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1.
Arsenic(V), as the arsenate (AsO4 3?) ion and its conjugate acids, has a strong affinity on Fe, Mn, and Al (oxyhydr)oxides and clay minerals. Removal of arsenate from aqueous solution by poorly crystalline ferrihydrite (hydrous ferric oxide) via a combination of macroscopic (equilibria and kinetics of sorption) and X-ray absorption spectroscopic studies was investigated. The removal of arsenate significantly decreased with increasing pH and sorption maxima of approximately 1.994 mmol/g (0.192 molAs/molFe) were achieved at pH 2.0. The Langmuir isotherm is most appropriate for arsenate sorption over the wide range of pH, indicating that arsenate sorption preferentially takes place at relatively homogenous and monolayer sites rather than heterogeneous and multilayer surfaces. The kinetic study demonstrated that arsenate sorption onto 2-line ferrihydrite is considerably fast, and sorption equilibrium was achieved within the reaction time of 2 h. X-ray absorption near-edge structure spectroscopy indicates no change in oxidation state of arsenate following interaction with the ferrihydrite surfaces. Extended X-ray absorption fine structure spectroscopy supports the efficient removal of arsenate by the 2-line ferrihydrite through the formation of highly stable inner-sphere surface complexes, such as bidentate binuclear corner-sharing (2C) and bidentate mononuclear edge-sharing (2E) complexes.  相似文献   

2.
Mineral-associated organic matter (OM) represents a large reservoir of organic carbon (OC) in natural environments. The factors controlling the extent of the mineral-mediated OC stabilization, however, are poorly understood. The protection of OM against biodegradation upon sorption to mineral phases is assumed to result from the formation of strong bonds that limit desorption. To test this, we studied the biodegradation of OM bound to goethite (α-FeOOH), pyrophyllite, and vermiculite via specific mechanisms as estimated from OC uptake in different background electrolytes and operationally defined as ‘ligand exchange’, ‘Ca2+ bridging’, and ‘van der Waals forces’. Organic matter extracted from an Oa forest floor horizon under Norway spruce (Picea abies (L.) Karst) was reacted with minerals at dissolved OC concentrations of ∼5-130 mg/L at pH 4. Goethite retained up to 30.1 mg OC/g predominantly by ‘ligand exchange’; pyrophyllite sorbed maximally 12.5 mg OC/g, largely via ‘van der Waals forces’ and ‘Ca2+ bridging’, while sorption of OM to vermiculite was 7.3 mg OC/g, mainly due to the formation of ‘Ca2+ bridges’. Aromatic OM components were selectively sorbed by all minerals (goethite ? phyllosilicates). The sorption of OM was strongly hysteretic with the desorption into 0.01 M NaCl being larger for OM held by ‘Ca2+ bridges’ and ‘van der Waals forces’ than by ‘ligand exchange’. Incubation experiments under aerobic conditions (initial pH 4; 90 days) revealed that OM mainly bound to minerals by ‘ligand exchange’ was more resistant against mineralization than OM held by non-columbic interactions (‘van der Waals forces’). Calcium bridges enhanced the stability of sorbed OM, especially for vermiculite, but less than the binding via ‘ligand exchange’. Combined evidence suggests that the extent and rate of mineralization of mineral-associated OM are governed by desorption. The intrinsic stability of sorbed OM as related to the presence of resistant, lignin-derived aromatic components appears less decisive for the sorptive stabilization of OM than the involved binding mechanisms. In a given environment, the type of minerals present and the solution chemistry determine the operating binding mechanisms, thereby the extent of OM sorption and desorption, and thus ultimately the bioavailability of mineral-associated OM.  相似文献   

