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1.
The mechanisms of photodegradation of binary iron- and uranium-citrate and ternary iron-uranium-citrate complexes were elucidated. Citric acid degradation products were identified by HPLC and GC, and the metal precipitates were identified by XRD and EXAFS. Photodegradation of a binuclear iron-citrate complex occurred as a result of two one-electron oxidations of citric acid with the formation of 3-oxoglutarate and two ferrous ions. The ferrous ions were reoxidized by a photo-Fenton reaction, resulting in the precipitation of iron as two-line ferrihydrite Fe(OH)3. The citric acid in the uranium-citrate complex underwent a two-electron oxidation to acetoacetate with the concomitant reduction of U(VI) to U(IV). The U(IV) was subsequently photooxidized in the presence of dioxygen with precipitation of uranium as the mineral schoepite (UO3 x 2H2O). A two-step electron reduction of two ferric ions to two ferrous ions wasthe primary mechanism for photodegradation of the ternary iron-uranium-citrate complex with oxidation of citric acid to 3-oxoglutarate; reduction of uranium was not observed. The iron precipitated as ferrihydrite and the uranyl ion as a uranyl hydroxide species. These results show the potential application of photochemical treatment of wastewater and decontamination solutions containing binary and ternary iron- and uranium-citrate complexes.  相似文献   

2.
We investigated the performance of a lighted upflow anaerobic sludge blanket (LUASB) reactor for wastewater treatment and poly-beta-hydroxybutyrate (PHB) production. Phototrophic bacteria were induced from UASB (upflow anaerobic sludge blanket) granules under light conditions (100 microE.m(-2).s(-1)). The ammonium and phosphate ion removal efficiencies of the LUASB reactor were higher than those of the UASB reactor. The difference in the results from runs under light and dark conditions suggested that the ammonium and phosphate ion removal efficiencies were improved by increasing the amount of phototrophic bacteria in the LUASB reactor. The average production rate of PHB from the biomass in the effluent from the LUASB reactor was 6.6-14.0 mg.l(-1)-reactor.d(-1) using acetate-based media and the average PHB content based on the dry bacterial biomass was 15.1-25.3%. The PHB concentration increased by reincubation of the effluent from the LUASB reactor with sodium acetate under light conditions. The UASB granular sludge can decompose a variety of organic substances and in addition the LUASB method can remove ammonium and phosphate ions. The LUASB method thus appears to be appropriate for wastewater treatment and production of phototrophic bacteria and PHB from various wastewaters.  相似文献   

3.
We developed a simple, safe method to remove uranium from contaminated metallic surfaces so that the materials can be recycled or disposed of as low-level radioactive or nonradioactive waste. Surface analysis of rusted uranium-contaminated plain carbon-steel coupons by X-ray photoelectron spectroscopy and Rutherford backscattering spectroscopy showed that uranium was predominantly associated with ferrihydrite, lepidocrocite, and magnetite, or occluded in the matrix of the corrosion product as uranyl hydroxide and schoepite (UO3 x 2H2O). Citric acid formulations, consisting of oxalic acid-hydrogen peroxidecitric acid (OPC) or citric acid-hydrogen peroxidecitric acid (CPC), were used to remove uranium from the coupons. The efficiency of uranium removal varied from 68% to 94% depending on the extent of corrosion, the association of uranium with the iron oxide matrix, and the accessibility of the occluded contaminant. Decontaminated coupons clearly showed evidence of the extensive removal of rust and uranium. The waste solutions containing uranium and iron from decontamination by OPC and CPC were treated first by subjecting them to biodegradation followed by photodegradation. Biodegradation of a CPC solution by Pseudomonas fluorescens resulted in the degradation of the citric acid with concomitant precipitation of Fe (>96%), whereas U that remained in solution was recovered (>99%) by photodegradation as schoepite. In contrast, in an OPC solution citric acid was biodegraded but not oxalic acid, and both Fe and U remained in solution. Photodegradation of this OPC solution resulted in the precipitation of iron as ferrihydrite and uranium as uranyl hydroxide.  相似文献   

