Comprehensive characterization of industrial wastewaters using EEM fluorescence, FT-IR and 1H NMR techniques

The organic matter present in six industrial wastewaters (pulp and paper mill, brewery, textile, dairy, slaughterhouse effluents and a municipal landfill leachate) has been studied in this work using three analytical techniques: excitation-emission matrix fluorescence (EEMF), proton nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform infrared spectroscopy (FTIR). The pulp and paper mill effluent shows characteristic signals of the presence of lignins, carbohydrates and carboxylic acids, as well as sulfate, carbonate and sulfonates (coming from surfactants used in the cleaning of tanks). The main constituents of the brewery effluent are peptides and proteins coming mainly from spent yeast and diatomite filters (the presence of the latter was confirmed by Sisingle bondO bands in the FTIR spectrum). The municipal landfill leachate is characterized by the majority presence of humic substances (typical of an old landfill) and a residual presence of small peptides, amino acids and carboxylic acids. Additionally, several inorganic compounds were identified by FTIR, such as nitrate, sulfate, phosphate and cyanide ions. The textile effluent from a cotton-based industry contains carbohydrates, carboxylic acids and sulfonates, which can act as auxochromes in the textile industry. The dairy effluent comprises amino acids and small peptides coming from the biodegradation of milk and whey in addition to carbohydrates (lactose) and carboxylic acids (mainly lactic acid). The presence of tyrosine-like peaks B in the EEMF spectrum of the slaughterhouse effluent indicates the existence of small peptides and amino acids coming from the biodegradation of blood proteins. Additionally, residual glucose, fatty acids, phosphate and sulfate were also identified in this effluent

Assessment of energy poverty in Andalusian municipalities. Application of a combined indicator to detect priorities

This study aims to assess the energy poverty risk in the municipalities in Andalusia (Spain) to know their existing differences to prioritise the aids in the municipalities with greater needs. For this purpose, a composed indicator is developed. This new indicator is based on the so-called High Energy Requirements (HER) index, where proxy indicators related to the building energy efficiency are joint and where climate severity indicators, together with the income conditions and the gender gap of the population, are included. This new indicator assesses energy poverty globally, joining the indicators related to the characteristics of the dwelling stock with other factors related to energy poverty, such as monetary poverty or gender gap. The results are analysed at a municipal level, so the cases with greater problems both in general terms and those particularly from partial aspects (such as the conservation state or the type of climate) are identified. This characterisation of the phenomenon allows the most appropriate policies to be identified according to the indicators presenting the most unfavourable values, thus constituting a useful tool to prioritise and to implement measures adapted to each municipality’s needs

Influence of Fruit Ripening on the Total and Individual Capsaicinoids and Capsiate Content in Naga Jolokia Peppers (Capsicum chinense Jacq.)

"Naga Jolokia" (Capsicum chinense Jacq.) is a hot pepper variety native to India which has received the attention of the global scientific community due to its high capsaicinoid concentration. The present study evaluated the influence of fruit ripening on the total and individual capsaicinoids, as well as capsiate content. The aim was to determine the optimal moment to harvest the peppers depending on their pungent properties. Ultrasound-assisted extraction (UAE) using methanol as the extraction solvent and reverse-phase ultra-high-performance liquid chromatography (UHPLC-photodiode array (PDA)) were employed. Capsaicinoids gradually accumulated in the peppers from the moment they started growing until they reached a maximum concentration (7.99 +/- 0.11 mg g(-1) of fresh weight (FW)) at 33 days postanthesis (dpa). For this reason, based on its content of pungent compounds, as it is one of the main attributes of this variety, the optimal time for collection would be on day 33. From then on, there was a sharp decrease (96.35% of the total concentration) due to the peroxidase enzymes. The evolution of the principal capsaicinoids in "Naga Jolokia" peppers had a different behavior with respect to literature reports. After this investigation, these changes in content can be attributed to each pepper genotype. Capsiate content reached it maximum value at 19 dpa (0.27 +/- 0.01 mg g(-1) of FW). Then, there was a gradual drop due to the activities of different peroxidases. Given the important biological activity of capsaicinoids and capsinoids, the information described here allows for determining the ideal time to harvest "Naga Jolokia" peppers

Development of a Rapid UHPLC-PDA Method for the Simultaneous Quantification of Flavonol Contents in Onions (Allium cepa L.)

Onion, one of the most consumed vegetables in the world, is also known to contain high levels of antioxidant compounds, with protective effects against different degenerative pathologies. Specifically, onion is rich in flavonols, mainly quercetin derivatives, which are compounds with high antioxidant and free radical scavenging power. For this reason, it is of the utmost importance to count on optimal analytical methods that allow for the determination and quantification of these compounds of interest. A rapid ultra-high performance liquid chromatography (UHPLC)-photo-diode array (PDA) method for the separation of the major flavonols in onions was developed using a Box-Behnken design in conjunction with multiresponse optimization on the basis of the desirability function. The conditions that provided a successful separation were 9.9% and 53.2% of phase B at the beginning and at the end of the gradient, respectively; 55 degrees C column working temperature; and 0.6 mL min(-1) flow rate. The complete separation was achieved in less than 2.7 min with excellent chromatographic characteristics. The method was validated, and its high precision, low detection and quantification limits, good linearity, and robustness were confirmed. The correct applicability of the method improves the analysis of the raw material, increasing the quality of onions and its subproducts in terms of bioactive compounds and functional characteristics for consumers