3.
Many studies have proposed that silicic acid and phosphate (PV) can displace arsenic sorbed to iron oxides leading to elevated As concentrations in aquatic systems. While surface complexation models are adept at quantifying sorption to synthetic oxides in laboratory systems their application to complex natural systems remains challenging. In this study we provide a systematic approach to developing a robust use of models for understanding AsV distribution in natural systems in which hydrated iron oxides are the main adsorptive phase. The Waikato River provides a useful laboratory for this work because it contains high H4SiO4, AsV and PV loadings due to geothermal and agricultural inputs. A 15 min oxalate extraction and a 48 h ethylenediaminetetraacetic acid (EDTA) extraction of river sediment contained the same ratios of As:Fe, P:Fe and Si:Fe. Both of these extracts target the poorly ordered iron oxide phases (typically ferrihydrite) and by following the release of elements over time in the EDTA extraction it was possible to demonstrate that the extracted As, P, and Si were associated with the ferrihydrite. This demonstrates for the first time that a single oxalate extraction can quantify ferrihydrite sorbed H4SiO4, As and PV and provides a basis to quantify the role of these ligands in inhibiting AsV sorption to sediments. The measured concentrations of ferrihydrite sorbed AsV, PV and H4SiO4 for the Waikato River suspended sediment allow for the informed selection of appropriate model parameters for applying the Diffuse Layer Model to the system. In this way it was possible to quantify the effect of the individual components in the river water on AsV sorption. This study provides an explanation for the observation that the proportion of sorbed As in the Waikato River is generally significantly lower than that observed in rivers closer to the world average concentrations. More generally the study provides a method to quantify the role of individual water chemistry components on AsV distribution in natural systems.  相似文献   

4.
The mineralogy of natural ferromanganese coatings on quartz grains and the crystal chemistry of associated trace elements Ni, Zn, Ba, and As were characterized by X-ray microfluorescence, X-ray diffraction, and EXAFS spectroscopy. Fe is speciated as ferrihydrite and Mn as vernadite. The two oxides form alternating Fe- and Mn-rich layers that are irregularly distributed and not always continuous. Unlike naturally abundant Fe-vernadite, in which Fe and Mn are mixed at the nanoscale, the ferrihydrite and vernadite are physically segregated and the trace elements clearly partitioned at the microscopic scale. Vernadite consists of two populations of interstratified one-water layer (7 Å phyllomanganate) and two-water layer (10 Å phyllomanganate) crystallites. In one population, 7 Å layers dominate, and in the other 10 Å layers dominate. The three trace metals Ni, Zn, and Ba are associated with vernadite and the metalloid As with ferrihydrite. In vernadite, nickel is both substituted isomorphically for Mn in the manganese layer and sorbed at vacant Mn layer sites in the interlayer. The partitioning of Ni is pH-dependent, with a strong preference for the first site at circumneutral pH and for the second at acidic pH. Thus, the site occupancy of Ni in vernadite may be an indicator of marine vs. continental origin, and in the latter, of the acidity of streams, lakes, or soil pore waters in which the vernadite formed. Zinc is sorbed only in the interlayer at vacant Mn layer sites. It is fully tetrahedral at a Zn/Mn molar ratio of 0.0138, and partly octahedral at a Zn/Mn ratio of 0.1036 consistent with experimental studies showing that the VIZn/IVZn ratio increases with Zn loading. Barium is sorbed in a slightly offset position above empty tetrahedral cavities in the interlayer. Arsenic tetrahedra are retained at the ferrihydrite surface by a bidentate-binuclear attachment to two adjacent iron octahedra, as commonly observed. Trace elements in ferromanganese precipitates are partitioned at a few, well-defined, crystallographic sites that have some elemental specificity, and thus selectivity. The relative diversity of sorption sites contrasts with the simplicity of the layer structure of vernadite, in which charge deficit arises only from Mn4+ vacancies (i.e., no Mn3+ for Mn4+ substitution). Therefore, sorption mechanisms primarily depend on physical and chemical properties of the sorbate and competition with other ions in solution, such as protons at low pH for Ni sorption.  相似文献   

5.
Iron oxides may undergo structural transformations when entering an anoxic environment. These transformations were investigated using the isotopic exchange between aqueous Fe(II) and iron oxides in experiments with 55Fe-labelled iron oxides. 55Fe was incorporated congruently into a ferrihydrite, two lepidocrocites (#1 and #2), synthesised at 10°C and 25°C, respectively, a goethite and a hematite. The iron oxides were then submerged in Fe2+ solutions (0-1.0 mM) with a pH of 6.5. In the presence of aqueous Fe2+, an immediate and very rapid release of 55Fe was observed from ferrihydrite, the two lepidocrocites and goethite, whereas in the absence of Fe2+ no release was observed. 55Fe was not released from hematite, even at the higher Fe2+ concentration. The release rate is mainly controlled by characteristics of the iron oxides, whereas the concentration of Fe2+ only has minor influence. Ferrihydrite and 5-nm-sized lepidocrocite crystals attained complete isotopic equilibration with aqueous Fe(II) within days. Within this timeframe ferrihydrite transformed completely into new and more stable phases such as lepidocrocite and goethite. Lepidocrocite #2 and goethite, having larger particles, did not reach isotopic equilibrium within the timeframe of the experiment; however, the continuous slow release of 55Fe suggests that isotopic equilibrium will ultimately be attained.Our results imply a recrystallization of solid Fe(III) phases induced by the catalytic action of aqueous Fe(II). Accordingly, iron oxides should properly be considered as dynamic phases that change composition when exposed to variable redox conditions. These results necessitate a reevaluation of current models for the release of trace metals under reducing conditions, the sequestration of heavy metals by iron oxides, and the significance of stable iron isotope signatures.  相似文献   

