Deposition of uranium precipitates in dolomitic gravel fill

Uranium-containing precipitates have been observed in a dolomitic gravel fill near the Department of Energy (DOE) S-3 Ponds former waste disposal site as a result of exposure to acidic (pH 3.4) groundwater contaminated with U (33 mg L(-1)), Al3+ (900 mg L(-1)), and NO3- (14 000 mg L(-1)). The U containing precipitates fluoresce a bright green under ultraviolet (UV) short-wave light which identify U-rich coatings on the gravel. Scanning electron microscopy (SEM) microprobe analysis show U concentration ranges from 1.6-19.8% (average of 7%) within the coatings with higher concentrations at the interface of the dolomite fragments. X-ray absorption near edge structure spectroscopy (XANES) indicate that the U is hexavalent and extended X-ray absorption fine structure spectroscopy (EXAFS) shows that the uranyl is coordinated by carbonate. The exact nature of the uranyl carbonates are difficult to determine, but some are best described by a split K(+)-like shell similar to grimselite [K4Na(UO2)(CO3)3 x H2O] and other regions are better described by a single Ca(2+)-like shell similar to liebigite [Ca2(UO2)(CO3)3 x 11(H2O)] or andersonite [Na2CaUO2(CO3)3 x 6H2O]. The U precipitates are found in the form of white to light yellow cracked-formations as coatings on the dolomite gravel and as detached individual precipitates, and are associated with amorphous basalumnite [Al4(SO4)(OH)10 x 4H2O].     

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.     

Effect of Ca2+ and Zn2+ on UO2 dissolution rates

The dissolution of UO(2) in a continuously stirred tank reactor (CSTR) in the presence of Ca(2+) and Zn(2+) was investigated under experimental conditions relevant to contaminated groundwater systems. Complementary experiments were performed to investigate the effect of adsorption and precipitation reactions on UO(2) dissolution. The experiments were performed under anoxic and oxic conditions. Zn(2+) had a much greater inhibitory effect on UO(2) dissolution than did Ca(2+). This inhibition was most substantial under oxic conditions, where the experimental rate of UO(2) dissolution was 7 times lower in the presence of Ca(2+) and 1450 times lower in the presence of Zn(2+) than in water free of divalent cations. EXAFS and solution chemistry analyses of UO(2) solids recovered from a Ca experiment suggest that a Ca-U(VI) phase precipitated. The Zn carbonate hydrozincite [Zn(5)(CO(3))(2)(OH)(6)] or a structurally similar phase precipitated on the UO(2) solids recovered from experiments performed in the presence of Zn. These precipitated Ca and Zn phases can coat the UO(2) surface, inhibiting the oxidative dissolution of UO(2). Interactions with divalent groundwater cations have implications for the longevity of UO(2) and the mobilization of U(VI) from these solids in remediated subsurface environments, waste disposal sites, and natural uranium ores.     

Cryogenic laser induced fluorescence characterization of U(VI) in Hanford Vadose Zone pore waters

Ambient and liquid helium temperature laser-induced time-resolved uranyl fluorescence spectroscopy was applied to study the speciation of aqueous uranyl solutions containing carbonate and phosphate and two porewater samples obtained by ultracentrifugation of U(VI)-contaminated sediments. The significantly enhanced fluorescence signal intensity and spectral resolution found at liquid helium temperature allowed, for the first time, direct fluorescence spectroscopic observation of the higher aqueous uranyl complexes with carbonate: UO2(CO3)2(2-), UO2(CO3)3(4-), and (UO2)2(OH)3CO3-. The porewater samples were nonfluorescent at room temperature. However, at liquid helium temperature, both porewater samples displayed strong, well-resolved fluorescence spectra. Comparisons of the spectroscopic characteristics of the porewaters with those of the standard uranyl-carbonate complexes confirmed that U(VI) in the porewaters existed primarily as UO2(CO3)3(4-) along with a small amount of other minor components, such as dicalcium-urano-tricarbonate complex, Ca2UO2(CO3)3, consistent with thermodynamic calculation. The U(VI)-carbonate complex is apparently the mobile species responsible for the subsurface migration of U(VI), even though the majority of the in-ground U(VI) inventory at the site from which the samples were obtained exists as intragrain U(VI)-silicate precipitates.     

