Processing of Thin Films Based on Cellulose Nanocrystals and Biodegradable Polymers by Space-Confined Solvent Vapor Annealing and Morphological Characteristics.

L-poly(lactic acid), poly(3-hydroxybutyrate), and poly-hydroxybutyrate-co-hydroxyvalerate are biodegradable polymers that can be obtained from renewable biomass sources. The aim of this study was to develop three types of environmentally friendly film biocomposites of altered microstructure by combining each of the above-mentioned polymers with cellulose nanocrystal fillers and further processing the resulting materials via space-confined solvent vapor annealing. Cellulose was previously obtained from renewable biomass and further converted to cellulose nanocrystals by hydrolysis with the lactic acid. The solutions of biodegradable polymers were spin-coated onto solid substrates before and after the addition of cellulose nanocrystals. The obtained thin film composites were further processed via space-confined solvent vapor annealing to eventually favor their crystallization and, thus, to alter the final microstructure. Indeed, atomic force microscopy studies have revealed that the presence of cellulose nanocrystals within a biodegradable polymer matrix promoted the formation of large crystalline structures exhibiting fractal-, spherulitic- or needle-like morphologies.

Activated natural zeolites for beer filtration: A pilot scale approach.

A clinoptilolite-rich natural zeolite was tested as a substitute for kieselguhr as a filtering material to eliminate ingredients that cause beer haze formation. Two-grain sizes of micronized natural zeolite were thermally activated to 400 °C, to enhance its adsorption performance and remove the impurities adsorbed in the microporous system of zeolites, followed by their physicochemical characterization. The activated zeolites mixed with four commercial filter aids in different ratios were used for beer filtration at the pilot scale. Most of the physicochemical and sensory characteristics of beers filtered with commercial filter aids and with zeolites were similar. Using zeolite in filtering mixtures significantly reduces the number of microorganisms present in the filtered beer, which can eliminate the necessity of beer sterilization after filtration. The results evidenced that activated natural zeolites, which are cheap materials, are promising candidates as filter aids and can replace kieselguhr without producing any degradation of the beer filtration process.

Rowanberry-A Source of Bioactive Compounds and Their Biopharmaceutical Properties.

After a period of intense development in the synthesis pharmaceutical industry, plants are making a comeback in the public focus as remedies or therapeutic adjuvants and in disease prevention and ensuring the wellbeing and equilibrium of the human body. Plants are being recommended more and more in alimentation, in their natural form, or as extracts, supplements or functional aliments. People, in general, are in search of new sources of nutrients and phytochemicals. As a result, scientific research turns to lesser known and used plants, among them being rowanberries, a species of fruit very rich in nutrients and underused due to their bitter astringent taste and a lack of knowledge regarding the beneficial effects of these fruit. Rowan fruits (rowanberries) are a rich source of vitamins, polysaccharides, organic acids and minerals. They are also a source of natural polyphenols, which are often correlated with the prevention and treatment of modern world diseases. This article presents the existing data regarding the chemical composition, active principles and biopharmaceutical properties of rowan fruits and the different opportunities for their usage.

Chemical Analysis of Various Tea Samples Concerning Volatile Compounds, Fatty Acids, Minerals and Assessment of Their Thermal Behavior.

Tea is the most consumed drink worldwide due to its pleasant taste and various beneficial effects on human health. This paper assesses the physicochemical analysis of different varieties of tea (leaves, flowers, and instant) after prior drying and fine grinding. The thermal decomposition behavior of the tea components shows that the tea has three stages of decomposition, depending on temperature. The first stage was attributed to the volatilization of water, while the second stage involved the degradation of volatiles, polyphenols, and fatty acids. The degradation of cellulose, hemicellulose, and lignin content occurs at the highest temperature of 400 °C in the third stage. A total of 66 volatile compounds, divided into eight classes, were identified in the tea samples. The volatile compounds were classified into nine odor classes: floral, fruity, green, sweet, chemical, woody, citrus, roasted, and alcohol. In all flower and leaf tea samples, monounsaturated (MUFAs), polyunsaturated (PUFAs), and saturated fatty acids (SFAs) were identified. A high content of omega-6 was quantified in acacia, Saint John's Wort, rose, and yarrow, while omega-3 was found in mint, Saint John's Wort, green, blueberry, and lavender samples. The flower and leaf tea samples studied could be a good dietary source of polyphenolic compounds, essential elements. In instant tea samples, a low quantity of polyphenols and major elements were identified. The physicochemical analysis demonstrated that both flower and leaf teas have high-quality properties when compared to instant tea.