6.
Iron (hydr)oxides are common in natural environments and typically contain large amounts of impurities, presumably the result of coprecipitation processes. Coprecipitation of Al with Fe (hydr)oxides occurs, for example, during alternating reduction-oxidation cycles that promote dissolution of Fe from Fe-containing phases and its re-precipitation as Fe-Al (hydr)oxides. We used chemical and spectroscopic analyses to study the formation and transformation of Al coprecipitates with Fe (hydr)oxides. In addition, periodic density functional theory (DFT) computations were performed to assess the structural and energetic effects of isolated or clustered Al atoms at 8 and 25 mol% Al substitution in the goethite structure. Coprecipitates were synthesized by raising the pH of dilute homogeneous solutions containing a range of Fe and Al concentrations (100% Fe to 100% Al) to 5. The formation of ferrihydrite in initial suspensions with ?20 mol% Al, and of ferrihydrite and gibbsite in initial suspensions with ?25 mol% Al was confirmed by infrared spectroscopic and synchrotron-based X-ray diffraction analyses. While base titrations showed a buffer region that corresponded to the hydrolysis of Fe in initial solutions with ?25 mol% Al, all of the Al present in these solutions was retained by the solid phases at pH 5, thus indicating Al coprecipitation with the primary Fe hydroxide precipitate. In contrast, two buffer regions were observed in solutions with ?30 mol% Al (at pH ∼2.25 for Fe3+ and at pH ∼4 for Al3+), suggesting the formation of Fe and Al (hydr)oxides as two separate phases. The Al content of initial coprecipitates influenced the extent of ferrihydrite transformation and of its transformation products as indicated by the presence of goethite, hematite and/or ferrihydrite in aged suspensions. DFT experiments showed that: (i) optimized unit cell parameters for Al-substituted goethites (8 and 25 mol% Al) in clustered arrangement (i.e., the formation of diaspore-like clusters) were in good agreement with available experimental data whereas optimized unit cell parameters for isolated Al atoms were not, and (ii) Al-substituted goethites with Al in diaspore-like clusters resulted in more energetically favored structures. Combined experimental and DFT results are consistent with the coprecipitation of Al with Fe (hydr)oxides and with the formation of diaspore-like clusters, whereas DFT results suggest isomorphous Al for Fe substitution within goethite is unlikely at ?8 mol% Al substitution.  相似文献   

7.
Microbial sulfidogenesis plays a potentially important role in Fe and As biogeochemistry within wetland soils, sediments and aquifers. This study investigates the specific effects of microbial sulfidogenesis on Fe mineralogy and associated As mobility in mildly acidic (pH 6) and mildly basic (pH 8) advective-flow environments. A series of experiments were conducted using advective-flow columns, with an initial solid-phase comprising As(III)-bearing ferrihydrite-coated quartz sand. Columns for each pH treatment were inoculated with the sulfate-reducing bacteria Desulfovibrio vulgaris, and were compared to additional abiotic control columns. Over a period of 28 days, microbial sulfidogenesis (as coupled to the incomplete oxidation of lactate) caused major changes in Fe mineralogy, including replacement of ferrihydrite by mackinawite and magnetite at the in-flow end of the inoculated columns. At pH 8, the Fe2+ produced by electron transfer between sulfide and ferrihydrite was mainly retained near its zone of formation. In contrast, at pH 6, much of the produced Fe2+ was transported with advecting groundwater, facilitating the downstream Fe2+-catalyzed transformation of ferrihydrite to goethite. At both pH 6 and pH 8, the sulfide-driven reductive dissolution of ferrihydrite and its replacement by mackinawite at the in-flow end of the inoculated columns resulted in substantial mobilization of As into the pore-water. At pH 8, this caused the downstream As concentrations within the inoculated columns to be greater than the corresponding abiotic column. However, the opposite occurred under pH 6 conditions, with the Fe2+-catalyzed transformation of ferrihydrite to goethite in the inoculated columns causing a decrease in downstream As concentrations compared to the abiotic column. Although thermodynamically favorable at intermediate times and depth intervals within the inoculated columns, solid As sulfide phases were undetectable by As XANES spectroscopy. Our findings show that microbial sulfidogenesis can trigger significant As mobilization in subsurface environments with advective groundwater flow. The results also demonstrate that formation of mackinawite by sulfidization of ferric (hydr)oxides is not effective for the immobilization of As, whereas the Fe2+-catalyzed transformation of ferrihydrite to goethite under mildly acidic conditions may mitigate As mobility.  相似文献   

