Removal of uranium(VI) from aqueous solutions using Eucalyptus citriodora distillation sludge

Adsorption and desorption of uranium(VI) from dilute aqueous solutions by Eucalyptus citriodora distillation sludge was studied in a batch mode. The potential of Eucalyptus citriodora distillation sludge to remove uranium(VI) from aqueous solutions has been investigated at different conditions of solution pH, metal ion concentrations, biosorbent dosage, biosorbent particle size, contact time and temperature. The results indicated that biosorption capacity of Eucalyptus citriodora distillation sludge was strongly affected by the medium pH, the biosorbent dose, metal ion concentrations and medium temperature. Reduction in particle size increased the biosorption capacity. Langmuir and Freundlich isotherm models were applied to biosorption data to determine the biosorption characteristics. An optimum biosorption capacity (57.75 mg/g) was achieved with pH 4.0, particle size 0.255 mm, biosorbent dose 0.5 g/100 mL and initial uranium(VI) concentration of 100 mg/L. Uranium(VI) removal by Eucalyptus citriodora distillation sludge was rapid, the equilibrium was established within 60 min and pseudo-second-order model was found to fit with the experimental data. The biosorption process decreased with an increase in the temperature indicating its exothermic nature. Pretreatments of biomass with different reagents affected its biosorption capacity. A significant increase (34 %) in biosorption capacity (83.25 mg/g) was observed with benzene treatment. Fourier-transform infra-red studies showed the involvement of carbonyl, carboxyl and amide groups in the biosorption process. The results indicated that sulfuric acid had the best effects as an eluent showing 93.24 % desorption capacity.     

Study of mango biomass (Mangifera indica L) as a cationic biosorbent

Unfertilizable fruiting buds of mango plant Mangifera Indica L, an agrowaste, is used as a biomass in this study. The efficacy of the biosorbent was tested for the removal of lead, copper, zinc and nickel metal ions using batch experiments in single and binary metal solution under controlled experimental conditions. It is found that metal sorption increases when the equilibrium metal concentration rises. At highest experimental solution concentration used (150 mg/L), the removal of metal ions were 82.76 % for lead, 76.60 % for copper, 63.35 % for zinc and 59.35 % for nickel while at lowest experimental solution concentration (25 mg/L), the removal of metal ions were 92.00% for lead, 86.84 % for copper, 83.96 % for zinc and 82.29 % for nickel. Biosorption equilibrium isotherms were plotted for metal uptake capacity (q) against residual metal concentrations (C_f) in solution. The q versus C_f sorption isotherm relationship was mathematically expressed by Langmuir and Freundlich models. The values of separation factor were between zero and one indicating favourable sorption for four tested metals on the biosorbent. The surface coverage values were approaching unity with increasing solution concentration indicating effectiveness of biosorbent under investigation. The non-living biomass of Mangifera indica L present comparable biosorption capacity for lead, copper, zinc and nickel metal ions with other types of biosorbent materials found in literature and is effective to remove metal ions from single metal solutions as well as in the presence of other co-ions with the main metal of solution.     

Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.     

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

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

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.     

Comparison of fast elimination of Cr(VI) by alumina nanofiber and alumina nanoporous

The goal of this study is examination of the mixture between adsorption and permeation process for removing chromium (VI) from the water. Two types of supported membranes are developed: The first one which was made by sol–gel method is called nanoporous and the second one which was made by electrospinning is called nanofiber. The sorption capacity of nanoporous and nanofiber is examined in single batch experiments at various pH values, and it is found that maximum chromium removal is observed for both nanoporous and nanofiber at pH 3.5. Adsorption studies illustrated that the Cr(VI) adsorption onto alumina nanoporous and nanofiber is affected by changes in pH, contact time, dosage of adsorbent, concentration of chromium and solution volume. Langmuir and Freundlich isotherms can be used to explain the adsorption equilibria of Cr(VI) onto alumina nanoporous and nanofiber. It was found that balance adsorption data adequate Langmuir isotherm more than Freundlich model. Adsorption kinetics was found to be fitted to pseudo-second order and Weber and Morris model. The output of multiple linear regressions was run for the second-order response surface model implied that the linear agents of pH, sorbent dosage and Cr(VI) concentration are more significant factors. Manufacturing electrospun alumina nanofiber and sol–gel nanoporous with these cheap materials, renewable and fast methods are so important although the removal percentage is significant.     