Impact of Low Lithium Concentrations on the Fatty Acids and Elemental Composition of Salvinia natans.

The photosynthetic pigments, protein, macro and microelements concentrations, and fatty acids composition of Salvinia natans, a free-floating aquatic plant, were analyzed after exposure to Hoagland nutrient solution containing 1, 3, and 5 mg/L Li. The Li content of Salvinia natans grew exponentially with the Li concentration in the Hoagland nutrient solution. The exposure to Li did not induce significant changes in Na, Mg, K, Cu, and Zn content but enhanced the Ba, Cr, Mn, Ni and Mo absorption in Salvinia natans. The most abundant fatty acids determined in oils extracted from Salvinia natans were C16:0, C18:3(n6), C18:2(n6), and C18:3(n3). The photosynthetic pigments did not change significantly after exposure to Li. In contrast, chlorophyll and protein content decreased, whilst monounsaturated and polyunsaturated fatty acids content increased after the exposure to 1 mg/L Li. The results indicated that Salvinia natans exposed to low Li concentrations may be a good source of minerals, omega 6 and omega 3.

L-Poly(lactic acid) Production by Microwave Irradiation of Lactic Acid Obtained from Lignocellulosic Wastes.

L-polylactic acid (PLA), a semi-crystalline aliphatic polyester, is one of the most manufactured biodegradable plastics worldwide. The objective of the study was to obtain L-polylactic acid (PLA) from lignocellulosic plum biomass. Initially, the biomass was processed via pressurized hot water pretreatment at a temperature of 180 °C for 30 min at 10 MPa for carbohydrate separation. Cellulase and the beta-glucosidase enzymes were then added, and the mixture was fermented with Lacticaseibacillus rhamnosus ATCC 7469. The resulting lactic acid was concentrated and purified after ammonium sulphate and n-butanol extraction. The productivity of L-lactic acid was 2.04 ± 0.18 g/L/h. Then, the PLA was synthesized in two stages. Firstly, lactic acid was subjected to azeotropic dehydration at 140 °C for 24 h in the presence of xylene, using SnCl2 (0.4 wt.%) as a catalyst, resulting in lactide (CPLA). Secondly, microwave-assisted polymerization was carried out at 140 °C for 30 min with 0.4 wt.% SnCl2. The resulting powder was purified with methanol to produce PLA with 92.1% yield. The obtained PLA was confirmed using electrospray ionization mass spectrometry, nuclear magnetic resonance, thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction. Overall, the resulting PLA can successfully replace the traditional synthetic polymers used in the packaging industry.

Preparation and Characterization of the Composition of Volatile Compounds, Fatty Acids and Thermal Behavior of Paprika.

This study aimed to investigate the thermal behavior and composition of volatile compounds, fatty acids and polyphenols in paprika obtained from peppers of different countries. The thermal analysis revealed various transformations in the paprika composition, namely drying, water loss and decomposition of volatile compounds, fatty acids, amino acids, cellulose, hemicellulose and lignin. The main fatty acids found in all paprika oils were linoleic (20.3-64.8%), palmitic (10.6-16.0%) and oleic acid (10.4-18.1%). A notable amount of omega-3 was found in spicy paprika powder varieties. The volatile compounds were classified into six odor classes (citrus (29%), woody (28%), green (18%), fruity (11%), gasoline (10%) and floral (4%)). The total polyphenol content ranged between 5.11 and 10.9 g GA/kg.

Poly(3-hydroxybutyrate) Production from Lignocellulosic Wastes Using Bacillus megaterium ATCC 14581.

