Removal of As(III) from Aqueous Solution Using Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles: Process Modeling and Optimization Using Statistical Design

In this study, Extran (biodegradable surfactant) was used for the preparation of Fe₃O₄ nanoparticles by microemulsion process to improve removal efficiency of As(III) from aqueous solution. Fe₃O₄ nanoparticles were characterized by XRD, FTIR, FESEM, TEM, HRTEM, and VSM instrumental techniques. The effect of different parameters such as adsorbent dose, initial As(III) concentration, and solution pH were studied by response surface methodology (RSM) based on Box-Behnken design (BBD). The optimized condition for adsorption of As(III) from aqueous solution was obtained as adsorbent dose of 0.70 mg/g, solution pH of 7.7, and initial As(III) concentration of 33.32 mg/L. In this optimum condition, about 90.5% of As(III) was removed from the aqueous solution. Isotherm studies have been done at optimal condition, and it was observed that the Langmuir isotherm models were fitted well with experimental data having a high correlation coefficient of 0.993. From the Langmuir isotherm data, the maximum adsorption capacity of Fe₃O₄ nanoparticles was found to be 7.18 mg/g at pH 7.7 in room temperature. This study revealed that Fe₃O₄ nanoparticles can be used as an efficient, eco-friendly, and effective material for the adsorptive removal of As(III) from aqueous system.     

Preparation of High Surface Area Oxidized Activated Carbon from Peanut Shell and Application for the Removal of Organic Pollutants and Heavy Metal Ions

A peanut shell-derived oxidized activated carbon (OAC) with high surface area was prepared by zinc chloride (ZnCl₂) chemical activation and subsequent nitric acid oxidation. OAC was characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and N₂ adsorption-desorption. The results showed that OAC had the surface area of 1807 m² g^?1, with the total pore volume of 0.725 cm³ g^?1 and average pore diameter of 3.8 nm. More importantly, when OAC acted as an adsorbent, it exhibited high efficiency to remove basic blue 41 (BB-41), congo red (CR), phenol, Cr(VI), and Pb(II) from aqueous solution due to its universality in adsorption. Batch adsorption experiments were carried out to study the effect of various parameters such as pH, initial concentration, temperature, and contact time. Also, the isotherms, kinetic models, and thermodynamics of adsorption process were investigated. The equilibrium data for CR and Pb(II) were fitted to Langmuir isotherm model, while Freundlich model was suitable for the equilibrium isotherm of BB-41, phenol, and Cr(VI), respectively. As the result indicated, peanut shell was a suitable raw material to synthesize OAC which could be employed as an efficient and universal adsorbent for removing organic pollutants and heavy metal ions from wastewater.     

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.     

Pb(II) Removal Using TiO<Subscript>2</Subscript>-Embedded Monolith Composite Cryogel as an Alternative Wastewater Treatment Method

Different from direct application of free nanoparticles (NPs) in water treatment, a composite material is used to reduce the release and potential toxic effects of NPs with maintained adsorption capacity and kinetics. Novel monolithic composites with TiO₂ NPs incorporated into the walls of macroporous cryogels were synthesized and evaluated for material characteristics and their efficiency for removal of Pb(II) from aqueous solution in batch test and continuous mode. The uniformly distributed 6% TiO₂-cryogel is shown to be optimal for minimizing TiO₂ NP losses while maximizing Pb(II) removal. Under (25.0 ± 0.1) °C with the initial Pb(II) concentration of 10 mg/l, TiO₂-cryogels exhibit excellent adsorption characteristic for Pb(II) removal with adsorption capacity up to 23.27 mg/g TiO₂, which is even a little higher than that of TiO₂ NPs (21.58 mg/g TiO₂), and the results fit well with Langmuir–Freundlich isotherm. Both adsorbents work well in higher pH range with the highest removal rate at pH 6 for TiO₂-cryogel, and the adsorption mechanism might be strong chemical interaction. Pseudo-second-order process can better describe the adsorption process rather than pseudo-first-order for both adsorbents. The external mass transfer process of Pb(II) on TiO₂ NPs is much faster than that on TiO₂-cryogel, and the ultimate equilibrium time is about the same (3 h) on both adsorbents. The synthesized composites could also withstand a continuous treatment, and the effect of competing and co-existing constituents such as Cd²⁺, SO₄ ^2? and dissolved organic matter (DOM) is almost negligible. The composite design with small particles embedded into cryogels is proved to successfully keep the adsorption activity of TiO₂ NPs and prevent them from releasing into the environment in engineering practice.     

