Concept for the valorization of cereal processing waste: Recovery of phenolic acids by using waste-derived tetrahydrofurfuryl alcohol and biochar.

Valorization of agro-food waste by converting it into a renewable resource plays a crucial role in a bio-based circular economy. Therefore, this study was designed to evaluate the suitability of distillery stillage (DS), which comes from alcohol production from cereals, for producing value-added products that can be used synergistically. The main objective was to investigate the usefulness of two substances for the recovery of phenolic acids, which have antioxidant activity, from the liquid fraction of DS: namely, tetrahydrofurfuryl alcohol (THFA) as a solvent and biochar as an adsorbent, both produced from the solid fraction of cereal processing waste. The effect of THFA concentration (80 and 100%) on phenolic acid yield in ultrasound-assisted extraction was studied. The solubilization predictions of phenolic compounds by the Hansen solubility parameters were in accordance with the experimental results: the yield of phenolic acids in the extracts was highest (3.76 µg g-1 dry mass) with 80% THFA. Among the extracted phenolic acids, hydroxycinnamic acids predominated over hydroxybenzoic acids, which may affect the bioactive properties of the extracts and their future applications for industrial purposes. Phenolic acids from the extracts were adsorbed on 17-170 g biochar L-1 and desorbed into water at 40-60 °C. The phenolic acid recovery was highest (∼92%) when the biochar dose was 85 g L-1 and when desorption was performed at 50 °C. After adsorption/desorption, ∼95% of the antioxidant activity of the phenolic acids in the extracts was maintained. As biochar has a smaller specific surface area than commercial powdered activated carbon (PAC), the biochar dose should be about 5 times higher than an equivalent PAC dose for adsorption efficiency above 90%.

Valorization of distillery stillage by polyphenol recovery using microwave-assisted, ultrasound-assisted and conventional extractions.

An increasing understanding of the negative environmental effects of waste discharges has made valorization of distillery by-products to recover added-value compounds a sound option for distillery stillage management. In this study, the recovery of bioactive compounds, i.e. polyphenols, from distillery stillage was performed by microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE) and conventional solid-liquid extraction (CSLE) to investigate the effects of extraction time, the concentration of ethyl acetate (EA) in a solvent mixture with ethanol and water, and solid-to-solvent ratio on the recovery yield and antioxidant activity of the extracts. The highest yields of total polyphenol content (TPC) (3.73 mg gallic acid equivalent/g) and phenolic acid content (2.51 µg/g) were obtained with 8-min MAE with 70% EA. MAE provided 1.2- and 1.4-times higher yield of phenolic acids and 1.2- and 1.6-times higher antioxidant activity than UAE and CSLE, respectively. Due to the approximately 3-times higher rate of extraction, the ratio between energy consumption and extraction yield was better in MAE than in UAE. Principal component analysis (PCA) showed that the antioxidant activity of the extracts was positively correlated with TPC and phenolic acid content. Six phenolic acids that were identified were present mainly in their free forms (up to 95% of the total), with a predominance of ferulic (up to 0.80 µg/g) and p-coumaric (up to 0.72 µg/g) acids.

Subcritical water extraction of bioactive phenolic compounds from distillery stillage.

Distilleries generate huge amounts of by-products that have a negative impact on the environment, so the management of wastes generated by this sector should be improved. Because distillery by-products are a source of bioactive compounds, the recovery of these compounds not only reduces issues with environmental protection but also provides the basis for a waste-to-profit solution. Following the latest trends in the search for so-called green extraction techniques for recovering valuable products, this study investigated the effect of subcritical water extraction (SWE) conditions (temperature (25-260 °C), time (5-90 min), and solid-to-solvent ratio (1:5-1:50, w:v)) on the efficiency of recovery of bioactive compounds, i.e., polyphenols from distillery stillage, and on the antioxidant activity of the extracts. The highest extraction yield was obtained with 30-min SWE with a solid-to-solvent ratio of 1:15 at either 140 °C (for total polyphenol content and phenolic acid content) or 200 °C (for total flavonoid content), as indicated by the Response Surface Methodology analysis. Phenolic acids in the extracts were present mainly in free forms (up to 88% of the total content). The antioxidant activity, which was measured using several assays, correlated positively with the content of phenolic acids, which confirmed their significant contribution to the bioactive properties of the extracts. The antioxidant effects of the extracts were mostly due to hydroxycinnamic acids (especially ferulic and p-coumaric acids). Principal component analysis showed that the temperature and time of SWE were the factors that can explain the greatest amount of variation in the extraction yield, composition, and bioactive properties of the polyphenols. These results will influence the design of further processes, such as purification and concentration, which are necessary before using the extracted compounds as substrates that are applicable in various industries. Based on the analysis of the elemental composition, the biomass remaining after SWE was evaluated to consider the possibilities of its further utilization.