This study aimed to analyze the production of poly(3-hydroxybutyrate) (PHB) from lignocellulosic biomass through a series of steps, including microwave irradiation, ammonia delignification, enzymatic hydrolysis, and fermentation, using the Bacillus megaterium ATCC 14581 strain. The lignocellulosic biomass was first pretreated using microwave irradiation at different temperatures (180, 200, and 220 °C) for 10, 20, and 30 min. The optimal pretreatment conditions were determined using the central composite design (CCD) and the response surface methodology (RSM). In the second step, the pretreated biomass was subjected to ammonia delignification, followed by enzymatic hydrolysis. The yield obtained for the pretreated and enzymatically hydrolyzed biomass was lower (70.2%) compared to the pretreated, delignified, and enzymatically hydrolyzed biomass (91.4%). These hydrolysates were used as carbon substrates for the synthesis of PHB using Bacillus megaterium ATCC 14581 in batch cultures. Various analytical methods were employed, namely nuclear magnetic resonance (1H-NMR and13C-NMR), electrospray ionization mass spectrometry (EI-MS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA), to identify and characterize the extracted PHB. The XRD analysis confirmed the partially crystalline nature of PHB.

High-Pressure Supercritical CO2 Pretreatment of Apple Orchard Waste for Carbohydrates Production Using Response Surface Methodology and Method Uncertainty Evaluation.

This study's objective was to separate cellulose, hemicellulose, and lignin after high-pressure supercritical carbon dioxide pretreatment for further valorization. The study investigated the supercritical carbon dioxide pretreatment of apple orchard waste at temperatures of 160-200 °C, for 15-45 min, at a pressure of 10 MPa. Response Surface Methodology (RSM) was used to optimize the supercritical process and to improve its efficiency. The change of functional groups during different pretreatment conditions was examined by Fourier transform infrared (FTIR) spectroscopy. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) confirmed the structural changes in the biomass structure before and after pretreatment. A new ultra-high performance liquid chromatography (UHPLC) coupled with an evaporative light scattering detector (ELSD) method was developed and validated for the determination of carbohydrates in the liquid fraction that resulted after pretreatment. The estimated uncertainty of the method ranged from 16.9 to 20.8%. The pre-treatment of high-pressure supercritical CO2 appears to be an effective and promising technique for the recovery of sugars and secondary by-products without the use of toxic solvents.

The Potential Application of Natural Clinoptilolite-Rich Zeolite as Support for Bacterial Community Formation for Wastewater Treatment.

The aim of this study was to investigate the use of natural zeolite as support for microbial community formation during wastewater treatment. Scanning electron microscopy (SEM), thermal decomposition and differential thermogravimetric curves (TGA/DGT) techniques were used for the physicochemical and structural characterization of zeolites. The chemical characterization of wastewater was performed before and after treatment, after 30 days of using stationary zeolite as support. The chemical composition of wastewater was evaluated in terms of the products of nitrification/denitrification processes. The greatest ammonium (NH4+) adsorption was obtained for wastewater contaminated with different concentrations of ammonium, nitrate and nitrite. The wastewater quality index (WWQI) was determined to assess the effluent quality and the efficiency of the treatment plant used, showing a maximum of 71% quality improvement, thus suggesting that the treated wastewater could be discharged into aquatic environments. After 30 days, NH4+ demonstrated a high removal efficiency (higher than 98%), while NO3+ and NO2+ had a removal efficiency of 70% and 54%, respectively. The removal efficiency for metals was observed as follows (%): Mn > Cd > Cr > Zn > Fe > Ni > Co > Cu > Ba > Pb > Sr. Analysis of the microbial diversity in the zeolite samples indicated that the bacteria are formed due to the existence of nutrients in wastewater which favor their formation. In addition, the zeolite was characterized by SEM and the results indicated that the zeolite acts as an adsorbent for the pollutants and, moreover, as a support material for microbial community formation under optimal conditions. Comparing the two studied zeolites, NZ1 (particle size 1−3 mm) was found to be more suitable for wastewater treatment. Overall, the natural zeolite demonstrated high potential for pollutant removal and biomass support for bacteria community growth in wastewater treatment.