Development of Optimized Ultrasound-Assisted Extraction Methods for the Recovery of Total Phenolic Compounds and Anthocyanins from Onion Bulbs

Allium cepa L. is one of the most abundant vegetable crops worldwide. In addition to its versatile culinary uses, onion also exhibits quite interesting medicinal uses. Bulbs have a high content of bioactive compounds that are beneficial for human health. This study intends to develop and optimize two appropriate ultrasound-assisted methods for the extraction of the phenolic compounds and anthocyanins present in red onion. A response surface methodology was employed and, specifically, a Box-Behnken design, for the optimization of the methods. The optimal conditions for the extraction of the phenolic compounds were the follows: 53% MeOH as solvent, pH 2.6, 60 & DEG;C temperature, 30.1% amplitude, 0.43 s cycle, and 0.2:11 g sample/mL solvent ratio. On the other hand, the optimal conditions for the anthocyanins were as follows: 57% MeOH as solvent, pH 2, 60 & DEG;C temperature, 90% amplitude, 0.64 s cycle, and 0.2:15 g sample/mL solvent ratio. Both methods presented high repeatability and intermediate precision, as well as short extraction times with good recovery yields. These results illustrate that the use of ultrasound-assisted extraction, when properly optimized, is suitable for the extraction and quantification of the compounds of interest to determine and improve the quality of the raw material and its subproducts for consumers.This work has been supported by the project "EQC2018-005135-P" (Equipment for liquid chromatography using mass spectrometry and ion chromatography), of the State Subprogram of Research Infrastructures and Technical Scientific Equipment. This research was funded by the University of Cadiz, by the INIA (National Institute for Agronomic Research), and FEDER (European Regional Development Fund, within the framework of the Operational Programme under the Investment for Growth 2014-2020) who provided financial support (Project RTA2014-00083-C03-03), and by the Ministry of Science and Innovation of Spain (FPU grant AP-2018-03811 to Ana Velasco Gonzalez de Peredo)

Flavonol Composition and Antioxidant Activity of Onions (Allium cepa L.) Based on the Development of New Analytical Ultrasound-Assisted Extraction Methods

The onion is one of the most cultivated and consumed vegetables, and is a very valuable source of antioxidant substances. Every onion variety is rich in flavonols-mainly quercetin derivatives which makes onions the main dietary source of these compounds. This study intends to develop an ultrasound-assisted extraction method (UAE), an economical, green, and efficient technique, that allows us to determine the quality of onion extracts in terms of flavonol composition and antioxidant activity. For this purpose, an ultrasound-assisted extraction method has been optimized to obtain extracts with a high amount of flavonols, as well as with a high antioxidant activity, not only separately using a Box-Behnken design, but also simultaneously, based on multi-response optimization. Multiple response optimization has not only demonstrated an efficacy level similar to that of the individual ones, but it also represents a considerable reduction in terms of cost, time and work. The optimal conditions for simultaneous extractions were determined as follows: 76.8% methanol as an extraction solvent at pH 2 and 58.5 degrees C temperature, 85% amplitude, 0.9 s cycle, and 0.2:13 g:mL sample mass/solvent volume ratio. Furthermore, the developed method exhibited a high precision level and great recoveries in a rather short extraction time (2 min). These results, together with the development of a fast and simple UHPLC analysis method, lead us to consider the developed UAE method as a suitable technique for the extraction of bioactive compounds from onion matrices.This work has been supported by the project "EQC2018-005135-P" (Equipment for liquid chromatography by means of mass spectrometry and ion chromatography), of the State Subprogram of Research Infrastructures and Technical Scientific Equipment. This research was funded by University of Cadiz, by the INIA (National Institute for Agronomic Research) and FEDER (European Regional Development Fund, within the framework of the Operational Programme under the Investment for Growth 2014-2020) for their financial support (Project RTA2014-00083-C03-03), and by the Ministry of Science and Innovation of Spain (FPU grant AP-2018-03811 to Ana Velasco Gonzalez de Peredo)

Assessment of Ultrasound Assisted Extraction as an Alternative Method for the Extraction of Anthocyanins and Total Phenolic Compounds from Maqui Berries (Aristotelia chilensis (Mol.) Stuntz)