Processing of Distillery Stillage to Recover Phenolic Compounds with Ultrasound-Assisted and Microwave-Assisted Extractions.

This study investigated the effect of ultrasound-assisted extraction (UAE) and microwave-assisted extraction (MAE) conditions (extraction time, acetone concentration, solid-to-solvent ratio) on the efficiency of polyphenol recovery from distillery stillage and antioxidant activity of the extracts. The highest total polyphenol content, flavonoid content, and phenolic acid content were obtained with 10-min UAE and 5-min MAE at a solid-to-acetone ratio of 1:15 (w:v). Recovery yield was the highest with an aqueous solution of 60% acetone, confirming the results of Hansen Solubility Parameter analysis. Although UAE resulted in approximately 1.2 times higher extraction yield, MAE showed a better balance between extraction yield and energy consumption exhibited by its 3-fold higher extraction rate than that of UAE. Content of total polyphenols and phenolic acids strongly correlated with antioxidant activity, indicating that these compounds provide a substantial contribution to the bioactive properties of the extracts. Six phenolic acids were extracted, predominately ferulic and p-coumaric acids, and free forms of these acids constituted 91% of their total content, which opens various possibilities for their application in the food, cosmetics, and pharmaceutical industries.

Recovery of polyphenols from distillery stillage by microwave-assisted, ultrasound-assisted and conventional solid-liquid extraction.

Recovery of bioactive compounds from distillery waste could be an option for valorizing this waste. This study investigated how the extraction of polyphenols (which have antioxidant activity) from distillery stillage was affected by solvent type and concentration, extraction time, and method of extraction (conventional solid-liquid extraction, CSLE; ultrasound-assisted extraction, UAE; microwave-assisted extraction, MAE). Although recovery was similar with UAE and MAE, 3 min MAE with 80% ethanol and 80% methanol produced the highest yields of total phenolic content (TPC), total flavonoid content (TFC) and phenolic acids. With CSLE, TPC was 2.1-1.8-times lower than with MAE and 1.7-1.4-times lower than with UAE. Increasing the solvent concentration to 100% significantly decreased recovery. Six phenolic acids were recovered (ferulic and p-coumaric acid predominated), which were present mainly in the free form. There was a significant positive correlation between antioxidant activity, as measured with three methods (one based on the hydrogen atom transfer and two based on single electron transfer mechanisms), and phenolic acid content. With MAE and UAE, polyphenols were recovered more efficiently, with 2.1 times and 1.5 times higher antioxidant activity, and with 15 times and 9 times shorter extraction times, respectively, than with CSLE; thus, they can be considered "green" alternatives to CSLE.

Insights into mechanisms of bisphenol A biodegradation in aerobic granular sludge.

Wastewater is the major source of bisphenol A (BPA) in the environment, however, the results regarding main mechanisms of BPA biodegradation in wastewater treatment systems are divergent. The effect of BPA concentration in wastewater (0, 2, 6, 12 mg BPA/L) on respirometric activity and expression of selected genes in aerobic granules was examined. A real-time protocol for analysis of direct BPA-degrader activity targeting gene coding for ferredoxin was developed. At 2 mg BPA/L, respirometric activity of granules was the highest, which favored the fastest pollutant removal, and BPA-degraders were active at the beginning of the reactor cycle and no by-products of BPA degradation were detected. At 6 and 12 mg BPA/L, the activity of BPA-degraders was much higher, peaking after feeding and again when a BPA metabolite (3-(benzyloxy)benzoic acid) appeared in the reactor. The upregulation of gene coding for ammonia monooxygenase indicated that co-metabolism occurred mostly at 12 mg BPA/L.

Effect of different nitrogen fertilizer treatments on the conversion of Miscanthus×giganteus to ethanol.

Miscanthus×giganteus is a perennial rhizomatous grass which is used as a biofuel crop. Due to its high yields, low production costs, resistance to low temperatures, low soil requirements and, above all, high cellulose content, miscanthus can be a useful resource for ethanol production. The aim of this study was to determine the effect of two fertilization regimes (sewage sludge/mineral NPK) during miscanthus cultivation on the chemical composition of biomass, the content of major lignocellulosic factions and the effectiveness of miscanthus conversion to bioethanol. The results indicate that fertilization treatments influenced biomass yield and the content of major lignocellulosic fractions. Bioethanol production was higher when hydrolysis and fermentation processes were conducted separately than when saccharification and fermentation were conducted simultaneously. Ethanol production increased by 30% and 40% in response to sewage sludge and NPK (equivalent nitrogen content=160kgN/ha) fertilization, respectively, in comparison with unfertilized crops.