Adsorption,Kinetics and Equilibrium Studies on Removal of Catechol and Resorcinol from Aqueous Solution Using Low-Cost Activated Carbon Prepared from Sunflower (<Emphasis Type="Italic">Helianthus annuus</Emphasis>) Seed Hull Residues

This study reports on the feasibility of remediation of catechol- and resorcinol-contaminated water using low-cost sunflower seed hull activated carbon (SSHAC). Sunflower seed hull (SSH), an abundant agricultural waste in Malawi, was used as precursor to prepare highly porous activated carbon by physicochemical activation, with zinc chloride (ZnCl₂) as an activating agent. The activated carbon was characterized by FTIR, SEM-EDS, XRD and BET analyses. In this work, pertinent parameters that affect the adsorption efficiency—pH, initial adsorbate concentration, contact time, adsorbent dosage, and solution temperature—were investigated in batch mode. At the same experimental conditions, more catechol was adsorbed than resorcinol may be due to the compound’s affinity towards water and the position of the hydroxyl group on the benzene ring. A maximum equilibrium adsorption of 271 and 250 mg/g was obtained at pH 9.0 and pH 8.0 for catechol and resorcinol, respectively. The adsorption behaviour of both adsorbates (catechol and resorcinol) on SSHAC can be well described by Langmuir isotherm model and pseudo-second-order kinetic model. The value ?G, ?S and ?H indicated spontaneous and endothermic adsorption process. The adsorption process was readily reversible allowing reusability of the adsorbate. This study’s outcome is value addition to this category of wastes for environmental protection.     

Copper Binding by Activated Biochar Fibres Derived from <Emphasis Type="Italic">Luffa cylindrica</Emphasis>

The adsorption of copper (Cu(II)) from aqueous solutions by activated Luffa cylindrica biochar fibres has been investigated by means of batch equilibrium experiments and FTIR spectroscopy. The effect of various physicochemical parameters, such as pH, initial metal concentration, ionic strength, mass of the adsorbent, contact time and temperature, has been evaluated by means of batch type adsorption experiments. FTIR spectroscopy, as well as acid-base titrations, was used for the characterization of the material and the surface species formed. According to the experimental results even at pH 3, the relative sorption is above 85% and the adsorption capacity of the activated biochar fibres for Cu(II) is q _max = 248 g kg^?1. Moreover, the interaction between the surface carboxylic moieties and Cu(II) results in the formation of very stable inner-sphere complexes (?G ^o = ?11.2 kJ mol^?1 at pH 3 and ?22.4 kJ mol^?1 at pH 5.5).     

Adsorption of Copper(II) Ion from Aqueous Solution Using Biochar Derived from Rambutan (Nepheliumlappaceum) Peel: Feedforward Neural Network Modelling Study

Biochars, derived from rambutan (Nepheliumlappaceum) peel through slow pyrolysis, were characterised and investigated as potential adsorbent for the removal of copper ion, Cu(II) from aqueous solution. Characteristics of five biochars of rambutan peel with different pyrolytic temperatures ranging from 300 to 700 °C (B300, B400, B500, B600, B700) were studied, and adsorption abilities of respective biochars were evaluated. Adsorption experiments were carried out by varying adsorbent dosage (0.2, 0.4, 0.8, 1.0, 2.0, and 4.0 g/L) and initial copper ion, Cu(II) concentrations (50 and 100 mg/L) to determine the optimum pyrolytic temperature of biochar with high adsorption affinity. The adsorption kinetics were best described by the pseudo-second order model for all the tested biochars, while the adsorption equilibrium best fitted by Langmuir isotherm. The overall results showed that biochar derived at 600 °C can be used as an effective adsorbent for removal of Cu(II) from aqueous solutions. Furthermore, feedforward artificial neural network (FFBP) modelling was performed to compare the simulated results with experimental output data of Thermogravimetric analysis (TGA) and atomic absorption spectroscopy (AAS) analysis which were trained using Levenberg-Marquardt (LM) backpropagation algorithm. The FFBP structure for pyrolysis process comprised of TGA temperature as input and biomass final weight as output. The adsorption modelling was simulated using adsorption time, temperature, biochar dosage and initial Cu(II) concentration as input data, while final Cu(II) concentration was used as output data to the network. Finally, modelling structure of 1-9-1 and 4-8-1 gave best performance with regression, R ² value of 0.9999 and 0.9547 for TGA and AAS analysis, respectively.     

