Selective/simultaneous batch adsorption of binary textile dyes using amorphous perlite powder: aspects of central composite design optimization and mechanisms.

Herein, the selectivity/simultaneously adsorption associated with Congo Red (CR) and Methylene Blue (MB) has been efficiently undertaken via amorphous perlite. Under optimum conditions of 38 min, 96 mg/L and 312°K for the contact time, the dye concentration, and the temperature, respectively, the optimization study using central composite design (CCD) matrix gave rise to high adsorption yields of 82.22 and 96.65% for CR and MB, respectively. Importantly, kinetic and isotherm studies attested that the batch adsorption occurs as intra-diffusional mass transport onto porous material. The obtained thermodynamic parameters are indicative of an endothermic/spontaneous physisorption process. Whereas SEM-EDS characterization revealed the superficial adsorption process of both CR and MB onto perlite. In addition, the FTIR analysis suggests that the adsorption process disrupted the short-range compounds order of perlite samples, revealing the marked crystallinity decrease of the adsorbent after adsorption. Finally, application of these optimum conditions tests on real industrial wastewater show that the adsorption was simultaneous at neutral pH and at 312°K, whereas CR and MB can be selectively adsorbed at pH 4 and 9, respectively. Supplementary Information: The online version contains supplementary material available at 10.1007/s40201-023-00870-1.

Insights into the Synthesis Parameters Effects on the Structural, Morphological, and Magnetic Properties of Copper Oxide Nanoparticles.

The present study aims at the integration of the "oxalic conversion" route into "green chemistry" for the synthesis of copper oxide nanoparticles (CuO-NPs) with controllable structural, morphological, and magnetic properties. Two oxalate-containing precursors (H2C2O4.2H2O and (NH4)2C2O4.H2O) and different volume ratios of a mixed water/glycerol solvent were tested. First, the copper oxalates were synthesized and then subjected to thermal decomposition in air at 400 °C to produce the CuO powders. The purity of the samples was confirmed by X-ray powder diffraction (XRPD), and the crystallite sizes were calculated using the Scherrer method. The transmission electron microscopy (TEM) images revealed oval-shaped CuO-NPs, and the scanning electron microscopy (SEM) showed that morphological features of copper oxalate precursors and their corresponding oxides were affected by the glycerol (V/V) ratio as well as the type of C2O42- starting material. The magnetic properties of CuO-NPs were determined by measuring the temperature-dependent magnetization and the hysteresis curves at 5 and 300 K. The obtained results indicate the simultaneous coexistence of dominant antiferromagnetic and weak ferromagnetic behavior.

A facile approach for the synthesis of porous hematite and magnetite nanoparticles through sol-gel self-combustion.

Porous magnetite (Fe3O4) and hematite (α-Fe2O3) nanoparticles were prepared via the sol-gel auto-combustion method. The gels were prepared by reacting ferric nitrates (as oxidants) with starch (as fuel) at an elevated temperature of 200 °C. Different ratios (Φ) of ferric nitrates to starch were used for the synthesis (Φ = fuel/oxidant). The synthesized iron oxides were characterized by Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmet-Teller (BET) and vibrating sample magnetometer (VSM) analysis techniques. The crystal structure, morphology, and specific surface area of the iron oxide nanoparticles (Fe3O4 and α-Fe2O3) were found to be dependent on the starch content. The FT-IR, XRD and VSM analysis of the iron oxides for Φ = 0.3 and 0.7 confirmed the formation of the α-Fe2O3 core, whereas at Φ = 1, 1.7, and 2 showed that Fe3O4 cores were formed with the highest saturation magnetization of 60.36 emu/g at Φ = 1. The morphology of the Fe3O4 nanoparticles exhibited a quasi-spherical shape, while α-Fe2O3 nanoparticles appeared polygonal and formed clusters. The highest specific surface area was found to be 48 m2 g-1 for Φ = 1.7 owing to the rapid thermal decomposition process. Type II and type III isotherms indicated mesoporous structures.

Highly Selective Copper Ion Imprinted Clay/Polymer Nanocomposites Prepared by Visible Light Initiated Radical Photopolymerization.

