Activated Biochar Prepared by Pomelo Peel Using H<Subscript>3</Subscript>PO<Subscript>4</Subscript> for the Adsorption of Hexavalent Chromium: Performance and Mechanism

Adsorption of hexavalent chromium (Cr(VI)) using pomelo peel activated biochar (PPAB) as a adsorbent was investigated. The characterization of the adsorbent was studied by Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and zeta potentials analysis. The results showed that the PPAB had a high microporous structure and the existence of organic compounds such as hemicellulose, cellulose, and lignin. Various parameters including initial Cr(VI) concentration, pH, and adsorbent dosage were studied. The results indicated that the adsorption process was pH dependent and maximum adsorption capacity of Cr(VI) was 57.637 mg/g at pH 2.0 and 35 °C with PPAB dosage of 0.05 g. The adsorption kinetics fitted well to the pseudo-second-order model and the correlation coefficients were greater than 0.999. The adsorption isotherm data could be better described with the Langmuir model, suggesting the homogeneous and monolayer adsorption. Moreover, the scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), and Fourier transform infrared spectrum (FTIR) results showed that the surface of PPAB had plenty of developed pores after activation and the modification process was deemed to proceed between the O–H groups from pomelo peel and H₃PO₄ molecules. The main adsorption mechanism was attributed electrostatic interaction and ion exchange between the surface of PPAB and Cr(VI).     

Synthesis and Characterisation of Novel-Activated Carbon from Waste Biomass Pine Cone and Its Application in the Removal of Congo Red Dye from Aqueous Solution by Adsorption

The present study deals with the synthesis and subsequent application of Fe₃O₄@n-SiO₂ nanoparticles for the removal of Cr(VI) from aqueous solutions. Rice husk, an agrowaste material, was used as a precursor for the synthesis of nanoparticles of silica. Synthesized nanoparticles were characterized by XRD and SEM to investigate their specific characteristics. Fe₃O₄@n-SiO₂ nanoparticles were used as adsorbent for the removal of Cr(VI) from their aqueous solutions. The effects of various important parameters, such as initial Cr(VI) concentration, adsorbent dose, temperature, and pH, on the removal of Cr(VI) were analyzed and studied. A pH of 2.0 was found to be optimum for the higher removal of Cr(VI) ions. It was observed that removal (%) decreased by increasing initial Cr(VI) concentration from 1.36?×?10^-2 to 2.4?×?10^-2 M. The process of removal was found to be endothermic, and the removal increased with the rise in temperature from 25 to 45 °C. The kinetic data was better fitted in pseudo-second-order model in comparison to pseudo-first-order model. Langmuir and Freundlich adsorption capacities were determined and found to be 3.78 and 1.89 mg/g, respectively, at optimum conditions. The values of ΔG ⁰ were found to be negative at all temperatures, which confirm the feasibility of the process, while a positive value of ΔH ⁰ indicates the endothermic nature of the adsorption process. The present study revealed that Fe₃O₄@n-SiO₂ nanoparticles can be used as an alternate for the costly adsorbents, and the outcome of this study may be helpful in designing treatment plants for treatment of Cr(VI)-rich effluents.     

Single and competitive adsorption isotherms of some heavy metals onto a light textured calcareous soil amended with agricultural wastes-biochars

This study investigated the adsorption behavior of selected heavy metals (Pb, Cu, and Ni) under single and multi-metal conditions by a light textured calcareous soil amended with plant residue biochars (corn straw, wheat straw, rice husk and licorice root pulp each at 3% w/w). The Freundlich isotherm best described the heavy metal adsorption suggesting multilayer adsorption. For all treatments under both adsorption conditions, the heavy metal adsorption capacity followed the order of Pb > Cu > Ni, which was associated with the hydrolysis constant, ionic radius, and electronegativity of these metals. Simultaneous presence of multiple metals decreased the adsorption capacity for each metal and the sequence was in the order of Ni > Pb > Cu. The corn straw biochar (CSB) had the highest adsorption capacity (Freundlich K_f (mg g^?1) for Ni = 0.23, Cu = 1.41 and Pb = 2.73) and medium distribution coefficient (K_{d medium}(L kg^?1) for Ni = 59.30, Cu = 1961.00 and Pb = 2602.00), indicating the CSB is the best treatment for stabilization of heavy metals in the soil. This was associated with the chemical characteristics of the CSB (high amounts of CaCO₃ and P) and the greatest increase in soil pH value.     