Performance Parameters of Inductively Coupled Plasma Optical Emission Spectrometry and Graphite Furnace Atomic Absorption Spectrometry Techniques for Pd and Pt Determination in Automotive Catalysts.

Palladium (Pd) and platinum (Pt) are extensively used as catalysts in the petrochemical and automotive industries, and due to high demand for them on the market, their recycling from spent supported catalysts is clearly needed. To assess the content of Pd and Pt in catalysts in order to establish their commercial value or to evaluate the recovery efficiency of technologies used for recycling, reliable analytical methods for determination of these elements are required. Spectrometric methods, such as inductively coupled plasma optical emission spectrometry (ICP-OES) and graphite furnace atomic absorption spectrometry (GFAAS) are powerful tools that can be employed for the determination of Pd and Pt in various sample matrices. However, these methods allow only the injection of liquid samples. In this regard, the digestion of solid sample by microwave-assisted acid extraction procedures at high pressures and temperatures is often used. In this study, a microwave acid digestion method was optimized for the extraction of Pd and Pt from spent catalysts, using a four-step program, at a maximum 200 °C. The resulting solutions were analyzed using ICP-OES, at two different wavelengths for each metal (Pd at 340.458 and 363.470 nm, and Pt at 265.945 and 214.423 nm, respectively) and using GFAAS (Pd at 247.64 nm, Pt at 265.94 nm). Five types of spent catalyst were analyzed and the standard deviations of repeatability for five parallel samples were less than predicted relative standard deviations (PRSD%) calculated using Horvitz's equation for all the analyzed samples.

Bioethanol Production from Vineyard Waste by Autohydrolysis Pretreatment and Chlorite Delignification via Simultaneous Saccharification and Fermentation.

In this paper, the production of a second-generation bioethanol from lignocellulosic vineyard cutting wastes was investigated in order to define the optimal operating conditions of the autohydrolysis pretreatment, chlorite delignification and simultaneous saccharification and fermentation (SSF). The autohydrolysis of vine-shoot wastes resulted in liquors containing mainly a mixture of monosaccharides, degradation products and spent solids (rich in cellulose and lignin), with potential utility in obtaining valuable chemicals and bioethanol. The autohydrolysis of the vine-shoot wastes was carried out at 165 and 180 °C for 10 min residence time, and the resulted solid and liquid phases composition were analysed. The resulted liquid fraction contained hemicellulosic sugars as a mixture of alpha (α) and beta (ß) sugar anomers, and secondary by-products. The solid fraction was delignified using the sodium chlorite method for the separation of lignin and easier access of enzymes to the cellulosic sugars, and then, converted to ethanol by the SSF process. The maximum bioethanol production (6%) was obtained by autohydrolysis (165 °C), chlorite delignification and SSF process at 37 °C, 10% solid loading, 72 h. The principal component analysis was used to identify the main parameters that influence the chemical compositions of vine-shoot waste for different varieties.

Mercury Determination in Natural Zeolites by Thermal Decomposition Atomic Absorption Spectrometry: Method Validation in Compliance with Requirements for Use as Dietary Supplements.

Natural zeolites are hydrated aluminosilicate minerals that, due to their remarkable physical-chemical properties of being molecular sieves and cation exchangers, have applications in different areas such as environmental protection, catalysis, animal feed, and dietary supplements. Since natural zeolites may contain traces of undesirable compounds such as toxic metals, the accurate quantification of these elements is necessary. In this study, a direct method for Hg determination in zeolite samples based on the thermal desorption atomic absorption spectrometry (TD-AAS) technique is fully validated, taking into account the legislative requirements in the field. The chosen quantification limit was 0.9 µg kg-1, which is satisfactory for intended use. Trueness was evaluated by recovery rate using certified reference materials containing mercury, with satisfactory results. Other figures of merit, such as repeatability and measurement uncertainty, also fulfill the legislative requirements related to the analysis of dietary supplements. This paper presents, for the first time, a fully validated method for mercury determination in zeolite samples, and the obtained results reveal that the method can be applied successfully for the intended purpose.

