Comparison of arsenic(V) and arsenic(III) sorption onto iron oxide minerals: implications for arsenic mobility

Arsenic derived from natural sources occurs in groundwater in many countries, affecting the health of millions of people. The combined effects of As(V) reduction and diagenesis of iron oxide minerals on arsenic mobility are investigated in this study by comparing As(V) and As(III) sorption onto amorphous iron oxide (HFO), goethite, and magnetite at varying solution compositions. Experimental data are modeled with a diffuse double layer surface complexation model, and the extracted model parameters are used to examine the consistency of our results with those previously reported. Sorption of As(V) onto HFO and goethite is more favorable than that of As(III) below pH 5-6, whereas, above pH 7-8, As(II) has a higher affinity for the solids. The pH at which As(V) and As(III) are equally sorbed depends on the solid-to-solution ratio and type and specific surface area of the minerals and is shifted to lower pH values in the presence of phosphate, which competes for sorption sites. The sorption data indicate that, under most of the chemical conditions investigated in this study, reduction of As(V) in the presence of HFO or goethite would have only minor effects on or even decrease its mobility in the environment at near-neutral pH conditions. As(V) and As(III) sorption isotherms indicate similar surface site densities on the three oxides. Intrinsic surface complexation constants for As(V) are higher for goethite than HFO, whereas As(III) binding is similar for both of these oxides and also for magnetite. However, decrease in specific surface area and hence sorption site density that accompanies transformation of amorphous iron oxides to more crystalline phases could increase arsenic mobility.     

Solid-solution reactions in As(V) sorption by schwertmannite

Sorption behavior of As(V) by synthesized schwertmannite was examined under pH 3.3 as a function of As(V) concentration in the initial solution and interpreted in term of solid-solution reactions. Results showed that schwertmannite released 0.62 mmol of SO4(2-) for every 1 mmol of H2AsO4- and 0.24 mmol of OH- that has been sorbed. As(V) replaced SO4 up to half of the total SO4 in schwertmannite. The quantitative relationship among the three chemical compositions indicated that As(V)-sorbed schwertmannite would behave as a solid solution between the As(V) free schwertmannite and schwertmannite containing the maximum level of As(V). The equilibrium constant for the anion exchange in the solid-solution reaction estimated from the reacted solution chemistry depicts the As(V) content found in precipitates formed in acid mine drainage and laboratory experiments. Although schwertmannite is metastable with respect to goethite, the transformation is significantly inhibited by sorption of As(V). The solid-solution reactions also explain the stabilization of schwertmannite by sorption of As(V).     

Sorption of Sb(III) and Sb(V) to goethite: influence on Sb(III) oxidation and mobilization

Antimony is an element of growing interest for a variety of industrial applications, even though Sb compounds are classified as priority pollutants by the Environmental Protection Agency of the United States. Iron (Fe) hydroxides appear to be important sorbents for Sb in soils and sediments, but mineral surfaces can also catalyze oxidation processes and may thus mobilize Sb. The aim of this study was to investigate whether goethite immobilizes Sb by sorption or whether Sb(III) adsorbed on goethite is oxidized and then released. The sorption of both Sb(III) and Sb(V) on goethite was studied in 0.01 and 0.1 M KClO4 M solutions as a function of pH and Sb concentration. To monitor oxidation processes Sb species were measured in solution and in the solid phase. The results show that both Sb(III) and Sb(V) form inner-sphere surface complexes at the goethite surface. Antimony(III) strongly adsorbs on goethite over a wide pH range (3-12), whereas maximum Sb(V) adsorption is found below pH 7. At higher ionic strength, the desorption of Sb(V) is shifted to lower pH values, most likely due to the formation of ion pairs KSb(OH)6 degrees. The sorption data of Sb(V) can be fitted by the modified triple-layer surface complexation model. Within 7 days, Sb(III) adsorbed on goethite is partly oxidized at pH 3, 5.9 and 9.7. The weak pH-dependence of the rate coefficients suggests that adsorbed Sb(III) is oxidized by 02 and that the coordination of Sb(III) to the surface increases the electron density of the Sb atom, which enhances the oxidation process. At pH values below pH 7, the oxidation of Sb(III) did not mobilize Sb within 35 days, while 30% of adsorbed Sb(III) was released into the solution at pH 9.9 within the same time. The adsorption of Sb(III) on Fe hydroxides over a wide pH range may be a major pathway for the oxidation and release of Sb(V).     