Determination of the formation constants of ternary complexes of uranyl and carbonate with alkaline earth metals (Mg2+, Ca2+, Sr2+, and Ba2+) using anion exchange method

The formation constants of ternary complexes (MUO2(CO3)3(2-) and M2UO2(CO3)3(0)) of uranyl and carbonate with alkaline earth metals (M2+ denotes Mg2+, Ca2+, Sr2+, and Ba2+) were determined with an anion exchange method by varying the metal concentrations (0.1-5 mmol/L) at pH 8.1 and a constant ionic strength (0.1 mol/L NaNO3) under equilibrium with atmospheric CO2. The results indicate that the complexes of MUO2(CO3)3(2-) and M2UO2(CO3)3 are simultaneously formed for Ca2+ and Ba2+, while Mg2+ and Sr2+ form only the MUO2(CO3)3(2-) complex under our experimental conditions. The cumulative stability constants for the MUO2(CO3)3(2-) complex obtained at / = 0 are as follows: logbeta113 = 26.11 +/- 0.04, 27.18 +/- 0.06, 26.86 +/- 0.04, and 26.68 +/- 0.04 for Mg2+, Ca2+, Sr2+, and Ba2+, respectively. For M2UO2(CO3)3(0), the value of logbeta213 at / = 0 was measured to be 30.70 +/- 0.05 and 29.75 +/- 0.07 for Ca2+ and Ba2+, respectively. Based on the formation constants obtained in this study, speciation calculations indicate that at low Ca2+ concentration (e.g., <2.2 mmol/L), CaUO2(CO3)3(2-) is more important than Ca2UO2(CO3)3 and that the Ca2UO2(CO3)3 distribution increased with increasing Ca2+ concentration. Uranium sorption onto anion-exchange resins is inhibited by the formation of the neutral Ca2UO2(CO3)3(0) species.     

Surface chemical characterization of 2.5-microm particulates (PM2.5) from air pollution in Salt Lake City using TOF-SIMS, XPS, and FTIR

Particulate matter with a diameter of 2.5 microm collected in Salt Lake City (SLC PM2.5) was studied using TOF-SIMS (time-of-flight secondary-ion mass spectrometry), XPS (X-ray photoelectron spectroscopy), and FTIR (Fourier transform infrared spectroscopy). The high spatial resolution and high surface sensitivity of TOF-SIMS allow the surfaces of individual particulates to be analyzed. The high mass-resolution of TOF-SIMS provides good separation of signals from different chemical species at the same nominal mass, and the extremely high detection sensitivity of TOF-SIMS makes the detection of trace elements possible. Metallic elements such as Li, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Cu, Zn, Cs, and Bi were detected by TOF-SIMS on the surface of SLC PM25. The uranium ion U+ together with its oxide ions UO+ and UO2+ were also found. Inorganic compounds detected include oxides, hydroxides, nitrates, sulfates, silicates, borates, chlorides, etc. Organic compounds detected include hydrocarbons, alcohols, aldehydes, ethers, carboxylic acids, amines, amides, nitriles, etc. A number of polycyclic aromatic hydrocarbons (PAH) and nitrated polycyclic aromatic hydrocarbons were detected by TOF-SIMS. High-resolution XPS Cls spectrum shows functional groups such as C-O, CO2, C-CO2, C-C, and C-H and aromatic pi-pi* shake-up transitions. High-resolution XPS O 1s spectrum indicates the coexistence of different oxygen compounds on the surface of PM2.5. FTIR results confirm the presence of various organic compounds in SLC PM2.5 detected by TOF-SIMS and XPS.     

