Kinetics and thermodynamics of U reduction by natural and simple organic matter

The hypothesized reaction mechanisms for U reduction by the dehydrogenation of hydroxyl groups and aliphatic hydrocarbonaceous moieties of lignite were verified by kinetic U reduction experiments using simple alcohols (1-octadecanol and 2-propanol) and aliphatic hydrocarbons (n-octacosane). The rate constants and activation energies for U reduction by these alcohols are similar to those obtained for U reduction by lignite. The rate-determining step for U reduction by both simple and natural organic matter is hypothesized to be controlled by oxygen diffusion through U oxides. The equilibria of the system lignite-aqueous uranyl have been used to calculate standard free energy changes ΔG° for lignite dehydrogenation. Their comparison with those for the dehydrogenation of simple organic molecules supports the proposed reactions thermodynamically.     

Products of abiotic U(VI) reduction by biogenic magnetite and vivianite

Reductive immobilization of uranium by the stimulation of dissimilatory metal-reducing bacteria (DMRB) has been investigated as a remediation strategy for subsurface U(VI) contamination. In those environments, DMRB may utilize a variety of electron acceptors, such as ferric iron which can lead to the formation of reactive biogenic Fe(II) phases. These biogenic phases could potentially mediate abiotic U(VI) reduction. In this work, the DMRB Shewanella putrefaciens strain CN32 was used to synthesize two biogenic Fe(II)-bearing minerals: magnetite (a mixed Fe(II)-Fe(III) oxide) and vivianite (an Fe(II)-phosphate). Analysis of abiotic redox interactions between these biogenic minerals and U(VI) showed that both biogenic minerals reduced U(VI) completely. XAS analysis indicates significant differences in speciation of the reduced uranium after reaction with the two biogenic Fe(II)-bearing minerals. While biogenic magnetite favored the formation of structurally ordered, crystalline UO₂, biogenic vivianite led to the formation of a monomeric U(IV) species lacking U-U associations in the corresponding EXAFS spectrum. To investigate the role of phosphate in the formation of monomeric U(IV) such as sorbed U(IV) species complexed by mineral surfaces, versus a U(IV) mineral, uranium was reduced by biogenic magnetite that was pre-sorbed with phosphate. XAS analysis of this sample also revealed the formation of monomeric U(IV) species suggesting that the presence of phosphate hinders formation of UO₂. This work shows that U(VI) reduction products formed during in situ biostimulation can be influenced by the mineralogical and geochemical composition of the surrounding environment, as well as by the interfacial solute-solid chemistry of the solid-phase reductant.     

Chloride retention in forest soil by microbial uptake and by natural chlorination of organic matter

Inorganic chlorine (i.e. chloride; Cl_in) is generally considered inert in soil and is often used as a tracer of soil and ground water movements. However, recent studies indicate that substantial retention or release of Cl_in can occur in soil, but the rates and processes responsible under different environmental conditions are largely unknown. We performed ³⁶Cl tracer experiments which indicated that short-term microbial uptake and release of Cl_in, in combination with more long-term natural formation of chlorinated organic matter (Cl_org), caused Cl_in imbalances in coniferous forest soil. Extensive microbial uptake and release of Cl_in occurred over short time scales, and were probably associated with changes in environmental conditions. Up to 24% of the initially available Cl_in within pore water was retained by microbial uptake within a week in our experiments, but most of this Cl_in was released to the pore water again within a month, probably associated with decreasing microbial populations. The natural formation of Cl_org resulted in a net immobilization of 4% of the initial pore water Cl_in over four months. If this rate is representative for the area where soil was collected, Cl_org formation would correspond to a conversion of 25% of the yearly wet deposition of Cl_in. The study illustrates the potential of two Cl_in retaining processes in addition to those previously addressed elsewhere (e.g. uptake of chloride by vegetation). Hence, several processes operating at different time scales and with different regulation mechanisms can cause Cl_in imbalances in soil. Altogether, the results of the present study (1) provide evidence that Cl_in cannot be assumed to be inert in soil, (2) show that microbial exchange can regulate pore water Cl_in concentrations and (3) confirm the controversial idea of substantial natural chlorination of soil organic matter.     

