissolution of mesoporous silica materials raises questions about their use under neutral and alkaline pH in aqueous solutions, because silica dissolution might compromise the behavior of the material.