8.
Experiments of Zn2+ and Fe3+ coprecipitation as a function of pH were conducted in the laboratory at ambient temperature and pressure. X-ray diffraction patterns of the coprecipitates show two broad peaks at 0.149 and 0.258 nm, which is consistent with published patterns for pure 2-line ferrihydrite. Zn2+ uptake occurred at pH ≥5 while Fe3+ precipitation occurred between pH 3 and 4, although both Zn2+ and Fe3+ were present in the same solution during the entire range of pH titration. High-resolution transmission electron microscopy shows that the coprecipitates are 2 to 6 nm sized single crystalline particles but aggregated to 50 to 400 nm sized clusters. Analytical electron microscopy indicated that the 5% atomic Zn with respect to Fe was homogeneously distributed. No segregated phases were found in the clusters or at single crystal edges, which is consistent with published extended X-ray absorption fine structure (EXAFS) results at similar Zn/(Zn + Fe) ratios. Hence, occlusion and surface precipitation may be excluded as possible coprecipitation mechanisms. The bulk solution Zn2+ sorption edge was fitted to both solid solution and generalized diffuse layer surface complexation models. However, a solid solution model is inconsistent with published EXAFS results that show tetrahedral polydentate Zn2+ complexes sharing apices with Fe3+octahedra.  相似文献   

9.
Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10−11 mol Fe(II) m−2 g−1), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)aq and bacterially-generated Fe(II)aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area.  相似文献   

10.
Sorption of Cm(III) and Eu(III) at trace concentrations onto Ca-montmorillonite (SWy-1) and Na-illite (Illite du Puy) has been studied under anaerobic conditions by batch sorption experiments and time-resolved laser fluorescence spectroscopy (TRLFS). Comparison of the results from spectroscopic and batch sorption experiments with Cm and Eu indicates the existence of outer-sphere complexes at pH <4 in the experiments with Na-illite (0.25 g/L solid; 2.5 × 10−7 mol/L Cm; 0.1 mol/L NaClO4). In the case of Ca-montmorillonite, (0.25 g/L solid, 2.5 × 10−7 mol/L Cm or 10−6 mol/L Eu, 0.066 mol/L Ca(ClO4)2), Cm/Eu outer-sphere complexes do not form at significant levels due to the Ca2+ competition for the clay mineral cation-exchange sites. TRLFS spectra indicate the formation of inner-sphere surface complexes at pH >5 for both clay minerals. Five H2O/OH− molecules remain in the first metal ion coordination sphere of the sorbed Eu/Cm. Measured fluorescence lifetimes of sorbed Eu/Cm and peak deconvolution of Cm-spectra are consistent with the formation of surface complexes of the form ≡S-O-Eu/Cm(OH)x(2−x)(H2O)5−x. At pH ≥ 12 Cm becomes incorporated into a surface precipitate at the Ca-montmorillonite surface presumably composed of Ca(OH)2 or calcium silicate hydrate. A dramatic shift of the fluorescence emission band by more than 20 nm and a clear increase in the fluorescence lifetime suggests the almost complete displacement of coordinated H2O and OH−. The pH dependent Eu sorption data obtained in batch experiments are consistent with spectroscopic data on Eu and Cm within experimental uncertainties thus demonstrating the validity of Eu as a homologue for trivalent actinides. Parameterization of a two-site protolysis nonelectrostatic surface complexation and cation exchange model using the batch sorption data and spectroscopic results is discussed in Part 2 of this work.  相似文献   