Oxidation of aqueous Cr(III) at birnessite surfaces: constraints on reaction mechanism

X-ray Photoelectron Spectroscopy (XPS) was used to investigate oxidation of aqueous Cr(III) at the surface of 7 Å-birnessite [MnO_1.75(OH)_0.25]. Special emphasis was placed on detection of intermediate oxidation states of chromium due to their critical environmental significance. No previous studies have been able to identify these intermediate oxidation states of chromium (namely, Cr[IV] and Cr[V]) on mineral surfaces or in natural solutions. Mn(2p_3/2), Cr(2p_3/2) and O(1s) spectra of the reacted surfaces reveal that Mn(IV) of synthetic birnessite undergoes reductive dissolution in two steps. The first step involves Mn(IV) reduction to Mn(III),that forms at the oxide surface probably as an oxyhydroxide (MnOOH), and in the second step Mn(III) is reduced to Mn(II) that is subsequently taken into solution. Each reductive reaction step involves transfer of only one electron to the Mn ion. After Cr(III)_aq is adsorbed onto the MnO₂ surface, it undergoes oxidation in three separate steps, each involving the loss of one electron to Mn ions, so that Cr(IV), Cr(V) and Cr(VI) are produced. The intermediate reaction products, namely Mn(III), and Cr(V) were positively identified by XPS spectral analyses. Similarity in XPS binding energy values of Cr(III) and Cr(IV) as well as that of Cr(V) and Cr(VI), however, preclude separate identification of Cr(III) from Cr(IV) and Cr(VI) from Cr(V) multiplets on the near-surface of the solid. A parallel reaction scheme (exclusive of sorption reactions) best describes the birnessite-Cr(III)_aq redox reactions. The two parallel reactions proceed by separate mechanisms with a monodentate complex formed in one mechanism and a bidentate complex in another. The bulk of Cr(IV) probably is formed via the monodentate complex and Cr(V) via the bidentate complex. The rate expressions associated with these reactions display near-perfect correlation with changing surface abundances of Cr(IV) and Cr(V) as a function of reaction time. Copyright © 1999 Elsevier Science Ltd.     

Treatment of Cr(VI) contaminated water with Pannonibacter phragmitetus BB

Pannonibacter phragmitetus BB was utilized to treat hexavalent chromium [Cr(VI)] contaminated water. Cr(VI) concentration of the contaminated water (pH 10.85) was 534 mg/L. With the inoculum size ranging from 1 to 20 %, P. phragmitetus BB completely reduced Cr(VI) within 27 h when the initial medium concentration exceeded 20 g/L. The lag time of bio-reduction by Cr(VI)-induced cells was 24 h, which was longer than the non-Cr(VI)-induced cells. Under the agitation condition, an obvious bio-reduction lag phase existed and Cr(VI) was completely reduced within 24 h. However, the lag phase was not observed under the static condition, Cr(VI) was reduced continuously after inoculation and Cr(VI) was completely reduced after 27 h incubation. The main chromium components after Cr(VI) reduction were Cr(OH)₃, Cr₂O₃ and CrCl₃. The results of this study are fundamentally significant to the application of P. phragmitetus BB in the treatment of Cr(VI) contaminated water.     

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.     

Assessing the effectiveness of nanoscale zero-valent iron particles produced by green tea for Cr(VI)-contaminated groundwater remediation

Nanoscale zero-valent iron particles (NZVI) produced by using green tea (GT) extract as a reductant can remove Cr(VI) from water effectively, which can be utilized in groundwater remediation. In order to define the reaction mechanism and removal effect in the aquifer, in this study, GT-NZVI particles were prepared and measured by some characterization methods to define their surface performance, and then batch and one-dimensional experiments were carried out to reveal the reaction properties of GT-NZVI and Cr(VI) in groundwater. The results showed that the prepared GT-NZVI particles were regular spherical with a diameter of 10–20 nm, which could disperse in water stably. The main component of GT-NZVI was α-Fe with superficial polyphenols as a stabilizer. GT-NZVI suspension had good ability to reduce the Cr(VI) to Cr(III) in water. When the concentration of GT-NZVI was 1 g/L, the removal efficiency of Cr(VI) with an initial concentration of 100 mg/L reached 92.8% in 1 h reaction. In column tests, GT-NZVI passed through the natural sand column successfully with an average outflow percentage of 71.2%. The simulated in-situ reaction zone (IRZ) with GT-NZVI was used to remediate Cr(VI) contaminated groundwater. The outflow concentration of Cr(VI) kept in 0.14–0.32 mg/L corresponding to the outflow rate below 0.32% within 15 days, and the removal efficiency of Cr(VI) by IRZ with GT-NZVI decreased with the increase of aquifer medium particle size, groundwater flow rate and ionic strength. Most of Cr(III) as reduzate was adsorbed or immobilized on the surface or in the lattice of GT-NZVI, which indicated effective immobilization for chromium.     