There is an urgent demand worldwide for the development of highly selective adsorbents and sensors of heavy metal ions and other organic pollutants. Within these environmental and public health frameworks, we are combining the salient features of clays and chelatant polymers to design selective metal ion adsorbents. Towards this end, the ion imprinting approach has been used to develop a novel nanohybrid material for the selective separation of Cu2+ ions in an aqueous solution. The Cu2+-imprinted polymer/montmorillonite (IIP/Mt) and non-imprinted polymer/montmorillonite (NIP/Mt) nanocomposites were prepared by a radical photopolymerization process in visible light. The ion imprinting step was indeed important as the recognition of copper ions by IIP/Mt was significantly superior to that of NIP/Mt, i.e., the reference nanocomposite synthesized in the same way but in the absence of Cu2+ ions. The adsorption process as batch study was investigated under the experimental condition affecting same parameters such as contact time, concentration of metal ions, and pH. The adsorption capacity of Cu2+ ions is maximized at pH 5. Removal of Cu2+ ion achieved equilibrium within 15 min; the results obtained were found to be fitted by the pseudo-second-order kinetics model. The equilibrium process was well described by the Langmuir isothermal model and the maximum adsorption capacity was found to be 23.6 mg/g. This is the first report on the design of imprinted polymer nanocomposites using Type II radical initiators under visible light in the presence of clay intercalated with hydrogen donor diazonium. The method is original, simple and efficient; it opens up new horizons in the general domain of clay/polymer nanocomposites.

Towards sustainable removal of methylthioninium chloride by using adsorption-electroradical regeneration.

The current need for effective regeneration processes to be used in valorization of spent adsorbent demands the research of novel alternative techniques such as application of Advances Oxidation Processes. In this sense, the recent application of electroradical (ER) processes turned out to be very promising in terms of the drugs degradation from different environments. Thus, in this study, harnessing of a low cost natural adsorbent, Tunisian bentonite (BE), was evaluated for the removal of a model drug such as methylthioninium chloride (MC), and then its regeneration by ER processes was demonstrated. Initially, the BE was characterized and the adsorption of the MC was studied. This process followed a pseudo-first order kinetic and Langmuir isotherm fitted well to data reaching uptake values around 145-155 mg g-1. After that, BE regeneration by an ER process such as electro-Fenton process was ascertained. Due to the high buffering capacity of the BE, the addition of citric acid (1 mM) was necessary in order to assure the acidic medium to favor the oxidation reaction. By operating under optimized experimental conditions (current intensity 300 mA, pH 3, Fe2+ (1 mM) and citric acid (1 mM)) near complete adsorbent regeneration was achieved after 300 min of treatment and the pseudo-first-order model fitted well the degradation data. Furthermore, the adsorbent was efficiently used in successive cycles of adsorption-regeneration without operational problems that proved the efficiency of this technology. From the obtained results, a side-by-side configuration was designed and simulated, confirming the viability of the design at large scale.

Electrochemical treatment of aqueous solutions of organic pollutants by electro-Fenton with natural heterogeneous catalysts under pressure using Ti/IrO2-Ta2O5 or BDD anodes.

The treatment of toxic organic pollutants by electro-Fenton (EF) presents some drawbacks such as the necessity to work at low pH and the low solubility of oxygen in water contacted with air or oxygen at room pressure that results often in slow and relatively low abatements. Here, the coupled adoption of natural heterogeneous catalysts and of relatively high pressure was proposed in order to improve the performances of EF for the treatment of organic pollutants. Caffeic acid (CA) and 3-chlorophenol were used as model resistant organic pollutants. EF process was performed using both conventional homogeneous FeSO4 and natural heterogeneous catalysts (pyrite, chalcopyrite, Fe2O3 and Fe3O4) as iron catalysts and oxygen at various pressures in the absence or in the presence of BDD anode. The effect of the nature of the catalyst, the oxygen pressure, the current density and the catalyst load was widely investigated in order to optimize the process. It was shown that the coupled utilization of a natural heterogeneous catalyst such as chalcopyrite and a relatively high pressure allows to obtain the total removal of CA and a high removal of the TOC (about 75%) in short times (2 h) with relatively high current efficiencies using an Iridium based anode. In the case of 3-chlorophenol, the utilization of a BDD anode was necessary to achieve a high removal of the pollutant and the TOC. It was shown that the removal of 3-chlorophenol can be effectively performed in different water bodies and with different initial concentrations of 3-chlorophenol.

Electro-Fenton oxidation of reverse osmosis concentrate from sanitary landfill leachate: Evaluation of operational parameters.

The electro-Fenton oxidation of a concentrate from reverse osmosis of a sanitary landfill leachate, with an initial chemical oxygen demand (COD) of 42 g L-1, was carried out using a carbon-felt cathode and a boron doped diamond anode. The influence of the applied current intensity, initial pH and dissolved iron initial concentration on the electro-Fenton process was assessed. For the experimental conditions used, results showed that the initial pH is the parameter that more strongly influences the current efficiency of the electro-Fenton process, being this influence more pronounced on the oxidation rate than on the mineralization rate of the organic matter. The increase in iron initial concentration was found to be detrimental, since the natural amount of iron present in the effluent, 73 mg L-1 of total iron and 61 mg L-1 of dissolved iron, was sufficient to ensure the electro-Fenton process at the applied intensities - 0.2-1.4 A. For the more favourable conditions studied, initial pH of 3 and natural iron concentration, it was found an increase in the organic load and nitrogen removals with the applied current intensity. For the highest current intensity applied, a COD removal of 16.7 g L-1 was achieved after 8-h experiments.