Development of Analytical Procedure for the Determination of Exchangeable Cr(VI) in Soils by Anion-exchange Fast Protein Liquid Chromatography with Electrothermal Atomic Absorption Spectrometry Detection

Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH₂PO₄–K₂HPO₄ buffer solutions (0.015 up to 0.2 mol l^?1), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l^?1 and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g^?1 of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g^?1.     

Removal of Pb(II), Cr(III) and Cr(VI) from Aqueous Solutions Using Alum-Derived Water Treatment Sludge

The sorption of Pb(II), Cr(III) and Cr(VI) from aqueous solution using alum-derived water treatment sludge was investigated using the batch adsorption technique. Samples of sludge from two separate water treatment plants were used (one where alum was used alone and one where it was used in combination with activated C). The sorption characteristics of the two samples were generally very similar. Sorption isotherm data for all three ions fitted equally well to both Freundlich and Langmuir equations. Maximum sorption capacity and indices of sorption intensity both followed the order: Cr(III)?>?Pb(II)?>?Cr(VI). Kinetic data correlated well with a pseudo-second-order kinetic model suggesting the process involved was chemisorption. Sorption was pH-dependant with percentage sorption of Cr(III) and Pb(II) increasing from <30% to 100% between pH?3 and 6 whilst that of Cr(VI) declined greatly between pH?5 and 8. HNO₃ at a concentration of 0.1?M was effective at removing sorbed Cr(III) and Pb(II) from the sludge surfaces and regeneration was successful for eight sorption/removal cycles. It was concluded that water treatment sludge is a suitable material from which to develop a low-cost adsorbent for removal of Cr and Pb from wastewater streams.     

Synthetic Iron Oxides for Adsorptive Removal of Arsenic

Removal of arsenic from water reservoirs is the issue of great concern in many places around the globe. As adsorption is one of the most efficient techniques for treatment of As-containing media, thus the present study concerns application of iron oxides-hydroxides (akaganeite) as adsorbents for removal of this harmful metal from aqueous solution. Two types of akaganeite were tested: synthetic one (A) and the same modified using hexadecyltrimethylammonium bromide (A_M). Removal of As was tested in batch studies in function of pH, adsorbent dosage, contact time, and initial arsenic concentration. The adsorption isotherms obey Langmuir mathematical model. Adsorption kinetics complies with pseudo-second-order kinetic model, and the constant rates were defined as 2.07?×?10^?3and 0.92?×?10^?3 g mg^?1 min^?1 for the samples (A) and (A_M), respectively. The difference was caused by significant decrease in adsorption rate in initial state of the process carried out for the sample A_M. The maximum adsorption capacity achieved for (A) and (A_M) akaganeite taken from Langmuir isotherm was 148.7 and 170.9 mg g^?1, respectively. The results suggest that iron oxides-hydroxides can be used for As removal from aqueous solutions.     

Feasibility Assessment of Chromium Removal from Groundwater for Drinking Purposes by Sorption on Granular Activated Carbon and Strong Base Anion Exchange