A Stable Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Expanded Perlite Composite Catalyst for Degradation of Rhodamine B in Heterogeneous Photo-Fenton System

A stable and efficient Fe₂O₃/expanded perlite (Fe₂O₃-Ep) composite catalyst was synthesized by a simple hydrothermal method for degradation of refractory contaminants in heterogeneous photo-Fenton system. X-ray diffraction and FT-IR analyses confirmed the presence of the Fe₂O₃ in the synthesized catalyst. The catalytic activity of the Fe₂O₃-Ep catalyst was evaluated by the degradation of rhodamine B (RhB, 5 mg/L) and metronidazole (MET, 5 mg/L) in the presence of H₂O₂ under visible light irradiation. The Fe₂O₃-Ep catalyst exhibited high efficiency for degradation of RhB at a wide pH range from 2 to 10 and showed excellent catalytic property for decomposition of MET as well. The degradation ratio of RhB was achieved 99%, and the removal ratio of COD was 62% within 90 min at the best experimental conditions (0.5 g/L of Fe₂O₃-Ep catalyst, 2 mL/L of H₂O₂). Furthermore, iron leaching of the Fe₂O₃-Ep catalyst during the catalytic degradation reaction was negligible and the catalyst still exhibited high catalytic activity and stability after five cycles. These results show that the catalyst can be used as a highly efficient heterogeneous photo-Fenton catalyst for the degradation of non-biodegradable refractory pollutants in water.     

Intracellular chromium accumulation by <Emphasis Type="Italic">Streptomyces</Emphasis> sp. MC1

Streptomyces sp. MC1, previously isolated from sugar cane, has shown ability to reduce Cr(VI) in liquid minimal medium and soil samples. The objective of this work was to demonstrate the intracellular chromium accumulation by Streptomyces sp. MC1 under different culture conditions. This strain was able to accumulate up to 3.54 mg of Cr(III) per gram of wet biomass, reducing the 98% of Cr(VI) and removing 13.9% of chromium from the culture medium supernatants. Streptomyces sp. MC1 chromium bioaccumulation ability was corroborated by using Timm’s reagent technique, a low-cost method, which has been used by first time to detect chromium deposits in bacteria. The results of atomic absorption spectrometry, scanning electron microscopy, and energy dispersive X-ray analysis suggest that the mechanism of Cr(VI) resistance observed in Streptomyces sp. MC1 includes adsorption coupled with reduction to Cr(III), and finally, Cr(III) bioaccumulation. This mechanism have special relevance to remediation of Cr(VI) contaminated environments by Streptomyces sp. MC1.     

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.     

Porous Materials Modified with Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles for Arsenic Removal in Drinking Water

The contamination of drinking water with arsenic has been a problem in a lot of countries around the world because of its toxicological and carcinogenic effects on human health. Porous materials modified with Fe₃O₄ nanoparticles (Fe₃O₄ NPs) represent convenient removers for that contaminant. A co-precipitation method of Fe(III) and Fe(II) in alkaline media was applied to obtain Fe₃O₄ NPs. In a first stage, single nanoparticles were synthesized and stabilized with carboxylic acids. A characterization with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), Raman spectroscopy, and X-ray diffraction (XRD) confirms a magnetite-type structure. Moreover, transmission electron microscopy (TEM) and calculations from XRD data using Scherrer’s equation indicate an average particle size of 13 nm and an average crystallite size of 10 nm, both independent of the stabilizer used. Then, the co-precipitation method studied was applied to modify kaolin, bentonite, diatomite, and silica and thus prepare magnetic composites having support-magnetite weight ratios of 2:1. Among them, silica-modified material presented the best hydraulic characteristics, an important aspect for large-scale applications such as removal under gravity. This composite has the capacity to remove up to 80 and 70% for initial concentrations of 25 and 50 μg/L, respectively, representing a convenient remover for processes developed in subsequent stages or in continuous flow.     

