A novel and sustainable composite of L@PSAC for superior removal of pharmaceuticals from different water matrices: Production, characterization, and application.

This study endeavors to develop cost-effective environmentally friendly technology for removing harmful residual pharmaceuticals from water and wastewater by utilizing the effective adsorption of pistachio shell (PS) biochar and the degradation potency of laccase immobilized on the biochar (L@PSAC). The carbonatization and activation of the shells were optimized regarding temperature, time, and NH4NO3/PS ratio. This step yielded an optimum PS biochar (PSAC) with the highest porosity and surface area treated at 700 °C for 3 h using an NH4NO3/PS ratio of 3% wt. The immobilization of laccase onto PSAC (L@PSAC) was at its best level at pH 5, 60 U/g, and 30 °C. The optimum L@PSAC maintained a high level of enzyme activity over two months. Almost a complete removal (>99%) of diclofenac, carbamazepine, and ciprofloxacin in Milli-Q (MQ) water and wastewater was achieved. Adsorption was responsible for >80% of the removal and the rest was facilitated by laccase degradation. L@PSAC maintained effective removal of pharmaceuticals of ≥60% for up to six treatment cycles underscoring the promising application of this material for wastewater treatment. These results indicate that activated carbon derived from the pistachio shell could potentially be utilized as a carrier and adsorbent to efficiently remove pharmaceutical compounds. This enzymatic physical elimination approach has the potential to be used on a large-scale.

A sustainable nano-hybrid system of laccase@M-MWCNTs for multifunctional PAHs and PhACs removal from water, wastewater, and lake water.

This study examined the use of modified multiwall carbon nanotubes (M-MWCNTs) with immobilized laccase (L@M-MWCNTs) for removing ciprofloxacin (Cip), carbamazepine (Cbz), diclofenac (Dcf), benzo[a]pyrene (Bap), and anthracene (Ant) from different water samples. The synthesized materials were characterized using an array of advanced analytical techniques. The physical immobilization of laccase onto M-MWCNTs was confirmed through Scanning electron microscope (SEM)-dispersive X-ray spectroscopy (EDS) analysis and Brunner-Emmet-Teller (BET) surface area measurements. The specific surface area of M-MWCNTs decreased by 65% upon laccase immobilization. There was also an increase in nitrogen content seen by EDS analysis asserting successful immobilization. The results of Boehm titration and Fourier transform infrared (FTIR) exhibited an increase in acidic functional groups after laccase immobilization. L@M-MWCNTs storage for two months maintained 77.8%, 61.6%, and 57.6% of its initial activity for 4 °C, 25 °C, and 35 °C, respectively. In contrast, the free laccase exhibited 55.3%, 37.5%, and 23.5% of its initial activity at 4 °C, 25 °C, and 35 °C, respectively. MWCNTs improved storability and widened the working temperature range of laccase. The optimum removal conditions of studied pollutants were pH 5, 25 °C, and 1.6 g/L of M-MWCNTs. These parameters led to >90% removal of the targeted pollutants for four treatment cycles of both synthetic water and spiked lake water. L@M-MWCNTs demonstrated consistent removal of >90% for up to five cycles even with spiked wastewater. The adsorption was endothermic and followed Langmuir isotherm. Oxidation, dehydrogenation, hydroxylation, and ring cleavage seem to be the dominant degradation mechanisms.

Glass Fibre-Reinforced Extrusion 3D-Printed Composites: Experimental and Numerical Study of Mechanical Properties.

The properties of 3D-printed bodies are an essential part of both the industrial and research sectors, as the manufacturers try to improve them in order to make this now additive manufacturing method more appealing compared to conventional manufacturing methods, like injection moulding. Great achievements were accomplished in both 3D printing materials and machines that made 3D printing a viable way to produce parts in recent years. However, in terms of printing parameters, there is still much room for advancements. This paper discusses four of the 3D printing parameters that affect the properties of the final products made by chopped glass fibre-filled nylon filaments; these parameters are the printing temperature, nozzle diameter, layer height, and infill orientation. Furthermore, a polynomial function was fitted to the measured data points, which made it possible to calculate the tensile strength, flexural strength, and Young's modulus of the 3D-printed samples based on their printing parameters. A Pearson correlation analysis was also carried out to determine the impact of each parameter on all three mechanical properties studied. Both the infill orientation and printing temperature had a significant effect on both strengths and Young's modulus, while the effect of nozzle diameters and layer heights were dependent on the infill orientation used. Also, a model with excellent performance was established to predict the three mechanical properties of the samples based on the four major parameters used. As expected from a fibre-reinforced material, the infill orientation had the most significant effect on the tensile strength, flexural strength, and Young's modulus. The temperature was also quite significant, while the nozzle diameters and layer height effect were situational. The highest values for the tensile strength, flexural strength, and Young's modulus were 72 MPa, 78.63 MPa, and 4243 MPa, respectively, which are around the same values the manufacturer states.

Studying the effect of reactor design on the electrocoagulation treatment performance of oily wastewater.