The goal of this study was to compare the performances of strong base anion (SBA) exchange and activated carbon adsorption in the removal of hexavalent chromium, Cr(VI), from a real groundwater matrix exploited for drinking purposes. Two SBA resins and three granular activated carbons (GAC) were tested by batch experiments for kinetics and equilibrium isotherm determination. SBA resins showed higher affinity toward Cr(VI) (present in raw water at about 20 μg L^?1) with respect to the GACs, with faster kinetics and higher equilibrium adsorption capacities. Among GACs, vegetal-based carbons showed higher Cr(VI) removal efficiencies than the mineral-based carbon, which can be related to the more developed textural properties. SBA resins also displayed relevant removal capacities towards nitrate and sulfate (present at mg L^?1 concentration levels), while boron (present at about 60 μg L^?1) was effectively removed by GACs. Batch experiment results were elaborated to estimate the chromium throughputs for the studied materials, to preliminary compare their performances in a real-scale application. The monitoring of a real-scale GAC adsorption stage permitted to validate throughputs estimation and confirmed that, despite being effective toward synthetic organics, GAC adsorption is a not feasible solution for Cr(VI) removal, with extremely early breakthrough. SBA exchange process resulted to be the most suitable solution, providing the best sorbent usage rates. However, SBA resin usage rates can strongly increase when considering the removal of nitrate and sulfate ions, requiring much shorter cycle times.     

Adsorptive Potential of 2-Mercaptobenzimidazole-Immobilized Organophilic Hydrotalcite for Mercury(II) Ions from Aqueous Phase and Its Kinetic and Equilibrium Profiles

An organophilic calcined hydrotalcite (OHTC) was prepared by treating calcined hydrotalcite (HTC) with sodium dodecylbenzene sulphonate (an anionic surfactant) to achieve a high loading of thiol functionality through the immobilization of 2-mercaptobenzimidazole (MBI) as a chelating agent. The adsorbent (MBI-OHTC) obtained was characterized using XRD, FTIR, SEM, TG/DTG, surface area analysis and potentiometric titration. The adsorption of MBI-OHTC to remove Hg(II) ions from aqueous solutions was studied as a function of pH, contact time, metal ion concentration, ionic strength and adsorbent dose. The optimum pH range for the maximum removal of Hg(II) was 6.0–8.0. The maximum value of Hg(II) adsorption was found to be 11.63 and 21.52 mg g^?1 for an initial concentration of 25 and 50 mg l^?1, respectively at pH 8.0. The equilibrium conditions were achieved within 3 h under the mixing conditions employed. A reversible pseudo-first-order used to test the adsorption kinetics. The adsorption mechanism consisted of external diffusion and intraparticle diffusion and the intraparticle mass transfer diffusion was predominated after 20 min of experiment. Extent of adsorption decreased with increase of ionic strength. The experimental isotherm was analyzed with two parameters (Langmuir and Freundlich) and three parameters (Redlich–Peterson) equations. The isotherm data were best modeled by the Freundlich isotherm equation. Complete removal (≈100%) of Hg(II) from 1.0 l of chlor-alkali industry wastewater containing 9.86 mg Hg(II) ions, was possible with 3 g of the adsorbent dose at pH 8.0. About 95.0% of Hg(II) can be recovered from the spent adsorbent using 0.1 M HCl.     

Removal of Phenolic Compounds from Aqueous Solutions Using Sludge-Based Activated Carbons Prepared by Conventional Heating and Microwave-Assisted Pyrolysis

Sludge-derived activated carbons (ACs) were prepared by conventional heating and microwave pyrolysis. The ACs were characterized using several analytical and functional techniques and used for removal of six phenolic compounds from aqueous solutions. The adsorbents exhibited similar features and possessed hydrophobic surfaces. The ACs were assigned mesoporous materials, with specific surface areas of up to 641 and 540 m² g^?1 for CAC-500 and MAC-980, respectively. The preliminary results indicated that phenol removal onto the ACs increased in the order: m-cresol?<?phenol?<?o-cresol?<?2-chrorophenol?<?2-nitrophenol?<?hydroquinone. Hydroquinone exhibited the highest adsorption capacity and was chosen to continue the remaining part of the experimental work—kinetic and isothermal studies. The adsorption kinetic and isotherm data were well described by the Avrami fractionary order and Redlich–Peterson models, respectively. The maximum amounts (Q _max) of hydroquinone adsorbed at 25 °C were too high, reaching 1218.3 and 1202.1 mg g^?1 for CAC-500 and MAC-980, respectively. The mechanism of adsorption was proposed in this work, and it was suggested that donor–acceptor complex and π–π interactions play major roles in the adsorption process. The adsorbents were also tested on simulated effluents. The two ACs displayed good efficiency for the treatment of industrial simulated effluents.     

