Materials Derived from Olive Pomace as Effective Bioadsorbents for the Process of Removing Total Phenols from Oil Mill Effluents.

This work investigates olive pomace from olive mill factories as an adsorbent for the removal of total phenols from olive mill effluent (OME). This pathway of valorization of olive pomace reduces the environmental impact of OME while providing a sustainable and cost-effective wastewater treatment approach for the olive oil industry. Olive pomace was pretreated with water washing, drying (60 °C) and sieving (<2 mm) to obtain the raw olive pomace (OPR) adsorbent material. Olive pomace biochar (OPB) was obtained via carbonization of OPR at 450 °C in a muffle furnace. The adsorbent materials OPR and OPB were characterized using several basic analyzes (Scanning Electron Microscopy-Energy-Dispersive X-ray SEM/EDX, X-ray Diffraction XRD, thermal analysis DTA and TGA, Fourier transform infrared FTIR and Brunauer, Emmett and Teller surface BET). The materials were subsequently tested in a series of experimental tests to optimize the sorption of polyphenols from OME, investigating the effects of pH and adsorbent dose. Adsorption kinetics showed good correlation with a pseudo-second-order kinetic model as well as Langmuir isotherms. Maximum adsorption capacities amounted to 21.27 mg·g-1 for OPR and 66.67 mg·g-1 for OPB, respectively. Thermodynamic simulations indicated spontaneous and exothermic reaction. The rates of total phenol removal were within the range of 10-90% following 24 h batch adsorption in OME diluted at 100 mg/L total phenols, with the highest removal rates observed at pH = 10. Furthermore, solvent regeneration with 70% ethanol solution yielded partial regeneration of OPR at 14% and of OPB at 45% following the adsorption, implying a significant rate of recovery of phenols in the solvent. The results of this study suggest that adsorbents derived from olive pomace may be used as economical materials for the treatment and potential capture of total phenols from OME, also suggesting potential further applications for pollutants in industrial wastewaters, which can have significant implications in the field of environmental technologies.

Hybrid Alginate-Brushite Beads Easily Catalyze the Knoevenagel Condensation On-Water.

An innovative hybrid organic-inorganic material composed of alginate-brushite xerogel beads was successfully applied for the catalysis of the Knoevenagel condensation. The catalyst was derived from phosphated alginate xerogel microspheres formed from the ionotropic gelling effect of phosphated alginate. To this end, alginate was phosphated by the addition of diammonium hydrogen phosphate in a 1% w/w alginate gel. The phosphated alginate was subsequently precipitated by chelation of Ca2+ cations, generating a phosphated alginate hydrogel microsphere, which was washed and dried, forming hybrid organic-inorganic xerogel beads as a crystalline phosphate-rich mineral fraction covered by alginate. X-ray diffraction analysis revealed that the crystalline inorganic matrix of the material was composed predominantly of brushite. SEM analysis revealed plate-like, ribbon-like, or needle-like morphologies in the hybrid alginate-brushite beads. The hybrid material was tested as a catalyst for Knoevenagel condensation, which was performed ″on-water″ under mild conditions with aromatic aldehydes and activated methylene compounds, giving high yields (up to 97%). The reaction rate and product yield increased together with the reaction temperature for all reagents. The recyclable solid catalyst was effective for three runs, revealing the potential of the innovative hybrid catalyst as an eco-friendly heterogeneous catalyst.

Calcium-modified clinoptilolite as a recovery medium of phosphate and potassium from anaerobically digested olive mill wastewater.