U(VI) sorption and reduction kinetics on the magnetite (111) surface

Sorption of contaminants onto mineral surfaces is an important process that can restrict their transport in the environment. In the current study, uranium (U) uptake on magnetite (111) was measured as a function of time and solution composition (pH, [CO(3)](T), [Ca]) under continuous batch-flow conditions. We observed, in real-time and in situ, adsorption and reduction of U(VI) and subsequent growth of UO(2) nanoprecipitates using atomic force microscopy (AFM) and newly developed batch-flow U L(III)-edge grazing-incidence X-ray absorption spectroscopy near-edge structure (GI-XANES) spectroscopy. U(VI) reduction occurred with and without CO(3) present, and coincided with nucleation and growth of UO(2) particles. When Ca and CO(3) were both present no U(VI) reduction occurred and the U surface loading was lower. In situ batch-flow AFM data indicated that UO(2) particles achieved a maximum height of 4-5 nm after about 8 h of exposure, however, aggregates continued to grow laterally after 8 h reaching up to about 300 nm in diameter. The combination of techniques indicated that U uptake is divided into three-stages; (1) initial adsorption of U(VI), (2) reduction of U(VI) to UO(2) nanoprecipitates at surface-specific sites after 2-3 h of exposure, and (3) completion of U(VI) reduction after ~6-8 h. U(VI) reduction also corresponded to detectable increases in Fe released to solution and surface topography changes. Redox reactions are proposed that explicitly couple the reduction of U(VI) to enhanced release of Fe(II) from magnetite. Although counterintuitive, the proposed reaction stoichiometry was shown to be largely consistent with the experimental results. In addition to providing molecular-scale details about U sorption on magnetite, this work also presents novel advances for collecting surface sensitive molecular-scale information in real-time under batch-flow conditions.     

Dendritic chelating agents. 2. U(VI) binding to poly(amidoamine) and poly(propyleneimine) dendrimers in aqueous solutions

Chelating agents are widely employed in many separation processes used to recover uranyl [U(VI)] from contaminated aqueous solutions. This article describes an experimental investigation of the binding of U(VI) to poly(amidoamine) [PAMAM] and poly(propyleneimine) [PPI] dendrimers in aqueous solutions. We combine fluorescence spectroscopy with bench scale ultrafiltration experiments to measure the extent of binding and fractional binding of U(VI) in aqueous solutions of these dendrimers as a function of (i) metal-ion dendrimer loading, (ii) dendrimer generation, (iii) dendrimer core and terminal group chemistry, and (iv) solution pH and competing ligands (NO3-, PO4(3-), CO3(2-), and Cl-). The overall results of this study suggest that uranyl binding to PAMAM and PPI dendrimers in aqueous solutions involves the coordination of the UO2(2+) ions with the dendrimer amine, amide, and carboxylic groups. We find significant binding of U(VI) to PAMAM dendrimers in (i) acidic solutions containing up to 1.0 M HNO3 and H3PO4 and (ii) in basic solutions containing up to 0.5 M Na2CO3. However, no binding of U(VI) by PAMAM dendrimers is observed in aqueous solutions containing 1.0 M NaCl at pH 3.0. These results strongly suggest that PAMAM and PPI dendrimers can serve as high capacity and selective chelating ligands for U(VI) in aqueous solutions.     

Influence of calcite and dissolved calcium on uranium(VI) sorption to a hanford subsurface sediment

The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] = 10(-7)-10(-5) mol/L and final pH = 6.0-10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4 +/- 0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3(0)(aq) at pH < 8.4 and thatformation of Ca2UO2(CO3)3(0)(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3(4-) in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity.     