11.
The behaviour of trace amounts of arsenate coprecipitated with ferrihydrite, lepidocrocite and goethite was studied during reductive dissolution and phase transformation of the iron oxides using [55Fe]- and [73As]-labelled iron oxides. The As/Fe molar ratio ranged from 0 to 0.005 for ferrihydrite and lepidocrocite and from 0 to 0.001 for goethite. For ferrihydrite and lepidocrocite, all the arsenate remained associated with the surface, whereas for goethite only 30% of the arsenate was desorbable. The rate of reductive dissolution in 10 mM ascorbic acid was unaffected by the presence of arsenate for any of the iron oxides and the arsenate was not reduced to arsenite by ascorbic acid. During reductive dissolution of the iron oxides, arsenate was released incongruently with Fe2+ for all the iron oxides. For ferrihydrite and goethite, the arsenate remained adsorbed to the surface and was not released until the surface area became too small to adsorb all the arsenate. In contrast, arsenate preferentially desorbs from the surface of lepidocrocite. During Fe2+ catalysed transformation of ferrihydrite and lepidocrocite, arsenate became bound more strongly to the product phases. X-ray diffractograms showed that ferrihydrite was transformed into lepidocrocite, goethite and magnetite whereas lepidocrocite either remained untransformed or was transformed into magnetite. The rate of recrystallization of ferrihydrite was not affected by the presence of arsenate. The results presented here imply that during reductive dissolution of iron oxides in natural sediments there will be no simple correlation between the release of arsenate and Fe2+. Recrystallization of the more reactive iron oxides into more crystalline phases, induced by the appearance of Fe2+ in anoxic aquifers, may be an important trapping mechanism for arsenic.  相似文献   

12.
Lead coprecipitation with iron oxyhydroxide nano-particles   总被引：1，自引：0，他引：1  
Pb2+ and Fe3+ coprecipitation was studied with sorption edge measurements, desorption experiments, sorbent aging, High Resolution Transmission and Analytical Electron Microscopy (HR TEM-AEM), and geochemical modeling. Companion adsorption experiments were also conducted for comparison. The macroscopic chemical and near atomic scale HRTEM data supplemented our molecule scale analysis with EXAFS (Kelly et al., 2008). Coprecipitation of Pb2+ with ferric oxyhydroxides occurred at ∼pH 4 and is more efficient than adsorption in removing Pb2+ from aqueous solutions at similar sorbate/sorbent ratios and pH. X-ray Diffraction (XRD) shows peaks of lepidocrocite and two additional broad peaks similar to fine particles of 2-line ferrihydrite (2LFh). HRTEM of the Pb-Fe coprecipitates shows a mixture of 2-6 nm diameter spheres and 8-20 by 200-300 nm needles, both uniformly distributed with Pb2+. Geochemical modeling shows that surface complexation models fit the experimental data of low Pb:Fe ratios when a high site density is used. Desorption experiments show that more Pb2+ was released from loaded sorbents collected from adsorption experiments than from Pb to Fe coprecipitates at dilute EDTA concentrations. Desorbed Pb2+ versus dissolved Fe3+ data show a linear relationship for coprecipitation (CPT) desorption experiments but a parabolic relationship for adsorption (ADS) experiments.Based on these results, we hypothesize that Pb2+ was first adsorbed onto the nanometer-sized, metastable, iron oxyhydroxide polymers of 2LFh with domain size of 2-3 nm. As these nano-particles assembled into larger particles, some Pb2+ was trapped in the iron oxyhydroxide structure and re-arranged to form solid solutions. Therefore, the CPT contact method produced more efficient removal of Pb2+ than the adsorption contact method, and Pb2+ bound in CPT solids represent a more stable sequestration of Pb2+ in the environment than Pb2+ adsorbed on iron oxyhydroxide surfaces.  相似文献   

13.
The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite–water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8–9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)–Fe bond distances of ∼2.92–2.94 and 3.41–3.44 Å, respectively. The As–Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As–Fe bonding mechanisms.  相似文献   

14.
The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid 55Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments.  相似文献   