天然黄铁矿除Cr（Ⅵ）中Cr2S3物相的发现

利用天然黄铁矿处理含Cr(Ⅵ)废水实验,在反应中与反应后黄铁矿表面和胶体沉淀物中明显出现Cr2p的XPS能谱峰,能拟合出574.7～575.1eV、576.6～576.9eV和578.2～578.7eV3个峰位,分别代表Cr2S3、Cr2O3和CrO3物相。在实验过程中新发现Cr2S3沉淀物相,表明在常温常压下的水溶液介质中也能产生铬的硫化物物相。充分利用这些含铬物相,能使天然黄铁矿包括天然磁黄铁矿在还原Cr(Ⅵ)的同时,无需加碱就可将Cr(Ⅲ)沉淀转移到胶体沉淀物中,处理后的上清液中全Cr含量低于1.5mg/L的国家允许排放标准。天然黄铁矿自身溶解出的重金属含量很低,不影响处理后的出水水质。开发利用Cr2S3等含铬沉淀物相,便于推广应用天然黄铁矿和磁黄铁矿还原Cr(Ⅵ)同时沉淀Cr(Ⅲ)的一步法除铬新工艺。     

Reduction of iron(III) minerals by natural organic matter in groundwater

Construction of the entrance tunnel to the Äspö Hard Rock Laboratory, a prototype repository in Sweden for research into the geological disposal of spent nuclear fuel, has resulted in increased transport of organic carbon from the surface into the groundwater. This increased input of organic matter has induced accelerated oxidation of organic carbon associated with reduction of iron(III) minerals as the terminal electron acceptor in microbial respiration. Hydrochemical modeling of major solute ions at the site indicates an apparent first-order decay constant for organic carbon of 3.7 ± 2.6/yr. This rapid turnover is not accompanied by an equivalent mobilization of ferrous iron. Thermodynamic calculation of iron mineral solubility suggests that ferrous clay minerals may form in hydraulically transmissive fractures. The conditional potentials for the oxidation–reduction of such phases coincide with measured redox potentials at the site. The calculated potential is sufficiently low so that such phases would provide reducing capacity against future intrusion of O₂ into the groundwater, thus buffering a repository against oxic corrosion of the engineered barriers.     

不同土壤有机质组分对憎水有机物的吸附机理研究

采用完全混合一步平衡反应实验方法，选择菲、萘、三氯苯和二甲苯作为憎水有机物(HOCs)的探针，研究了它们在土壤及其中的胡敏酸、胡敏素等有机质组分中的等温平衡吸附行为，探讨了非线性吸附的机制。结果表明，HOCs在水与土壤体系中表现为非线性吸附，其非线性的吸附行为主要受到土壤有机质(SOMs)的控制。SOMs具有高度不均匀的性质，HOCs表现出非线性吸附行为是其在不同的SOMs相扩散转移以及在相对聚结的胡敏素和“黑炭”的表面吸附的结果。     

Biotite dissolution and Cr(VI) reduction at elevated pH and ionic strength

The effects of elevated pH, ionic strength, and temperature on sediments in the vadose zone are of primary importance in modeling contaminant transport and understanding the environmental impact of tank leakage at nuclear waste storage facilities like those of the Hanford site. This study was designed to investigate biotite dissolution under simulated high level waste (HLW) conditions and its impact on Cr(VI) reduction and immobilization. Biotite dissolution increased with NaOH concentrations in the range of 0.1 to 2 mol L^-1. There was a corresponding release of K, Fe, Si, and Al to solution, with Si and Al showing a complex pattern due to the formation of secondary zeolite minerals. Dissolved Fe concentrations were an order of magnitude lower than the other elements, possibly due to the formation of green rust and Fe(OH)₂. The reduction of Cr(VI) to Cr(III) also increased with increased NaOH concentration. A homogeneous reduction of chromate by Fe(II)_aq released through biotite dissolution was probably the primary pathway responsible for this reaction. Greater ionic strengths increased biotite dissolution and consequently increased Fe(II)_aq release and Cr(VI) removal. The results indicated that HLW would cause phyllosilicate dissolution and the formation of secondary precipitates that would have a major impact on radionuclide and contaminant transport in the vadose zone at the Hanford site.     