4.
We tested the hypothesis that runoff of uranium-bearing particles from mining waste disposal areas was a significant mechanism for redistribution of uranium in the northeastern part of the Upper Puerco River watershed (New Mexico). However, our results were not consistent with this hypothesis. Analysis of > 100 sediment and suspended sediment samples collected adjacent to and downstream from uranium source areas indicated that uranium levels in the majority of the samples were not elevated above background. Samples collected within 50 m of a known waste disposal site were subjected to detailed geochemical characterization. Uranium in these samples was found to be highly soluble; treatment with synthetic pore water for 24 h caused dissolution of 10--50% of total uranium in the samples. Equilibrium uranium concentrations in pore water were > 4.0 mg/L and were sustained in repeated wetting events, effectively depleting soluble uranium from the solid phase. The dissolution rate of uranium appeared to be controlled by solid-phase diffusion of uranium from within uranium-bearing mineral particles. X-ray adsorption spectroscopy indicated the presence of a soluble uranyl silicate, and possibly a uranyl phosphate. These phases were exhausted in transported sediment suggesting that uranium was readily mobilized from sediments in the Upper Puerco watershed and transported in the dissolved load. These results could have significance for uranium risk assessment as well as mining waste management and cleanup efforts.  相似文献   

5.
Green rusts, which are mixed ferrous/ferric hydroxides, are found in many suboxic environments and are believed to play a central role in the biogeochemistry of Fe. Analysis by U LIII-edge X-ray absorption near edge spectroscopy of aqueous green rust suspensions spiked with uranyl (U(VI)) showed that U(VI) was readily reduced to U(IV) by green rust The extended X-ray absorption fine structure (EXAFS) date for uranium reduced by green rust indicate the formation of a UO2 phase. A theoretical model based on the crystal structure of UO2 was generated by using FEFF7 and fitted to the data for the UO2 standard and the uranium in the green rust samples. The model fits indicate that the number of nearest-neighbor uranium atoms decreases from 12 for the UO2 structure to 5.4 forthe uranium-green rust sample. With an assumed four near-neighbor uranium atoms per uranium atom on the surface of UO2, the best-fit value for the average number of uranium atoms indicates UO2 particles with an average diameter of 1.7 +/- 0.6 nm. The formation of nanometer-scale particles of UO2, suggested by the modeling of the EXAFS data, was confirmed by high-resolution transmission electron microscopy, which showed discrete particles (approximately 2-9 nm in diameter) of crystalline UO2. Our results clearly indicate that U(VI) (as soluble uranyl ion) is readily reduced by green rust to U(IV) in the form of relatively insoluble UO2 nanoparticles, suggesting that the presence of green rusts in the subsurface may have significant effects on the mobility of uranium, particularly under iron-reducing conditions.  相似文献   

6.
The solubility of uranium-containing minerals can control the mobility of uranium in contaminated soil and groundwater. The identity and solubility of these minerals are strongly influenced by solution composition. The influence of dissolved sodium and cesium on the solubility of uranyl oxide hydrates has been investigated in a series of batch experiments conducted with synthetic metaschoepite ((UO2)8O2(OH)12 x 10H2O). During reaction of metaschoepite in NaNO3, CsNO3, and NaF solutions, an initial increase in the dissolved uranium concentration was followed by a decrease as uranium was incorporated into a secondary solid phase. Given sufficient reaction time, metaschoepite was completely transformed to a clarkeite-like sodium uranyl oxide hydrate or a cesium uranyl oxide hydrate that has not previously been described. These secondary solid phases exhibited X-ray diffraction patterns and Raman spectra that were distinct from those of the original metaschoepite. Dissolved uranium concentrations in equilibrium with the sodium and cesium uranyl oxide hydrates can be more than 2 orders of magnitude lower than those in equilibrium with metaschoepite. Initial changes in metaschoepite solubility may also result from particle growth induced by sodium and cesium incorporation into the solid phase.  相似文献   

