Immobilised humic substances as low-cost sorbents for emerging contaminants

Funding Information: Funding: This research was supported by the Latvian Council of Science, Fundamental and Applied Research Project No. lzp-2018/1-0009 “Properties and structure of peat humic substances and possibilities of their modification”. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.Environmental pollution with contaminants of emerging concern (CECs) is a worldwide problem that is receiving increasing attention. Although these substances have been released in the aquatic environment for a long time, wastewater treatment plants are still incapable of removing emerging contaminants completely. Consequently, trace metals, metalloids and pharmaceuticals, as well as surfactant leftovers, are often found in environmental samples. Environmentally friendly and cost-effective sorbents such as humic substances can be used for purification if their sorption properties are increased by immobilization. To our knowledge, immobilized humic substances have not been widely studied as sorbents up to now. In this study, humic substances were immobilized to obtain low-cost sorbents. The chosen methods for characterization of the obtained sorbents showed successful immobilization. Traditional pollutants, such as Cr(III) (a metal), As(V) (a metalloid) and chlorpromazine (a pharmaceutical), were used as representative contaminants. Sorption experiments were conducted using the batch system, and sorption was also studied based on the sorbent dosage, initial concentration of the studied element or substance, solution pH and sorption time. The results show that all the obtained immobilized humic substances in this study can be used as sorbents to remove contaminants from water. At the same time, from these humic substances, only those immobilized using iron compounds are suitable for the removal of arsenic.publishersversionPeer reviewe

Temperature has a major effect on the cuticular wax composition of bilberry (Vaccinium myrtillus L.) fruit

Cuticle is the first layer protecting plants against external biotic and abiotic factors and is responsive to climatic factors as well as determined by genetic adaptations. In this study, the chemical composition of bilberry fruit cuticular wax was investigated through a latitudinal gradient from Latvia (56◦N 24◦E) through Finland (65◦N 25◦E) to northern Norway (69◦N 18◦E) in two seasons 2018 and 2019. Changes in the major cuticular wax compounds, including triterpenoids, fatty acids, alkanes, aldehydes, ketones, and primary alcohols, were detected by GC-MS analysis. Generally, a decreasing trend in the proportion of triterpenoids from southern to northern latitudes, accompanied with an increase in proportion of fatty acids, aldehydes, and alkanes, in bilberry fruit cuticular wax was observed. A correlation analysis between climatic factors with proportion of wax compounds indicated that temperature was the main factor affecting the cuticular wax composition in bilberries. A controlled phytotron experiment with southern and northern bilberry ecotypes confirmed the major effect of temperature on bilberry fruit cuticular wax load and composition. Elevated temperature increased wax load most in berries of northern ecotypes. The level of triterpenoids was higher, while levels of fatty acids and alkanes were lower, in wax of bilberry fruits ripened at 18◦C compared to 12◦C in both northern and southern ecotypes. Based on our results, it can be postulated that the predicted increase in temperature due to climate change leads to alterations in fruit cuticular wax load and composition. In northern ecotypes, the alterations were especially evident

Effect of Essential Oils Supplemented with Caprylic Acid and Sodium Chloride against Faecal ESBL-Producing <i>Escherichia coli</i> Isolated from Pigs

The purpose of the present investigation was to compare the antibacterial activity of six commercial and lab-scale extracted essential oils (EOs) alone or in combination with caprylic acid (CA) and sodium chloride (NaCl) against faecal Escherichia coli with and without extended-spectrum beta-lactamase (ESBL) encoding genes, and of isolates classified as multidrug-resistant (MDR). Gas chromatography–mass spectrometry (GC–MS) was used for the analysis of chemical composition of EOs, while the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) assays were carried out to elucidate the antibacterial activity of non-supplemented and supplemented EOs against different resistance levels of E. coli strains. The main compounds in commercial EOs were aromatic monoterpenoids (30–56%) and p-cymene (8–35%), while the main compounds in the lab-scale EOs were aromatic monoterpenoids (12–37%) and γ-terpinene (18–22%). Commercial EOs exhibited superior inhibitory activity of E. coli in comparison to lab-scale produced EOs. Antibacterial activity of EOs was significantly enhanced by enrichment of the EOs with NaCl (p p = 0.012). Most of the non-supplemented EOs exhibited lower activity against MDR and ESBL producing E. coli. In contrast, EOs supplemented with CA and especially NaCl was equally effective against ESBL and non-ESBL as well as MDR and non-MDR E. coli. It was found that supplementation of EOs with NaCl could enhance the antibacterial activity towards ESBL and MDR E. coli isolates. However, additional studies are needed to clarify the potential risks of developing resistance

