Influence of soil minerals on chromium(VI) reduction by sulfide under anoxic conditions

The effects of soil minerals on chromate (Cr^VIO₄ ^2-, noted as Cr(VI)) reduction by sulfide were investigated in the pH range of 7.67 to 9.07 under the anoxic condition. The examined minerals included montmorillonite (Swy-2), illite (IMt-2), kaolinite (KGa-2), aluminum oxide (γ-Al₂O₃), titanium oxide (TiO₂, P-25, primarily anatase), and silica (SiO₂). Based on their effects on Cr(VI) reduction, these minerals were categorized into three groups: (i) minerals catalyzing Cr(VI) reduction – illite; (ii) minerals with no effect – Al₂O₃; and (iii) minerals inhibiting Cr(VI) reduction- kaolinite, montmorillonite, SiO₂ and TiO₂ . The catalysis of illite was attributed primarily to the low concentration of iron solubilized from the mineral, which could accelerate Cr(VI) reduction by shuttling electrons from sulfide to Cr(VI). Additionally, elemental sulfur produced as the primary product of sulfide oxidation could further catalyze Cr(VI) reduction in the heterogeneous system. Previous studies have shown that adsorption of sulfide onto elemental sulfur nanoparticles could greatly increase sulfide reactivity towards Cr(VI) reduction. Consequently, the observed rate constant, k _obs, increased with increasing amounts of both iron solubilized from illite and elemental sulfur produced during the reaction. The catalysis of iron, however, was found to be blocked by phenanthroline, a strong complexing agent for ferrous iron. In this case, the overall reaction rate at the initial stage of reaction was pseudo first order with respect to Cr(VI), i.e., the reaction kinetics was similar to that in the homogeneous system, because elemental sulfur exerted no effect at the initial stage prior to accumulation of elemental sulfur nanoparticles. In the suspension of kaolinite, which belonged to group (iii), an inhibitive effect to Cr(VI) reduction was observed and subsequently examined in more details. The inhibition was due to the sorption of elemental sulfur onto kaolinite, which reduced or completely eliminated the catalytic effect of elemental sulfur, depending on kaolinite concentration. This was consistent with the observation that the catalysis of externally added elemental sulfur (50 μM) on Cr(VI) reduction would disappear with a kaolinite concentration of more than 5.0 g/L. In kaolinite suspension, the overall reaction rate law was:

Enhanced microbial reduction of Cr(VI) and U(VI) by different natural organic matter fractions

Although direct microbial reduction of Cr(VI) and U(VI) is known, few studies have examined the kinetics and the underlying mechanisms of the reduction of these contaminants by different natural organic matter (NOM) fractions in the presence or absence of microorganisms. In this study, NOM was found to chemically reduce Cr(VI) at pH 3, but the reduction rates were negligible at pH ∼7. The abiotic reduction of U(VI) by NOM was not observed, possibly because of the presence of small amounts of nitrate in the reactant solution. However, all NOM fractions, particularly the soil humic acid (HA), enhanced the bioreduction of Cr(VI) or U(VI) in the presence of Shewanella putrefaciens CN32. The reduction rates varied greatly among NOM fractions with different chemical and structural properties: the polyphenolic-rich NOM-PP fraction appeared to be the most reactive in abiotically reducing Cr(VI) at a low pH, but soil HA was more effective in mediating the microbial reduction of Cr(VI) and U(VI) under anaerobic, circumneutral pH conditions. These observations are attributed to an increased solubility and conformational changes of the soil HA with pH and, more importantly, its relatively high contents of polycondensed and conjugated aromatic organic moieties. An important implication of this study is that, depending on chemical and structural properties, different NOM components may play different roles in enhancing the bioreduction of Cr(VI) and U(VI) by microorganisms. Polycondensed aromatic humic materials may be particularly useful in mediating the bioreduction and rapid immobilization of these contaminant metals in soil.     

Removal of chromium (VI) from aqueous solutions using Lewatit FO36 nano ion exchange resin

The removal of the chromium (VI) ion from aqueous solutions with the Lewatit FO36 ion-exchange resin is described at different conditions. The effects of adsorbent dose, initial metal concentration, contact time and pH on the removal of chromium (VI) were investigated. The batch ion exchange process was relatively fast and it reached equilibrium after about 90 min of contact. The ion exchange process, which is pH dependent showed maximum removal of chromium (VI) in the pH range 5.0–8.0 for an initial chromium (VI) concentration of 0.5 mg/dm³. The equilibrium related to Lewatit FO36 ion- exchange capacity and the amounts of the ion exchange were obtained using the plots of the Langmuir adsorption isotherm. It was observed that the maximum ion exchange capacity of 0.29 mmol of chromium (VLVg for Lewatit FO36 was achieved at optimum pH value of 6.0. The ion exchange of chromium (VI) on this cation-exchange resin followed first-order reversible kinetics.     