7.
研究了Fe3+存在下处理制浆中段废水的好氧活性污泥的驯化过程。首先通过Fe3+对微生物生长曲线的影响确定Fe3+最佳用量为30 mg/L;然后在Fe3+用量为30 mg/L下,采用制浆中段废水对好氧活性污泥进行驯化,并设置不加Fe3+的空白组对照。结果表明,整个驯化过程中,加Fe3+组CODCr去除率和污染物去除率(以UV-254减少率表示)均高于空白组;驯化结束后,加Fe3+组和空白组CODCr去除率分别达78.2%和76.0%,污染物去除率分别为50.0%和37.7%。通过对脱氢酶活性的分析表明,加Fe3+组活性高于空白组。  相似文献   

8.
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.  相似文献   

9.
Uranium binding to bone charcoal and bone meal apatite materials was investigated using U L(III)-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations < or = 5500 microg U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations > or = 5500 microg U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12,300 microg U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.  相似文献   

10.
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.  相似文献   

11.
Time-resolved laser-induced fluorescence spectroscopy (TRLFS) was applied to study the U(VI) surface complexes on kaolinite in the presence and absence of humic acid (HA). Two uranyl surface species with fluorescence lifetimes of 5.9 +/- 1.4 and 42.5 +/- 3.4 micros and 4.4 +/- 1.2 and 30.9 +/- 7.2 micros were identified in the binary (U(VI)-kaolinite) and ternary system (U(VI)-HA-kaolinite), respectively. The fluorescence spectra of adsorbed uranyl surface species are described with six and five fluorescence emission bands in the binary and ternary system, respectively. The positions of peak maxima are shifted significantly to higher wavelengths compared to the free uranyl ion in perchlorate medium. HA has no influence on positions of the fluorescence emission bands. In the binary system, both surface species can be attributed to adsorbed bidentate mononuclear surface complexes, which differ in the number of water molecules in their coordination environment. In the ternary system, U(VI) prefers direct binding on kaolinite rather than via HA, but it is sorbed as a uranyl-humate complex. Consequently, the hydration shell of the U(VI) surface complexes is displaced with complexed HA, which is simultaneously distributed between kaolinite particles. Aluminol binding sites are assumed to control the sorption of U(VI) onto kaolinite.  相似文献   

12.
The objective of this work was to compare two anaerobic reactor configurations, a hybrid upflow anaerobic sludge blanket (UASBh) reactor and an anaerobic sequencing batch reactor with immobilised biomass (ASBBR) treating dairy effluents. The reactors were fed with effluent from the milk pasteurisation process (effluent 1—E1) and later with effluent from the same process combined with the one from the cheese manufacturing (effluent 2—E2). The ASBBR reactor showed average organic matter removal efficiency of 95.2% for E1 and 93.5% for E2, while the hybrid UASB reactor showed removal efficiencies of 90.3% and 80.1% respectively.  相似文献   

13.
The conditions leading to the Donnan membrane equilibrium arise from the inability of ions to diffuse out from one phase in a heterogeneous system. In a polymeric cation exchanger, negatively charged sulfonic acid groups are covalently attached to the polymer chains, and thus, they cannot permeate out of the polymer phase. Conversely, a polymeric anion exchanger contains a high concentration of non-diffusible positively charged quaternary ammonium functional groups. It is well-established that submicron or nanoscale hydrated iron(III) oxide (HFO) particles exhibit high sorption affinity toward both arsenates and arsenites. In this study, commercially available cation and anion exchangers were used as host materials for dispersing HFO nanoparticles within the polymer phase using a technique previously developed. The resulting polymeric/inorganic hybrid sorbent particles were subsequently used for arsenic removal in the laboratory. The most significant finding of the study is that the anion exchanger as a substrate containing dispersed HFO offered substantially higher arsenate removal capacity as compared to the cation exchanger, all other conditions remaining identical. In fact, HFO nanoparticles dispersed within the gel-type cation exchanger were unable to remove arsenic. The Donnan membrane effect resulting from the nondiffusible negatively charged sulfonic acid groups in the cation exchanger did not allow permeation of arsenate into the polymer phase (i.e., arsenate was excluded from the spherical beads dispersed with HFO nanoparticles). On the contrary, anion-exchanger-supported HFO particles or HAIX offered very high arsenic removal capacity; less than 10% of influent arsenic broke through after 10 000 bed vol. HAIX was also amenable to efficient regeneration with 2% NaOH and 3% NaCl and capable of simultaneously removing both perchlorate and arsenic selectively. According to the information in the open literature, HAIX is the first hybrid sorbent that utilizes the Donnan membrane effect of the host material for sorption enhancement. From a generic viewpoint, other metal oxide/metal nanoparticles may also be judiciously embedded in appropriate support materials that would reject or enhance permeation of targeted ionic solutes.  相似文献   