Feasibility of using humic substances from compost to remove heavy metals (Cd, Cu, Ni, Pb, Zn) from contaminated soil aged for different periods of time.

There is a need for inexpensive, readily-available and environmentally-friendly soil washing agents to remediate polluted soils. Thus, batch washing experiments were performed to evaluate the feasibility of using a solution of humic substances (HS) extracted from compost as a washing agent for simultaneous removal of Cu, Cd, Zn, Pb and Ni from artificially contaminated soils aged for 1 month, 12 months and 24 months. The efficiency of metal removal in single and multiple washings and kinetic constants (equilibrium metal concentration qe and rate constant k from the second-order kinetic equation) were determined. On average, triple washing removed twice as much metal as that removed with a single washing. At pH 7 and a HS concentration of 2.2 g C L(-1), metal removal from all soils decreased in this order: Cd (79.1-82.6%) > Cu (51.5-71.8%) > Pb (44.8-47.6%) > Ni (35.4-46.1%) > Zn (27.9-35.8%). However, based on qe (mg kg(-1)), metal removal was in this order: Pb > Zn ≈ Cu > Ni > Cd. This difference was due to different concentrations of metals, which is typical for multi-metal contaminated soils. Regardless of washing mode, removal of Cd and Pb was not affected by soil age, whereas removal of Cu, Ni and Zn was higher in soils that had been aged for a shorter time. These results indicate that HS are suitable for remediating soil contaminated with multiple heavy metals in extremely high concentrations.

Humic substances from sewage sludge compost as washing agent effectively remove Cu and Cd from soil.

Although commercially available biosurfactants are environmentally friendly and effectively remove heavy metals from soil, they are costly. Therefore, this study investigated whether inexpensive humic substances (HS) from sewage sludge compost could effectively remove copper (Cu) and cadmium (Cd) from highly contaminated sandy clay loam (S1) and clay (S2). The optimum HS concentration and pH were determined, as well process kinetics. Under optimum conditions, a single washing removed 80.7% of Cu and 69.1% of Cd from S1, and 53.2% and 36.5%, respectively, from S2. Triple washing increased removal from S1 to almost 100% for both metals, and to 83.2% of Cu and 88.9% of Cd from S2. Triple washing lowered the potential ecological risk (Er(i)) of the soils, especially the risk from Cd. HS substances show potential for treating soils highly contaminated with heavy metals, and HS from other sources should be tested with these and other contaminants.

Removal of bisphenol A (BPA) in a nitrifying system with immobilized biomass.

The potential for bisphenol A (BPA) removal by mixed consortia of immobilized microorganisms with high nitrification activity was investigated with BPA concentrations in the influent from 2.5 to 10.0 mg/L. The presence of BPA limited ammonium oxidation; nitrification efficiency decreased from 91.2±1.3% in the control series to 47.4±9.4% when BPA concentration in wastewater was the highest. The efficiency of BPA removal rose from 87.1±5.5% to 92.9±2.9% with increased BPA concentration in the influent. Measurement of oxygen uptake rates by biomass exposed to BPA showed that BPA was mainly removed by heterotrophic bacteria. A strong negative correlation between the BPA removal efficiency and nitrification efficiency indicated the limited contribution of ammonia-oxidizing bacteria (AOB) to BPA biodegradation. Exposure of biomass to BPA changed the quantity and diversity of AOB in the biomass as shown by real-time PCR and denaturing gradient gel electrophoresis.

Ribosomal intergenic spacer analysis as a tool for monitoring methanogenic Archaea changes in an anaerobic digester.

The applicability of a newly-designed PCR primer pair in examination of methanogenic Archaea in a digester treating plant biomass was evaluated by Ribosmal Intergenic Spacer Analysis (RISA). To find a suitable approach, three variants of RISA were tested: (1) standard, polyacrylamide gel-based, (2) automated, utilized capillary electrophoresis (GA-ARISA), and (3) automated microfluidics-based (MF-ARISA). All three techniques yielded a consistent picture of archaeal community structure changes during anaerobic digestion monitored for more than 6 weeks. While automated variants were more practical for handling and rapid analysis of methanogenic Archaea, the gel-based technique was advantageous when micro-organism identification was required. A DNA-sequence analysis of dominant bands extracted from the gel revealed that the main role in methane synthesis was played by micro-organisms affiliated with Methanosarcina barkeri. The obtained results revealed that RISA is a robust method allowing for detailed analysis of archaeal community structure during organic biomass conversion into biogas. In addition, our results showed that GA-ARISA has a higher resolution and reproducibility than other variants of RISA and could be used as a technique for tracking changes in methanogenic Archaea in an anaerobic digester.