Chromium(VI) Removal from Water by Lanthanum Hybrid Modified Activated Carbon Produced from Coconut Shells.

Cr(VI) is considered to be the most hazardous and toxic oxidation state of chromium and hence the development of effective removal technologies, able to provide water with Cr(VI) below the drinking water limits (US EPA 100 µg/L, European Commission 50 µg/L, which will be reduced to 25 by 2036) is a very important issue in water treatment. This study aimed at examining the performance of activated carbon produced from coconut shells, modified by lanthanum chloride, for Cr(VI) removal from waters. The structure of the formed material (COC-AC-La) was characterized by the application of BET, FTIR and SEM techniques. The effect of the adsorbent's dosage, pH value, contact time, initial Cr(VI) concentration and water matrix was examined with respect to Cr(VI) removal. The results indicated that the maximum Cr(VI) removal was observed at pH 5; 4 h contact time and 0.2 g/L of adsorbent's dosage was adequate to reduce Cr(VI) from 100 µg/L to below 25 µg/L. Freundlich isotherm and pseudo-second order kinetic models fitted the experimental data sufficiently. The maximum adsorption capacity achieved was 6.3 µg/g at pH 5. At this pH value, the removal percentage of Cr(VI) reached 95% for an initial Cr(VI) concertation of 30 µg/L. At pH 7 the corresponding efficiency was roughly 60%, resulting in residual Cr(VI) concentrations below the anticipated drinking water limit of 25 µg/L of total chromium, when the initial Cr(VI) concentration was 50 µg/L. Consecutive adsorption and regeneration studies were conducted using 0.01 M of NaOH as an eluent to evaluate the reusability of the adsorbents, Results showed 20% decrease of adsorption capacity after 5 regeneration cycles of operation.

Green Bioanalytical Applications of Graphene Oxide for the Extraction of Small Organic Molecules.

Bioanalysis is the scientific field of the quantitative determination of xenobiotics (e.g., drugs and their metabolites) and biotics (e.g., macromolecules) in biological matrices. The most common samples in bioanalysis include blood (i.e., serum, plasma and whole blood) and urine. However, the analysis of alternative biosamples, such as hair and nails are gaining more and more attention. The main limitations for the determination of small organic compounds in biological samples is their low concentration in these matrices, in combination with the sample complexity. Therefore, a sample preparation/analyte preconcentration step is typically required. Currently, the development of novel microextraction and miniaturized extraction techniques, as well as novel adsorbents for the analysis of biosamples, in compliance with the requirements of Green Analytical Chemistry, is in the forefront of research in analytical chemistry. Graphene oxide (GO) is undoubtedly a powerful adsorbent for sample preparation that has been successfully coupled with a plethora of green extraction techniques. GO is composed of carbon atoms in a sp2 single-atom layer of a hybrid connection, and it exhibits high surface area, as well as good mechanical and thermal stability. In this review, we aim to discuss the applications of GO and functionalized GO derivatives in microextraction and miniaturized extraction techniques for the determination of small organic molecules in biological samples.

Magnetic solid-phase extraction of caffeine from surface water samples with a micro-meso porous activated carbon/Fe3O4 nanocomposite prior to its determination by GC-MS.

A novel micro-meso porous activated carbon/Fe3O4 (Bm) composite was synthesized from the active charcoal precursor BAX-1500 and used in the magnetic solid-phase extraction (MSPE) of caffeine prior to its determination by gas chromatography-mass spectrometry (GC-MS). The main factors affecting the extraction and desorption steps of the MSPE procedure were investigated and optimized. These factors include extraction time, sorbent mass and salt addition for the adsorption step and type of eluent, desorption time and volume of desorption solution for the desorption step. Under optimum conditions, the absolute extraction recovery was found to be 91.1% and good linearity was observed in the investigated concentration range of 0.6-12.5 ng mL-1 (R 2 = 0.9997). The limit of detection was 0.18 ng mL-1 and the limit of quantification was 0.60 ng mL-1. The method was successfully applied to the analysis of surface water samples. The proposed MSPE method is simple, rapid, sensitive and environmentally friendly.

On the use of metal-organic frameworks for the extraction of organic compounds from environmental samples.

The determination of trace metals and organic contaminants in environmental samples, such as water, air, soil, and sediment, is until today a challenging process for the analytical chemistry. Metal-organic frameworks (MOFs) are novel porous nanomaterials that are composed of metal ions and an organic connector. These materials are gaining more and more attention due to their superior characteristics, such as high surface area, tunable pore size, mechanical and thermal stability, luminosity, and charge transfer ability between metals and ligands. Among the various applications of MOFs are gas storage, separation, catalysis, and drug delivery. Recently, MOFs have been successfully introduced in the field of sample preparation for analytical chemistry and they have been used for sample pretreatment of various matrices. This review focuses on the applications of MOFs as novel adsorbents for the extraction of organic compounds from environmental samples.