Fluorescence spectroscopy of U(VI)-silicates and U(VI)-contaminated Hanford sediment

Time-resolved U(VI) laser fluorescence spectra (TRLFS) were recorded for a series of natural uranium-silicate minerals including boltwoodite, uranophane, soddyite, kasolite, sklodowskite, cuprosklodowskite, haiweeite, and weeksite, a synthetic boltwoodite, and four U(VI)-contaminated Hanford vadose zone sediments. Lowering the sample temperature from RT to ∼ 5.5 K significantly enhanced the fluorescence intensity and spectral resolution of both the minerals and sediments, offering improved possibilities for identifying uranyl species in environmental samples. At 5.5 K, all of the uranyl silicates showed unique, well-resolved fluorescence spectra. The symmetric O = U = O stretching frequency, as determined from the peak spacing of the vibronic bands in the emission spectra, were between 705 to 823 cm⁻¹ for the uranyl silicates. These were lower than those reported for uranyl phosphate, carbonate, or oxy-hydroxides. The fluorescence emission spectra of all four sediment samples were similar to each other. Their spectra shifted minimally at different time delays or upon contact with basic Na/Ca-carbonate electrolyte solutions that dissolved up to 60% of the precipitated U(VI) pool. The well-resolved vibronic peaks in the fluorescence spectra of the sediments indicated that the major fluorescence species was a crystalline uranyl mineral phase, while the peak spacing of the vibronic bands pointed to the likely presence of uranyl silicate. Although an exact match was not found between the U(VI) fluorescence spectra of the sediments with that of any individual uranyl silicates, the major spectral characteristics indicated that the sediment U(VI) was a uranophane-type solid (uranophane, boltwoodite) or soddyite, as was concluded from microprobe, EXAFS, and solubility analyses.     

Removal of Cr(VI) and phenol coupled with the reduction of sulfate by sulfate-reducing bacteria sludge

Biological treatment of industrial wastewater containing heavy metal and organic pollutant has attracted extensive attention. In this study, Cr(VI) reduction coupled with phenol degradation was investigated by the sulfate-reducing bacteria (SRB) sludge with addition of zero-valent iron (ZVI). The results showed that the SRB wet sludge (SWS) had a good bioactivity in the reduction of Cr(VI) only when the initial concentration of Cr(VI) was below 60 mg L^?1. The addition of ZVI significantly enhanced the bioactivity and reusability of SWS, and the reduction percentage of Cr(VI) achieved 98% after SWS was successively used for seven cycles. SWS coupled with ZVI showed a high activity in phenol degradation, with more than 94% phenol being degraded in each cycle. However, in the simultaneous removal of Cr(VI) and phenol, phenol degradation was inhibited due to the toxicity of Cr(VI) to phenol degrading microbes in SWS. On the other hand, reduction of sulfate and Cr(VI) was not affected by the presence of phenol, with more than 95% of sulfate and Cr(VI) being removed at the end of the 5th cycle. This study enriches our understanding on the applications of the SRB sludge in the removal of organic and inorganic contaminants in wastewater.     

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10⁻¹³ to 7.16 × 10⁻¹² mol Hg (mg C)⁻¹ m⁻²s⁻¹. Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R² = 0.88), aromaticity (R² = 0.80), and molecular weight (R² = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.     

Complexation of trace metals by adsorbed natural organic matter

The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu²⁺ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter.     

Effects of indigenous bacteria on Cr(VI) reduction in Cr-contaminated sediment with industrial wastes

Black, clay-like sediments have been obtained from the area of the pigment manufacturing factories in Dongducheon city, Korea. These sediments were contaminated by heavy metals, especially chromium (700 mg/kg). Indigenous bacteria in the sediments were isolated to investigate their ability to reduce Cr(VI) to Cr(III). The enriched bacterial consortium reduced over 99% of dissolved Cr(VI) in 96 h from the onset of the experiments under anaerobic condition, while there was no change in Cr(VI) concentration until 300 h in abiotic controls. Total amount of dissolved Cr decreased simultaneously when Cr(VI) was reduced, which was likely due to precipitation of Cr(OH)₃ after microbial reduction of Cr(VI) to Cr(III). Under aerobic condition, only 30% of dissolved Cr(VI) was reduced by indigenous bacteria until 900 h. The reduction of Cr(VI) did not accompany bacterial growth since the amount of protein did not show a significant change with time both in the presence and absence of O₂. These indigenous bacteria may play a role in the treatment of Cr(VI)-contaminated sediments.     

Interaction of phenanthrene with dissolved organic matter and its fractions from leachate of different landfill ages

Dissolved organic matter (DOM) in leachate from landfills of three different ages (0, 5, and 10?year) was partitioned into hydrophobic acid, hydrophobic neutral, and hydrophilic matter fractions using the fractionation method employing XAD-8 resin. The spectroscopic characteristics of these fractions were determined through constant-wavelength synchronous fluorescence spectrometry (CWSFS). The interaction characteristic of phenanthrene with these fractions was determined through the fluorescence quenching method and CWSFS. The results revealed that the composition of DOM became complex with the increase in landfill age. The partition coefficients (K _doc) for the three DOM samples of different landfill ages are in the order 10?a DOM?>?5?a DOM?>?0?a DOM. The hydrophobic fraction showed the highest K _doc value among the DOM fractions. Lower linearity Stern?CVolmer plots were observed in 10?a DOM and its hydrophobic fractions. CWSFS spectra showed that a special site was fully occupied with the addition of the quencher. Desorption was found in some fractions. Therefore, CWSFS is a sensitive tool for the detection of DOM-polycyclic aromatic hydrocarbon interaction.     

