Valorization of loquat seeds by hydrothermal carbonization for the production of hydrochars and aqueous phases as added-value products.

In the framework of circular bio-economy, waste loquat seeds were utilized for the production of two added-value products. The seeds were hydrothermally carbonized at a temperature range of 150-250 °C and time range 2-6 h and the resultant hydrochars and aqueous phases were characterized using various methods. The optimum higher heating value of 30.64 MJ kg-1, ash content of 1.99 wt % and alkali index of 0.05 were achieved for the hydrochar prepared at 250 °C and 6 h, establishing its suitability for energy-related applications. The aqueous phase obtained at 250 °C and 6 h achieved 90% scavenging of the 2,2-diphenyl-1-picryl-hydrazyl-hydrate (DPPH) radical and had a IC50 value of 43.71 µg mL-1. Principal component analysis showed that the production of phenols, ketones, alkenes and organic acids was favored at >200 °C, whereas furans and aldehydes were primarily formed at 150 °C. Conclusively, both added-value products were obtained at the same optimum hydrothermal carbonization conditions of 250 °C and 6 h treatment time. In a bio-refinery context, this has the practical implication that both bio-products be obtained simultaneously, without the need to switch between different temperatures and residence times.

Removal of imipramine using advanced oxidation processes: Degradation products and toxicity evolution.

Pharmaceuticals are frequently detected in natural and wastewater bodies, and are very important in environmental toxicology because of their stable nature. Advanced oxidation methods used to remove contaminants are of great benefit, especially removing pharmaceuticals unsuitable for biodegradation. In this study, imipramine was degraded by anodic oxidation and subcritical water oxidation, which are advanced oxidation methods. The determination of degradation products was performed by Q-TOF LC/MS analysis. The genotoxicity and cytotoxicity of the degradation samples were determined by the in vivo Allium Cepa method. Among the anodic oxidation samples, the lowest cytotoxicity was obtained after using 400 mA current, and 420 min of degradation time. No cytotoxic effect was observed in any subcritical water oxidation sample. However, when 10 mM hydrogen peroxide as an oxidant was used at 150 °C and the reaction time was 90 min, the subcritical water oxidation sample showed a genotoxic effect. The results of the study showed that it is crucial to evaluate the toxicity levels of the degradation products and which advanced oxidation methods are preferred for removing imipramine. The optimum conditions determined for both oxidation methods can be used as a preliminary step for biological oxidation methods in the degradation of imipramine.

Degradation of emerging contaminant coumarin based on anodic oxidation, electro-Fenton and subcritical water oxidation processes.

The degradation of emerging contaminant coumarin was separately investigated in anodic, electro-Fenton and subcritical water oxidation processes. With respect to the anodic and electro-Fenton oxidation, the influence of constant current, treatment time and initial concentration of coumarin was studied. Regarding subcritical water oxidation, the effect of the oxidant concentration, temperature, treatment time and initial coumarin concentration was investigated. In anodic and electro-Fenton oxidation processes, coumarin degradation proceeded in a similar manner, achieving 99% degradation, after 180 min at a constant current of 200 mA. In both set-ups, further increasing the applied current lowered the degradation efficiency due to the formation of by-products and the increasing occurrence of side-reactions. The highest degradation of 88% was achieved in subcritical conditions, specifically at 200 °C, using 150 mM H2O2 and after 37.5 min of treatment. Under subcritical conditions, temperature was the most prominent parameter, followed by the H2O2 concentration. Under all methodologies, increasing treatment time had a small positive effect on coumarin degradation, indicating that time is not the most influential parameter. A comparison of the three methodologies in terms of performance as well as energy consumption and simplicity of operation highlighted the advantages of subcritical water oxidation.

Hydrothermal Synthesis of Siderite and Application as Catalyst in the Electro-Fenton Oxidation of p-Benzoquinone.

A weak aspect of the electro-Fenton (EF) oxidation of contaminants is the dependence of the Fenton reaction on acidic pH values. Therefore, the rationale of this work was to develop a novel catalyst capable of promoting the EF oxidation process at near-neutral and basic pH values. In this framework, rhombohedral FeCO3 was synthesized hydrothermally and used as a catalyst in the EF oxidation of p-benzoquinone (BQ). The catalyst was characterized using various surface and spectroscopic methods. Moreover, the effects of applied current (100-500 mA), time (1-9 h), catalyst dosage (0.25-1.00 g L-1), and initial concentration of BQ (0.50-1.00 mM) on the total organic carbon removal efficiency were determined. The results indicated that a 400 mA current was sufficient for a 95% total organic carbon removal and that the increase in catalyst dosage had a positive effect on the mineralization of BQ. It was determined that at pH 3, FeCO3 behaved like a homogeneous catalyst by releasing Fe3+ ions; whereas, at the pH range of 5-7, it shifted to a homogeneous/heterogeneous catalyst. At pH 9, it worked solely as a heterogeneous catalyst due to the decrease of Fe ions passing into the solution. Finally, the spent catalyst did not undergo structural deformations after the EF treatment at higher pH values and could be regenerated and used several times.

Subcritical water oxidation of propham by H2O2 using response surface methodology (RSM).