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.     

Adsorption of chromium (VI) from aqueous solution by the iron (III)-impregnated sorbent prepared from sugarcane bagasse

An iron (III)-impregnated sorbent was prepared from sugarcane bagasse and ferric chloride solution via carbonization/activation in a muffle furnace at 500?°C for 4?h. The adsorption removal of chromium (VI) from aqueous solution by the iron (III)-impregnated sorbent was then studied in a batch system. With increasing initial chromium (VI) concentration from 25 to 130?mg/L at an adsorbent dose of 300?mg/50?mL, the amount of adsorbed chromium (VI) increased from 4.15 to 12.20?mg/g at 20?°C, from 4.16 to 12.50?mg/g at 30?°C, and from 4.16 to 13.72?mg/g at 40?°C. The dynamical data fit very well with the pseudo-second-order kinetic model, and the calculated adsorption capacities of 4.16, 8.37, and 13.37?mg/g were equal to the actual values of the experiments at the initial chromium (VI) concentrations of 25, 50, and 100?mg/L, respectively. The Langmuir isotherm could yield better fits than the Freundlich isotherm. The calculated isotherm parameters confirmed the favorable adsorption of chromium (VI) on the iron (III)-impregnated sorbent.     

Valorization of olive stone as adsorbent of chromium(VI): comparison between laboratory- and pilot-scale fixed-bed columns

The main aim of this work is to study the effect of scaling in the biosorption of chromium(VI) onto olive stone in two different fixed-bed columns. Firstly, the effect of flow rate, bed depth and inlet concentration of Cr(VI) in both columns was analyzed. The results revealed a better operation for lower flow rates, higher bed heights and lower inlet concentrations of metal. When decreasing flow rate, the operation time of the column increases. Therefore, as the solution flow rate increased the breakthrough and the exhaustion times decreased. An increase in bed depth increases the quantity of chromium eliminated and thus, the higher sorption capacity of the system. A decrease in the inlet concentration of chromium produces a delay in exhaustion time, and larger volumes of solution could be treated. The results were fitted to the BDST model, obtaining that the adsorptive capacity of the bed depth is similar in laboratory- and pilot-scale fixed-bed columns, considering the biosorption capacity as a biosorption-coupled reduction process. Results also could indicate that scaling affects more to the reduction process than properly biosorption process. The experimental data were also fitted to Adams–Bohart, Thomas, Yoon–Nelson and dose–response models. A good fit of the biosorption process of Cr(VI) was found for dose–response and Adams–Bohart models.     

Relevant approach to assess the performance of sawdust as adsorbent of chromium (VI) ions from aqueous solutions

The biosorption of chromium (VI) ions from aqueous solutions by two adsorbents viz. mango and neem sawdust was studied under a batch mode. An initial pH of 2.0 was most favorable for chromium (VI) removal by both the adsorbents. The results obtained for the final concentration of chromium (VI) and chromium (DI) at a pH range of 2–8 indicated that a combined effect of biosorption and reduction was involved in the chromium (VI) removal specially when the pH value is lower than 3. The maximum loading capacity was calculated from adsorption isotherms by applying the Langmuir model and found to be higher for neem sawdust (58.82 mg/g). Evaluation of experimental data in terms of biosorption kinetics showed that the biosorption of chromium (VI) by neem sawdust followed pseudo second-order kinetics. Therefore, the rate limiting step may be chemical sorption or chemisorption. The efficiency of this process was examined in using tannery wastewater contaminated with chromium (VI) ions in column mode.     