Distinctive arsenic(V) trapping modes by magnetite nanoparticles induced by different sorption processes

Arsenic sorption onto iron oxide spinels such as magnetite may contribute to arsenic immobilization at redox fronts in soils, sediments, and aquifers, as well as in putative remediation and water treatment technologies. We have investigated As(V) speciation resulting from different sorption processes on magnetite nanoparticles, including both adsorption and precipitation, using X-ray absorption fine structure (XAFS) spectroscopy and transmission electron microscopy (TEM). XAFS results suggest that AsO(4) tetrahedra form predominantly inner-sphere bidentate corner-sharing ((2)C) complexes and outer-sphere complexes on magnetite in the adsorption experiments. In the precipitation experiments, an increasing fraction of AsO(4) tetrahedra appears to be incorporated in clusters having a magnetite-like local structure with increasing As loading, the remaining fraction of As being adsorbed at the surface of magnetite particles. In the sample with the highest As loading (15.7 μmol/m(2)) XAFS data indicate that As(V) is fully incorporated in such clusters. Such processes help to explain the significantly higher arsenic uptake in precipitation samples compared to those generated in adsorption experiments. In addition, for the precipitation samples, TEM observations indicate the formation of amorphous coatings and small (~3 nm) nanoparticles associated with larger (~20-40 nm) magnetite nanoparticles, which are absent in the adsorption samples. These results suggest that As(V) could form complexes at the surfaces of the small nanoparticles and could be progressively incorporated in their structure with increasing As loading. These results provide some of the fundamental knowledge about As(V)-magnetite interactions that is essential for developing effective water treatment technologies for arsenic.     

TiO2-photocatalyzed As(II) oxidation in aqueous suspensions: reaction kinetics and effects of adsorption

Oxidation of arsenite, As(III), to arsenate, As(V), is required for the efficient removal of arsenic by many water treatment technologies. The photocatalyzed oxidation of As(III) on titanium dioxide, TiO2, offers an environmentally benign method for this unit operation. In this study, we explore the efficacy and mechanism of TiO2-photocatalyzed As(III) oxidation at circumneutral pH and over a range of As(III) concentrations approaching those typically encountered in water treatment systems. We focus on the effect of As adsorption on observed rates of photooxidation. Adsorption (in the dark) of both As(III) and As(V) on Degussa P25 TiO2 was examined at pH 6.3 over a range in dissolved arsenic concentrations, [As]diss, of 0.10-89 microM and 0.2 or 0.05 g L(-1) TiO2 for As(III) and As(V), respectively. Adsorption isotherms generally followed the Langmuir-Hinshelwood model with As(III) exhibiting an adsorption maxima of 32 micromol g(-1). As(V) adsorption did not reach a plateau under the experimental conditions examined; the maximum adsorbed concentration observed was 130 micromol g(-1). The extent of As(III) and As(V) adsorption observed at the beginning and end of the kinetic studies was consistent with that observed in the adsorption isotherms. Kinetic studies were performed in batch systems at pH 6.3 with 0.8-42 microM As(III) and 0.05 g L(-1) TiO2; complete oxidation of As(III) was observed within 10-60 min of irradiation at 365 nm. The observed effect of As(III) concentration on reaction kinetics was consistent with surface saturation at higher concentrations. Addition of phosphate at 0.5-10 microM had little effect on either As(III) sorption or its photooxidation rate but did inhibit adsorption of the product As(V). The selective use of hydroxyl radical quenchers and superoxide dismutase demonstrated that superoxide, O2-, plays a major role in the oxidation of As(III) to As(V).     

Arsenic adsorption by Fe(III)-loaded open-celled cellulose sponge. Thermodynamic and selectivity aspects