15.
《Applied Geochemistry》2003,18(5):693-710
In experiments of 7 days duration using voltammetric and radiotracer measurement techniques, the role of different particle types in the sorption of dissolved metal species in a disturbed deep-sea bottom seawater system were investigated. Resuspension of oxic to suboxic surface sediment into the bottom water in the deep sea (either by natural events or industrial activities like Mn nodule mining) has been shown to be followed quickly by scavenging of dissolved heavy metals, e.g. released from interstitial water, on the resuspended particles. Compared to other deep-sea particles (like clay minerals, calcite and apatite), Mn and Fe oxides and oxyhydroxides were found to be by far the most important phases in scavenging many dissolved heavy metals. Only Pb was sorbed strongly on all particles used, with highest affinity to carbonate fluorapatite. Caesium+ was significantly scavenged only by clay minerals like illite. The sorption experiments support a simple electrostatic model: Hydrated cations and labile cationic chloro-complexes in seawater like Mn2+, MnCl+, Co2+, Ni2+, Cu2+, Zn2+, Ba2+, and PbCl+, are preferentially adsorbed or ion-exchanged on the negatively charged surfaces of Mn oxides. In contrast, oxyanions and neutrally or negatively charged complexes like HVO42−, MoO42−, HAsO42−, UO2(CO3)22−, and PbCO30 associate with neutral to slightly positive amphoteric Fe oxyhydroxide particles. Metals forming strong chloro-complexes in seawater like Cd (CdCl20), are less readily sorbed by oxides than others. A comparison of the results of voltammetric and radiotracer techniques revealed that after fast sorption within the first hour, isotopic exchange dominated reactions on MnO2-rich particles in the following days. This was especially pronounced for Mn and Co which are bound to the Mn oxide surface via a redox transformation.  相似文献   

16.
Arsenate and antimonate are water-soluble toxic mining waste species which often occur together and can be sequestered with varying success by a hydrous ferric oxide known as ferrihydrite. The competitive adsorption of arsenate and antimonate to thin films of 6-line ferrihydrite has been investigated using primarily adsorption/desorption kinetics monitored by in situ attenuated total reflectance infrared (ATR-IR) spectroscopy on flowed solutions containing 10−3 and 10−5 mol L−1 of both species at pH 3, 5, and 7. ICP-MS analysis of arsenate and antimonate adsorbed to 6-line ferrihydrite from 10−3 mol L−1 mixtures in batch adsorption experiments at pH 3 and 7 was carried out to calibrate the relative surface concentrations giving rise to the IR spectral absorptions. The kinetic data from 10−3 and 10−5 mol L−1 mixtures showed that at pH 3 antimonate achieved a greater surface concentration than arsenate after 60 min adsorption on 6-line ferrihydrite. However, at pH 7, the adsorbed arsenate surface concentration remained relatively high while that of adsorbed antimonate was much reduced compared with pH 3 conditions. Both species desorbed slowly into pH 3 solution while at pH 7 most adsorbed arsenate showed little desorption and adsorbed antimonate concentration was too low to register its desorption behaviour. The nature of arsenate which is almost irreversibly adsorbed to 6-line ferrihydrite remains to be clarified.  相似文献   

17.
Arsenic (As) and fluoride (F?) in groundwater are increasing global water quality and public health concerns. The present study provides a deeper understanding of the impact of seasonal change on the co-occurrence of As and F?, as both contaminants vary with climatic patterns. Groundwater samples were collected in pre- and post-monsoon seasons (n = 40 in each season) from the Brahmaputra flood plains (BFP) in northeast India to study the effect of season on As and F? levels. Weathering is a key hydrogeochemical process in the BFP and both silicate and carbonate weathering are enhanced in the post-monsoon season. The increase in carbonate weathering is linked to an elevation in pH during the post-monsoon season. A Piper diagram revealed that bicarbonate-type water, with Na+, K+, Ca2+, and Mg2+ cations, is common in both seasons. Correlation between Cl? and NO3 ? (r = 0.74, p = 0.01) in the post-monsoon indicates mobilization of anthropogenic deposits during the rainy season. As was within the 10 µg L?1 WHO limit for drinking water and F? was under the 1.5 mg L?1 limit. A negative correlation between oxidation reduction potential and groundwater As in both seasons (r = ?0.26 and ?0.49, respectively, for pre-monsoon and post-monsoon, p = 0.05) indicates enhanced As levels due to prevailing reducing conditions. Reductive hydrolysis of Fe (hydr)oxides appears to be the predominant process of As release, consistent with a positive correlation between As and Fe in both seasons (r = 0.75 and 0.73 for pre- and post-monsoon seasons, respectively, at p = 0.01). Principal component analysis and hierarchical cluster analysis revealed grouping of Fe and As in both seasons. F? and sulfate were also clustered during the pre-monsoon season, which could be due to their similar interactions with Fe (hydr)oxides. Higher As levels in the post-monsoon appears driven by the influx of water into the aquifer, which drives out oxygen and creates a more reducing condition suitable for reductive dissolution of Fe (hydr)oxides. An increase in pH promotes desorption of As oxyanions AsO4 3? (arsenate) and AsO3 3? (arsenite) from Fe (hydr)oxide surfaces. Fluoride appears mainly released from F?-bearing minerals, but Fe (hydr)oxides can be a secondary source of F?, as suggested by the positive correlation between As and F? in the pre-monsoon season.  相似文献   

