Response surface methodology directed modeling of the biosorption of progesterone onto acid activated Moringa oleifera seed biomass: Parameters and mechanisms.

In this study, chemically activated fat-free powdered Moringa oleifera seed biomass (MOSB) was synthesized, characterized, and utilized as a cost-effective biosorbent for the abstraction of progesterone (PGT) hormone from synthetic wastewater. Natural PGT is a human steroid hormone from the progestogen family. Synthetic PGT is approved for the regulation of the menstrual cycle, aiding contraception, and is administered as a hormone replacement therapy in menopausal and post-menopausal women. PGT is an endocrine disrupting chemical (EDC) with negative health impacts on biota. The X-ray diffractogram (XRD), Scanning electron microscopy-Energy-dispersive X-ray spectroscopy (SEM-EDS), and Brunauer-Emmet-Teller (BET) analyses displayed a porous, amorphous biosorbent with an elemental composition of 72.5% carbon and 22.5% oxygen and a specific surface area of 210.0 m2 g-1. The process variables including temperature (298-338 K), pH (2-10), contact time (10-180 min), adsorbate concentration (20-500 µg L-1), and adsorbent dosage (0.1-2.0 g) were optimized using response surface methodology (RSM) to obtain the greatest efficacy of MOSB during biosorption of PGT. The optimum parameters for PGT biosorption onto MOSB were: 86.8 min, 500 µg L-1 adsorbate concentration, 298 K, and 0.1 g adsorbent dosage. PGT removal from aqueous solutions was pH-independent. The Langmuir isotherm best fitted the equilibrium data with maximal monolayer biosorption capacity of 135.8 µg g-1. The biosorption rate followed the pseudo-first-order (PFO) kinetic law. The thermodynamic functions (ΔG < 0, ΔH = -9.258 kJ mol-1 and ΔS = +44.16 J mol-1) confirmed that the biosorption of PGT onto MOSB is a spontaneous and exothermic process with increased randomness at the adsorbent surface. The biosorption mechanism was physisorption and was devoid of electrostatic interactions. The findings from this study indicate that MOSB is an inexpensive, low-carbon, and environmentally friendly biosorbent that can effectively scavenge PGT from aqueous solutions.

Modeling adsorption and photocatalytic treatment of recalcitrant contaminant on multi-walled carbon/TiO2 nanocomposite.

A nanocomposite photocatalyst consisting of titanium dioxide (TiO2) supported on multiwalled carbon nanotubes (MWCNTs) has been successfully prepared and used for the treatment of wastewater contaminated with tetracycline (TC), a recalcitrant antibiotic pollutant. The TiO2/MCNT composites were prepared by a simple evaporation-drying method. The properties of MWCNT/TiO2 were optimized by dispersing different amounts of TiO2 onto MWCNT. The structural and optical characteristics of the nano-engineered photocatalyst composite were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR) techniques. Photocatalytic degradation of TC was conducted in a quartz glass reactor. Different kinetic models were used to demonstrate the governing mechanisms. The findings revealed that the TiO2/MWCNT composite had enhanced photocatalytic activity (95% TC removal) compared to TiO2 (86% removal). The photocatalyst nanocomposite exhibited overall pseudo-second-order reaction kinetics and favored the Langmuir adsorption isotherm. Although up to 95% degradation of TC was achieved, only 75% of it was mineralized as a result of the formation of stable refractory intermediates.

Modeling ozonation pretreatment parameters of distillery wastewater for improved biodegradability.

In this study, ozonation pretreatment of real distillery wastewater (DWW) for biodegradability enhancement was undertaken. Response surface methodology was used to model the value of effective parameters, including ozonation duration and initial chemical oxygen demand (COD) concentration, and to estimate linear interactions and quadratic effects. The analysis of variance confirmed the adequate description of all the responses by the quadratic model employed. During ozonation, the pH of the DWW increased in acidity from 4.53 to 4.05, indicating the formation of acidic intermediates. A 60% reduction in color was observed signifying the oxidation of the color causing biorecalcitrant aromatic compounds and confirmed by the reduction in ultraviolet absorbance at λmax of 254 nm. Moreover, an increase in change in oxidation state from -0.1 to 0.4 was attributed to the declined aromaticity and the formation of aliphatic structures. From the measurement of the ratio of biochemical: chemical oxygen demand (BOD5:COD), an increase from 0.48 to 0.72 confirmed improved biodegradability. Optimization studies aimed at achieving maximum improved biodegradability at maximum ozone transfer efficiency yielded optimum ozonation pretreatment parameters of initial COD of 4.1 g L-1 and duration of 64 min.