Nowadays there is a great concern on the study of new adsorbent materials for either the removal or fixation of arsenic species because of their high toxicity and the health problems associated to such substances. The present paper reports a basic study of the adsorption of arsenic inorganic species from aqueous solutions using an open-celled cellulose sponge with anion-exchange and chelating properties (Forager Sponge). Consequences of preloading the adsorbentwith Fe(III) to enhance the adsorption selectivity are discussed and compared with the nonloaded adsorbent properties. The interactions of arsenic species with the Fe(III)-loaded adsorbent are accurately determined to clarify the feasibility of an effective remediation of contaminated waters. Arsenate is effectively adsorbed by the nonloaded and the Fe(III)-loaded sponge in the pH range 2-9 (maximum at pH 7), whereas arsenite is only slightly adsorbed by the Fe(III)-loaded sponge in the pH range 5-10 (maximum at pH 9), being that the nonloaded sponge is unable to adsorb As(III). The maximum sorption capacities are 1.83 mmol As(V)/g (pH approximately 4.5) and 0.24 mmol As(lII)/g (pH approximately 9.0) for the Fe(III)-loaded adsorbent. This difference is explained in terms of the different acidic behavior of both arsenic species. The interaction of the arsenic species with the Fe(III) loaded in the sponge is satisfactorily modeled. A 1:1 Fe:As complex is found to be formed for both species. H2AsO4- and H3AsO3 are determined to be adsorbed on Fe(III) with a thermodynamic affinity defined by log K = 2.5 +/- 0.3 and log K = 0.53 +/- 0.07, respectively. As(V) is, thus, found to be more strongly adsorbed than As(III) on the Fe(III) loaded in the sponge. A significant enhancement on As(V) adsorption selectivity by loading Fe(III) in the sponge is observed, and the effectiveness of the Fe(III)-loaded sponge for the As(V) adsorption is demonstrated, even in the presence of high concentrations of interfering anions (chloride, nitrate, sulfate, and phosphate).     

Impacts of Shewanella putrefaciens strain CN-32 cells and extracellular polymeric substances on the sorption of As(V) and As(III) on Fe(III)-(hydr)oxides

We investigated the effects of Shewanella putrefaciens cells and extracellular polymeric substances on the sorption of As(III) and As(V) to goethite, ferrihydrite, and hematite at pH 7.0. Adsorption of As(III) and As(V) at solution concentrations between 0.001 and 20 μM decreased by 10 to 45% in the presence of 0.3 g L(-1) EPS, with As(III) being affected more strongly than As(V). Also, inactivated Shewanella cells induced desorption of As(V) from the Fe(III)-(hydr)oxide mineral surfaces. ATR-FTIR studies of ternary As(V)-Shewanella-hematite systems indicated As(V) desorption concurrent with attachment of bacterial cells at the hematite surface, and showed evidence of inner-sphere coordination of bacterial phosphate and carboxylate groups at hematite surface sites. Competition between As(V) and bacterial phosphate and carboxylate groups for Fe(III)-(oxyhydr)oxide surface sites is proposed as an important factor leading to increased solubility of As(V). The results from this study have implications for the solubility of As(V) in the soil rhizosphere and in geochemical systems undergoing microbially mediated reduction and indicate that the presence of sorbed oxyanions may affect Fe-reduction and biofilm development at mineral surfaces.     

Arsenic-bicarbonate interaction on goethite particles

The As(V) and As(III) interaction with HCO3 has been studied for goethite systems using a pH and As concentration range that is relevant for field situations. Our study shows that dissolved bicarbonate may act as a competitor for both As(V) and As(III). In our closed systems, the largest effect of bicarbonate occurs at the lowest experimental pH values (pH approximately 6.5), which is related to the pH dependency of the carbonate adsorption process. The experimental data have been modeled with the charge distribution (CD) model. The CD model was separately parametrized for goethite with "single ion" adsorption data of HCO3, As(III), and As(V). The competitive effect of HCO3 on the As(III) and As(V) release could be predicted well. Application of the model shows that the natural As loading of aquifer materials (approximately < 0.01-0.1 micromol/m2 or < 1-5 mg/kg) is at least about > 1-2 orders of magnitude smaller than the As loading based on the competition of As-HCO3 alone. It indicates that another, very prominent competitor, like phosphate and natural organic matter, will strongly contribute to the control of As in natural systems.     

Adsorption mechanism of arsenic on nanocrystalline titanium dioxide

Arsenate [As(V)] and arsenite [As(III)] interactions at the solid-water interface of nanocrystalline TiO2 were investigated using electrophoretic mobility (EM) measurements, Fourier transform infrared (FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and surface complexation modeling. The adsorption of As(V) and As(III) decreased the point of zero charge of TiO2 from 5.8 to 5.2, suggesting the formation of negatively charged inner-sphere surface complexes for both arsenic species. The EXAFS analyses indicate that both As(V) and As(III) form bidentate binuclear surface complexes as evidenced by an average Ti-As(V) bond distance of 3.30 A and Ti-As(III) bond distance of 3.35 A. The FTIR bands caused by vibrations of the adsorbed arsenic species remained at the same energy levels at different pH values. Consequently, the surface complexes on TiO2 maintained the same nonprotonated speciation at pH values from 5 to 10, and the dominant surface species were (TiO)2AsO2- and (TiO)2AsO- for As(V) and As(III), respectively. The surface configurations constrained with the spectroscopic results were formulated in the diffuse layer model to describe the adsorption behavior of As in the pH range between 4 and 12. The study suggests that TiO2 is an effective adsorbent for As removal due to its high surface area and the presence of high affinity surface hydroxyl groups.     