A biomass-supported Na2CO3 sorbent for flue gas desulfurization

A novel sorbent for SO2 removal has been investigated. The sorbent is obtained by conventional incipient wetness impregnation of abandoned biomaterials (straw or dried leaves) with an aqueous solution of Na2CO3. A material with the composition 80 wt % Na2CO3/straw shows a desulfurization activity which is both higher and faster than that of the reference sample Na2CO3/gamma-Al2O3. The breakthrough and stoichiometric SO2 adsorption efficiencies for 80 wt % Na2CO3/straw reach 48.9% and 80.6%, respectively, at a temperature of 80 degrees C. The adsorption efficiencies are almost constant in the temperature range 70 to 300 degrees C. According to IR and XPS analysis the main products observed on the spent sorbent are sulfite below 150 degrees C and sulfate at 300 degrees C. The Na2CO3 in 80 wt % Na2CO3/straw can potentially be recycled by the oxidation of the straw with concomitant reduction of the sulfite species to elemental sulfur, making the proposed process CO2 neutral.     

Formation of aqueous MgUO2(CO3)3(2-) complex and uranium anion exchange mechanism onto an exchange resin

The formation of and stability constants for aqueous Mg-UO2-CO3 complexes were determined using an anion exchange method. Magnesium concentration was varied (up to 20 mmol/L) at constant ionic strength (I = 0.101, 0.202, 0.304, 0.406, and 0.509 mol/kg NaNO3), pH 8.1, total [U(VI)] = 10.4 micromol/L under equilibrium with atmospheric CO2. The results indicate that only the MgUO2(CO3)3(2-) complex is formed. The cumulative formation constant extrapolated to zero ionic strength is similar regardless of the activity correction convention used: logbeta113(0) = 25.8 +/- 0.5 using the Davies equation and = 25.02 +/- 0.08 using specific ion interaction theory (SIT). Uranium sorption onto the exchange resin decreased in the presence of Mg putatively due to the formation of MgUO2(CO3)3(2-) that had a lower affinity for the resin than UO2(CO3)3(4-). Uranium sorption results are consistent with an equivalent anion exchange reaction between NO3- and UO2(CO3)3(4-) species to retain charge neutrality regardless of Mg concentration. No Mg was associated with the anion exchange resin indicating that the MgUO2(CO3)3(2-) complex did not sorb.     

Diffusion and adsorption of uranyl carbonate species in nanosized mineral fractures

Atomistic simulations were performed to study the diffusion and adsorption of Ca(2)UO(2)(CO3)3 and of some of its constituent species, i.e., UO(2)2+, CO(3)2–, and UO(2)CO3, in feldspar nanosized fractures. Feldspar is important to uranium remediation efforts at the U.S. Department of Energy Hanford site as it has been found in recent studies to host contaminants within its intragrain fractures. In addition, uranyl carbonate species are known to dominate U(VI) speciation in conditions relevant to the Hanford site. Molecular dynamics (MD) simulations showed that the presence of the feldspar surface diminishes the diffusion coefficients of all of the species considered in this work and that the diffusion coefficients do not reach their bulk aqueous solution values in the center of a 2.5 nm fracture. Moreover, the MD simulations showed that the rate of decrease in the diffusion coefficients with decreasing distance from the surface is greater for larger adsorbing species. Free energy profiles of the same species adsorbing on the feldspar surface revealed a large favorable free energy of adsorption for UO(2)2+ and UO(2)CO3, which are able to adsorb to the surface with their uranium atom directly bonded to a surface hydroxyl oxygen, whereas adsorption of CO(3)2– and Ca(2)UO(2)(CO3)3, which attach to the surface via hydrogen bonding from a surface hydroxyl group to a carbonate oxygen, was calculated to be either only slightly favorable or unfavorable.     