Seasonal transport pattern of chromium(III and VI) in a stream receiving wastewater from tanneries

Water, suspended matter and sediment samples from a system heavily impacted by wastewater from numerous small tanneries (the upper Dunajec River, southern Poland) were collected to establish the annual cycle of Cr. To study possible oxidation processes the speciation of Cr and Mn concentrations were also investigated. This study showed that Cr(III and VI) temporal and spatial distributions are regulated by coupled anthropogenic (source location and emissions) and hydrologic factors (water flow and particle transport). Chromium(III) concentrations in all compartments varied seasonally as a function of the hydrological regime, production cycle in tanneries and distance from the discharge location. Cr(III) was largely associated with the particulate phase and rapidly deposited in river bed sediments. Contaminated river sediments were however flushed during flood periods to the reservoir located downstream from tanneries. During the tanning season (November to March), Chromium(III) concentrations in the water column and total Cr concentration in sediments exceeded relevant ecotoxicological guidelines only upstream from the reservoir, which trapped about 70% of the annual Cr(III) load transported by the Dunajec river. A correlation between Cr(VI)/Cr(III) ratios and Mn concentration in sediments downstream from the reservoir suggests the possibility of Cr(III) oxidation in natural conditions.     

Isothermal compression behavior of (Mg,Fe)O using neon as a pressure medium

We present isothermal volume compression behavior of two polycrystalline (Mg,Fe)O samples with FeO = 39 and 78 mol% up to ~90 GPa at 300 K using synchrotron X-ray diffraction and neon as a pressure-transmitting medium. For the iron-rich (Mg_0.22Fe_0.78)O sample, a structural transition from the B1 structure to a rhombohedral structure was observed at 41.6 GPa, with no further indication of changes in structural or compression behavior changes up to 93 GPa. In contrast, a change in the compression behavior of (Mg_0.61Fe_0.39)O was observed during compression at P ≥ 71 GPa and is indicative of a spin crossover occurring in the Fe²⁺ component of (Mg_0.61Fe_0.39)O. The low-spin state exhibited a volume collapse of ~3.5%, which is a larger value than what was observed for a similar composition in a laser-heated NaCl medium. Upon decompression, the volume of the high-spin state was recovered at approximately 65 GPa. We therefore bracket the spin crossover at 65 ≤ P (GPa) ≤ 77 at 300 K (Mg_0.61Fe_0.39)O. We observed no deviation from the B1 structure in (Mg_0.61Fe_0.39)O throughout the pressure range investigated.     

Retention studies of chromium (VI) from aqueous solution on the surface of a novel carbonaceous material

In the present study, the retention capacity of carbonaceous material obtained from the diesel engine exhaust mufflers for Cr(VI) removal has been investigated. The physicochemical properties such as density, pH of aqueous slurry, pH at point of zero charge, ash content, moisture content, volatile matter, surface area, scanning electron microscopy and electron dispersive spectroscopy of the carbonaceous material were determined. The capacity of adsorbent for removal of Cr(VI) from aqueous solution was observed under different experimental condition like contact time, initial concentration of metal ions, pH and temperatures on the adsorption capacity of the adsorbent. Maximum adsorption of Cr(VI) ions was found at low pH. The adsorption process was found to follow second-order kinetics. The rate constant was evaluated at different temperatures along with other thermodynamic parameters like activation energy, Gibbs free energy change, enthalpy change and entropy change. Both Langmuir and Freundlich isotherms were used to describe the adsorption equilibrium of carbonaceous material at different temperatures. Langmuir isotherm shows better fit than Freundlich isotherm at given conditions. The result shows that low-cost carbonaceous material from diesel engine exhaust mufflers can be efficiently used for wastewater treatment containing Cr(VI) ions.     

Potential biosorbents for treatment of chromium(VI)-contaminated water discharged into Asopos River

The present study reports on the preliminary investigation of three low-cost natural materials with respect to their chromium(VI) removal efficiency from contaminated water. The tested materials were reed, in milled and chopped form, compost, and dewatered sludge from a municipal wastewater treatment plant. The chromium(VI) removal capacity of the aforementioned materials was investigated by simulating the physicochemical conditions prevailing in a stormwater outfall flowing into the Asopos River in Inofyta, Central Greece. Thus, batch and column experiments were carried out using solutions of 3–5 mg/L chromium(VI) and pH value 8.5 ± 0.5. The results showed that the tested materials were capable of removing 3 mg/L chromium(VI), however by allowing different contact times for each material. The chromium(VI) removal kinetics were studied through batch experiments, and reed was found to be the most efficient material. Therefore, at a second series of batch and up-flow column experiments, the effect of the liquid-to-solid ratio, pH, and contact time on chromium(VI) removal using chopped reed was investigated. Chromium(VI) removal took place through both reduction and adsorption mechanisms, while the released soluble organic matter from reed seemed to favor the reduction mechanism. As a result, reed is a potential biosorbent capable of treating heavily chromium(VI)-contaminated water flows, although a high mass of reed is required for a treatment process, such in the case of the stormwater discharged into Asopos River.     