Sample Preparation Using Graphene-Oxide-Derived Nanomaterials for the Extraction of Metals.

Graphene oxide is a compound with a form similar to graphene, composed of carbon atoms in a sp2 single-atom layer of a hybrid connection. Due to its significant surface area and its good mechanical and thermal stability, graphene oxide has a plethora of applications in various scientific fields including heterogenous catalysis, gas storage, environmental remediation, etc. In analytical chemistry, graphene oxide has been successfully employed for the extraction and preconcentration of organic compounds, metal ions, and proteins. Since graphene oxide sheets are negatively charged in aqueous solutions, the material and its derivatives are ideal sorbents to bind with metal ions. To date, various graphene oxide nanocomposites have been successfully synthesized and evaluated for the extraction and preconcentration of metal ions from biological, environmental, agricultural, and food samples. In this review article, we aim to discuss the application of graphene oxide and functionalized graphene oxide nanocomposites for the extraction of metal ions prior to their determination via an instrumental analytical technique. Applications of ionic liquids and deep eutectic solvents for the modification of graphene oxide and its functionalized derivatives are also discussed.

Metal Organic Frameworks: Synthesis and Application.

The concept of metal-organic frameworks (MOFs) was first introduced in 1990; nowadays they are among the most promising novel materials. MOFs belong to a new class of crystalline materials that consist of coordination bonds between metal clusters (e.g., metal-carboxylate clusters and metal-azolate clusters), metal atoms, or rod-shaped clusters and multidentate organic linkers that contain oxygen or nitrogen donors (like carboxylates, azoles, nitriles, etc.); thus, a three-dimensional structure is formed [...].

Metal Organic Frameworks as Desulfurization Adsorbents of DBT and 4,6-DMDBT from Fuels.

Ultradeep desulfurization of fuels is a method of enormous demand due to the generation of harmful compounds during the burning of sulfur-containing fuels, which are a major source of environmental pollution. Among the various desulfurization methods in application, adsorptive desulfurization (ADS) has low energy demand and is feasible to be employed at ambient conditions without the addition of chemicals. The most crucial factor for ADS application is the selection of the adsorbent, and, currently, a new family of porous materials, metal organic frameworks (MOFs), has proved to be very effective towards this direction. In the current review, applications of MOFs and their functionalized composites for ADS are presented and discussed, as well as the main desulfurization mechanisms reported for the removal of thiophenic compounds by various frameworks. Prospective methods regarding the further improvement of MOF's desulfurization capability are also suggested.

Synthesis of Graphene Oxide Based Sponges and Their Study as Sorbents for Sample Preparation of Cow Milk Prior to HPLC Determination of Sulfonamides.

In the present study, a novel, simple, and fast sample preparation technique is described for the determination of four sulfonamides (SAs), namely Sulfathiazole (STZ), sulfamethizole (SMT), sulfadiazine (SDZ), and sulfanilamide (SN) in cow milk prior to HPLC. This method takes advantage of a novel material that combines the extractive properties of graphene oxide (GO) and the known properties of common polyurethane sponge (PU) and that makes sample preparation easy, fast, cheap and efficient. The PU-GO sponge was prepared by an easy and fast procedure and was characterized with FTIR spectroscopy. After the preparation of the sorbent material, a specific extraction protocol was optimized and combined with HPLC-UV determination could be applied for the sensitive analysis of trace SAs in milk. The proposed method showed good linearity while the coefficients of determination (R2) were found to be high (0.991-0.998). Accuracy observed was within the range 90.2-112.1% and precision was less than 12.5%. Limit of quantification for all analytes in milk was 50 µg kg-1. Furthermore, the PU-GO sponge as sorbent material offered a very clean extract, since no matrix effect was observed.

Degradation of endocrine disruptor, bisphenol-A, on an mixed oxidation state manganese oxide/modified graphite oxide composite: A role of carbonaceous phase.