Biogenic nano-magnetite and nano-zero valent iron treatment of alkaline Cr(VI) leachate and chromite ore processing residue

Highly reactive nano-scale biogenic magnetite (BnM), synthesized by the Fe(III)-reducing bacterium Geobacter sulfurreducens, was tested for the potential to remediate alkaline Cr(VI) contaminated waters associated with chromite ore processing residue (COPR). The performance of this biomaterial, targeting aqueous Cr(VI) removal, was compared to a synthetic alternative, nano-scale zero valent iron (nZVI). Samples of highly contaminated alkaline groundwater and COPR solid waste were obtained from a contaminated site in Glasgow, UK. During batch reactivity tests, Cr(VI) removal from groundwater was inhibited by ∼25% (BnM) and ∼50% (nZVI) when compared to the treatment of less chemically complex model pH 12 Cr(VI) solutions. In both the model Cr(VI) solutions and contaminated groundwater experiments the surface of the nanoparticles became passivated, preventing complete coupling of their available electrons to Cr(VI) reduction. To investigate this process, the surfaces of the reacted samples were analyzed by TEM-EDX, XAS and XPS, confirming Cr(VI) reduction to the less soluble Cr(III) on the nanoparticle surface. In groundwater reacted samples the presence of Ca, Si and S was also noted on the surface of the nanoparticles, and is likely responsible for earlier onset of passivation. Treatment of the solid COPR material in contact with water, by addition of increasing weight % of the nanoparticles, resulted in a decrease in aqueous Cr(VI) concentrations to below detection limits, via the addition of ⩾5% w/w BnM or ⩾1% w/w nZVI. XANES analysis of the Cr K edge, showed that the % Cr(VI) in the COPR dropped from 26% to a minimum of 4–7% by the addition of 5% w/w BnM or 2% w/w nZVI, with higher additions unable to reduce the remaining Cr(VI). The treated materials exhibited minimal re-mobilization of soluble Cr(VI) by re-equilibration with atmospheric oxygen, with the bulk of the Cr remaining in the solid fraction. Both nanoparticles exhibited a considerable capacity for the remediation of COPR related Cr(VI) contamination, with the synthetic nZVI demonstrating greater reactivity than the BnM. However, the biosynthesized BnM was also capable of significant Cr(VI) reduction and demonstrated a greater efficiency for the coupling of its electrons towards Cr(VI) reduction than the nZVI.     

Characterization and evaluation of a tropical peat for the removal of Cr(VI) from solution

Tropical peat soils present higher ash content than those generated at temperate climate areas. Therefore, this study evaluated the characteristics of a Brazilian organic soil (OS), commercialized as peat, as well as its capacity in removing Cr(VI) from contaminated waters. The OS is composed of 35.5 wt% of organic matter and 56 wt% of inorganic fraction (ash), which is formed by minerals and phytoliths rich in silica (29.2 wt%) and alumina (23.6 wt%). The Cr(VI) removal tests were carried out in batch and column systems using OS and solutions of Cr(VI) prepared with distilled water and groundwater. Batch tests revealed that the organic substances in the OS caused the reduction of Cr(VI) to Cr(III), with an efficiency depending on solution pH. At pH 5.0 the Cr(VI) removal was 0.45 mg g^?1 in 24 h; whereas at pH 2.0, this removal increased to 1.10 mg g^?1. Since this redox reaction is very slow, the removal of Cr(VI) at pH 5.0 increased to around 2 mg g^?1 after 5 days. The removal of Cr(VI) was more effective in the column tests than in the batch test due to the greater solid/solution ratio, and their half-lives were 4.4 and 26.2 h, respectively. Chemical analysis indicated that Cr(VI) was reduced by the humic substances of OS, followed by the precipitation and/or adsorption of Cr(III) into the organic and inorganic components, as anatase. The presence of Cr(III) increased the stability of anatase structure, avoiding its transformation into rutile, even after being heated at 800 °C/2 h.     