Effect of Essential Oils Supplemented with Caprylic Acid and Sodium Chloride against Faecal ESBL-Producing Escherichia coli Isolated from Pigs

The purpose of the present investigation was to compare the antibacterial activity of six commercial and lab-scale extracted essential oils (EOs) alone or in combination with caprylic acid (CA) and sodium chloride (NaCl) against faecal Escherichia coli with and without extended-spectrum beta-lactamase (ESBL) encoding genes, and of isolates classified as multidrug-resistant (MDR). Gas chromatography&ndash;mass spectrometry (GC&ndash;MS) was used for the analysis of chemical composition of EOs, while the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) assays were carried out to elucidate the antibacterial activity of non-supplemented and supplemented EOs against different resistance levels of E. coli strains. The main compounds in commercial EOs were aromatic monoterpenoids (30&ndash;56%) and p-cymene (8&ndash;35%), while the main compounds in the lab-scale EOs were aromatic monoterpenoids (12&ndash;37%) and &gamma;-terpinene (18&ndash;22%). Commercial EOs exhibited superior inhibitory activity of E. coli in comparison to lab-scale produced EOs. Antibacterial activity of EOs was significantly enhanced by enrichment of the EOs with NaCl (p &lt; 0.001) or CA (p = 0.012). Most of the non-supplemented EOs exhibited lower activity against MDR and ESBL producing E. coli. In contrast, EOs supplemented with CA and especially NaCl was equally effective against ESBL and non-ESBL as well as MDR and non-MDR E. coli. It was found that supplementation of EOs with NaCl could enhance the antibacterial activity towards ESBL and MDR E. coli isolates. However, additional studies are needed to clarify the potential risks of developing resistance

An Environmentally Friendly Approach for the Release of Essential Fatty Acids from Cereal By-Products Using Cellulose-Degrading Enzymes

The main intention of the present work was to investigate the ability of cellulose-degrading enzymes (C-DE) to release fatty acids (FAs) from complex matrices of cereal by-products during enzymatic hydrolysis (EH). For this purpose, three types of cereal bran (CB), i.e., wheat, rye, and oat, were used as lignocellulose substrates for three commercially available hydrolytic enzymes, i.e., Viscozyme L, Viscoferm, and Celluclast 1.5 L. The yield and composition of FAs after EH were assessed and compared with those obtained after either conventional Soxhlet extraction or after alkaline-assisted hydrolysis (A-AH) with 10% KOH in 80% MeOH and subsequent liquid&ndash;liquid extraction. The experimental results demonstrated that up to 6.3% and 43.7% higher total FA yield can be achieved by EH of rye bran using Celluclast 1.5 L than by A-AH and Soxhlet extraction, respectively. However, the application of Viscoferm for EH of wheat bran ensured up to 7.7% and 13.4% higher total FA yield than A-AH and Soxhlet extraction, respectively. The concentration of essential linolenic acid (C18:3) in lipids extracted after EH of rye bran with Celluclast 1.5 L was up to 24.4% and 57.0% higher than in lipids recovered by A-AH and Soxhlet extraction, respectively. In turn, the highest content of linolenic acid in wheat bran lipids was observed after EH with Viscoferm and Viscozyme L, ensuring 17.0% and 13.6% higher yield than after A-AH, respectively. SEM analysis confirmed substantial degradation of the CB matrix promoted by the ability of C-DE to act specifically on glycosidic bonds in cellulose and on xylosidic bonds in arabinoxylans, arabinans, and other arabinose-containing hemicelluloses. Structural alterations in cell integrity greatly contributed to the release of bound FAs and their better transfer into the extraction solvent. It has been shown that the proposed process of EH can be used for the efficient release of FAs from the CB matrix more sustainably and with a safer profile, thereby conveying greener production of FAs for certain purposes