Several conventional methods are employed to remove numerous pollutants from oily wastewater discharged from oil-field activities. The purpose of this study is to use a new design of an electrocoagulation reactor (ECR) to treat oily wastewater effluents from the Al-Muthanna petroleum plant to minimize a Total Dissolved Solids (TDS) to levels suitable for employment. In a continuous ECR, a One-Sided-Finned cathode tube (1SF) made of aluminum was inserted between a pair of aluminum-cylindrical anodes. The effects of the electrolysis period (4-60 min), current density (0.63-5.0 mA/cm2), and flow rate (50-150 ml/min) on Final TDS value were investigated. The increment of flow rate causes the final TDS value to be increased, while the extending of the electrolysis process and the raise in current density reduces it. The final TDS was 1842.54 mg/l (reduce by 307.46 mg/l) at optimum values of 1-h electrolysis, 5 mA/cm2 current density, and 50 ml/min flow rate, with an inner anode consumption of 0.13 g and an outer anode consumption of 0.43 g. Regression models with a p-value of 0.001 and F-value of 27.01 noted that the selected model components were important, and the estimated model is considered prominent. Furthermore, the regression coefficient (R2 = 97.99%) for the final TDS response revealed that the model fit the data well. This study confirmed the ability of the new electrocoagulation reactor to treat petroleum wastewater under significant conditions which overcomes the drawbacks of the conventional designs of electrocoagulation reactors.

Efficient removal of pharmaceutical contaminants from water and wastewater using immobilized laccase on activated carbon derived from pomegranate peels.

In this study, pomegranate peels (PPs) as an abundant fruit processing waste was used to produce cost-effective, eco-friendly, and high-quality activated carbon. The produced carbon (fossil free activated carbon) was used for immobilizing laccase to remove a range of emerging pollutants namely diclofenac, amoxicillin, carbamazepine, and ciprofloxacin from water and wastewater. The loaded activated carbon by laccase (LMPPs) and the unloaded one (MPPs) were characterized using advanced surface chemistry analysis techniques. MPPs was found to have a porous structure with a large surface area and an abundance of acidic functional groups. Laccase immobilization reduced surface area but added active degradation sites. The optimal immobilization parameters were determined as pH 4, 35 °C, and a laccase concentration of 2.5 mg/mL resulting in a 69.8% immobilization yield. The adsorption of the emerging pollutant onto MPPs is best characterized as a spontaneous endothermic process that adheres to the Langmuir isotherm and first-order kinetics. Using synergistic adsorption and enzymatic degradation, the target pollutants (50 mg/L) were eliminated in 2 h. In both water types, LMPPs outperformed MPPs. This study shows that pomegranate peels can effectively be harnessed as an enzyme carrier and adsorbent for the removal of emerging pollutants even from a complex sample matrix. The removal of contaminants from wastewater lasted five cycles, whereas it continued up to six cycles for water.

Ketoprofen and aspirin removal by laccase immobilized on date stones.

In recent years, enzymatic remediation/biocatalysis has gained prominence for the bioremediation of recalcitrant chemicals. Laccase is one of the commonly investigated enzymes for bioremediation applications. There is a growing interest in immobilizing this enzyme onto adsorbents for achieving high pollutant removal through simultaneous adsorption and biodegradation. Due to the influence of the biomolecule-support interface on laccase activity and stability, it is crucial to functionalize the solid carrier prior to immobilization. Date stone (PDS), as an eco-friendly, low-cost, and effective natural adsorbent, was utilized as a carrier for laccase (fungus Trametes versicolor). After activating PDS through chemical treatments, the surface area increased by thirty-six-fold, and carbonyl groups became more prominent. Batch experiments were carried out for ketoprofen and aspirin biodegradation in aqueous solutions. After six cycles, the laccase maintained 54% of its original activity confirmed by oxidation tests of 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) (ABTS). In addition, the storage, pH, and thermal stability of immobilized laccase on functionalized date stone (LFPDS) were found to be superior to that of free laccase, demonstrating its potential for ongoing applications. In the aqueous batch mode, this immobilized laccase system was used to degrade 25 mg L-1 of ketoprofen and aspirin, resulting in almost complete removal within 4 h of treatment. This study reveals that agricultural wastes such as date stone can successfully be valorized through simple activation techniques, and the final product can be used as an adsorbent and substrate for immobilization enzyme. The high efficiency of the LFPDS in removing ketoprofen and aspirin highlights the potential of this technology for removing pharmaceuticals and merits its continued development.

Characterization of Various Titanium-Dioxide-Based Catalysts Regarding Photocatalytic Mineralization of Carbamazepine also Combined with Ozonation.