Models of natural organic matter and interactions with organic contaminants

Adsorption of organic contaminants onto soils, sediments and other particulates has the potential to be a major controlling factor in their bioavailability, fate and behavior in the environment. Models for estimating the amount and stability of sorbed organic contaminants based on the fraction of organic carbon in a soil or sediment can oversimplify the process of sorption in the environment. In order to help understand sorption of organic contaminants in soils and sediments, we modeled various components of natural organic matter (NOM) that are possible substrates for sorption. These substrates include soot particles, lignin, humic and fulvic acids. The molecular scale interactions of selected aromatic hydrocarbons with different substrates were also simulated. Results of the simulations include the 3-D structures of the NOM components, changes in structure with protonation state and solvation and the sorption energy between PAH and substrate. This last parameter is an indicator of the amount of contaminant that will sorb and the energy required to free the contaminant from the substrate. Although the simulation results presented in this paper represent a first-order examination of NOM and contaminant interactions, the findings highlight a number of essential features that should be included in future molecular models of NOM and contaminant sorption.     

Association of specific organic matter compounds in size fractions of soils under different environmental controls

Inherent chemical recalcitrance and association of organic matter (OM) with minerals are mechanisms responsible for the long term preservation of OM in soils. The structural characteristics of OM are also believed to control specific interactions between OM and soil minerals. However, the extent of the relationship between recalcitrance and mineral protection and the specificity of these chemically driven interactions are not clearly understood at the molecular level. To measure chemical patterns of OM sequestration in sand-, silt-, clay-size and light fractions, we analyzed three soils, which mainly differed in carbon content and overlying vegetation, but have similar clay mineralogy, using biomarker analysis and nuclear magnetic resonance (NMR). Despite differences in environmental controls, long chain aliphatic compounds generally accumulated in the fine fractions of all soils. This accumulation is likely due to the strong interaction between recalcitrant forms of OM and soil minerals. For example, polymethylene and >C₂₀ organic acids accumulated in fine fractions, while lignin-derived phenols were protected from oxidation in silt-size fractions. Diffusion edited solution state ¹H NMR suggested that contributions from microbial-derived OM was greater in finer fractions, which is likely due to the accumulation of microbial-derived compounds or higher microbial activity in clay micro-sites. Our data suggest that, for these Prairie soils, the specific structure of OM and not environmental factors is responsible for long term preservation of OM in mineral fractions. Further research is necessary to understand the interplay between these preservation mechanisms such that the long term fate of OM can be further elucidated.     

Isotopic fractionation and reaction kinetics between Cr(III) and Cr(VI) in aqueous media

The redox-sensitive stable isotope geochemistry of chromium bears the potential to monitor the attenuation of chromate pollution and to investigate changes in environmental conditions in the present and the past. The use of stable Cr isotope data as a geo-environmental tracer, however, necessitates an understanding of the reaction kinetics and Cr fractionation behaviour during redox transition and isotope exchange. Here, we report stable chromium isotope fractionation data for Cr(VI) reduction, Cr(III) oxidation and isotopic exchange between soluble Cr(III) and Cr(VI) in aqueous media. The reduction of Cr(VI) to Cr(III) with H₂O₂ under strongly acidic conditions shows a near-equilibrium isotope fractionation of Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −3.54 ± 0.35‰. At pH neutrality, however, the reduction experiments show a kinetic isotope fractionation Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −5‰ for the extent of reduction of up to 85% of the chromium. The oxidation of Cr(III) to Cr(VI) in alkaline media, using H₂O₂ as the oxidant, cannot be explained by a single, unidirectional reaction. Our experiments indicate that the involvement of the unstable intermediates Cr(IV) and Cr(V) and their disproportionation during redox reactions between Cr(III) and Cr(VI) influence the overall fractionation factor, depending on the prevailing pH conditions and the reaction rates. No detectable isotope exchange between soluble Cr(VI) and Cr(III) species at pH values of 5.5 and 7 was revealed over a timescale of days to weeks. This means that, at least within such a time frame, the isotopic composition of Cr(VI) in a natural system will not be influenced by equilibration with any Cr(III) and thus reveal the true extent of reduction, given that the Cr isotope composition of the source Cr(VI) and the fractionation factor for the prevailing conditions are known.     