Olive mill wastewater (OMW) is characterized as a high-strength effluent due to the high organic load, low biodegradability, and presence of phytotoxic compounds. Most of the OMW treatment methods proposed, including adsorption, focus mainly on the reduction of chemical oxygen demand and recovery of polyphenols. Adsorption studies aiming at nutrient removal from OMW are very limited. In the present work, Ca(OH)2-treated zeolite (CaT-Z) in a granular form was used for simultaneous recovery of phosphate (PO43-) and potassium (K+) ions from two samples of anaerobically digested OMW. Nutrient adsorption was investigated as a function of contact time, pH and dilution of OMW with deionized water. The lower removal efficiency of phosphorus (P) by CaT-Z was observed at higher dilution ratios consisted of 3.125-6.25% OMW-1 and 5% OMW-2. The maximum P removal was 73.9% in 25% OMW-1 and 85.9% in 10% OMW-2. Potassium removal, as the predominant cation of OMW samples, increased from 17.3 to 46.1% in OMW-1 and from 15.1 to 57.7% in OMW-2 with increasing dilution. The maximum experimental adsorption capacities were 15.8 mg K and 2.14 mg P per gram of CaT-Z. Five sequential treatments of 50% OMW-2 with fresh CaT-Z at each stage ensured a cumulative removal of 87.5% for P and 74.9% for K. Adsorption kinetics were faster for K than for P. The plant-available P was found to be the predominant fraction on the loaded CaT-Z. Electron Probe Micro-analysis confirmed the enhanced content of K and P on the loaded CaT-Z, whereas X-ray mapping revealed the co-distribution of Ca and P. This study demonstrates the potential usage of CaT-Z as an immobilization medium of P and K from anaerobically treated OMW.

Exponential model describing methane production kinetics in batch anaerobic digestion: a tool for evaluation of biochemical methane potential assays.

Biochemical methane potential assays, usually run in batch mode, are performed by numerous laboratories to characterize the anaerobic degradability of biogas substrates such as energy crops, agricultural residues, and organic wastes. Unfortunately, the data obtained from these assays lacks common, universal bases for comparison, because standard protocols did not diffuse to the entire scientific community. Results are usually provided as final values of the methane yields of substrates. However, methane production curves generated in these assays also provide useful information about substrate degradation kinetics, which is rarely exploited. A basic understanding of the kinetics of the biogas process may be a first step towards a convergence of the assay methodologies on an international level. Following this assumption, a modeling toolbox containing an exponential model adjusted with a simple data-fitting method has been developed. This model should allow (a) quality control of the assays according to the goodness of fit of the model onto data series generated from the digestion of standard substrates, (b) interpretation of substrate degradation kinetics, and (c) estimate of the ultimate methane yield at infinite time. The exponential model is based on two assumptions: (a) the biogas process is a two-step reaction yielding VFA as intermediate products, and methane as the final product, and (b) the digestible substrate can be divided into a rapidly degradable and a slowly degradable fraction.

Modified batch anaerobic digestion assay for testing efficiencies of trace metal additives to enhance methane production of energy crops.

Batch biochemical methane potential (BMP) assays to evaluate the methane yield of biogas substrates such as energy crops are usually carried out with undiluted inoculum. A BMP assay was performed on two energy crops (green cuttings and grass silage). Anaerobic digestion was performed both with and without supplementation of three commercial additives containing trace metals in liquid, solid or adsorbed form (on clay particles). In order to reveal positive effects of trace metal supplementation on the methane yield, besides undiluted inoculum, 3-fold and 10-fold dilutions of the inoculum were applied for substrate digestion. Diluted inoculum variants were supplemented with both mineral nutrients and pH-buffering substances to prevent a collapse of the digestion process. As expected, commercial additives had no effect on the digestion process performed with undiluted inoculum, while significant increases of methane production through trace element supplementation could be observed on the diluted variants. The effect of inoculum dilution may be twofold: (1) decrease in trace metal supplementation from the inoculum and (2) reduction in the initial number of bacterial cells. Bacteria require higher growth rates for substrate degradation and hence have higher trace element consumption. According to common knowledge of the biogas process, periods with volatile fatty acids accumulation and decreased pH may have occurred in the course ofanaerobic digestion. These effects may have led to inhibition, not only ofmethanogenes and acetogenes involved in the final phases of methane production, but also offibre-degrading bacterial strains involved in polymer hydrolysis. Further research is required to confirm this hypothesis.