Thermodynamic and kinetic studies of As(V) removal from water by zirconium oxide-coated marine sand

Arsenic contamination of groundwater is a major threat to human beings globally. Among various methods available for arsenic removal, adsorption is fast, inexpensive, selective, accurate, reproducible and eco-friendly in nature. The present paper describes removal of arsenate from water on zirconium oxide-coated sand (novel adsorbent). In the present work, zirconium oxide-coated sand was prepared and characterised by infrared and X-ray diffraction techniques. Batch experiments were performed to optimise different adsorption parameters such as initial arsenate concentration (100–1,000 μg/L), dose (1–8 g/L), pH of the solution (2–14), contact time (15–150 min.), and temperature (20, 30, 35 and 40 °C). The experimental data were analysed by Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. Furthermore, thermodynamic and kinetic parameters were evaluated to know the mode of adsorption between ZrOCMS and As(V). The maximum removal of arsenic, 97 %, was achieved at initial arsenic concentration of 200 μg/L, after 75 min at dosage of 5.0 g/L, pH?7.0 and 27?±?2 °C. For 600 μg/L concentration, the maximum Langmuir monolayer adsorption capacity was found to be 270 μg/g at 35 °C. Kinetic modelling data indicated that adsorption process followed pseudo-second-order kinetics. The mechanism is controlled by liquid film diffusion model. Thermodynamic parameter, ΔH°, was ?57.782, while the values of ΔG° were ?9.460, ?12.183, ?13.343 and ?13.905 kJ/mol at 20, 30, 35 and 40 °C, respectively, suggesting exothermic and spontaneous nature of the process. The change in entropy, ΔS°?=??0.23 kJ/mol indicated that the entropy decreased due to adsorption of arsenate ion onto the solid adsorbent. The results indicated that the reported zirconium oxide-coated marine sand (ZrOCMS) was good adsorbent with 97 % removal capacity at 200 μg/L concentration. It is interesting to note that the permissible limit of arsenic as per World Health Organization is 10 μg/L, and in real situation, this low concentration can be achieved through this adsorbent. Besides, the adsorption capacity showed that this adsorbent may be used for the removal of arsenic from any natural water resource.     

Accumulation, transformation, and release of inorganic arsenic by the freshwater cyanobacterium Microcystis aeruginosa

Arsenic (As) as a major hazardous metalloid was affected by phytoplankton in many aquatic environments. The toxic dominant algae Microcystis aeruginosa was exposed to different concentrations of inorganic arsenic (arsenate or arsenite) for 15 days in BG11 culture media. Arsenic accumulation, toxicity, and speciation in M. aeruginos as well as the changes of As species in media were examined. M. aeruginosa has a general well tolerance to arsenate and a definite sensitivity to arsenite. Additionally, arsenate actively elevated As methylation by the algae but arsenite definitely inhibited it. Interestingly, the uptake of arsenite was more pronounced than that of arsenate, and it was correlated to the toxicity. Arsenate was the predominant species in both cells and their growth media after 15 days of exposure to arsenate or arsenite. However, the amount of the methylated As species in cells was limited and insignificantly affected by the external As concentrations. Upon uptake of the inorganic arsenic, significant quantities of arsenate as well as small amounts of arsenite, DMA, and MMA were produced by the algae and, in turn, released back into the growth media. Bio-oxidation was the first and primary process and methylation was the minor process for arsenite exposures, while bioreduction and the subsequent methylation were the primary metabolisms for arsenate exposures. Arsenic bioaccumulation and transformation by M. aeruginosa in aquatic environment should be paid more attention during a period of eutrophication.     