Modified graphite oxide (ΝGO) was used as a support of a manganese oxide of hausmannite type (Mn3O4) nanocatalyst and applied for the degradation of an endocrine disruptor, bisphenol-A (BPA). The prepared nanocomposite/catalyst (NGO-Mn3O4), as well as pure modified graphite oxide and manganese oxide, were characterized by X-ray diffraction, Scanning Electron Microscopy, nitrogen adsorption, X-ray photoelectron spectroscopy, Fourier Transform Infrared Spectroscopy, and potentiometric titration. The maximum removal activity for all the materials was measured at pH = 3. The NGO-Mn3O4 nanocomposite showed the highest removal efficiency of BPA at an ambient temperature without light irradiation and/or the addition of chemicals, which can be attributed to the synergistic effect of the composite formation. The nanocomposite exhibited a high catalytic activity for the degradation/oxidation of BPA, which was dramatically higher than that of the pristine Mn3O4 phase. Modified graphite oxide showed also an enhanced capability for the BPA removal, which was linked to an increased physical adsorption component.

Applications of Metal-Organic Frameworks in Food Sample Preparation.

Food samples such as milk, beverages, meat and chicken products, fish, etc. are complex and demanding matrices. Various novel materials such as molecular imprinted polymers (MIPs), carbon-based nanomaterials carbon nanotubes, graphene oxide and metal-organic frameworks (MOFs) have been recently introduced in sample preparation to improve clean up as well as to achieve better recoveries, all complying with green analytical chemistry demands. Metal-organic frameworks are hybrid organic inorganic materials, which have been used for gas storage, separation, catalysis and drug delivery. The last few years MOFs have been used for sample preparation of pharmaceutical, environmental samples and food matrices. Due to their high surface area MOFs can be used as adsorbents for the development of sample preparation techniques of food matrices prior to their analysis with chromatographic and spectrometric techniques with great performance characteristics.

Fabrication and evaluation of magnetic activated carbon as adsorbent for ultrasonic assisted magnetic solid phase dispersive extraction of bisphenol A from milk prior to high performance liquid chromatographic analysis with ultraviolet detection.

In the present study, the impregnation of a micro - meso porous activated carbon with magnetite (Fe3O4) was successfully achieved by sonication and the magnetic activated carbon prepared (Bmi) was evaluated as a new adsorbent for ultrasonic assisted magnetic solid phase dispersive extraction of Bisphenol A (BPA) from cow milk and human breast milk samples, prior to the determination by HPLC with UV detection. The prepared Bmi was characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). The effect of pH on adsorption, initial concentration, contact time and desorption were studied. The main experimental parameters influencing extraction efficiency of BPA, such as type and amount of the adsorbent, sample amount, type of desorption solvent, time of adsorption and desorption, type of precipitation solvent, were investigated and optimized. Under the optimal extraction conditions the absolute recovery of BPA was 81% and 95% in cow milk and human breast milk samples, respectively. Good linearity was observed in the investigated concentration range of 2.5µgkg-1-5000µgkg-1 (R2=0.9997). Limit of detection (LOD) was 0.75µgL-1, which is in accordance with the specific migration limit (SML) established by the European Union, and limit of quantification (LOQ) was 2.5µgL-1. Within-day and between-day recoveries ranged from 91.4% to 98.6% and 89.1% to 99.4% respectively and the RSDs were less than 3.7%. Due to the excellent magnetic behavior of Bmi the proposed method was shown to be simple and rapid. Besides these, this method is sensitive, low cost, efficient and environmentally friendly.

Comparison of activation media and pyrolysis temperature for activated carbons development by pyrolysis of potato peels for effective adsorption of endocrine disruptor bisphenol-A.

Activated carbon prepared from potato peels, a solid waste by product has been studied for the adsorption of an endocrine disruptor, Bisphenol-A, from aqueous solutions. The potato peels biomass was activated with H3PO4, KOH and ZnCl2 in order the effect of the activation agent to be evaluated. The activated biomass was carbonized at 400, 600 and/or 800 °C in order the effect of carbonization temperature on the texture, surface chemistry and adsorption properties to be found. The activated carbons prepared were characterized by nitrogen adsorption, Scanning Electron Microscope, thermal analysis and Fourier Transform Infrared Spectroscopy. Equilibrium adsorption data followed both Langmuir and Freundlich isotherms. Adsorption followed second order rate kinetics. The adsorption capacity calculated from the Langmuir isotherm was found 454.62 mg g(-1) at an initial pH 3 at 25 °C for the phosphoric acid activated carbon carbonized at 400 °C that proved to be the best adsorbent.

Magnetic modification of microporous carbon for dye adsorption.