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.     

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.     

Efficient removal of hexavalent chromium from aqueous solutions using autohydrolyzed Scots Pine (Pinus Sylvestris) sawdust as adsorbent

In this work, a low-cost lignocellulosic adsorbent with high biosorption capacity is proposed, suitable for the efficient removal of hexavalent chromium from water and wastewater media. The adsorbent was produced by autohydrolyzing Scots Pine (Pinus Sylvestris) sawdust. The effect of the autohydrolysis conditions, i.e., pretreatment time and temperature, on hexavalent chromium biosorption was investigated using energy-dispersive X-ray spectroscopy (EDS) and UV–visible spectrophotometry. The Freundlich, Langmuir, Sips, Radke-Prausnitz, Modified Radke-Prausnitz, Tóth, UNILAN, Temkin and Dubinin-Radushkevich adsorption capacities and the rate constant values for pseudo-first- and pseudo-second-order kinetics indicated that the autohydrolyzed material exhibits significantly enhanced hexavalent chromium adsorption properties comparing with the untreated sawdust. The Freundlich’s adsorption capacity K _F increased from 2.276 to 8.928 (mg g^?1)(L mg^?1)^1/n , and the amount of hexavalent chromium adsorbed at saturation (Langmuir constant q _m) increased from 87.4 to 345.9 mg g^?1, indicating that autohydrolysis treatment at 240 °C for 50 min optimizes the adsorption behavior of the lignocellulosic material.     

Influence of Mn oxides on the reduction of uranium(VI) by the metal-reducing bacterium Shewanella putrefaciens

The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by the subsurface bacterium Shewanella putrefaciens strain CN32 was investigated using synthetic Mn(III/IV) oxides (pyrolusite [β-MnO₂], bixbyite [Mn₂O₃] and K⁺-birnessite [K₄Mn₁₄O₂₇ · 8H₂O]). In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO₂[s]) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence or in the presence of gibbsite (Al[OH]₃) added as a non-redox-reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43 to 100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. However, in the absence of Mn(III/IV) oxides, UO₂(s) accumulated as copious fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments. However, the accumulation of U(IV) in the cell periplasm may physically protect reduced U from oxidation, promoting at least a temporal state of redox disequilibria.     

The effects of uranium speciation on the rate of U(VI) reduction by Shewanella oneidensis MR-1

We measured the kinetics of U(VI) reduction by Shewanella oneidensis MR-1 under anaerobic conditions in the presence of variable concentrations of either EDTA or dissolved Ca. We measured both total dissolved U and U(VI) concentrations in solution as a function of time. In separate experiments, we also measured the extent of U(VI) adsorption onto S. oneidensis in order to quantify the thermodynamic stabilities of the important U(VI)-bacterial surface complexes. In the EDTA experiments, the rate of U(IV) production increased with increasing EDTA concentration. However, the total dissolved U concentrations remained constant and identical to the initial U concentrations during the course of the experiments for all EDTA-bearing systems. Additionally, the U(VI) reduction rate in the EDTA experiments exhibited a strong correlation to the concentration of the aqueous U⁴⁺-EDTA complex. We conclude that the U(VI) reduction rate increases with increasing EDTA concentration, likely due to U⁴⁺-EDTA aqueous complexation which removes U(IV) from the cell surface and prevents UO₂ precipitation.In the Ca experiments, the U(VI) reduction rate decreased as Ca concentration increased. Our thermodynamic modeling results based on the U(VI) adsorption data demonstrate that U(VI) was adsorbed onto the bacterial surface in the form of a Ca-uranyl-carbonate complex in addition to a number of other Ca-free uranyl complexes. The observed U(VI) reduction rates in the presence of Ca exhibit a strong negative correlation to the concentration of the Ca-uranyl-carbonate bacterial surface complex, but a strong positive correlation to the total concentration of all the other Ca-free uranyl surface complexes. Thus, the concentration of these Ca-free uranyl surface complexes appears to control the rate of U(VI) reduction by S. oneidensis in the presence of dissolved Ca. Our results demonstrate that U speciation, both of U(VI) before reduction and of U(IV) after reduction, affects the reduction kinetics, and that thermodynamic modeling of the U speciation may be useful in the prediction of reduction kinetics in realistic geologic settings.