Alginate beads containing water treatment residuals for arsenic removal from water—formation and adsorption studies

Water treatment residuals (WTRs) produced in large quantities during deironing and demanganization of infiltration water, due to high content of iron and manganese oxides, exhibit excellent sorptive properties toward arsenate and arsenite. Nonetheless, since they consist of microparticles, their practical use as an adsorbent is limited by difficulties with separation from treated solutions. The aim of this study was entrapment of chemically pretreated WTR into calcium alginate polymer and examination of sorptive properties of the obtained composite sorbent toward As(III) and As(V). Different products were formed varying in WTR content as well as in density of alginate matrix. In order to determine the key parameters of the adsorption process, both equilibrium and kinetic studies were conducted. The best properties were exhibited by a sorbent containing 5 % residuals, formed in alginate solution with a concentration of 1 %. In slightly acidic conditions (pH 4.5), its maximum sorption capacity was 3.4 and 2.9 mg g^?1 for As(III) and As(V), respectively. At neutral pH, the adsorption effectiveness decreased to 3.3 mg As g^?1 for arsenites and to 0.7 mg As g^?1 for arsenates. The presence of carboxylic groups in polymer chains impeded in neutral conditions the diffusion of anions into sorbent beads; therefore, the main rate-limiting step of the adsorption, mainly in the case of arsenates, was intraparticle diffusion. The optimal condition for simultaneous removal of arsenates and arsenites from water by means of the obtained composite sorbent is slightly acidic pH, ensuring similar adsorption effectiveness for both arsenic species.     

Photocatalytic oxidation and removal of arsenite from water using slag-iron oxide-TiO2 adsorbent

Photocatalytic oxidation of arsenite and simultaneous removal of the generated arsenate from aqueous solution were investigated. The whole process was performed using an adsorbent developed by loading iron oxide and TiO2 on municipal solid waste melted slag. The loading was carried out through chemical reactions and high-temperature process. In the removal process, arsenite was first oxidized to arsenate, and then was removed by adsorption. The oxidation of arsenite was rapid, but the adsorption of the generated arsenate was slow. A concentration of 100 mg l(-1) arsenite could be entirely oxidized to arsenate within 3 h in the presence of the adsorbent and under UV-light irradiation, but the equilibrium adsorption of the generated arsenate needed 10 h. Arsenite could also be oxidized to arsenate only by UV-light, but the reaction rate was approximately 1/3 of that of the photocatalyzed reaction. Both acidic and alkaline conditions were favorable for the oxidation reaction, and the optimum pH value for the oxidation and adsorption was proposed to be around 3. To oxidize and remove original 20 mg l(-1) or 50 mg l(-1) arsenite from aqueous solution, the necessary adsorbent amount was 2 g l(-1) or 5 g l(-1), respectively. Furthermore, the surface properties of the adsorbent were examined and the oxidation mechanism of arsenite was discussed. It is believed that the adsorbent developed in this study is efficient, cost-effective and environment-friendly for application in arsenic-contaminated wastewater treatment.     

Arsenic accumulation and speciation in the submerged macrophyte Ceratophyllum demersum L.

Introduction

Ceratophyllum demersum L. is a widespread submerged macrophyte in aquatic environments.

Methods

Simulation experiments were conducted in the laboratory to investigate arsenic (As) accumulation, speciation, and efflux of C. demersum exposed to arsenate and arsenite solutions.

Results

Plant shoots showed a significant accumulation of As with a maximum of 862 and 963???g?As?g^?1 dry weight after 4?days of exposure to 10???M arsenate and arsenite, respectively. Regardless of whether arsenate or arsenite was supplied to the plants, arsenite was the predominant species in plant shoots. Furthermore, a dramatically higher influx rate of arsenate compared with arsenite was observed in C. demersum exposed to As solutions without the addition of phosphate (P). Arsenate uptake was considerably inhibited by P in this study, suggesting that arsenate is taken up by C. demersum via the phosphate transporters. However, arsenite uptake was unaffected by P and markedly reduced in the presence of glycerol and antimonite (Sb), indicating arsenite shares the aquaporin transport pathway. In addition, C. demersum rapidly reduces arsenate to arsenite in the shoot of the plant and extrudes most of them (>60?%) to the external solutions. The efflux of arsenite was much higher than that of arsenate; the former is supposed to be both active and passive processes, and the latter through passive leakage.

Conclusion

C. demersum is a strong As accumulator and an interesting model plant to study As uptake and metabolism due to the lack of a root-to-shoot translocation barrier.     