In this study, impregnation of microporous activated carbon with magnetite was achieved by co-precipitation of iron salts onto activated carbon. The evaluation of the adsorption ability of this material was examined using the anionic dye Reactive Black 5 as model dye pollutant (adsorbate). The effect of pH, ionic strength, contact time and initial dye concentration were also studied. It was found that high pH and high ionic strength favor the adsorption of Reactive Black 5. The adsorption kinetics and isotherms were well fitted by the fractal BS model and Langmuir model, respectively. The impregnation with magnetite decreases the adsorption capacity of activated carbon. Thermal re-activation of dye-loaded activated carbons was also succeeded. The characterization of the magnetic carbons was investigated by various techniques (SEM/EDAX, VSM, BET, FTIR, XRD, DTG) revealing many possible interactions in the carbon-dye system.

Removal of dorzolamide from biomedical wastewaters with adsorption onto graphite oxide/poly(acrylic acid) grafted chitosan nanocomposite.

A novel graphite oxide/poly(acrylic acid) grafted chitosan nanocomposite (GO/CSA) was prepared and used as biosorbent for the removal of pharmaceutical compound (dorzolamide) from biomedical synthetic wastewaters. The performance was evaluated taking into account pH, kinetics and thermodynamics of adsorption. GO/CSA presented higher adsorption capacity in comparison with the parent materials (graphite oxide and poly(acrylic acid) grafted chitosan). All adsorbents prepared were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and potentiometric titration. The surface features were also evaluated after the dorzolamide adsorption in order to derive the adsorption mechanism. It was suggested that the reactive groups of GO and CSA can interact with the amino groups of dorzolamide and mainly the abundance of carboxyl groups of GO/CSA composite was the main reason for its enhanced adsorption capacity.

The role of chitosan as nanofiller of graphite oxide for the removal of toxic mercury ions.

The present study focuses on the role of chitosan (CS) as nanofiller of graphite oxide (GO) in order to prepare composite materials with improved Hg(II) adsorption properties. The removal of Hg(II) from aqueous solutions was studied using adsorbents as graphite oxide (GO), graphite oxide nanofilled with chitosan (GO/CS) and magnetic chitosan (GO/mCS). Many possible interactions between materials and Hg(II) were observed after adsorption and explained via characterization with various techniques (SEM/EDAX, FTIR, XRD, DTG). The adsorption evaluation was done studying various parameters as the effect of pH (both in adsorption and desorption), contact time (pseudo-second order fitting), temperature (isotherms at 25, 45, 65 °C), in line with a brief thermodynamic analysis (ΔG(0), ΔH(0), ΔS(0)). The maximum adsorption capacity (fitting with Langmuir model) of GO at 25 °C was Qmax=187 mg/g, while after the CS nanofilling (formation of the composite GO/CS), Qmax was increased to 381 mg/g with a further enhancement for GO/mCS (Qmax=397 mg/g).

Mercury(II) removal with modified magnetic chitosan adsorbents.

Two modified chitosan derivatives were prepared in order to compare their adsorption properties for Hg(II) removal from aqueous solutions. The one chitosan adsorbent (CS) is only cross-linked with glutaraldehyde, while the other (CSm), which is magnetic, is cross-linked with glutaraldehyde and functionalized with magnetic nanoparticles (Fe3O4). Many possible interactions between materials and Hg(II) were observed after adsorption and explained via characterization with various techniques (SEM/EDAX, FTIR, XRD, DTG, DTA, VSM, swelling tests). The adsorption evaluation was done studying various parameters as the effect of pH (optimum value 5 for adsorption and 2 for desorption), contact time (fitting to pseudo-first, -second order and Elovich equations), temperature (isotherms at 25, 45, 65 °C), in line with a brief thermodynamic analysis (ΔG° < 0, ΔH° > 0, ΔS° > 0). The maximum adsorption capacity (fitting with Langmuir and Freundlich model) of CS and CSm at 25 °C was 145 and 152 mg/g, respectively. The reuse ability of the adsorbents prepared was confirmed with sequential cycles of adsorption-desorption.

Functionalization of graphite oxide with magnetic chitosan for the preparation of a nanocomposite dye adsorbent.