Adsorption and Desorption of Boron as Influenced by Soil Properties in Temperate Soils of Lesser Himalayas

Boron (B) adsorption increased with increasing concentration. Langmuir adsorption isotherm was curvilinear. The maximum value of adsorption maxima (b1) was observed Sagipora soil and maximum bonding energy (k) constant was in Anantnag soil. The Langmuir isotherm best explains the adsorption trend at low adsorbent concentrations. A significant correlation among b1, clay, and cation exchange capacity was observed. Linear affiliation was observed in all the soils at all concentration, indicating that B adsorption data conform to the Freundlich equation. Soils with greater affinity for B adsorption, like Sagipora, tended to desorb less B. Boron desorption was positively and significantly correlated with sand content and negatively with clay content and cation exchange capacity. The maximum value of 50.76 mg g^?1 for desorption maxima (Dm) was observed in Sagipora soil, and mobility constant (Kd) was maximum in Khag soil (0.412 ml kg^?1).     

Hexavalent Chromium Removal by Candida sp. in a Concentric Draft-Tube Airlift Bioreactor

The main purpose of this work was to conduct a kinetic study on cell growth and hexavalent chromium [Cr(VI)] removal by Candida sp. FGSFEP in a concentric draft-tube airlift bioreactor. The yeast was batch-cultivated in a 5.2-l airlift bioreactor containing culture medium with an initial Cr(VI) concentration of 1.5 mM. The maximum specific growth rate of Candida sp. FGSFEP in the airlift bioreactor was 0.0244 h^?1, which was 71.83% higher than that obtained in flasks. The yeast strain was capable of reducing 1.5 mM Cr(VI) completely and exhibited a high volumetric rate [1.64 mg Cr(VI) l^?1 h^?1], specific rate [0.95 mg Cr(VI) g^?1 biomass h^?1] and capacity [44.38 mg Cr(VI) g^?1 biomass] of Cr(VI) reduction in the airlift bioreactor, with values higher than those obtained in flasks. Therefore, culture of Candida sp. FGSFEP in a concentric draft-tube airlift bioreactor could be a promising technological alternative for the aerobic treatment of Cr(VI)-contaminated industrial effluents.     

Zirconium-Modified Activated Sludge as a Low-Cost Adsorbent for Phosphate Removal in Aqueous Solution

A highly effective zirconium-modified activated sludge (Zr(IV)-AS) adsorbent was prepared from activated sludge and applied to remove phosphate from aqueous solutions by batch and column experiments. Characterized results revealed that zirconium was successfully loaded onto the activated sludge (AS), and the specific surface area and pore volume were substantially improved after zirconium loading on the AS. Zr(IV)-AS exhibited a high adsorption affinity for phosphate and the maximum adsorption amount was 27.55 mg P·g^?1 at 25 °C. Adsorption isotherms of phosphate could be described by the Langmuir model, and the adsorption kinetics were well described by the pseudo-second-order model. Phosphate adsorption on Zr(IV)-AS increased monotonically with decreasing solution pH. The presence of SO₄^2? in water resulted in slightly decreased phosphate adsorption on the adsorbent even at a high concentration (25 mmol/L), and a greater influence of HCO₃^? on adsorption could be ascribed to the increased solution pH with the addition of the HCO₃^?. Column adsorption experimental results showed that the adsorbent has excellent phosphate adsorption properties and that the effluent can meet the requirement of phosphorus in the national wastewater discharge standard of China. Phosphate-saturated Zr(IV)-AS can be effectively desorbed in 0.1 mol L^?1 NaOH solution, and the regenerated adsorbent still possessed the high capacity. The adsorption between the adsorbent and the phosphate is due to the electrostatic interaction and anionic exchange at the surface of the Zr(IV)-AS. Furthermore, this approach provides a possibility of treating wastewater with waste and has the potential for industrial applications for the removal of phosphate from wastewater.     