Biosorption of Cr(III) and Cr(VI) species from aqueous solution by Cabomba caroliniana: kinetic and equilibrium study

This study reports the potential ability of non-living biomass of Cabomba caroliniana for biosorption of Cr(III) and Cr(VI) from aqueous solutions. Effects of contact time, biosorbent dosage, pH of the medium, initial concentration of metal ion and protonation of the biosorbent on heavy metal–biosorbent interactions were studied through batch sorption experiments. Cr(III) was sorbed more rapidly than Cr(VI) and the pH of the medium significantly affected the extent of biosorption of the two metal species differently. Surface titrations showed that the surface of the biosorbent is positively charged at low pH while it is negatively charged at pH higher than 4.0. Protonation of the biosorbent increased its capacity for removal of Cr(III), while decreasing that of Cr(VI). FT-IR spectra of the biosorbent confirmed the involvement of –OH groups on the biosorbent surface in the chromium removal process. Kinetic and equilibrium data showed that the sorption process of each chromium species followed pseudo second-order kinetic model and both Langmuir and Freundlich isothermal models. A possible mechanism for the biosorption of chromium species by non-living C. caroliniana is suggested.     

Mineral phases formed in anoxic sediments by microbial decomposition of organic matter

Microbial decomposition of organic matter in recent sediments of the Landsort Deep—an anoxic basin of the central Baltic Sea—resulted in the formation of a characteristic assemblage of authigenic mineral precipitates of carbonates, sulfides. phosphates and amorphous silica, The dominant crystalline phases are a mixed Mn-carbonate [(Mn_0.85Ca_0.10Mg_0.05)CO₃]. Mn-sulfide [MnS] and Fecarbonate [FeCO₃]. Amorphous Fe-sulfide [FeS]. Mn-phosphate [Mn₃(PO₄)₂] and a mixed Fe-Ca-phosphate [(Fe_0.86Ca_0.14)₃(PO₄)₂] were identified by their chemical compositions only. The variability in composition of these solid phases and their mode of occurrence as a co-existing assemblage constrains the conditions and solution composition from which they precipitated. Estimates of activities for dissolved Fe. Mn. PO₄, CO₃ and S in equilibrium with such an assemblage are close to those found in recent anoxic interstitial water-sediment systems. It is important to have detailed knowledge of the composition and stability conditions of these solid precipitates in order to refine stoichiometric models of interstitial nutrient regeneration in anoxic sediments.     

Aqueous Cr(VI) reduction by pyrite: Speciation and characterisation of the solid phases by X-ray photoelectron, Raman and X-ray absorption spectroscopies

Optical microscopy, confocal Raman micro-spectrometry, X-ray photoelectron micro-spectroscopy (XPS) and synchrotron based micro-X-ray fluorescence (XRF), micro-X-ray absorption near edge spectroscopy (XANES) and micro-extended X-ray absorption fine structure (EXAFS) were used to investigate the reduction of aqueous Cr(VI) by pyrite. Special emphasis was placed on the characterisation of the solid phase formed during the reaction process. Cr(III) and Fe(III) species were identified by XPS analyses in addition to non-oxidised pyrite. Optical microscopy images and the corresponding Raman spectra reveal a strong heterogeneity of the samples with three different types of zones. (i) Reflective areas with E_g and A_g Raman wavenumbers relative to non-oxidised pyrite are the most frequently observed. (ii) Orange areas that display a drift of the E_g and A_g pyrite vibration modes of −3 and −6 cm⁻¹, respectively. Such areas are only observed in the presence of Cr(VI) but are not specifically due to this oxidant. (iii) Bluish areas with vibration modes relative to a corundum-like structure that can be assigned to a solid solution Fe_2−xCr_xO₃, x varying between 0.2 and 1.5. The heterogeneity in the spatial distribution of chromium observed by optical microscopy and associated Raman microspectroscopy is confirmed by μ-XRF. In agreement with both solution and XPS analyses, these spectroscopies clearly confirm that chromium is in the trivalent state. XANES spectra in the iron K-edge pre-edge region obtained in rich chromium areas reveal the presence of ferric ion thus revealing a systematic association between Cr(III) and Fe(III). In agreement with Raman analyses, Cr K-edge EXAFS can be interpreted as corresponding to Cr atoms involved in a substituted-type hematite structure Fe_2−xCr_xO₃.