Modelling the adsorption of mercury onto natural and aluminium pillared clays

Introduction

The removal of heavy metals by natural adsorbent has become one of the most attractive solutions for environmental remediation. Natural clay collected from the Late Cretaceous Aleg formation, Tunisia was used as a natural adsorbent for the removal of Hg(II) in aqueous system.

Methods

Physicochemical characterization of the adsorbent was carried out with the aid of various techniques, including chemical analysis, X-ray diffraction, Fourier transform infrared and scanning electron micrograph. Batch sorption technique was selected as an appropriate technique in the current study. Method parameters, including pH, temperature, initial metal concentration and contact time, were varied in order to quantitatively evaluate their effects on Hg(II) adsorption onto the original and pillared clay samples. Adsorption kinetic was studied by fitting the experimental results to the pseudo-first-order and pseudo-second-order kinetic models. The adsorption data were also simulated with Langmuir, Freundlich and Temkin isotherms.

Results

Results showed that the natural clay samples are mainly composed of silica, alumina, iron, calcium and magnesium oxides. The sorbents are mainly mesoporous materials with specific surface area of <250 m² g^?1. From the adsorption of Hg(II) studies, experimental data demonstrated a high degree of fitness to the pseudo-second-order kinetics with an equilibration time of 240 min. The equilibrium data showed the best model fit to Langmuir model with the maximum adsorption capacities of 9.70 and 49.75 mg g^?1 for the original and aluminium pillared clays, respectively. The maximum adsorption of Hg(II) on the aluminium pillared clay was observed to occur at pH 3.2. The calculated thermodynamic parameters (?G°, ?H° and ?S°) showed an exothermic adsorption process. The entropy values varied between 60.77 and 117.59 J?mol^?1 K^?1, and those of enthalpy ranged from 16.31 to 30.77 kJ mol^?1. The equilibrium parameter (R _L) indicated that the adsorption of Hg(II) on Tunisian smectitic clays was favourable under the experimental conditions of this study.

Conclusion

The clay of the Aleg formation, Tunisia was found to be an efficient adsorbent for Hg(II) removal in aqueous systems.     

Use of activated dry flowers (ADF) of Alstonia Scholaris for chromium (Vl) removal: equilibrium, kinetics and thermodynamics studies

In this study, a natural adsorbent (activated dry flowers (ADF)) was prepared from plant-derived waste biomass by chemical activation and employed for chromium (VI) removal from aqueous medium using experimental batch technique. Experiments were carried out as function of adsorbent dosage, pH, and contact time. The maximum chromium (Vl) removal was observed at initial pH 3 (~94 % removal). The equilibrium data was fitted well to Langmuir isotherm. The adsorption capacity of ADF was found to be 4.40 (mg chromium (Vl)/g) which was comparable to the adsorption capacity of some other adsorbents documented. Among various kinetic models applied, pseudo second-order model was found to explain the kinetics of chromium (VI) adsorption most effectively (R ² >0.99). Thermodynamic parameters such as ΔG, ΔS, and ΔH shows that adsorption process was spontaneous and endothermic at all the concentration ranges studied. Desorption of chromium (Vl) with 2 N NaOH was effective (~71 %) and, hence, there exists the possibility of recycling the ADF. The major advantages of using ADF as an adsorbent are due to its effectiveness in reducing the concentration of chromium (Vl) to very low levels. It requires little processing and is reversible as well as eco-friendly in contrast to traditional methods.     

Novel chitosan/PVA/zerovalent iron biopolymeric nanofibers with enhanced arsenic removal applications