Biosorption of Methylene Blue from Aqueous Solutions by Hazelnut Shells: Equilibrium, Parameters and Isotherms

This paper presents a study on the batch adsorption of a basic dye, methylene blue (MB), from aqueous solution onto ground hazelnut shell in order to explore its potential use as a low-cost adsorbent for wastewater dye removal. A contact time of 24 h was required to reach equilibrium. Batch adsorption studies were carried out by varying initial dye concentration, initial pH value (3–9), ionic strength (0.0–0.1 mol L^?1), particle size (0–200 μm) and temperature (25–55°C). The extent of the MB removal increased with increasing in the solution pH, ionic strength and temperature but decreased with increase in the particle size. The equilibrium data were analysed using the Langmuir and Freundlich isotherms. The characteristic parameters for each isotherm were determined. By considering the experimental results and adsorption models applied in this study, it can be concluded that equilibrium data were represented well by Langmuir isotherm equation. The maximum adsorption capacities for MB were 2.14?×?10^?4, 2.17?×?10^?4, 2.20?×?10^?4 and 2.31?×?10^?4 mol g^?1 at temperature of 25, 35, 45 and 55°C, respectively. Adsorption heat revealed that the adsorption of MB is endothermic in nature. The results indicated that the MB strongly interacts with the hazelnut shell powder.     

Treatment of Cr(VI)-spiked soils using sulfur-based amendments

The objective of this research was to assess the hexavalent chromium (Cr(VI)) reducing efficiency of sulfur-based inorganic agents including calcium polysulfide (CPS), iron sulfide (FeS), pyrite (FeS₂) and sodium sulfide (Na₂S) in three soils. An alkaline soil (soil 1), a neutral soil (soil 2) and a slightly acid soil (soil 3) constituted the investigated soils. The soils were spiked with two levels of Cr(VI) (100 and 500 mg Cr(VI) kg^?1 soil) and incubated at field capacity (FC) for one month. Then, CPS, FeS, FeS₂ and Na₂S were added at 0, 5 and 10 g kg^?1 and the concentrations of exchangeable Cr(VI) were measured after 0.5, 4, 48 and 168 h in a batch experiment. The pH and organic carbon content of the soils played predominant role in Cr(VI) self-reduction by the soil itself. Complete self-reduction of Cr(VI) from soils 1, 2 and 3 was achieved at maximum Cr(VI) levels of 1, 50 and 500 mg kg^?1, respectively. Therefore, the concentration of Cr(VI) should not exceed the given levels in order to ensure that Cr(VI) is not released into the environment from contaminated sites. Moreover, decreasing pH in the alkaline soil caused significant increase of Cr(VI) reducing efficiency. Na₂S, CPS and FeS, in contrast to FeS₂, were efficient Cr(VI) reducing agents in all three soils. For all added amendments the following order of Cr(VI) reducing capacity was observed: Na₂S > CPS > FeS > FeS₂ in soil 1, Na₂S ? CPS ~ FeS > FeS₂ in soil 2 and Na₂S ? FeS > CPS ~ FeS₂ in soil 3.     

Equilibrium and Kinetic Studies on Biosorption of Heavy Metals by Leaf Powder of Paper Mulberry (Broussonetia papyrifera)

Paper mulberry (Broussonetia papyrifera) leaf powder was used to remove heavy metal ions from aqueous solutions. The specific uptakes of Cu (II), Pb (II), and Cd (II) by the leaf powder were 43.40?±?0.2, 43.9?±?0.5, and 30.65?±?0.9 mg g^?1, respectively, when 500 mg L^?1 of the metal solutions were used. The data fitted well to the Langmuir isotherm. The process followed the pseudo-second-order kinetic equation and intraparticle diffusion played an important role in the adsorption process. On the basis of the calculated thermodynamic parameters such as standard enthalpy (??H°), entropy (??S°) and free energy change (??G°), it was inferred that the sorption process was endothermic and spontaneous in nature. The surface properties of the leaf powder (revealed by scanning electron microscopic observations) were suitable for the metal adsorption process. Energy dispersive X-ray fluorescence analysis confirmed the sequestration of the metal ions by the leaf powder. Fourier transform infrared spectroscopy implicated that different functional groups on the leaf powder were involved in the metal adsorption process. The results obtained from this study implicated that the B. papyrifera leaf powder was a good choice as a metal adsorbent. This abundantly available natural and eco-friendly biosorbent could be effectively used to develop a technology in the future.     