In the current study, the functionalization of graphite oxide (GO) with magnetic chitosan (Chm) was investigated to prepare a nanocomposite material (GO-Chm) for the adsorption of a reactive dye (Reactive Black 5). The synthesis mechanism was investigated by various techniques (SEM/EDAX, FTIR spectroscopy, XRD, XPS, DTA, DTG, VSM). Characterization results indicated that a significant fraction of the amines of the chitosan (i) were inserted between the GO layers and (ii) reacted with carboxyl and epoxy groups of GO, leading to its reduction and hence the destruction of the layered structure. The concentrations of iron were found to be ∼25% for Chm and ∼12% for GO-Chm. A VSM plot presents the value of 9 emu/g for the saturation magnetization of GO-Chm. The adsorption behavior of the prepared composite was elucidated with a series of experiments. The tests of the effects of pH revealed that the adsorption mechanism dominated (between dye molecules and the GO-Chm matrix) and showed that acidic conditions were the optimum for the adsorption process (pH 3). Kinetic experiments presented the relatively "fast" adsorption phenomenon using pseudo-first-order, pseudo-second-order, and modified pseudo-second-order equations. The equilibrium data were fitted to the Langmuir, Freundlich, and Langmuir-Freundlich (L-F) models, calculating the maximum adsorption capacities at 25, 45, and 65 °C (391, 401, and 425 mg/g, respectively). Thermodynamic analysis was also performed to calculate the changes in free energy (ΔG(0)), enthalpy (ΔH(0)), and entropy (ΔS(0)).

Magnetic Graphene Oxide: Effect of Preparation Route on Reactive Black 5 Adsorption.

In this study, the effect of preparation route of magnetic graphene oxide (mGO) on Reactive Black 5 (RB5) adsorption was investigated. The synthesis of mGO was achieved both with (i) impregnation method (mGOi nanoparticles), and (ii) co-precipitation (mGOp nanoparticles). After synthesis, the full characterization with various techniques (SEM, FTIR, XRD, DTA, DTG, VSM) was achieved revealing many possible interactions/forces of dye-composite system. Effects of initial solution pH, effect of temperature, adsorption isotherms and kinetics were investigated in order to conclude about the aforementioned effect of the preparation method on dye adsorption performance of the magnetic nanocomposites. The adsorption evaluation of the magnetic nanoparticles presented higher adsorption capacity of mGOp derivative (188 mg/g) and lower of mGOi (164 mg/g). Equilibrium experiments are also performed studying the effect of contact time (pseudo-first and -second order equations) and temperature (isotherms at 25, 45 and 65 °C fitted to Langmuir and Freundlich model). A full thermodynamic evaluation was carried out, calculating the parameters of enthalpy, free energy and entropy (ΔH°, ΔG° and ΔS°).

Nanocrystalline Akaganeite as Adsorbent for Surfactant Removal from Aqueous Solutions.

The present study presents the effective use of nanocrystalline akaganeite for the adsorption of an anionic (SDS), a cationic (CTAB), and a nonionic (tween80) surfactant from wastewater. Equilibrium experiments, as well as thermodynamic analysis, were performed. The maximum SDS adsorption occurs at the lowest pH value (5), the opposite is observed for CTAB (pH = 11), while for tween80, the change of pH value did not affect the adsorption. The equilibrium data could be described by Freundlich and Langmuir isotherms. The maximum adsorption capacity at 25 °C (pH = 8) was 823.96 mg/g for SDS, 1007.93 mg/g for CTAB, and 699.03 mg/g for tween80. The thermodynamic parameters revealed the exothermic and spontaneity nature of the process. Also, FTIR measurements established that surfactants are adsorbed on the surface of akaganeite, replacing adsorbed water.

Metals removal from aqueous solution by iron-based bonding agents.

UNLABELLED: GOAL AND SCOPE AND BACKGROUND: The application of a promising method, termed sorptive flotation, for the removal of chromium(VI) and zinc ions was the aim of the present paper. A special case of sorptive flotation is adsorbing colloid flotation. Suitable sorbent preparation techniques have been developed in the laboratory. METHODS: Sorptive flotation, consisting of the sorption and flotation processes combined in series, has proved to give fast and satisfactory treatment of the industrial streams and effluents bearing dilute aqueous solutions of zinc and chromium(VI). RESULTS AND DISCUSSION: Goethite has proved to be effective for the removal of chromium(VI) and zinc ions. Also, adsorbing colloid flotation with ferric hydroxide (as the co-precipitant) could be an alternative method to the above-mentioned separation of metal ions. In both cases, chromium(VI) (pH=4) and zinc (pH=7) removal was about 100%. CONCLUSION: The reasons for selecting the iron-based bonding materials, like goethite and/or in-situ produced ferric hydroxide, are that they are cheap, easily synthesized, suitable both for cation and anion sorption, and, furthermore, that they present low risks for adding a further pollutant to the system. Promising results were obtained. RECOMMENDATION AND OUTLOOK: The application of goethite and in-situ produced ferric hydroxide has demonstrated their effectiveness in the removal of heavy metal ions, such as chromium anions and zinc cations. A proposed continuation of current work is the utilization of similar iron oxides, for instance synthesized akaganeite. The comparison between the results reported in this paper with the results reported in the literature, also deserves attention.