Significance of co-immobilized activated carbon and Bacillus subtilis on removal of Cr(VI) from aqueous solutions

Batch sorption system using co-immobilized (activated carbon and Bacillus subtilis) beads as adsorbent was investigated to remove Cr(VI) from aqueous solution. Fourier transform infrared spectroscopy analysis showed the functional groups of both bacteria and activated carbon in co-immobilized beads. Experiments were carried out as a function of contact time (5–300 min), initial metal concentration (50–200 mg L^?1), pH (2–8), and adsorbent dose (0.2–1 g L^?1). The maximum percentage of removal was found to be 99 %. Langmuir model showed satisfactory fit to the equilibrium adsorption data of co-immobilized beads. The kinetics of the adsorption followed pseudo-second-order rate expression, which demonstrates that chemisorption plays a significant role in the adsorption mechanism. The significant shift in the Fourier transform infrared spectroscopy peaks and a Cr peak in the scanning electron microscope–energy dispersive spectroscopy spectra further confirmed the adsorption. The results indicate that co-immobilized beads can be used as an effective adsorbent for the removal of Cr(VI) from the aqueous solution.     

Removal of arsenic (V) from aqueous solutions using chemically modified sawdust of spruce (Picea abies): Kinetics and isotherm studies

Arsenic is a ubiquitous element in the environment and occurs naturally in both organic and inorganic forms. Under aerobic condition, the dominant form of arsenic in waters is arsenate, which is highly mobile and toxic. Arsenic poisoning from drinking water remains a serious world health issue. There are various standard methods for arsenic removal from drinking waters (coagulation, sorption, ion-exchange reactions or methods of reverse osmosis) and alternative methods, such as biosorption. Biosorption of arsenic from natural and model waters by native or chemically modified (with urea or ferric oxyhydroxides) plant biomass prepared from sawdust of Picea abies was studied. The kinetic of the adsorption process fitted well the pseudo second order adsorption model and equilibrium was achieved after 2 h. The results showed that biosorption was well described by both Langmuir and Freundlich isotherms. The maximum biosorption capacity of the sawdust modified with ferric oxyhydroxides, evaluated by Langmuir adsorption model, was 9.259 mg/g, while the biosorption capacity of unmodified biosorbent or biosorbent modified with urea was negligible. The adsorption capacity is comparable to results published by other authors, suggesting that the prepared chemically modified biosorbent has potential in remediation of contaminated waters.     

Sorption isotherms and kinetics of chromium uptake from wastewater using natural sorbent material

Chromium (VI) which exists in many industrial wastewater is considered highly toxic. The aim of the present investigation was to study the reduction of chromium (VI) to chromium (III) and then removing it with the help of weathered basalt andesite products. Reduction of the chromium (VI) to chromium (III) by hydrazinium sulfate was investigated. The influence of hydronium ion concentration, contact time, hydrazinium sulphate dosage and temperature has been tested in batch runs. The process was found to be acid, temperature and concentration dependent. The suitability of weathered basalt andesite products as a potential sorbent was assessed for the removal of chromium (III) following batch mode of operation. The effect of various parameters such as hydronium ion concentration, shaking time, sorbent dose, initial metal ion concentration and temperature on the removal of chromium (III) from aqueous solution was studied. Thermodynamic parameters (?H°, ?S° and ?G°) for the sorption process were evaluated. Analysis of sorption obtained results showed that the sorption pattern followed the Freundlich, Langmuir and Dubinin-Kaganer-Radushkevich isotherms. The process follows pseudo second order rate and surface diffusion is identified as the predominating mechanism. The sorption process was shown to be reversible by the recovery of sorbed chromium (III) upon extraction with 0.5 M nitric acid. The sorbent, before and after sorption, was characterized by fourier transform infrared spectrometer, X-ray diffraction, scanning electron microscope, transmision electron microscope and thermogravimetric analyse methodes. An increase in crystallanity after sorption of chromium was observed. An industrial effluent was successfully treated with the same sorbent with convincing results.     

Saraca indica leaf powder for decontamination of Pb: removal, recovery, adsorbent characterization and equilibrium modeling

The present study explores the effectiveness of Saraca indica leaf powder, a surplus low value agricultural waste, in removing Pb ions from aqueous solution. The influence of pH, biomass dosage, contact time, particle size and metal concentration on the removal process were investigated. Batch studies indicated that maximum biosorption capacity for Pb was 95.37% at the pH 6.5. The sorption process followed the first order rate kinetics. The adsorption equilibrium data fitted best to both Langmuir and Freundlich isotherms. Morphological changes observed in scanning electron micrographs of untreated and metal treated biomass confirmed the phenomenon of biosorption. Fourier transform infrared spectroscopy of native and exhausted leaf powder confirmed lead biomass interactions responsible for sorption. Acid regeneration was tried for several cycles with a view to recover the sorbed metal ion and also to restore the sorbent to its original state. The findings showed that Saraca indica leaf powder can easily be envisaged as a new, vibrant, low cost biosorbent for metal clean up operations.     

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.     