Assessment on the Removal of Methylene Blue Dye using Tamarind Fruit Shell as Biosorbent

Tamarind fruit shell was used as a low-cost biosorbent for the removal of methylene blue from aqueous solution. The various factors affecting adsorption, such as agitation, pH, initial dye concentration, contact time, and temperature, were investigated. The dye adsorption capacity was strongly dependent on solution pH as well as temperature. The Langmuir isotherm model showed good fit to the equilibrium adsorption data, and the maximum adsorption capacity obtained was 1.72 mg g^?1 at 303 K. The kinetics of adsorption followed the pseudo-second-order model and the rate constant increased with increase in temperature, indicating endothermic nature of adsorption. The Arrhenius equation was used to obtain the activation energy (E _a) for the adsorption system. The activation energy was estimated to be 19.65 kJ mol^?1. Thermodynamic parameters such as Gibbs free energy (ΔG ⁰), enthalpy (ΔH ⁰), and entropy (ΔS ⁰) were also investigated. Results suggested that adsorption of methylene blue onto tamarind fruit shell was a spontaneous and endothermic process. The present investigation suggests that tamarind fruit shell may be utilized as a low-cost adsorbent for methylene blue removal from aqueous solution.     

Cuprous Oxide-Modified Diatomite Waste from the Brewery Used as an Effective Adsorbent for Removal of Organic Dye: Adsorption Performance,Kinetics and Mechanism Studies

Cuprous oxide-modified diatomite waste (Cu₂O-DW) as a low-cost and effective adsorbent was prepared via a hydrothermal route combined with acid-alkali treatment. The microstructure and surface properties of the obtained Cu₂O-DW composite was characterized by Brunauer-Emmett-Teller, scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The adsorption behaviors of three different types of dyes such as cationic dye methyl blue (MB), anionic dye acid orange (AO), and reactive dye reactive yellow (RY) onto the as-prepared Cu₂O-DW were investigated. Several experimental parameters such as contact time, adsorbent dosage, initial dye concentration, and initial pH values were systematically estimated. The experimental results indicated that as-prepared Cu₂O-DW have a better adsorption performance for MB, AO, and RY. Moreover, the kinetic and isotherm models were also used to account for the adsorption mechanism of dye molecules onto Cu₂O-DW. The results demonstrated that three different dyes are all fitted well with pseudo-first-order kinetic model. Additionally, the Langmuir and Freundlich isotherm model is more suitable for describing the adsorption process of RY and MB on the as-prepared Cu₂O-DW, respectively, and the AO adsorption is propitious to the D-R isotherm model. The value of adsorption energy (E?<?8 kJ mol^?1) confirmed that the physical adsorption is dominator during the adsorption process. The findings of the study demonstrated that the synthesized Cu₂O-DW composite can be a promising adsorbent for the removal of organic dyes from wastewater and it provided a sustainable development method for cycling the diatomite waste from the brewery.     

Chromium Speciation in Water by Sorption on Calcite and Determination by Electrothermal Atomic Absorption Spectrometry

Abstract

A rapid, sensitive, and accurate method for the separation and speciative determination of chromium (Cr)(VI) and Cr(III) in water samples has been developed using sorption as the separation technique in conjunction with final determination by electrothermal atomic absorption spectroscopy (ETAAS). The present method, where granular calcite is used as selective sorbent, separates Cr(III) with retention values up to 99%, resulting in high accuracy determination of Cr(VI). Total Cr was likewise determined by ETAAS after an efficient reduction of Cr(VI) to Cr(III) using ascorbic acid as reducing agent, deriving Cr(III) concentration from the difference between total Cr and Cr(VI). The parameters of the separation technique, solution pH (4.5–5.5), solution flow rate through the calcite column (0.14–0.42 mL min^?1), and calcite column internal diameter (1.5–3.0 cm), were evaluated. Best results were achieved with pH of 5.5, flow rate of 0.42 mL min^?1, and column internal diameter of 1.5 cm. Optimum determination conditions were found using magnesium nitrate [Mg(NO₃)₂] as chemical modifier, pyrolysis, and atomization temperatures of 1400 and 2200°C, respectively. In such conditions, the detection limits (n=10) were 1.5 and 0.8 µg L^?1 for Cr(III) and Cr(VI), respectively.     