Effects of Zwitterionic buffers on sorption of ferrous iron at goethite and its oxidation by CCl4

A major factor which controls sorption and oxidation of Fe(II) at the mineral-water interface is pH, hence buffers are commonly used to control pH in experimental studies. Here, we examined the effects of widely used organic buffers (3-morpholinopropane-1-sulfonic acid (MOPS) and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES)) on Fe(II) uptake and oxidation by CCl(4) in aqueous suspensions of goethite. Significant sorption of these zwitterionic buffers occurred only at Fe(II)-loaded goethite but not at native goethite. The addition of MOPS and HEPES caused substantial release of Fe(II) from goethite, retarded the oxidation of surface-bound Fe(II) by CCl(4) and changed the reaction pathway as indicated by lower yields of CHCl(3). To explore electrostatic and steric contributions of MOPS and HEPES to the observed phenomena we studied sorption and competitive effects of model sorbates (Ca(2+), sulfonates) which suggest the formation of a complex between surface-bound Fe(II) and MOPS or HEPES. Our study shows for the first time that these frequently used zwitterionic organic buffers may interfere significantly with the surface chemistry and thus with redox reactions of Fe(II) at goethite. Hence, kinetic or mechanistic information obtained in such systems requires careful interpretation.     

Photoinduced oxidation of arsenite to arsenate in the presence of goethite

The photochemistry of an aqueous suspension of goethite in the presence of arsenite (As(III)) was investigated with X-ray absorption near edge structure (XANES) spectroscopy and solution-phase analysis. Irradiation of the arsenite/goethite under conditions where dissolved oxygen was present in solution led to the presence of arsenate (As(V)) product adsorbed on goethite and in solution. Under anoxic conditions (absence of dissolved oxygen), As(III) oxidation occurred, but the As(V) product was largely restricted to the goethite surface. In this circumstance, however, there was a significant amount of ferrous iron release, in stark contrast to the As(III) oxidation reaction in the presence of dissolved oxygen. Results suggested that in the oxic environment ferrous iron, which formed via the photoinduced oxidation of As(III) in the presence of goethite, was heterogeneously oxidized to ferric iron by dissolved oxygen. It is likely that aqueous reactive oxygen species formed during this process led to the further oxidation of As(III) in solution. Results from the current study for As(III)/goethite also were compared to results from a prior study of the photochemistry of As(III) in the presence of another iron oxyhydroxide, ferrihydrite. The comparison showed that at pH 5 and 2 h of light exposure the instantaneous rate of aqueous-phase As(V) formation in the presence of goethite (12.4 × 10(-5) M s(-1) m(-2)) was significantly faster than in the presence of ferrihydrite (6.73 × 10(-6) M s(-1) m(-2)). It was proposed that this increased rate of ferrous iron oxidation in the presence of goethite and dissolved oxygen was the primary reason for the higher As(III) oxidation rate when compared to the As(III)/ferrihydrite system. The surface area-normalized pseudo-first-order rate constant, for example, associated with the heterogeneous oxidation of Fe(II) by dissolved oxygen in the presence of goethite (1.9 × 10(-6) L s(-1) m(-2)) was experimentally determined to be considerably higher than if ferrihydrite was present (2.0 × 10(-7) L s(-1) m(-2)) at a solution pH of 5.     