Effects of common groundwater ions on chromate removal by magnetite: importance of chromate adsorption

Background

Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (<a few hr) reduction of soluble Cr(VI) to insoluble Cr(III) species by Fe(II) in magnetite has been the primary focus of the Cr(VI) removal process in the past. However, the contribution of simultaneous Cr(VI) adsorption processes in aged magnetite has been largely ignored, leaving uncertainties in evaluating the application of in situ Cr remediation technologies for aqueous systems. In this study, effects of common groundwater ions (i.e., nitrate and sulfate) on Cr(VI) sorption to magnetite were investigated using batch geochemical experiments in conjunction with X-ray absorption spectroscopy.

Results

In both nitrate and sulfate electrolytes, batch sorption experiments showed that Cr(VI) sorption decreases with increasing pH from 4 to 8. In this pH range, Cr(VI) sorption decreased with increasing ionic strength of sulfate from 0.01 to 0.1 M whereas nitrate concentrations did not alter the Cr(VI) sorption behavior. This indicates the background electrolyte specific Cr(VI) sorption process in magnetite. Under the same ionic strength, Cr(VI) removal in sulfate containing solutions was greater than that in nitrate solutions. This is because the oxidation of Fe(II) by nitrate is more thermodynamically favorable than by sulfate, leaving less reduction capacity of magnetite to reduce Cr(VI) in the nitrate media. X-ray absorption spectroscopy analysis supports the macroscopic evidence that more than 75 % of total Cr on the magnetite surfaces was adsorbed Cr(VI) species after 48 h.

Conclusion

This experimental geochemical study showed that the adsorption process of Cr(VI) anions was as important as the reductive precipitation of Cr(III) in describing the removal of Cr(VI) by magnetite, and these interfacial adsorption processes could be impacted by common groundwater ions like sulfate and nitrate. The results of this study highlight new information about the large quantity of adsorbed Cr(VI) surface complexes at the magnetite-water interface. It has implications for predicting the long-term stability of Cr at the magnetite-water interface.

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Graphical abstract Effects of background anions (sulfate and nitrate) on the Cr(VI) surface coverage at the magnetite-waterinterface at pH 4 and 9

     

Adsorption of heavy metals in glacial till soil

The charged sites on soil particles are important for the retention/adsorption of metals. Metallic counterions can neutralize the intrinsic charges on the surfaces of soil particles by forming complexes. In this study, efforts have been made to determine the effect of surface potential, pH, and ionic strength on the adsorption of four metal ions, hexavalent chromium Cr(VI), trivalent chromium Cr(III), nickel Ni(II) and cadmium Cd(II), in glacial till soil. Batch tests were performed to determine the effect of pH (2–12) and ionic strength (0.001–0.1 M KCl) on zeta potential of the glacial till soil. The point of zero charge (pH _PZC ) of glacial till was found to be 7.0±2.5. Surface charge experiments revealed the high buffering capacity of the glacial till. Batch adsorption experiments were conducted at natural pH (8.2) using various concentrations of selected metals. The adsorption data was described by the Freundlich adsorption model. Overall glacial till shows lower adsorption affinity to Cr(VI) as compared to cationic metals, Cr(III), Ni(II) and Cd(II).     

Comparative study on adsorption of chromium(VI) from industrial wastewater onto nature-derived adsorbents (brown coal and zeolite)

The removal of hexavalent chromium from wastewater streams has received an considerable attention in recent years, since it can cause harmful effects on the environment. Several approaches, including adsorption, are recognized to tackle this problem, but unfortunately most of these processes are impressed with practical conditions of the experiments. The main objective of this study was to recognize applicable conditions for Cr(VI) removal from an industrial drainage using nature-derived adsorbents (brown coal and modified zeolite) and to make the process more adaptive by using adsorbents conjointly. Batch experiments were carried out by agitating Cr(VI) stock solution with adsorbents at room temperature. The influence of main operating parameters was explored, and the best proportion of the adsorbents was determined. Maximum sorption of Cr(VI) onto brown coal was observed at pH = 4 by adding 60 g L^?1 adsorbent to contaminated solution. In case of using zeolite, the modification process was required, and the pH indicated a weak influence in a wide range (2–8). Optimum dosage of modified zeolite for Cr(VI) removal was 10 g L^?1. The hybrid application of adsorbents with the mass ratio of brown coal/modified zeolite at (3:1) was capable of removing more than 99% of Cr(VI) from contaminated wastewater in the natural pH range of the wastewater. The adsorption of Cr(VI) by brown coal and modified zeolite followed Langmuir and Freundlich isotherm models, respectively. Sorption of Cr(VI) onto both brown coal and modified zeolite fitted well to pseudo-second-order rate reaction.