Residual waste from Hanford tanks 241-C-203 and 241-C-204. 1. Solids characterization

Bulk X-ray diffraction (XRD), synchrotron X-ray microdiffraction (microXRD), and scanning electron microscopy/ energy-dispersive X-ray spectroscopy (SEM/EDS) were used to characterize solids in residual sludge from single-shell underground waste tanks C-203 and C-204 at the U.S. Department of Energy's Hanford Site in southeastern Washington state. Cejkaite [Na4(UO2)(CO3)3] was the dominant crystalline phase in the C-203 and C-204 sludges. This is one of the few occurrences of cejkaite reported in the literature and may be the first documented occurrence of this phase in radioactive wastes from DOE sites. Characterization of residual solids from water leach and selective extraction tests indicates that cejkaite has a high solubility and a rapid rate of dissolution in water at ambient temperature and that these sludges may also contain poorly crystalline Na2U207 [or clarkeite Na[(UO2)O(OH)](H2O)0-1] as well as nitratine (soda niter, NaNO3), goethite [alpha-FeO(OH)], and maghemite (gamma-Fe2O3). Results of the SEM/EDS analyses indicate that the C-204 sludge also contains a solid that lacks crystalline form and is composed of Na, Al, P, O, and possibly C. Other identified solids include Fe oxides that often also contain Cr and Ni and occur as individual particles, coatings on particles, and botryoidal aggregates; a porous-looking material (or an aggregate of submicrometer particles) that typically contain Al, Cr, Fe, Na, Ni, Si, U, P, O, and C; Si oxide (probably quartz); and Na-Al silicate(s). The latter two solids probably represent minerals from the Hanford sediment, which were introduced into the tank during prior sampling campaigns or other tank operation activities. The surfaces of some Fe-oxide particles in residual solids from the water leach and selective extraction tests appear to have preferential dissolution cavities. If these Fe oxides contain contaminants of concern, then the release of these contaminants into infiltrating water would be limited by the dissolution rates of these Fe oxides, which in general have lowto very low solubilities and slow dissolution rates at near neutral to basic pH values under oxic conditions.     

Spectroscopic evidence for uranium bearing precipitates in vadose zone sediments at the Hanford 300-area site

Uranium (U) solid-state speciation in vadose zone sediments collected beneath the former North Process Pond (NPP) in the 300 Area of the Hanford site (Washington) was investigated using multi-scale techniques. In 30 day batch experiments, only a small fraction of total U (approximately 7.4%) was released to artificial groundwater solutions equilibrated with 1% pCO2. Synchrotron-based micro-X-rayfluorescence spectroscopy analyses showed that U was distributed among at least two types of species: (i) U discrete grains associated with Cu and (ii) areas with intermediate U concentrations on grains and grain coatings. Metatorbernite (Cu[UO2]2[PO4]2 x 8H2O) and uranophane (Ca[UO2]2[SiO3(OH)]2 x 5H2O) at some U discrete grains, and muscovite at U intermediate concentration areas, were identified in synchrotron-based micro-X-ray diffraction. Scanning electron microscopy/energy dispersive X-ray analyses revealed 8-10 microm size metatorbernite particles that were embedded in C-, Al-, and Si-rich coatings on quartz and albite grains. In mu- and bulk-X-ray absorption structure (mu-XAS and XAS) spectroscopy analyses, the structure of metatorbernite with additional U-C and U-U coordination environments was consistently observed at U discrete grains with high U concentrations. The consistency of the mu- and bulk-XAS analyses suggests that metatorbernite may comprise a significant fraction of the total U in the sample. The entrapped, micrometer-sized metatorbernite particles in C-, Al-, and Si-rich coatings, along with the more soluble precipitated uranyl carbonates and uranophane, likely control the long-term release of U to water associated with the vadose zone sediments.     

Spectroscopic and diffraction study of uranium speciation in contaminated vadose zone sediments from the Hanford site, Washington state