Arsenic(III) oxidation by birnessite and precipitation of manganese(II) arsenate

Solution chemical techniques were used to investigate the oxidation of As(III) to As(V) in 0.011 M arsenite suspension of well-crystallized hexagonal birnessite (H-birnessite, 2.7 g L(-1)) at pH 5. Products of the reaction were studied by scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), atomic force microscopy (AFM), and X-ray absorption near-edge structure spectroscopy (XANES). In the initial stage (first 74 h), chemical results have been interpreted quantitatively, and the reaction is shown to proceed in two steps as suggested by previous authors: 2>Mn(IV)O2 + H3AsO3 + H2O --> 2>Mn(III)OOH + H2AsO4- + H+ and 2>Mn(III)OOH + H3AsO3 + 3H+ --> 2Mn2+ + H2AsO4- + 2H2O. The As(III) depletion rate was lower (0.02 h(-1)) than measured in previous studies because of the high crystallinity of the H-birnessite sample used in this study. The surface reaction sites are likely located on the edges of H-birnessite layers rather than on the basal planes. The ion activity product of Mn(II) and As(V) reached after 74 h reaction time was the solubility product of a protonated manganese arsenate, having a chemical composition close to that of krautite as identified by XANES and EDS. Krautite precipitation reaction can be written as follows: Mn2+ + H2AsO4- + H2O = MnHAsO4 x H2O + H+ log Ks approximately -0.2. Equilibrium was reached after 400 h. The manganese arsenate precipitate formed long fibers that aggregated at the surface of H-birnessite. The oxidation reaction transforms a toxic species, As(III), to a less toxic aqueous species, which further precipitates with Mn2+ as a mixed As-Mn solid characterized by a low solubility product.     

Sorption of oxytetracycline to iron oxides and iron oxide-rich soils

The sorption interactions of oxytetracycline with goethite, hematite, and two iron oxide-rich soils were investigated using batch sorption experiments. Oxytetracycline sorption coefficients for goethite and hematite increased with pH to maximum values at pH approximately 8. The sorption edge shape and desorption treatments were consistent with a surface complexation mechanism and could be described by the interaction of divalent anion species with the oxide surface. Oxytetracycline sorption to Georgeville and Orangeburg Ultisol soils decreased with pH. Chemical digestion treatments were used to deduce that soil sorption occurred by complexation to oxide coatings on clay and quartz grains. These results indicate that sorption models must consider the interaction of oxytetracycline, and other similar ionogenic compounds, with soil oxide components in addition to clays and organic matter when predicting sorption in whole soils.     

Bidentate complexation modeling of heavy metal adsorption and competition on goethite

Accurate sorption modeling is critical for environmental risk assessment and development of sound remedial technologies. Adsorption to iron oxide phases is one of the important sorption processes regulating the bioavailability and toxicity of metal ions in natural systems. In this study, we used spectroscopically derived bidentate surface species to constrain surface complexation modeling in addressing Ni(ll) and Zn(ll) adsorption and competition on goethite surfaces. The 2-pK(a) triple layer model successfully predicted adsorption in single adsorbate systems. The curvature in adsorption isotherms was accurately depicted using two types of sites: high affinity and low affinity, and mononuclear bidentate surface complexes. A constrained set of parameters was found for each metal (log K(L) = -6.63 and log K(H) = -2.45 for Ni, log K(L) = -3.92 and log K(H) = 2.14 for Zn) that successfully described adsorption over a large range of experimental conditions, covering 6 to 7 orders of magnitude in concentration, ionic strength from 10(-3) to 10(-2), and environmentally relevant pH range between 4 and 6.5. Adsorption competition was predicted using the bidentate surface species with parameters calibrated using single adsorbate data.     

Influence of arsenate adsorption to ferrihydrite, goethite, and boehmite on the kinetics of arsenate reduction by Shewanella putrefaciens strain CN-32

The kinetics of As(V) reduction by Shewanella putrefaciens strain CN-32 was investigated in suspensions of 0.2, 2, or 20 g L(-1) ferrihydrite, goethite, or boehmite at low As (10 μM) and lactate (25 μM) concentrations. Experimental data were compared with model predictions based on independently determined sorption isotherms and rates of As(V) desorption, As(III) adsorption, and microbial reduction of dissolved As(V), respectively. The low lactate concentration was chosen to prevent significant Fe(III) reduction, but still allowing complete As(V) reduction. Reduction of dissolved As(V) followed first-order kinetics with a 3 h half-life of As(V). Addition of mineral sorbents resulted in pronounced decreases in reduction rates (32-1540 h As(V) half-life). The magnitude of this effect increased with increasing sorbent concentration and sorption capacity (goethite < boehmite < ferrihydrite). The model consistently underestimated the concentrations of dissolved As(V) and the rates of microbial As(V) reduction after addition of S. putrefaciens (～5 × 10(9) cells mL(-1)), suggesting that attachment of S. putrefaciens cells to oxide mineral surfaces promoted As(V) desorption and thereby facilitated As(V) reduction. The interplay between As(V) sorption to mineral surfaces and bacterially induced desorption may thus be critical in controlling the kinetics of As reduction and release in reducing soils and sediments.     