Electrochemical treatment of concentrate from reverse osmosis of sanitary landfill leachate.

Conventional sanitary landfill leachate treatment has recently been complemented and, in some cases, completely replaced by reverse osmosis technology. Despite the good quality of treated water, the efficiency of the process is low and a large volume of reverse osmosis concentrate has to be either discharged or further treated. In this study, the use of anodic oxidation combined with electro-Fenton processes to treat the concentrate obtained in the reverse osmosis of sanitary landfill leachate was evaluated. The anodic oxidation pretreatment was performed in a pilot plant using an electrochemical cell with boron-doped diamond electrodes. In the electro-Fenton experiments, a boron-doped diamond anode and carbon-felt cathode were used, and the influence of the initial pH and iron concentration were studied. For the experimental conditions, the electro-Fenton assays performed at an initial pH of 3 had higher organic load removal levels, whereas the best nitrogen removal was attained when the electrochemical process was performed at the natural pH of 8.8. The increase in the iron concentration had an adverse impact on treatment under natural pH conditions, but it enhanced the nitrogen removal in the electro-Fenton assays performed at an initial pH of 3. The combined anodic oxidation and electro-Fenton process is useful for treating the reverse osmosis concentrate because it is effective at removing the organic load and nitrogen-containing species. Additionally, this process potentiates the increase in the biodegradability index of the treated effluent.

A comparative study in fixation methods of medial malleolus fractures between tension bands wiring and screw fixation.

OBJECTIVES: The aim of this study is to compare two methods of internal fixations of fractured medial malleolus which are simple screw fixation and tension band wiring. PATIENTS AND METHODS: Over 5 years we grouped 20 patients with fractured medial malleolus into two groups of operative treatments, group1 treated by malleolar screw fixation and group2 by tension band wiring. The patients were with same age group, gender, fracture type, and etiology. We use statistical analysis for make a comparative study between the two ways of surgical treatment. RESULTS: The mean time for radiologic bone union was 11.8 weeks in group1 patients and 9.4 weeks in group2 patients (P = 0.03). No patients had any sign of fixation failure or Kirschner wires migration. According to the modified ankle scoring system of Olerud and Molander, excellent and good results were achieved in 80 % in group1 patients and 90 % in group2 patients (P = 0.049). CONCLUSIONS: Tension-band wiring may be better treatment option for internal fixation of medial malleolar fractures than screw fixation. RECOMMENDATIONS: From these findings we recommend a further randomized clinical trial of larger number of cases and longer follow-up duration in order to regard tension-band wiring a better operative option for fixation of medial malleolar fractures.

Pyrite as a sustainable catalyst in electro-Fenton process for improving oxidation of sulfamethazine. Kinetics, mechanism and toxicity assessment.

The degradation of 0.20 mM sulfamethazine (SMT) solutions was investigated by heterogeneous electro-Fenton (EF) process using pyrite as source of Fe(2+) (catalyst) and pH regulator in an undivided electrochemical cell equipped either with a Pt or a BDD anode and carbon-felt as cathode. Effect of pyrite concentration and applied current on the oxidative degradation kinetics and mineralization efficiency has been studied. The higher oxidation power of the process, named "Pyrite-EF″ using BDD anode was demonstrated. Pyrite-EF showed a better performance for the oxidation/mineralization of the drug SMT in comparison to the classic EF process: 95% and 87% TOC removal by Pyrite-EF with BDD and Pt anodes, respectively, versus 90% and 83% by classical EF with BDD and Pt anodes, respectively. The rate constant of the oxidation of SMT by OH was determined by the competition kinetics method and found to be 1.87 × 10(9) mol(-1) L s(-1). Based on the identified reaction intermediates by HPLC and GS-MS, as well as released SO4(2-), NH4(+) and NO3(-) ions, a plausible reaction pathway was proposed for the mineralization of SMT during Pyrite-EF process. Toxicity assessment by means of Microtox method revealed the formation of some toxic intermediates during the treatment. However, toxicity of the solution was removed at the end of treatment.

Electrochemical mineralization of the antibiotic levofloxacin by electro-Fenton-pyrite process.