Enhanced removal application of both forms of inorganic arsenic from arsenic-contaminated aquifers at near-neutral pH was studied using a novel electrospun chitosan/PVA/zerovalent iron (CPZ) nanofibrous mat. CPZ was carefully examined using scanning electron microscopy (SEM) equipped with energy-dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), atomic fluorescence spectroscopy (AFM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and thermal gravimetric analysis (TGA). Application of the adsorbent towards the removal of total inorganic arsenic in batch mode has also been studied. A suitable mechanism for the adsorption has also been discussed. CPZ nanofibers mat was found capable to remove 200.0?±?10.0 mg g^?1 of As(V) and 142.9?±?7.2 mg g^?1 of As(III) from aqueous solution of pH 7.0 at ambient condition. Addition of ethylenediaminetetraacetic acid (EDTA) enabled the stability of iron in zerovalent state (ZVI). Enhanced capacity of the fibrous mat could be attributed to the high surface area of the fibers, presence of ZVI, and presence of functional groups such as amino, carboxyl, and hydroxyl groups of the chitosan and EDTA. Both Langmuir and Freundlich adsorption isotherms were applicable to describe the removal process. The possible mechanism of adsorption has been explained in terms of electrostatic attraction between the protonated amino groups of chitosan/arsenate ions and oxidation of arsenite to arsenate by Fentons generated from ZVI and subsequent complexation of the arsenate with the oxidized iron. These CPZ nanofibrous mats has been prepared with environmentally benign naturally occurring biodegradable biopolymer chitosan, which offers unique advantage in the removal of arsenic from contaminated groundwater.     

Kinetics and isotherm analysis of Tropaeoline 000 adsorption onto unsaturated polyester resin (UPR): a non-carbon adsorbent

The presence of dyes in water is undesirable due to the toxicological impact of their entrance into the food chain. Owing to the recalcitrant nature of dyes to biological oxidation, a tertiary treatment like adsorption is required. In the present study, unsaturated polyester resin (UPR) has been used as a sorbent in the treatment of dye-contaminated water. Different concentrations of Tropaeoline 000 containing water were treated with UPR. The preliminary investigations were carried out by batch adsorption to examine the effects of pH, adsorbate concentration, adsorbent dosage, contact time, and temperature. A plausible mechanism for the ongoing adsorption process and thermodynamic parameters have also been obtained from Langmuir and Freundlich adsorption isotherm models. Thermodynamic parameter showed that the sorption process of Tropaeoline 000 onto activated carbon (AC) and UPR were feasible, spontaneous, and endothermic under studied conditions. The estimated values for (ΔG) are ?10.48?×?10³ and ?6.098?×?10³ kJ mol^?1 over AC and UPR at 303 K (30 °C), indicating towards a spontaneous process. The adsorption process followed pseudo-first-order model. The mass transfer property of the sorption process was studied using Lagergren pseudo-first-order kinetic models. The values of % removal and k _ad for dye systems were calculated at different temperatures (303–323 K). The mechanism of the adsorption process was determined from the intraparticle diffusion model.     

Iron oxide-loaded slag for arsenic removal from aqueous system

An effective adsorbent for arsenic removal from aqueous system was synthesized by loading iron(III) oxide on municipal solid waste incinerator melted slag. The loading was accomplished via chemical processes and thermal coating technique. The key point of the technique was the simultaneous generation of amorphous FeOOH sol and silica sol in-situ and eventually led to the formation of Fe-Si surface complexes which combined the iron oxide with the melted slag tightly. The surface morphology of the iron oxide-loaded slag was examined and the loading mechanisms were discussed in detail. The adsorbent was effective for both arsenate and arsenite removal and its removal capabilities for As(V) and As(III) were 2.5 and 3 times of those of FeOOH, respectively. Both affinity adsorption and chemical reactions contributed to arsenic removal. The effects of solution pH, contact time, arsenic concentration and adsorbent dosage on arsenic removal were examined and the optimum removal conditions were established. Furthermore, leaching of hazardous elements such as Cr(VI), As, Se, Cd and Pb from the adsorbent at a pH range of 2.5-12.5 was below the regulation values. Accordingly, it is believed that the iron oxide-loaded slag developed in this study is environmentally acceptable and industrially applicable for wastewater treatment.     