Contamination of vadose zone sediments under tank BX-102 at the Hanford site, Washington, resulted from the accidental release of 7-8 metric tons of uranium dissolved in caustic aqueous sludge in 1951. We have applied synchrotron-based X-ray spectroscopic and diffraction techniques to characterize the speciation of uranium in samples of these contaminated sediments. UIII-edge X-ray absorption fine structure (XAFS) spectroscopic studies demonstrate that uranium occurs predominantly as a uranium(VI) silicate from the uranophane group of minerals. XAFS cannot distinguish between the members of this mineral group due to the near identical local coordination environments of uranium in these phases. However, these phases differ crystallographically, and can be distinguished using X-ray diffraction (XRD) methods. As the concentration of uranium was too low for conventional XRD to detect these phases, X-ray microdiffraction (microXRD) was used to collect diffraction patterns on approximately 20 microm diameter areas of localized high uranium concentration found using microscanning X-ray fluorescence (microSXRF). Only sodium boltwoodite, Na(UO2)(SiO3OH) x 1.5H20, was observed; no other uranophane group minerals were present. Sodium boltwoodite formation has effectively sequestered uranium in these sediments under the current geochemical and hydrologic conditions. Attempts to remediate the uranium contamination will likely face significant difficulties because of the speciation and distribution of uranium in the sediments.     

Kinetics of uranium(VI) reduction by hydrogen sulfide in anoxic aqueous systems

Aqueous U(VI) reduction by hydrogen sulfide was investigated by batch experiments and speciation modeling; product analysis by transmission electron microscopy (TEM) was also performed. The molar ratio of U(VI) reduced to sulfide consumed, and the TEM result suggested that the reaction stoichiometry could be best represented by UO2(2+) + HS- = UO2+ S* + H+. At pH 6.89 and total carbonate concentration ([CO32-]T) of 4.0 mM, the reaction took place according to the following kinetics: -d[U(VI)]/dt = 0.0103[U(VI)][S2-]T0.54 where [U(VI)] is the concentration of hexavalent uranium, and [S2-]T is the total concentration of sulfide. The kinetics of U(VI) reduction was found to be largely controlled by [CO32-]T (examined from 0.0 to 30.0 mM) and pH (examined from 6.37 to 9.06). The reduction was almost completely inhibited with the following [CO32-]T and pH combinations: [(> or = 15.0 mM, pH 6.89); (> or = 4.0 mM, pH 8.01); and (> or = 2.0 mM, pH 9.06)]. By comparing the experimental results with the calculated speciation of U(VI), it was found that there was a strong correlation between the measured initial reaction rates and the calculated total concentrations of uranium-hydroxyl species; we, therefore, concluded that uranium-hydroxyl species were the ones being reduced by sulfide, not the dominant U-carbonate species present in many carbonate-containing systems.     

Efficient removal of Cr(VI) from aqueous solution with Fe@Fe2O3 core-shell nanowires

The batch removal of Cr(VI) from simulated wastewater with Fe@Fe2O3 core-shell nanowires (FCSNs) was investigated in this study. Itwas found that each gram of the FCSNs could remove 7.78 mg of Cr(VI) from simulated wastewater containing 8.0 mg L(-1) of Cr(VI) with an initial pH of 6.5 at room temperature. The Freundlich adsorption isotherm was applicable to describe the removal processes. Kinetics of the Cr(VI) removal was found to follow pseudo-second-order rate equation. Furthermore, the as-prepared and Cr(VI)-adsorbed FCSNs were carefully examined by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopic analysis (XPS). The characterization results suggested that the adsorbed Cr(VI) was partially reduced to Cr(lll) in Cr2O3/Cr(OH)3 on the FCSNs. The possible mechanism of removal of Cr(VI) on FCSNs was proposed, which involved the dominant Cr(VI) adsorption, followed by the partial reduction of Cr(VI) to Cr(III) (chromium(III) oxyhydroides) on the surface of FCSNs. These Fe@Fe2O3 core-shell nanowires with high specific surface area and strong magnetic property are very attractive for the removal of Cr(VI) from wastewater.     