Titanium-dioxide-based semiconductors proved to be appropriate for photocatalytic application to efficiently degrade emerging organic pollutants such as various herbicides, pesticides, and pharmaceuticals in waters of environmental importance. The characterization of various TiO2 catalysts, both bare and modified (Ag- and/or N-doped), by mechanochemical treatment was carried out in this work, regarding their structure, morphology, and photocatalytic activity. For the latter investigations, carbamazepine, an antidepressant, proved to be applicable and versatile. The photocatalytic behavior of the catalysts was studied under both UV and visible light. Besides the decomposition efficiency, monitoring the intermediates provided information on the degradation mechanisms. Mechanochemical treatment significantly increased the particle size (from 30 nm to 10 µm), causing a considerable (0.14 eV) decrease in the band gap. Depending on the irradiation wavelength and the catalyst, the activity orders differed, indicating that, in the mineralization processes of carbamazepine, the importance of the different oxidizing radicals considerably deviated, e.g., Ag-TiO2 < DP25-TiO2 < ground-DP25-TiO2 < N-TiO2 ≈ N-Ag-TiO2 for O2•− and N-TiO2 ≈ Ag-TiO2 < N-Ag-TiO2 < ground-DP25-TiO2 ≈ DP25-TiO2 for HO• generation under UV irradiation. Toxicity studies have shown that the resulting intermediates are more toxic than the starting drug molecule, so full mineralization is required. This could be realized by a synergistic combination of heterogeneous photocatalysis and ozonation.

Functionally Graded Al2O3-CTZ Ceramics Fabricated by Spark Plasma Sintering.

We studied the fabrication of functionally graded Al2O3-CeO2-stabilized-ZrO2 (CTZ) ceramics by spark plasma sintering. The ceramic composite exhibits a gradual change in terms of composition and porosity in the axial direction. The composition gradient was created by layering starting powders with different Al2O3 to CTZ ratios, whereas the porosity gradient was established with a large temperature difference, which was induced by an asymmetric graphite tool configuration during sintering. SEM investigations confirmed the development of a porosity gradient from the top toward the bottom side of the Al2O3-CTZ ceramic and the relative pore volume distributed in a wide range from 0.02 to 100 µm for the samples sintered in asymmetric configuration (ASY), while for the reference samples (STD), the size of pores was limited in the nanometer scale. The microhardness test exhibited a gradual change along the axis of the ASY samples, reaching 10 GPa difference between the two opposite sides of the Al2O3-CTZ ceramics without any sign of delamination or cracks between the layers. The flexural strength of the samples for both series showed an increasing tendency with higher sintering temperatures. However, the ASY samples achieved higher strength due to their lower total porosity and the newly formed elongated CeAl11O18 particles.

V2O5, CeO2 and Their MWCNTs Nanocomposites Modified for the Removal of Kerosene from Water.

In this paper, the application of multiwalled carbon nanotubes (MWCNTs) based on metal oxide nanocomposites as adsorbents for the removal of hydrocarbons such as kerosene from water was investigated. Functionalized MWCNTs were obtained by chemical oxidation using concentrated sulfuric and nitric acids. V2O5, CeO2, and V2O5:CeO2 nanocomposites were prepared using the hydrothermal method followed by deposition of these oxides over MWCNTs. Individual and mixed metal oxides, fresh MWCNTs, and metal oxide nanoparticle-doped MWCNTs using different analysis techniques were characterized. XRD, TEM, SEM, EDX, AFM, Raman, TG/DTA, and BET techniques were used to determine the structure as well as chemical and morphological properties of the newly prepared adsorbents. Fresh MWCNTs, Ce/MWCNTs, V/MWCNTs, and V:Ce/MWCNTs were applied for the removal of kerosene from a model solution of water. GC analysis indicated that high kerosene removal efficiency (85%) and adsorption capacity (4270 mg/g) after 60 min of treatment were obtained over V:Ce/MWCNTs in comparison with fresh MWCNTs, Ce/MWCNTs and V/MWCNTs. The kinetic data were analyzed using the pseudo-first order, pseudo-second order, and intra-particle diffusion rate equations.

Development of Waste-Based Alkali-Activated Cement Composites.

Nowadays, global warming and the ensuing climate change are one of the biggest problems for humanity, but environmental pollution and the low ratio of waste management and recycling are not negligible issues, either. By producing alkali-activated cements (AACs), it is possible to find an alternative way to handle the above-mentioned environmental problems. First, with a view to optimizing experimental parameters, metakaolin-based AACs were prepared, and in it, waste tire rubber was used as sand replacement (5-45 wt %). Insufficient wetting between the rubber particles and the matrix was corrected through different surface treatments of the rubber. For improving the mechanical/strength properties of the specimens, fibrous waste kaolin wool (0.5-1.5 wt %) was added to the AAC matrix. Considering the results of model experiments with metakaolin, blast-furnace-slag-based AAC composites were developed. The effects of storage conditions, specimen size and cyclic loading on the compressive strength were investigated, and the resulting figures were compared with the relevant values of classic binders. The strength (44.0 MPa) of the waste-based AAC composite significantly exceeds the required value (32.5 MPa) of clinker saving slag cement. Furthermore, following cyclic compressive loading, the residual strength of the waste-based AAC composite shows a slight increase rather than a decrease.