This study was conducted to investigate the degradation of propham, which is a compound that pollutes water and seriously threatens human health, by subcritical water oxidation and using H2O2 as an oxidising agent. The maximum total organic carbon removal rate of propham was obtained as 73.65% at 40 min of treatment time and 60 mM of H2O2 concentration and 373 K of temperature. In addition, response surface method based on the Box-Behnken design was applied to design the degradation experiments of propham for determination of the combined effects of process variables, namely temperature, concentration of oxidising agent and treatment time. The proposed quadratic model of propham degradation, which was examined with the analysis of variance, was used for navigating the design space. The R2 and adjusted R2 values of the model were determined as 0.9921 and 0.9819 respectively. It was shown that propham was effectively degraded, thus could be removed from the water by using an environmentally friendly method.

Degradation of isoniazid by anodic oxidation and subcritical water oxidation methods: Application of Box-Behnken design.

Pharmaceutical compounds released into the aquatic environment are known to cause toxic effects on the environment. Isoniazid is widely used in the treatment of tuberculosis and is, therefore, frequently encountered in environmental waters. In this study, the degradation of isoniazid was investigated by anodic oxidation and subcritical water oxidation method which are members of Advanced Oxidation Processes. The Box-Behnken Design was used to determine the effects of current, initial concentration, and electrolysis time on mineralization in the anodic oxidation process, which carried out a cell with a Pt cathode and boron-doped diamond anode. The highest mineralization value of 78.14% was achieved at optimal conditions of 300 mA, 3 h, and 100 mg/L initial concentration. The degradation of Isoniazid was also investigated under subcritical water conditions using an ecological oxidizing agent, H2O2. The maximum mineralization rate of 72.23% was obtained when 100 mM H2O2 was used for a 90 min treatment at 125 °C for 100 mg/L Isoniazid solution in the subcritical water oxidation process. The LC-MS results showed that the degradation products obtained by AO and SWO methods were different from each other. Finally, possible degradation mechanisms are proposed according to the degradation products obtained for both processes.

A dual purpose aluminum-based metal organic framework for the removal of chloramphenicol from wastewater.

The presence of antibiotics in the aquatic environment can cause significant environmental and human health problems even at trace concentrations. Conventional treatment systems alone are ineffective in removing these resistant antibiotics. To address this problem, oxidation and adsorption techniques were used to explore the removal of recalcitrant antibiotic chloramphenicol (CAP). An aluminum-based metal-organic framework (Al-MIL) with high surface area and extended porosity, was prepared and used both as adsorbent and catalyst for the oxidation of CAP. Characterization of the Al-MIL revealed a large surface area of 1137 m2 g-1, a homogeneous microporous structure, good crystallinity, and particle size in the range of 200-400 nm. Adsorption of CAP on Al-MIL achieved equilibrium after 1 h, reaching a maximum adsorption capacity of 96.1 mg g-1 at the optimum pH value of 5.3. The combination of adsorption and oxidation did not improve the % TOC reduction considerably, indicating an antagonistic rather than synergistic effect between the two processes. Oxidation alone in the presence of persulfate, achieved a % TOC reduction of 71% after 2 h, compared to 56% achieved by adsorption alone at the same duration. The optimum persulfate concentration was determined as 2.5 mM. The Al-MIL structure did not demonstrate any substantial deterioriation after six repeated runs, according to the reusability experiments.

CoFe2O4 nanoparticles decorated onto graphene oxide and graphitic carbon nitride layers as a separable catalyst for ultrasound-assisted photocatalytic degradation of Bisphenol-A.

The advanced oxidation process (AOP) through ultrasound-assisted photocatalytic degradation has attracted much attention in removing emerging contaminants. Herein, CoFe2O4-GO and CoFe2O4-g-C3N4 nanocomposites were synthesized using the ultrasound-assisted co-precipitation method. TEM, XRD, XPS, EDS, SEM, and FT-IR techniques characterized the structural, morphological, and chemical properties of the synthesized nanocomposites. The analyses showed that CoFe2O4 structure was nano-sized and distributed more homogeneously in graphene oxide (GO) layers with oxygenated functional groups than graphitic carbon nitride (g-C3N4). While the efficiency of composite catalysts, as photocatalysts, for degradation of bisphenol-A (BPA) was low in the visible region in the presence of persulfate, their catalytic efficacy was higher with sonolytic activation. The addition of persulfate as an oxidant remarkably enhanced the target pollutant degradation and TOC removal of BPA solution. Both composite catalysts showed 100 % BPA removal with the synergistic effect of visible region photocatalytic oxidation and sonocatalytic oxidation in the presence of persulfate at pH 6.8. In ultrasound-assisted photocatalytic oxidation of BPA, the highest mineralization efficiencies were obtained at 2 h treatment time, pH 6.8, 16 mM PS, catalyst dosages of 0.1 g/L CoFe2O4-GO, and 0.4 g/L CoFe2O4-g-C3N4 as 62 % and 55 %, respectively. An effective catalyst was obtained by reducing e-/h+ recombination and charge transfer resistance by decorating the GO layers with CoFe2O4.