14.
以K2S2O8作引发剂,将甲基丙烯酸十二氟庚酯(MFAA)、丙烯酸丁酯(BAA)、丙烯酸羟丙酯(HPAA)和甲基丙烯酸二甲氨乙酯(DM)进行乳液聚合,制得了一种稳定的阳离子氟代聚丙烯酸酯乳液。用红外光谱(IR)、核磁共振氢谱(1HNMR)对共聚物结构进行了表征,并用透射电镜(TEM)对乳液的胶粒形态及粒径进行了测试。  相似文献   

15.
Compliance with the U.S. drinking water standard for arsenic (As) of 10 microg L(-1) is required in January 2006. This will necessitate implementation of treatment technologies for As removal by thousands of water suppliers. Although a variety of such technologies is available, most require preoxidation of As(III) to As(V) for efficient performance. Previous batch studies with illuminated TiO2 slurries have demonstrated that TiO2-photocatalyzed AS(III) oxidation occurs rapidly. This study examined reaction efficiency in a flow-through, fixed-bed reactor that provides a better model for treatment in practice. Glass beads were coated with mixed P25/sol gel TiO2 and employed in an upflow reactor irradiated from above. The reactor residence time, influent As(III) concentration, number of TiO2 coatings on the beads, solution matrix, and light source were varied to characterize this reaction and determine its feasibility for water treatment. Repeated usage of the same beads in multiple experiments or extended use was found to affect effluent As(V) concentrations but not the steady-state effluent As(III) concentration, which suggests that As(III) oxidation at the TiO2 surface undergoes dynamic sorption equilibration. Catalyst poisoning was not observed either from As(V) or from competitively adsorbing anions, although the higher steady-state effluent As(III) concentrations in synthetic groundwater compared to 5 mM NaNO3 indicated that competitive sorbates in the matrix partially hinder the reaction. A reactive transport model with rate constants proportional to incident light at each bead layer fit the experimental data well despite simplifying assumptions. TiO2-photocatalyzed oxidation of As(III) was also effective under natural sunlight. Limitations to the efficiency of As(III) oxidation in the fixed-bed reactor were attributable to constraints of the reactor geometry, which could be overcome by improved design. The fixed-bed TiO2 reactor offers an environmentally benign method for As(III) oxidation.  相似文献   

16.
Uranium and arsenic often co-occur in nature, for example, in acid mine drainage waters. Interaction with arsenic is thus important to understand uranium mobility in aqueous solutions. For the present study, EXAFS spectroscopy was used to investigate the formation and identify the structure of aqueous uranyl arsenate species at pH 2. The nearest U-As distance of 3.39 ?, observed in shock-frozen liquid samples, was significantly shorter than that observed in solid uranyl arsenate minerals. The shorter bond length indicated that the solution contained a bidentate-coordinated species, in contrast to the monodentate coordination in solid uranyl arsenate minerals. The U-As coordination number of 1.6 implied that two uranyl arsenate species with U:As ratios of 1:1 and 1:2 formed in nearly equal proportions and that the hydrated uranyl ion was present only as a minor component. The two uranyl arsenate species could not be differentiated spectroscopically, since their U-As distances were equal. A comparison based on DFT modeling indicated for both the 1:1 and the 1:2 species, that the bidentate arsenates were bound to uranium with one of the binding oxygen atoms being protonated. Based on the present spectroscopic study, the two species that will have to be considered in acidic uranium-arsenic-rich solutions are thus UO(2)H(2)AsO(4)(+), and UO(2)(H(2)AsO(4))(2)(0).  相似文献   