Kinetic, equilibrium isotherm and thermodynamic studies of Cr(VI) adsorption onto low-cost adsorbent developed from peanut shell activated with phosphoric acid

A particular agricultural waste, peanut shell, has been used as precursor for activated carbon production by chemical activation with H₃PO₄. Unoxidized activated carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature to get oxidized activated carbon. The prepared carbons were characterized for surface area, surface morphology, and pore volume and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, particle size, adsorbent dose, initial concentration of adsorbate, and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly dependent on solution pH, and the optimum adsorption was observed at pH 2. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to analyze the kinetic data obtained at different initial Cr(VI) concentrations. The adsorption kinetic data were described very well by the pseudo-second-order model. Equilibrium isotherm data were analyzed by the Langmuir, Freundlich, and Temkin models. The results showed that the Langmuir adsorption isotherm model fitted the data better in the temperature range studied. The adsorption capacity which was found to increase with temperature showed the endothermic nature of Cr(VI) adsorption. The thermodynamic parameters, such as Gibb’s Free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were evaluated.     

Biosorption of arsenic in drinking water by submerged plant: Hydrilla verticilata

To evaluate the biosorption efficacy of submerged aquatic plant Hydrilla verticilata for arsenic uptake from drinking water. H. verticillata, a submerged aquatic plant was utilized successfully for arsenic uptake from aqueous solution. Batch studies with various parameters viz. pH, sorbent dose, contact time, initial metal ion concentration, and temperature were carried out. Data were utilized to plot Lagergren graph along with pseudo-second-order graphs for kinetic studies to estimate the removal efficacy and to determine the nature of reaction. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) have been performed for characterization of metals on biomass. The study showed 96.35 % maximum absorption of arsenic by H. verticilata at initial concentration of 100 ppb with 0.5 g of biomass/100 ml for 5 h contact time at pH?6.0 with 150 rpm agitation rate. Data followed Langmuir isotherm showing sorption to be monolayer on homogeneous surface of biosorbent. The negative values of ΔG° indicated spontaneous nature; whereas ΔH° indicates exothermic nature of system and negative value of ?S° entropy change correspond to a decrease in the degree of freedom to the adsorbed species followed by pseudo-second-order adsorption kinetics. FTIR and SEM results showed apparent changes in functional group regions after metal chelation and the changes in surface morphology of biosorbent. This is a comparatively more effective, economic, easily available, and environmentally safe source for arsenic uptake from solution due to its high biosorption efficacy than other biosorbents already used.     

Bioaccumulation and biotransformation of arsenic compounds in Hediste diversicolor (Muller 1776) after exposure to spiked sediments

This study focused on the exposure of the common ragworm Hediste diversicolor (Müller 1776) to sediments enriched with different arsenic compounds, namely arsenate, dimethyl-arsinate, and arsenobetaine. Speciation analysis was carried out on both the spiked sediments and the exposed polychaetes in order to investigate H. diversicolor capability of arsenic bioaccumulation and biotransformation. Two levels of contamination (acute and moderate dose) were chosen for enriched sediments to investigate possible differences in the arsenic bioaccumulation patterns. The highest value of arsenic in tissues was reached after 15 days of exposure to dimethyl-arsinate (acute dose) spiked sediment (1,172?±?176 μg/g). A significant increase was also obtained in worms exposed both to arsenate and arsenobetaine. Speciation analysis showed that trimethyl-arsine oxide was the predominant chemical form in tissues of H. diversicolor exposed to all the spiked sediments, confirming the importance of this intermediate in biological transformation of arsenic.     

Treatment of industrial wastewater containing Congo Red and Naphthol Green B using low-cost adsorbent

The present work investigates the potential use of metal hydroxides sludge (MHS) generated from hot dipping galvanizing plant for adsorption of Congo Red and Naphthol Green B dyes from aqueous solutions. Characterization of MHS included infrared and X-ray fluorescence analysis. The effect of shaking time, initial dye concentration, temperature, adsorbent dosage and pH has been investigated. The results of adsorption experiments indicate that the maximum capacity of Congo Red and Naphthol Green B dyes at equilibrium (q _e) and percentage of removal at pH 6 are 40 mg/g, 93 %, and 10 mg/g, 52 %, respectively. Some kinetic models were used to illustrate the adsorption process of Congo Red and Naphthol Green B dyes using MHS waste. Thermodynamic parameters such as (ΔG, ΔS, and ΔH) were also determined.     