Lignocellulose-Degrading Enzymes: A Biotechnology Platform for Ferulic Acid Production from Agro-Industrial Side Streams

Biorefining by enzymatic hydrolysis (EH) of lignocellulosic waste material due to low costs and affordability has received enormous interest amongst scientists as a potential strategy suitable for the production of bioactive ingredients and chemicals. In this study, a sustainable and eco-friendly approach to extracting bound ferulic acid (FA) was demonstrated using single-step EH by a mixture of lignocellulose-degrading enzymes. For comparative purposes of the efficiency of EH, an online extraction and analysis technique using supercritical fluid extraction&ndash;supercritical fluid chromatography&ndash;mass spectrometry (SFE-SFC-MS) was performed. The experimental results demonstrated up to 369.3 mg 100 g&minus;1 FA release from rye bran after 48 h EH with Viscozyme L. The EH of wheat and oat bran with Viscoferm for 48 h resulted in 255.1 and 33.5 mg 100 g&minus;1 of FA, respectively. The release of FA from bran matrix using supercritical fluid extraction with carbon dioxide and ethanol as a co-solvent (SFE-CO2-EtOH) delivered up to 464.3 mg 100 g&minus;1 of FA, though the extractability varied depending on the parameters used. The 10-fold and 30-fold scale-up experiments confirmed the applicability of EH as a bioprocessing method valid for the industrial scale. The highest yield of FA in both scale-up experiments was obtained from rye bran after 48 h of EH with Viscozyme L. In purified extracts, the absence of xylose, arabinose, and glucose as the final degradation products of lignocellulose was proven by high-performance liquid chromatography with refractive index detection (HPLC-RID). Up to 94.0% purity of FA was achieved by solid-phase extraction (SPE) using the polymeric reversed-phase Strata X column and 50% EtOH as the eluent

Valorization of Wild Apple (<i>Malus</i> spp.) By-Products as a Source of Essential Fatty Acids, Tocopherols and Phytosterols with Antimicrobial Activity

The amplified production of fruit as well as burgeoning demand for plant-made food products have resulted in a sharp increase of waste. Currently, millions of tons of by-products are either being discarded or utilized rather ineffectively. However, these by-products may be processed and further incorporated as functional ingredients in making high-value food products with many physiological and biochemical effects. The chemical analysis of pomace oils using gas chromatography-mass spectrometry (GC/MS) and reversed-phase-liquid chromatography coupled with fluorescence detector (RP-HPLC/FLD) systems led to the identification and quantification of 56 individual lipophilic compounds including unsaturated, polyunsaturated and saturated fatty acids, as well as phytosterols and four homologs of tocopherol. The oils recovered from by-products of Malus spp. (particularly cv. &#8220;Ola&#8222;) are rich in fatty acids such as linolenic (57.8%), &#945;-linolenic (54.3%), and oleic (25.5%). The concentration of total tocopherols varied among the Malus species and dessert apples investigated, representing the range of 16.8&#8315;30.9 mg mL&#8722;1. The highest content of total tocopherols was found in M. Bernu prieks, followed by M. cv. &#8220;Ola&#8222;, and M. &#215; Soulardii pomace oils. A significantly higher amount of &#948;-tocopherol was established in the oil of M. Bernu prieks, indicating that this species could be utilized as a natural and cheap source of bioactive molecules. &#946;-Sitosterol was the prevalent compound determined in all tested pomace oils with a percentage distribution of 10.3&#8315;94.5%. The main triterpene identified in the oils was lupeol, which varied in the range of 0.1&#8315;66.3%. A targeted utilization of apple pomace would facilitate management of tons of by-products and benefit the environment and industry