Kinetic Study of the Effect of pH on Hexavalent and Trivalent Chromium Removal from Aqueous Solution by <Emphasis Type="Italic">Cupressus lusitanica</Emphasis> Bark

Solution pH is among the most important parameters that influence heavy metal biosorption. This work presents a kinetic study of the effects of pH on chromium biosorption onto Cupressus lusitanica Mill bark from aqueous Cr(VI) or Cr(III) solutions and proposes a mechanism of adsorption. At all assayed contact times, the optimum pH for chromium biosorption from the Cr(III) solution was 5.0; in contrast, optimum pH for chromium biosorption from the Cr(VI) solution varied depending on contact time. The kinetic models that satisfactorily described the chromium biosorption processes from the Cr(III) and Cr(VI) solutions were the Elovich and pseudo second-order models, respectively. Diffuse reflectance infrared Fourier transform spectroscopy studies suggest that phenolic compounds present on C. lusitanica Mill bark play an important role in chromium biosorption from the Cr(III) solution. On the other hand, chromium biosorption from the Cr(VI) solution involved carboxyl groups produced on the bark by redox reactions between oxygen-containing groups and Cr(VI), and these were in turn responsible for the biosorption of Cr(III) produced by Cr(VI) reduction.     

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.     

Biosorption of Chromium (III) and Chromium (VI) by Untreated and Pretreated Cassia fistula Biomass from Aqueous Solutions

The present study explained the effect of pretreatments on the biosorption of Cr (III) and Cr (VI) by Cassia fistula biomass from aqueous solutions. For this purpose Cassia fistula biomass was pretreated physically by heating, autoclaving, boiling and chemically with sodium hydroxide, formaldehyde, gluteraldehyde, acetic acid, hydrogen peroxide, commercial laundry detergent, orthophosphoric, sulphuric acid, nitric acid, and hydrochloric acid. The adsorption capacity of biomass for Cr (III) and Cr (VI) was found to be significantly improved by the treatments of gluteraldehyde (95.41 and 96.21 mg/g) and benzene (85.71 and 90.81 mg/g) respectively. The adsorption capacity was found to depend on pH, initial metal concentration, dose, size, kinetics, and temperature. Maximum adsorption of both the Cr (III) and Cr (VI) was observed at pH 5 and 2. When Freundlich and Langmuir isotherms were tested, the latter had a better fit with the experimental data. The kinetic studies showed that the sorption rates could be described better by a second order expression than by a more commonly applied Lagergren equation.     

Optimization of the Adsorption Conditions for the Decolorization and COD Reduction of Methylene Blue Aqueous Solution using Low-Cost Adsorbent

The performance of raw bagasse (RB), and tartaric acid-modified bagasse (TAMB) as adsorbents on decolorization and chemical oxygen demand (COD) reduction of methylene blue (MB) aqueous solution was studied. The effects of five factors namely: adsorbent dosage, pH, shaking speed, contact time, and temperature on decolorization and COD reduction were studied and optimized using central composite design (CCD). The results of the analysis show that all selected factors exhibit significant effect on decolorization and COD reduction. Maximum decolorization (78.16%) and COD reduction (77.95%) for RB was achieved at 0.82 g of adsorbent dosage, pH 9.4, 122 rpm of shaking speed, 44 min of contact time, and 55°C. For TAMB, maximum decolorization (99.05%) and COD reduction (98.45%) was achieved at 0.78 g adsorbent dosage, pH 9.4, shaking speed of 120 rpm, 34 min contact time, and 49°C. TAMB was found to be more effective than RB in decolorization and COD reduction of MB aqueous solution.     