Uptake of Cm(III) and Eu(III) by calcium silicate hydrates: a solution chemistry and time-resolved laser fluorescence spectroscopy study

The interaction of the two chemical homologues [Cm(III) and Eu(III)] with calcium silicate hydrates (CSH phases) at pH 13.3 has been investigated in batch-type sorption studies using Eu(III) and complemented with time-resolved laser fluorescence spectroscopy (TRLFS) using Cm(III). The sorption data for Eu(III) reveal fast sorption kinetics and a strong uptake by CSH phases with distribution ratios of (6 +/- 3) x 10(5) L kg(-1). Three different Cm(III) species have been identified: A nonfluorescing species, which was identified as a curium hydroxide (surface) precipitate, and two fluorescing Cm(III)/CSH-sorbed species. The fluorescing sorbed species have characteristic emission spectra with main peak maxima at 618.9 and 620.9 nm and fluorescence emission lifetimes of 289 +/- 11 and 1482 +/- 200 micros, respectively. From the fluorescence lifetimes, it was calculated that the two fluorescing Cm(III) species have one or two and no water molecules left in their first coordination sphere, suggesting that these species are incorporated into the CSH structure. A structural model for Cm(III) and Eu(III) incorporation into CSH phases is proposed based on the substitution for Ca at two different types of sites in the CSH structure.     

氯化钠、蔗糖和碳酸钠对芡实淀粉糊化特性的影响

研究氯化钠、蔗糖和碳酸钠对芡实淀粉糊化特性的影响规律。采用差示扫描量热法等方法测定了不同质量分数氯化钠(1%、2%、3%、4%、5%)、蔗糖(4%、8%、12%、16%、20%)和碳酸钠(0.5%、1.0%、1.5%、2.0%、2.5%)对芡实淀粉的糊化温度、溶解度、膨胀度、冻融稳定性等糊化特性的影响。结果发现,氯化钠、蔗糖和碳酸钠均提高了芡实淀粉的糊化温度。原芡实淀粉透明度为1.3%,氯化钠的加入降低了透明度,而蔗糖和碳酸钠则提高其透明度。氯化钠、蔗糖和碳酸钠均增加了芡实淀粉糊的膨胀度和溶解度,并均降低其冻融稳定性。在凝沉性方面,三者表现不一,低含量的氯化钠(1%~3%)和碳酸钠(0.5%~1.5%)均有利于芡实淀粉糊的稳定;高含量的氯化钠(4%~5%)和碳酸钠(2.0%~2.5%)均促使淀粉糊凝沉增加,降低稳定性;而蔗糖则提高了芡实淀粉糊的凝沉稳定性。由此可见,在芡实淀粉糊化过程中,氯化钠、蔗糖和碳酸钠三者对其糊化特性的影响显著。     

Characterization of the enhancement effect of Na2CO3 on the sulfur capture capacity of limestones

It has been known for a long time that certain additives (e.g., NaCl, CaCl2, Na2CO3, Fe2O3) can increase the sulfur dioxide capture-capacity of limestones. In a recent study we demonstrated that very small amounts of Na2CO3 can be very beneficial for producing sorbents of very high sorption capacities. This paper explores what contributes to these significant increases. Mercury porosimetry measurements of calcined limestone samples reveal a change in the pore-size from 0.04-0.2 microm in untreated samples to 2-10 microm in samples treated with Na2CO3--a pore-size more favorable for penetration of sulfur into the particles. The change in pore-size facilitates reaction with lime grains throughout the whole particle without rapid plugging of pores, avoiding premature change from a fast chemical reaction to a slow solid-state diffusion controlled process, as seen for untreated samples. Calcination in a thermogravimetric reactor showed that Na2CO3 increased the rate of calcination of CaCO3 to CaO, an effect which was slightly larger at 825 degrees C than at 900 degrees C. Peak broadening analysis of powder X-ray diffraction data of the raw, calcined, and sulfated samples revealed an unaffected calcite size (approximately 125-170 nm) but a significant increase in the crystallite size for lime (approximately 60-90 nm to approximately 250-300 nm) and less for anhydrite (approximately 125-150 nm to approximately 225-250 nm). The increase in the crystallite and pore-size of the treated limestones is attributed to an increase in ionic mobility in the crystal lattice due to formation of vacancies in the crystals when Ca is partly replaced by Na.