Assessment of Availability and Human Health Risk Posed by Arsenic Contaminated Well Waters from Timis-Bega Area, Romania.

Mobilization of As from geological materials into ground and drinking water sources may represent an important threat to human health. The objective of this study was to assess the As concentration and availability in underground water used as drinking water sources. Water samples were collected from public and private wells in Timis-Bega area of Pannonian Basin, West Romania. Total-dissolved As measured after "classical" filtration of water samples was in the range of 0.10-168 µg L-1, thus exceeding the guideline value in majority of the samples. The aim of this study was also to assess the "truly dissolved" concentrations of As considered as available concentrations, in well waters, after passive sampling by Diffusive Gradients in Thin-films (DGT). The results showed that over 70% of total-dissolved As is in available forms. The obtained data were used to evaluate the risks of using the wells as drinking water source. Hazard quotients for ingestion and dermal pathways and hazard index (HI) for exposure to As were calculated. The HI values > 1 found that majority of samples indicated a health risk for local residents.

Assessment of metals bioavailability to vegetables under field conditions using DGT, single extractions and multivariate statistics.

BACKGROUND: The metals bioavailability in soils is commonly assessed by chemical extractions; however a generally accepted method is not yet established. In this study, the effectiveness of Diffusive Gradients in Thin-films (DGT) technique and single extractions in the assessment of metals bioaccumulation in vegetables, and the influence of soil parameters on phytoavailability were evaluated using multivariate statistics. Soil and plants grown in vegetable gardens from mining-affected rural areas, NW Romania, were collected and analysed. RESULTS: Pseudo-total metal content of Cu, Zn and Cd in soil ranged between 17.3-146 mg kg-1, 141-833 mg kg-1 and 0.15-2.05 mg kg-1, respectively, showing enriched contents of these elements. High degrees of metals extractability in 1M HCl and even in 1M NH4Cl were observed. Despite the relatively high total metal concentrations in soil, those found in vegetables were comparable to values typically reported for agricultural crops, probably due to the low concentrations of metals in soil solution (Csoln) and low effective concentrations (CE), assessed by DGT technique. Among the analysed vegetables, the highest metal concentrations were found in carrots roots. By applying multivariate statistics, it was found that CE, Csoln and extraction in 1M NH4Cl, were better predictors for metals bioavailability than the acid extractions applied in this study. Copper transfer to vegetables was strongly influenced by soil organic carbon (OC) and cation exchange capacity (CEC), while pH had a higher influence on Cd transfer from soil to plants. CONCLUSIONS: The results showed that DGT can be used for general evaluation of the risks associated to soil contamination with Cu, Zn and Cd in field conditions. Although quantitative information on metals transfer from soil to vegetables was not observed.

Mercury in soil and perennial plants in a mining-affected urban area from Northwestern Romania.

The mercury (Hg) concentrations were evaluated in soils and perennial plants sampled in four districts of Baia Mare city, a historical mining and ore processing center in Northwestern Romania. The results showed that the Hg concentration exceeded the guideline value of 1.0 mg kg(-1) dry weight (dw) established by the Romanian Legislation, in 24 % of the analyzed soil samples, while the median Hg concentration (0.70 mg kg(-1) dw) was lower than the guideline value. However, Hg content in soil was generally higher than typical values in soils from residential and agricultural areas of the cities all over the world. The median Hg concentration was 0.22 mg kg(-1) dw in the perennial plants, and exceeded the maximum level of Hg (0.10 mg kg(-1)) established by European Directive 2002/32/EC for plants used in animal feed in order to prevent its transfer and further accumulation in the higher levels of food chain. No significant correlations were found between soil Hg and other analyzed metals (Cd, Cu, Pb, Zn) resulted from the non-ferrous smelting activities, probably due to the different physicochemical properties, that led to different dispersion patterns.