Community Refinery Wastewater Photodegradation by Fe-Doped TiO<Subscript>2</Subscript> Films

Photocatalytic treatment of real community wastewater using Fe-doped TiO₂ nanofilm was prepared by modified sol-gel method together with a simple dip-coating technique. The process was investigated in a home-made batch photoreactor. The as-prepared nanocomposite film was characterized by UV-Vis diffuse, XRD, BET, and Fe-SEM analysis. The poultry processing wastewater was collected from Nakhonsawan Municipality. Subsequently, the photocatalytic treatment of the wastewater was performed using a home-made photoreactor operated in batch mode to demonstrate the effects of Fe-dopant concentration with various layer numbers. The catalysts were irradiated using four lamps of 15 W power that emitted visible light and performed at room temperature. The samples were collected every 15 min and analyzed for biochemical oxygen demand (BOD) and chemical oxygen demand (COD) removal efficiency compared to pure TiO₂ nanofilm and direct photolysis. From the results, the mixture of rutile and anatase was obtained with the maximum specific surface area of 150.12 mg²/g and the average particle size of 39.95 nm for 3 layers of 0.15% wt/v Fe-doped TiO₂. The BOD and COD value at 90 min time treatment was presented to be 8.87 and 32 mg L^?1, respectively, in the presence of 0.15% wt/v Fe-doped TiO₂ film photocatalysts. Moreover, atomic absorption spectrometric result ensured that no Ti contamination was detected in all parts of plants after watering by the treated water. Hence, the photocatalytic treatment markedly improved the quality of the community wastewater.     

Organic Matter Effects on the Cr(VI) Removal Efficiency and Tolerance of <Emphasis Type="Italic">Typha domingensis</Emphasis>

The removal efficiency and tolerance of Typha domingensis to Cr(VI) in treatments with and without organic matter (OM) addition were evaluated in microcosm-scale wetlands. Studied Cr(VI) concentrations were 15 mg L^?1, 30 mg L^?1, and 100 mg L^?1, in treatments with and without OM addition, arranged in triplicate. Controls (without neither metal nor OM addition—without metal with OM addition) were disposed. Cr(VI) was removed efficiently from water in all treatments. OM addition enhanced significantly Cr(VI) and total Cr removals from water. In the treatments with OM addition, significantly higher Cr concentrations were found in sediment than the treatments without OM addition. Plants of the treatments without OM addition showed significantly higher Cr concentrations in tissues but lower biomass increase than the treatments with OM addition. The highest Cr concentrations in tissues were observed in submerged parts of leaves, followed by roots. According to SEM analysis, in the 100 mg L^?1 treatments, the highest Cr accumulation was observed in the epidermis of old leaves. Although Cr(VI) produced changes in root morphology, the OM addition favored the plant growth. In T. domingensis, root morphological plasticity is an important mechanism to improve metal tolerance and Cr uptake in wetland systems minimizing the environmental impact.     

Heterogeneous Activation of Persulfate by Graphene Oxide-TiO<Subscript>2</Subscript> Nanosheet for Oxidation of Diclofenac: Optimization by Central Composite Design

In this study, the performance of oxidation with actived persulfate (PS) by graphene oxide-TiO₂ nanosheet (GO-TiO₂) was investigated for diclofenac (DCF) removal, an anti-inflammatory analgesic being widely used in human health care and veterinary treatment. GO-TiO₂ containing oxygen functional groups is employed as an activator for the activation of PS used as the oxidizing agent. Modeling and optimization of the process were performed by central composite design (CCD) as a response surface methodology (RSM). The effects of various factors, including PS concentration, GO-TiO₂ amount, initial pH of DCF solution, and reaction time on DCF oxidation, were evaluated. When the estimated values of the full quadratic model obtained with CCD were compared with the actual experimental results, a strong agreement was obtained with an R² value of 0.9553. Besides, the model consistency was verified by analysis of variance (ANOVA) with a value of 20.17 of F value and P value of less than 0.05. After the optimization run, maximum DCF removal of 93.06% occurred with contact time of 14 min, pH of 5.54, PS concentration of 10 g/L, and 0.1 g of GO-TiO₂ as optimal variable values.     

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.     

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.