Photocatalytic degradation of P-Cresol using TiO2/ZnO hybrid surface capped with polyaniline.

This study evaluated the photocatalytic activity of polyaniline (PANI)-capped titanium dioxide and zinc oxide (TiO2/ZnO) hybrid, for the degradation of P-Cresol. The hybrid was synthesized by precipitating ZnO on the surface of commercial TiO2. An "in situ" chemical oxidative polymerization method was used to prepare the PANI capped hybrid (TiO2/ZnO/PANI). The photocatalysts were characterized by powder X-ray diffraction (XRD), a Brunauer Emmett Teller (BET) analyzer, Fourier-transform infrared (FTIR) and photoluminescence spectroscopies, high resolution-transmission electron microscopy (HR-TEM) and thermogravimetric analysis (TGA). During photodegradation under ultraviolet (UV) irradiation, ZnO, TiO2, TiO2/ZnO hybrid and TiO2/ZnO/PANI composite had P-Cresol removal of 43%, 50%, 61% and 99%, respectively. The higher activity of the TiO2/ZnO hybrid as compared to TiO2 and ZnO was attributed to a reduced electron-hole pair recombination. The recombination was further significantly reduced upon introduction of PANI; hence, the highest activity observed with TiO2/ZnO/PANI. The initial reaction rate constant for TiO2/ZnO/PANI (0.9679 min-1) was more than twice compared to that for TiO2/ZnO hybrid (0.1259 min-1). A synergistic effect between PANI and TiO2/ZnO resulted in a highly efficient charge separation caused by the transfer of photogenerated holes from the hybrid to highest occupied molecular orbitals (HOMO) of PANI. The best TiO2/ZnO/PANI (PANI to TiO2/ZnO) ratio observed was 0.5:2 for the photodegradation of P-Cresol. Total organic carbon (TOC) analysis indicated a 97.4% mineralization of P-Cresol with PANI/TiO2/ZnO.

Photodecolorisation of melanoidins in vinasse with illuminated TiO2-ZnO/activated carbon composite.

A hybrid photo-catalyst, TiO2-ZnO, was synthesized by immobilizing ZnO on commercial TiO2 (aeroxide P25). Activated carbon (AC) was subsequently used to support the hybrid, thus forming a TiO2-ZnO/AC composite catalyst. Fourier transform infrared (FTIR) analysis and scanning electron microscopy integrated with energy-dispersive X-ray spectroscopy (SEM-EDX) investigations revealed successful catalyst synthesis. Optical properties of the hybrid determined from photoluminescence (PL) and Ultraviolet-visible (UV-vis) spectroscopy confirmed a restrained recombination of electron-hole pairs and reduced energy band gap due to a successful heterojunction formation. The prepared catalysts were used to photodecolorise vinasse in a 12-W UVC batch photoreactor. TiO2-ZnO had improved photocatalytic activity compared with TiO2 and ZnO separately. On supporting the hybrid onto AC, both adsorption and photocatalytic activities were further enhanced with improved overall color removal of 86% from 68%. Photodecolorisation followed the pseudo-first-order reaction model with the rate constant ([Formula: see text]) observed decreasing from 0.0701 to 0.0436 min-1 on increasing the initial concentration from 5,000 to 14,000 ppm. The UV process was found to be 33-fold less energy intensive for color reduction as compared to total organic carbon (TOC) reduction. Formation of nitrates during the photodecolorisation process was attributed to the mineralization of nitrogen heteroatoms in the color-causing melanoidin compounds.