Preparation of activated carbon from dried pods of Prosopis cineraria with zinc chloride activation for the removal of phenol

Utilization of agrowaste materials for the production of activated carbon, as an excellent adsorbent with large surface area, is well established industrially, for dephenolation of wastewater. In the present work, dried pods of Prosopis cineraria—a novel and low-cost agrowaste material—were used to prepare activated carbons by zinc chloride activation. Batch adsorption experiments were carried out to study the effects of various physicochemical parameters such as initial phenol concentration, adsorbent dose, initial solution pH, and temperature. Pseudo-first-order second-order and diffusion kinetic models were used to identify the possible mechanisms of such adsorption process. The Langmuir and Freundlich equations were used to analyze the adsorption equilibrium. Maximum removal efficiency of 86 % was obtained with 25 mg?L^?1 of initial phenol concentration. The favorable pH for maximum phenol adsorption was 4.0. Freundlich equation represented the adsorption equilibrium data more ideally than the Langmuir. The maximum adsorption capacity obtained was 78.32 mg?g^?1 at a temperature of 30 °C and 25 mg?L^?1 initial phenol concentration. The adsorption was spontaneous and endothermic. The pseudo-second-order model, an indication of chemisorption mechanism, fitted the experimental data better than the pseudo-first-order Lagergren model. Regeneration of spent activated carbon was carried out using Pseudomonas putida MTCC 2252 as the phenol-degrading microorganism. Maximum regeneration up to 57.5 % was recorded, when loaded phenol concentration was 25 mg?L^?1. The data obtained in this study would be useful in designing and fabricating an efficient treatment plant for phenol-rich effluents.     

Removal of Disperse Red dye by bamboo-based activated carbon: optimisation, kinetics and equilibrium

This research involved the use of response surface methodology (RSM) to investigate the adsorption of Disperse Red 167 dye onto the bamboo-based activated carbon activated with H₃PO₄ (PBAC) in a batch process. F400, a commercially available activated carbon, was used in parallel for comparison. Analysis of variance showed that input variables such as the contact time, temperature, adsorbent dosage and the interaction between the temperature and the contact time had a significant effect on the dye removal for both adsorbents. RSM results show that the optimal contact time, temperature, initial dye concentration and adsorbent dosage for both adsorbents were found to be 15.4 h, 50 °C, 50.0 mg L^?1 and 12.0 g L^?1, respectively. Under these optimal conditions, the removal efficiencies reached 90.23 % and 92.13 % for PBAC and F400, respectively, with a desirability of 0.937. The validation of the experimental results confirmed the prediction of the models derived from RSM. The adsorption followed a nonlinear pseudo-first-order model and agreed well with the Freundlich and Temkin isotherm as judged by the levels of the AICc and the Akaike weight. Furthermore, the thermodynamics analysis indicated that, for both adsorbents, the adsorption was a physical process that was spontaneous, entropy-increasing and endothermic.     

Adsorption/desorption of arsenite and arsenate on chitosan and nanochitosan

Equilibrium sorption studies of anionic species of arsenite, As(III) ions and arsenate As(V) ions onto two biosorbents, namely, chitosan and nanochitosan, have been investigated and compared. The results and trends in the sorption behavior are novel, and we have observed during the sorption process of the As(III) and As(V) on chitosan, a slow process of desorption occurred after an initial maximum adsorption capacity was achieved, before reaching a final but lower equilibrium adsorption capacity. The same desorption trend, however, is not observed on nanochitosan. The gradual desorption of As(III) and As(V) in the equilibrium sorption on chitosan is attributed to the different fractions of the dissociated forms of arsenic on the adsorbent surface and in solution and the extent of protonation of chitosan with the changing of solution pH during sorption. The change of solution pH during the sorption of arsenite ions on chitosan was also influenced by the interaction between the buffering effect of the arsenite species in the aqueous medium and the physical properties of chitosan. The final equilibrium adsorption capacity of chitosan for As(III) and As(V) was found to be around 500 and 8000 μg/g, respectively, whereas the capacities on nanochitosan are 6100 and 13,000 μg/g, respectively.