Removal of Cu(II) Ions from Aqueous Solution by Magnetic Chitosan-Tripolyphosphate Modified Silica-Coated Adsorbent: Characterization and Mechanisms

A magnetic chitosan-modified Fe₃O₄@SiO₂ with sodium tripolyphosphate adsorbent (MTPCS) was synthesized by surface modification of Fe₃O₄@SiO₂ with chitosan using sodium tripolyphosphate (STPP) as the cross-linker in buffer solution for the adsorption of Cu(II) ions from aqueous solution. The structure and morphology of this magnetic nanoadsorbent were examined by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), BET surface area measurements, Fourier transform infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS). The effects of initial pH, adsorbent amount, and initial concentration of heavy metal ions were investigated by batch experiments. Moreover, adsorption isotherms, kinetics, and thermodynamics were studied to understand the mechanism of adsorbing metal ions by synthesized MTPCS. The results revealed that adsorption kinetics was best depicted by the pseudo-second-order rate mode and intraparticle-diffusion models. The adsorption isotherm fitted well to the Langmuir model. Moreover, thermodynamic study verified the adsorption process was endothermic and spontaneous in nature. The maximum adsorption occurred at pH 5 ± 0.1, and the adsorbent could be used as a reusable adsorbent with convenient conditions.     

Sorption Characteristics of Chromium and Its Phytotoxic Effect with or without City Compost on Maize and Spinach in a Vertisol of Central India

Abstract

Phytotoxicity, due to chromium [Cr (VI)] additions from low to very high levels in a swell–shrink clayey soil (Haplustert), in maize and spinach was studied in a pot culture experiment. Six levels of Cr (VI) (0, 5, 10, 25, 50, and 75 mg kg^?1 soil) for maize and five levels for spinach (0, 2, 5, 10, and 25 mg kg^?1 soil) were applied singly and in combination with two doses (0 and 20 t ha^?1) of city compost. At levels of more than 75 mg Cr (VI) kg^?1 soil for maize there was virtually no growth after germination, whereas 25 mg Cr (VI) kg^?1 soil hindered the germination of spinach crop. Initial symptoms of Cr (VI) toxicity appeared as severe wilting of the tops of treated plants. Maize plants suffering from severe Cr (VI) toxicity had smaller roots and narrow brownish red leaves covered with small necrotic spots. In spinach, severe chlorosis was observed in leaves. Higher levels of Cr (VI) inhibited the growth and dry‐matter yield of the crops. However, application of city compost alleviated the toxic effect of Cr (VI). The concentration of Cr (VI) in plant parts increased when Cr (VI) was applied singly but decreased considerably when used in combination with city compost. There was evidence of an antagonistic effect of Cr (VI) on other heavy‐metal (Mn, Cu, Zn, and Fe) concentrations in plant tops. Thus, when Cr (VI) concentration increases, the concentration of other beneficial metals decreases. Chromium (VI) concentration in maize roots ranged from traces (control) to 30 mg kg^?1and were directly related to soil Cr (VI) concentration. At 25 mg Cr (VI) kg^?1 soil, yield of maize was reduced to 41% of control plants, whereas in spinach, 10 mg Cr (VI) kg^?1 soil caused a 33% yield reduction. Experimental results revealed that the maize top (cereal) is less effective in accumulating Cr (VI) than spinach (leafy vegetables). Laboratory studies were also conducted to know Cr (VI) sorption capacity of a swell–shrink clayey soil with and without city compost, and it was found that Cr (VI) sorption reaction was endothermic and spontaneous in nature.