Sorption mechanisms of zinc on hydroxyapatite: systematic uptake studies and EXAFS spectroscopy analysis

The systematics and mechanisms of Zn uptake by hydroxyapatite (HAP) in preequilibrated suspensions open to PCO2 were characterized using a combination of batch sorption experiments, X-ray diffraction (XRD), and extended X-ray absorption fine structure spectroscopy (EXAFS) over a wide range of pH and Zn concentrations. Sorption isotherms of Zn(II) on HAP at pH 5.0 and 7.3 show an initial steep slope at low Zn(II) concentrations, followed by a plateau up to [Zn] < approximately 750 microM, suggesting Langmuir-type behavior. At [Zn] > 750 microM, a sharp rise in the pH 5.0 isotherm suggests precipitation, whereas slight continued uptake in the pH 7.3 isotherm is suggestive of an additional uptake mechanism. The sorption isotherm at pH 9.0 shows a steep uptake step at [Zn] < or = 0.8 microM, followed by an increasing linear trend up to [Zn] = 5 microM, without any indication of a maximum, suggesting that precipitation is an important uptake process at this pH. Zn K edge EXAFS results show a first oxygen shell at 1.96-1.98 +/- 0.02 A in sorption samples with [Zn]tot < or = 250 microM at pH 5.0, 7.3, and 9.0, consistent with tetrahedral coordination. EXAFS results reveal additional P and Ca neighbors that support formation of an inner-sphere Zn surface complex where the Zn is coordinated to surface P04 tetrahedra in a corner-sharing bidentate fashion, bridging a Ca atom. In contrast, EXAFS and XRD data indicate that precipitation of Zn3(PO4)2-4H2O (hopeite) dominates the mode of Zn uptake at [Zn]tot > or = 3 mM at pH 5.0. Principal component analysis and linear combination fits of EXAFS data reveal a mixture of inner-sphere Zn surface complexation and precipitation of Zn5(OH)6(CO3)2 (hydrozincite) in sorption samples for [Zn]tot = 5 mM at pH 7.3 and for [Zn]tot = 1 mM at pH 9.0.     

Coprecipitation of arsenate with metal oxides. 2. Nature, mineralogy, and reactivity of iron(III) precipitates

Coprecipitation of arsenic with iron or aluminum occurs in natural environments and is a remediation technology used to remove this toxic metalloid from drinking water and hydrometallurgical solutions. In this work, we studied the nature, mineralogy, and reactivity toward phosphate of iron-arsenate coprecipitates formed at As(V)/Fe(III) molar ratios (R) of 0, 0.01, or 0.1 and at pH 4.0, 7.0, and 10.0 aged for 30 or 210 days at 50 degrees C and studied the desorption of arsenate. At R = 0, goethite and hematite (with ferrihydrite at pH 4.0 and 7.0) crystallized, whereas at R = 0.01, the formation of ferrihydrite increased and hematite crystallization was favored over goethite. In some samples, the morphology of hematite changed from rounded platy crystals to ellipsoids. At R = 0.1, ferrihydrite formed in all the coprecipitates and remained unchanged even after 210 days of aging. The surface area and chemical composition of the precipitates were affected by pH, R, and aging. Chemical dissolution of the samples showed that arsenate was present mainly in ferrihydrite, but at R = 0.01, it was partially incorporated into the structures of crystalline Fe oxides. The sorption of phosphate on to the coprecipitates was affected not only by the mineralogy and surface area of the samples but also by the amounts of arsenate present in the oxides. The samples formed at pH 4.0 and 7.0 and at R = 0.1 sorbed lower amounts of phosphate than the precipitates obtained at R = 0 or 0.01, despite the former having a larger surface area and showing only a presence of short-range ordered materials. This is mainly due to the fact that in the coprecipitates at R = 0.1 arsenate occupied many sorption sites, thus preventing phosphate sorption. Less than 20% of the arsenate present in the coprecipitates formed at R = 0.1 was removed by phosphate and more from the samples synthesized at pH 7.0 or 10.0 than at pH 4.0. Moreover, we found that more arsenate was desorbed by phosphate from a ferrihydrite on which arsenate was added than from an iron-arsenate coprecipitate, attributed to the partial occlusion of some arsenate anions into the framework of the coprecipitate. XPS analyses confirmed these findings.     