17.
纤维微塑料在印染废水产排污环节的赋存特征   总被引:1,自引:0,他引:1  
印染废水的末端排放是自然水体中纤维微塑料的重要来源之一,为了解长三角印染行业纤维微塑料的产排特征和环境归趋,采集了22家印染企业调节池进水及末端出水样品,分析纤维微塑料的丰度、形态、聚合物类型及去除率。结果表明:纤维微塑料在进出水样品中的平均丰度为(7 504.8±5 685.9)及(1 272.7±782.2)个/L,其中聚对苯二甲酸乙二醇酯为主要贡献者,Kruskal-Wallis检验并未发现织物原材料对聚合物组成有显著影响;进水中100~300 μm和无色透明的纤维微塑料占主导,处理后出水中尺寸小于100 μm和有色纤维的比例有所上升,这与纤维微塑料的性能和末端处理截留效率有关;尽管末端处理对纤维微塑料的平均去除率可达(78.3±10.2)%,纤维微塑料通过印染末端废水的排放量为(3.88±5.75)×109个/d,由此带来的水体生态风险是持续且积累的。该研究结果可为我国纺织污染新型污染物的评估及进一步去除微塑料的工艺设计提供数据和参考。  相似文献   

18.
应用生物鉴定技术测定杨木CTMP废液生物产甲烷势(BMP),进行废液中有毒物质对产甲烷菌的毒性鉴定(ATA),并从间歇除毒试验结果选择除硫方法和确定最佳投药量。杨木未漂CTMP废液总硫含量为2260mg/l,COD/S比值为3.7,采用接触法中温厌氧发酵达到的技术指标为:COD容积负荷4.4g/l·d;COD去除率达58%;甲烷产气率为130ml/去除lgCOD。  相似文献   

19.
采用改良式UASB反应器与SBR反应器组合对爆破法制浆废液进行了处理,研究结果发现,在厌氧处理段,当水力停留时间为1d时,容积负荷为5.3gCODCr/(L·d),CODCr的去除率可以达到75%,BOD5去除率达95%,平均甲烷产率为247.4ml/gCODCr。组合处理后,废液中BOD5总去除率达98%以上,达到新排放标准,CODCr总去除率为85.3%。  相似文献   

20.
Flow-through sediment column experiments examined the reoxidation of microbially reduced uranium with either oxygen or nitrate supplied as the oxidant. The uranium was reduced and immobilized via long-term (70 days) acetate biostimulation resulting in 62-92% removal efficiency of the 20 microM influent uranium concentration. Uranium reduction occurred simultaneously with iron reduction as the dominant electron accepting process. The columns were reoxidized by discontinuing the supply of acetate and either replacing the anaerobic gas used to purge the influent media with a gas mixture containing 20% oxygen (resulting in a dissolved oxygen concentration of 0.27 mM) or adding 1.6 mM nitrate to the influent media. Both oxygen and nitrate resolubilized the majority (88 and 97%, respectively) of the uranium precipitated during bioreduction within 54 days. Although oxygen is more thermodynamically favorable an oxidant than nitrate, nitrate-dependent uranium oxidation occurred significantly faster than oxygen-dependent uranium oxidation at the beginning of our experiment due, in part, to oxygen reacting more strongly with other reduced compounds. Nitrate breakthrough at the effluent of the column occurred within 12 h, which was significantly earlier than when oxygen was detected at the effluent (26 days). Although, over time, the majority of uranium was reoxidized by either oxidant, these results indicate that the type of oxidant and its reactivity with other reduced compounds will influence the fate of reduced uranium during a short-term oxidation event that may occur during a uranium bioremediation scenario.  相似文献   

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