Research interest regarding maqui (Aristotelia chilensis) has increased over the last years due to its potential health benefits as one of the most antioxidant-rich berries. Ultrasound-assisted extraction (UAE) is an advanced green, fast, and ecological extraction technique for the production of high quality extracts from natural products, so it has been proposed in this work as an ideal alternative extraction technique for obtaining extracts of high bioactivity from maqui berries. In order to determine the optimal conditions, the extraction variables (percentage of methanol, pH, temperature, ratio “sample mass/volume of solvent”, amplitude, and cycle) were analyzed by a Box-Behnken design, in conjunction with the response surface method. The statistical analysis revealed that the temperature and the percentage of methanol were the most influential variables on the extraction of the total phenolic compounds and total anthocyanins, respectively. The optimal extraction time was determined at 15 min for total phenolic compounds, while it was only 5 min for anthocyanins. The developed methods showed a high precision level with a coefficient of variation of less than 5%. Finally, the new methods were successfully applied to several real samples. Subsequently, the results were compared to those that were obtained in previous experiments by means of microwave assisted extraction (MAE). Similar extraction yields were obtained for phenolic compounds under optimized conditions. However, UAE proved to be slightly more efficient than MAE in the extraction of anthocyanins

Changes in Capsiate Content in Four Chili Pepper Genotypes (Capsicum spp.) at Di erent Ripening Stages

Interest in the consumption of the fruits of pepper (Capsicum spp.) is not only due to its organoleptic characteristics, but also due to its bioactive compounds content, which are reported to provide essential benefits to human health. However, the amount and diversity of these compounds in each fruit specimen depend on its genotype and on a number of environmental factors. This work describes the quantitative ultra-high-performance liquid chromatography coupled to photodiode-array (UHPLC-PDA) analysis of the capsinoids content in four varieties of pepper ('Habanero', 'Habanero Roxo', 'Bode', and 'Malagueta') grown until different development stages in a greenhouse under controlled conditions. In all the varieties analyzed, capsiate was the only capsinoid found. The accumulation of capsiate, in all the pepper varieties, started from the 10th to the 20th day post-anthesis (dpa), and increased during the first days (between the 20th and the 27th dpa). From that moment a drastic reduction took place until the end of the ripening stage, except for 'Bode' peppers, where the capsiate content increased from the first harvest point on the 20th dpa up to the 76th dpa. The capsiate accumulation patterns over the development of the fruit has been related to the capsaicionoids accumulation patterns in the same samples of the four varieties of pepper. According to our results, the content evolution of both families of compounds will vary depending on each fruit's genotype, as well as on environmental conditions. No clear trends have been established and, therefore, an in-depth analysis under controlled conditions should be carried out

Content of Capsaicinoids and Capsiate in “Filius” Pepper Varieties as A ected by Ripening

Peppers are fruits with wide genetic variability and multiple ways of being consumed that hold a relevant position in the human diet. Nowadays, consumers are interested in new gastronomic experiences provided by pepper cultivars that present new shapes, colors, and flavors while preserving their bioactive compounds, such as their capsaicinoids and capsinoids. However, numerous changes take place during their development that may alter their biological properties. Therefore, this work evaluates the capsaicinoid and capsiate contents in two traditional varieties of ornamental peppers ("Filius Blue" and "Filius Green'") during fruit maturation. The aim is to determine the ideal harvesting moment depending on the farmer's objective (e.g., achieving a specific color, shape, or flavor; achieving the maximum concentrations of bioactive compounds). The capsaicinoid contents followed different patterns in the two varieties analyzed. The "Filius Blue" variety exhibited increasing concentrations of capsaicinoids up to the 41st day post-anthesis (dpa), from which point on this trend was reversed. The concentrations in the "Filius Green" variety increased and decreased several times, reaching maximum concentrations on the 69th dpa. Regarding capsiate contents, both varieties varied in the same way, reaching maximum concentrations on the 34th dpa and then decreasing

Alternative Ultrasound-Assisted Method for the Extraction of the Bioactive Compounds Present in Myrtle (Myrtus communis L.)

The bioactive compounds in myrtle berries, such as phenolic compounds and anthocyanins, have shown a potentially positive effect on human health. Efficient extraction methods are to be used to obtain maximum amounts of such beneficial compounds from myrtle. For that reason, this study evaluates the effectiveness of a rapid ultrasound-assisted method (UAE) to extract anthocyanins and phenolic compounds from myrtle berries. The influence of solvent composition, as well as pH, temperature, ultrasound amplitude, cycle and solvent-sample ratio on the total phenolic compounds and anthocyanins content in the extracts obtained were evaluated. The response variables were optimized by means of a Box-Behnken design. It was found that the double interaction of the methanol composition and the cycle, the interaction between methanol composition and temperature, and the interaction between the cycle and solvent-sample ratio were the most influential variables on the extraction of total phenolic compounds (92.8% methanol in water, 0.2 s of cycle, 60 ◦C and 10:0.5 mL:g). The methanol composition and the interaction between methanol composition and pH were the most influential variables on the extraction of anthocyanins (74.1% methanol in water at pH 7). The methods that have been developed presented high repeatability and intermediate precision (RSD < 5%) and the bioactive compounds show a high recovery with short extraction times. Both methods were used to analyze the composition of the bioactive compounds in myrtle berries collected from different locations in the province of Cadiz (Spain). The results obtained by UAE were compared to those achieved in a previous study where microwave-assisted extraction (MAE) methods were employed. Similar extraction yields were obtained for phenolic compounds and anthocyanins by MAE and UAE under optimal conditions. However, UAE presents the advantage of using milder conditions for the extraction of anthocyanins from myrtle, which makes of this a more suitable method for the extraction of these degradable compounds