     

Arsenic sorption by red mud-modified biochar produced from rice straw

Red mud-modified biochar (RM-BC) has been produced to be utilized as a novel adsorbent to remove As because it can effectively combine the beneficial features of red mud (rich metal oxide composition and porous structure) and biochar (large surface area and porous structure properties). SEM-EDS and XRD analyses demonstrated that red mud had loaded successfully on the surface of biochar. With the increasing of pH in solution, arsenate (As(V)) adsorption on RM-BC decreased while arsenite (As(III)) increased. Arsenate adsorption kinetics process on RM-BC fitted the pseudo-second-order model, while that of As(III) favored the Elovich model. All sorption isotherms produced superior fits with the Langmuir model. RM-BC exhibited improved As removal capabilities, with a maximum adsorption capacity (Q_max) for As(V) of 5923 μg g^?1, approximately ten times greater than that of the untreated BC (552.0 μg g^?1). Furthermore, it has been indicated that the adsorption of As(V) on RM-BC may be strongly associated with iron oxides (hematite and magnetite) and aluminum oxides (gibbsite) by X-ray absorption near-edge spectroscopy (XANES), which was possibly because of surface complexation and electrostatic interactions. RM-BC may be used as a valuable adsorbent for removing As in the environment due to the waste materials being relatively abundant.     

Biosorption of arsenic from aqueous solution using dye waste

The purpose of this study is to examine on removal of arsenic from water by biosorption through potential application of herbal dye wastes. Four different flower dye residues (after extraction of natural dye) viz. Hibiscus rosasinensis, Rosa rosa, Tagetes erecta, and Canna indica were utilized successfully for the removal of arsenic from aqueous solution. Batch studies were carried out for various parameters viz. pH, sorbent dose, contact time, initial metal ion concentration, and temperature. Data were utilized for isothermal, kinetic, and thermodynamic studies. Scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDAX), and Fourier transform infrared (FTIR) analyses of biomass were performed. The results showed that 1 g/100 ml for 5.0–5.5 h contact time at pH 6.0–7.5 with agitation rate 150 rpm provided 98, 96, 92, and 85 % maximum absorption of arsenic by R. rosa, H. rosasinensis, T. erecta, and C. indica, respectively, at initial concentration of 500 ppb. Data followed Langmuir isotherm showing sorption to be monolayer on heterogeneous surface of biosorbent. Negative values of ΔG° indicated spontaneous nature, whereas ΔH° indicates exothermic nature of system followed by pseudo-first-order adsorption kinetics. FTIR results showed apparent changes in functional group regions after metal chelation. SEM and EDAX analyses showed the changes in surface morphology of all test biosorbents. Herbal dye wastes, used as biosorbent, exhibited significant (85–98 %) removal of arsenic from aqueous solution. Hence, these biosorbents are cost-effective, easily available, eco-friendly, and comparatively more effective than other biosorbents already in use. These may be used to remove arsenic and other toxic metals from water.     

The removal of arsenate from water using iron-modified diatomite (D-Fe): isotherm and column experiments

Iron hydroxide supported onto porous diatomite (D-Fe) is a low-cost material with potential to remove arsenic from contaminated water due to its affinity for the arsenate ion. This affinity was tested under varying conditions of pH, contact time, iron content in D-Fe and the presence of competitive ions, silicate and phosphate. Batch and column experiments were conducted to derive adsorption isotherms and breakthrough behaviours (50 μg L^?1) for an initial concentration of 1,000 μg L^?1. Maximum capacity at pH 4 and 17 % iron was 18.12–40.82 mg of arsenic/g of D-Fe and at pH 4 and 10 % iron was 18.48–29.07 mg of arsenic/g of D-Fe. Adsorption decreased in the presence of phosphate and silicate ions. The difference in column adsorption behaviour between 10 % and 17 % iron was very pronounced, outweighing the impact of all other measured parameters. There was insufficient evidence of a correlation between iron content and arsenic content in isotherm experiments, suggesting that ion exchange is a negligible process occurring in arsenate adsorption using D-Fe nor is there co-precipitation of arsenate by rising iron content of the solute above saturation.