18.
The distribution of Cd2+ in the presence of phthalic acid (H2Lp), ferrihydrite and bacteria (Comamonas spp.) was investigated in biologically active systems involving H2Lp biodegradation. Tests showed that Cd2+ sorption onto bacteria, ferrihydrite and bacteria-ferrihydrite mixture increased with pH in all systems, irrespective of H2Lp degradation or not. The use of bacterial growth medium, Bushnell Hass Broth modified for low phosphate, had negligible effect on Cd sorption. In the presence of ferrihydrite, no difference was observed between Cd2+ sorption in the ferrihydrite-live bacteria and in the ferrihydrite-dead bacteria systems as ferrihydrite proved to be the dominant sorption phase. Cadmium sorption to ferrihydrite and to bacterial cells was described using the diffuse layer model and a nonelectrostatic 4-site model, respectively, which were developed for systems lacking H2Lp degradation. For systems experiencing H2Lp degradation this modeling approach predicted the general trend of Cd2+ sorption-edge shift and gave good fits to the observed sorption data. The results obtained demonstrate that Cd2+ sorption in the biologically active system was reasonably estimated by a model developed for biologically inactive systems, although uncertainty exists due to processes involving H2Lp biodegradation products and changes in the bacterial population.  相似文献   

19.
Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides—collectively referred to as “oxides” hereafter—are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO2, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite Oi, Oe, and Oa horizon leachate (“O horizon leachate” hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy–near-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (r = 0.78, P < 0.0006) on the DOM–HMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2 × 102 μg C m?2), DOM desorption—assessed by 0.1 M NaH2PO4 extraction—is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 × 102 μg C m?2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOM–HMO complexes may be more vulnerable to reductive dissolution than DOM–goethite complexes.  相似文献   

20.
Aluminium smelters are major sources of F emission to the environment. We studied, in laboratory experiments, the sorption and desorption of fluoride on organic and mineral horizons of soils located within 2 km from one of these factories, situated in the northern coast of Galicia (NW Spain). The soils, developed from granite, are acid (pH H2O 3.9–5.5), rich in organic matter (4–16 % C in the A horizon) and most A horizons have high Al saturation in the exchange complex. All samples showed a notable F sorption, between 1,066 and 1,589 mg kg?1, after adding 200 mg F L?1, which accounts for 53–80 % of F added. The sorption was slightly higher in the A horizons than in the respective organic horizons (differences of up to 194 mg kg?1). The fluoride sorption upon addition of 200 mg F L?1 correlated significantly (p < 0.05) with soil pH in water (r = ?0.77), iron extracted by acid ammonium oxalate (r = 0.68), aluminium plus iron extracted by acid ammonium oxalate (r = 0.63), exchange aluminium (r = 0.52) and clay percentage in soil (r = 0.76). The F sorption fitted to both Langmuir and Freundlich models. Desorbed F accounted for only 12–22 % of sorbed fluoride and correlated (p < 0.05) negatively with non-crystalline (extracted by acid ammonium oxalate) Fe (r = ?0.51) and clay content (r = ?0.74) and positively with organic matter (r = 0.69) and with the effective cation exchange capacity of the soil (r = 0.50).  相似文献   

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