Reaction fronts in brick-sand layers: column experiments and modeling

Admixing waste materials with common raw materials in brick production is a promising treatment technology to overcome contamination problems, because organic pollutants are destroyed and inorganic contaminants are thought to be immobilized. During their use in constructions and after the use as part of the demolition masses bricks can be leached by runoff waters and seepage waters. A possible application of recycling crushed bricks consists of their use as a surface layer material on sports grounds or in road construction. To investigate the potential leaching during acidification of a brick-sand layer and the resultant leaching of heavy metals, crushed material from two bricks was examined in several column experiments. Deionized water at pH 4 percolated through the water-saturated columns at a Darcy velocity which was varied between 0.37 and 2.2 m/d. Another column was run under unsaturated conditions. A reaction front evolved in all experiments characterized by a pH increase from pH 4 to pH 8. The chemical composition of the percolating water changed at the reaction front. Several heavy metals (Cd, Co, Cu, Ni) and Al were immobilized at this front. Other parameters such as Ca, S as SO4, V, and Mo were depleted within several days. The reaction front moved forward depending on the Darcy velocity in the column and the buffer capacity of the brick sand. Thermodynamic calculations (PHREEQC 2.0) indicated that mobilization of As was influenced by Ba(AsO4)2. The solubility of Ba and Mn was controlled by barite and manganite, respectively. Reactive transport modeling was applied to describe the dissolution of the bricks with regard to their main components Ca, SO4, Al, and Si.     

Sorption of arsenate and arsenite on RuO2 x xH2O: a spectroscopic and macroscopic study

The sorption reactions of arsenate (As(V)) and arsenite (As(III)) on RuO2 x xH2O were examined using macroscopic and spectroscopic techniques. Constant solid:solution isotherms were constructed from batch sorption experiments and sorption kinetics assessed at pH 7. X-ray absorption near edge spectroscopy (XANES) was employed to elucidate the solid-state speciation of sorbed As. At all pH values studied (pH 4-8), RuO2 x xH2O showed a high affinity for As regardless of the initial As species present. Sorption was higher at all pH values when the initial As species was As(III). Oxidation of As(III) (250 mg/L solution) to As(V) was virtually complete (98-100%) within 5 s. XANES results showed the presence of only As(V) on the RuO2 x xH2O regardless of the initial As oxidation state. There was no change in the As oxidation state on the solid phase for 4 weeks in both oxic and anoxic environments. It is speculated that changes in the RuO2 x xH2O structure, due to oxidation reactions, caused the higher total As sorption capacity when As(III) was the initial species. The As sorption capacity of RuO2 x xH2O is greater than that of other metal oxides reviewed in this study. The ability of RuO2 x xH2O to rapidly oxidize As(III) is much greater than other oxides, such as MnO2.     

Molecular interfacial reactions between Pu(VI) and manganese oxide minerals manganite and hausmannite

The sorption of Pu(VI) onto manganite (MnOOH) and hausmannite (Mn3O4) was studied as a function of time, solution pH, and initial plutonium concentration. Kinetic experiments indicate that the surface complexation of plutonium occurs over the first 24 h of contact with the mineral surface. The sorption increases with pH beginning at pH 3 until it reaches a maximum value of 100% at pH 8 (0.0011-0.84 micromol of Pu/m2 of manganite and 0.98-1.2 micromol of Pu/m2 of hausmannite) and then decreases over the pH range from 8 to 10. The ratio of solid to solution was 10 mg/mL for manganite experiments and 4 mg/mL for hausmannite samples. Carbonate was not excluded from the experiments. The amount of plutonium removed from the solution by the minerals is determined by a combination of factors including the plutonium solution species, the surface charge of the mineral, and the mineral surface area. X-ray absorption fine structure taken at the Pu L(III) edge were compared to plutonium standard spectra and showed that Pu(VI) was reduced to Pu(IV) after contact with the minerals. Plutonium sorption to the mineral surface is consistent with an inner-sphere configuration, and no evidence of PuO2 precipitation is observed. The reduction and complexation of Pu(VI) by manganese minerals has direct implications on possible migration of Pu(VI) species in the environment.