Levofloxacin is a large spectrum antibiotic from fluoroquinolones family, widely used and detected in natural waters. Here, this drug was degraded by a novel heterogeneous electro-Fenton (EF) process, so-called EF-pyrite, in which pyrite powder in suspension regulates the solution pH to 3.0 and supplies 0.2mM Fe(2+) as catalyst to the solution. Trials were performed with a stirred boron-doped diamond (BDD)/carbon-felt cell under O2 bubbling for cathodic H2O2 generation. Hydroxyl radicals formed from water oxidation at the BDD anode and in the bulk from Fenton's reaction between Fe(2+) and H2O2 were the main oxidizing agents. The effect of applied current and antibiotic concentration over the mineralization rate and degree, mineralization current efficiency and specific energy consumption was studied. An almost total mineralization was achieved for a 0.23mM drug solution operating at 300mA for 8h. The kinetic decay of the drug was followed by reversed-phase HPLC and obeyed a pseudo-first-order reaction. Ion-exclusion HPLC analysis of treated solutions revealed that oxalic and oxamic acids, the most persistent final products, were the predominant pollutants remaining in solution at long electrolysis time. Ion chromatography analysis confirmed the release of F(-), NO3(-) and NH4(+) ions during levofloxacin mineralization.

Complete removal of AHPS synthetic dye from water using new electro-fenton oxidation catalyzed by natural pyrite as heterogeneous catalyst.

The mineralization of a new azo dye - the (4-amino-3-hydroxy-2-p-tolylazo-naphthalene-1-sulfonic acid) (AHPS) - has been studied by a novel electrochemical advanced oxidation process (EAOP), consisting in electro-Fenton (EF) oxidation, catalyzed by pyrite as the heterogeneous catalyst - the so-called 'pyrite-EF'. This solid pyrite used as heterogeneous catalyst instead of a soluble iron salt, is the catalyst the system needs for production of hydroxyl radicals. Experiments were performed in an undivided cell equipped with a BDD anode and a commercial carbon felt cathode to electrogenerate in situ H2O2 and regenerate ferrous ions as catalyst. The effects on operating parameters, such as applied current, pyrite concentration and initial dye content, were investigated. AHPS decay and mineralization efficiencies were monitored by HPLC analyses and TOC measurements, respectively. Experimental results showed that AHPS was quickly oxidized by hydroxyl radicals (OH) produced simultaneously both on BDD surface by water discharge and in solution bulk from electrochemically assisted Fenton's reaction with a pseudo-first-order reaction. AHPS solutions with 175 mg L(-1) (100 mg L(-1) initial TOC) content were then almost completely mineralized in 8h. Moreover, the results demonstrated that, under the same conditions, AHPS degradation by pyrite electro-Fenton process was more powerful than the conventional electro-Fenton process.

Degradation of tyrosol by a novel electro-Fenton process using pyrite as heterogeneous source of iron catalyst.

Tyrosol (TY) is one of the most abundant phenolic components of olive oil mill wastewaters. Here, the degradation of synthetic aqueous solutions of 0.30 mM TY was studied by a novel heterogeneous electro-Fenton (EF) process, so-called EF-pyrite, in which pyrite powder was the source of Fe(2+) catalyst instead of a soluble iron salt used in classical EF. Experiments were performed with a cell equipped with a boron-doped diamond anode and a carbon-felt cathode, where TY and its products were destroyed by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between Fe(2+) and H2O2 generated at the cathode. Addition of 1.0 g L(-1) pyrite provided an easily adjustable pH to 3.0 and an appropriate 0.20 mM Fe(2+) to optimize the EF-pyrite treatment. The effect of current on mineralization rate, mineralization current efficiency and specific energy consumption was examined under comparable EF and EF-pyrite conditions. The performance of EF-pyrite was 8.6% superior at 50 mA due to self-regulation of soluble Fe(2+) by pyrite. The TY decay in this process followed a pseudo-first-order kinetics. The absolute rate constant for TY hydroxylation was 3.57 × 10(9) M(-1) s(-1), as determined by the competition kinetics method. Aromatic products like 3,4-dihydroxyphenylethanol, 4-hydroxyphenylacetic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid and catechol, as well as o-benzoquinone, were identified by GC-MS and reversed-phase HPLC. Short-chain aliphatic carboxylic acids like maleic, glycolic, acetic, oxalic and formic were quantified by ion-exclusion HPLC. Oxalic acid was the major and most persistent product found. Based on detected intermediates, a plausible mineralization pathway for TY by EF-pyrite was proposed.

2-Phenyl-anilinium dihydrogen phosphate.

In the crystal structure of the title compound, C(12)H(12)N(+)·H(2)PO(4) (-), the dihydrogen phosphate anions and the 2-phenyl-anilinium cations are associated via O-H⋯O and N-H⋯O hydrogen bonds so as to build inorganic layers around the x = 1/2 plane. The organic entities are anchored between these layers through C-H⋯O hydrogen bonds, forming a three-dimensional infinite network. The dihedral angle between the aromatic rings is 44.7 (4)°.