Application of Dispersive Liquid-Liquid Aerosol Phase Extraction to the Analysis of Total and Individual Phenolic Compounds in Fried Extra Virgin Olive Oils.

Seventeen extra virgin olive oil samples from Valencian Community (Spain) were submitted to a domestic-frying process (180 °C) during different degradation times (5, 10, 30, 60, 120 min). A dispersive liquid-liquid aerosol phase extraction by using a methanol/water (50:50) extracting solution was used to isolate the polyphenol fraction. Total phenolic content (TPC) was determined, whereas the determination of seven individual target polyphenolic compounds (hydroxytyrosol, tyrosol, oleuropein, vanillic acid, p-coumaric acid, ferulic acid, and vanillin) was carried out by using ultrahigh-performance liquid chromatography coupled to a tandem mass spectrometer. Statistically significant differences in the TPC values were found for Blanqueta and Manzanilla samples from different harvesting years. The domestic-frying process impacted the TPC and the individual phenolic compounds content. Thermal treatment for 2 h gave rise to a 94% decrease in the TPC. A first-order kinetic model was suitable to accurately describe the degradation of the individual phenolic compounds.

Sensory Attributes and Instrumental Chemical Parameters of Commercial Spanish Cured Ewes' Milk Cheeses: Insights into Cheese Quality Figures.

The external appearance of some of the Protected Designation of Origin (PDO) cured cheeses is similar to other cheese samples made in Spain: 1 kg and 2.5-3 kg formats, cylindrical, and with or without a pleita mark on the surface. In this work, commercial cured ewe's milk cheese samples with a similar external appearance were analyzed, including five PDO and five non-PDO samples. The parameters analyzed were color, texture, pH, humidity, water activity, and the volatile profile. Additionally, a descriptive and consumer-sensory analysis of the cheese samples was carried out. Statistical analysis of the results showed that luminosity, color coordinates a* and b*, percentage of deformation, humidity, water activity, and acid contents were significantly higher in non-PDO cheese samples. The breaking force, maximum force, and the content of esters were significantly higher in those cheese samples with PDO. In addition, PDO cheese samples showed higher scores for all attributes evaluated by consumers, except for color. These results suggest that PDO cheeses are placed on the market with a higher degree of ripening than non-PDO ones and that consequently they are more positively valued by consumers.

Oxygen Scavenger and Antioxidant LDPE/EVOH/PET-Based Films Containing ß-Carotene Intended for Fried Peanuts (Arachis hypogaea L.) Packaging: Pilot Scale Processing and Validation Studies.

The aim of this study was to develop an oxygen scavenger and antioxidant active packaging material for fried peanuts. The packaging solution, which has been made at the laboratory previously, has been developed by cast film extrusion and is composed of low-density polyethylene-ethylene vinyl alcohol-polyethylene terephthalate (LDPE/EVOH/PET)-based films containing ß-carotene (CAR). In comparison with film without additive, developed film presented an orange colouring (higher L* and b* values and lower a* values) and an increase in oxygen induction time (OIt) from 4.5 to 14.1 min. The incorporation of ß-carotene to the formulation also brings about a significant effect on the thermal stability as maximum degradation temperatures increased around 1%. Regarding the oxygen absorption capacity of the films, values of 1.39 ± 0.10 mL O2 per g of film at laboratory scale and 1.7 ± 0.3 mL O2 per g of multilayer (ML)/LDPE_CAR were obtained, respectively, after 3 days, proving the suitability of the packaging solutions as oxygen absorbers. To validate the packaging solution, the oxidative stability of fried peanuts packed in fabricated multilayer ß-carotene bags was evaluated for 3 months at 40 °C. The hexanal content remained constant during this period. Meanwhile, peanuts packed in ML without ß-carotene increased their hexanal content to 294%. This fact indicated a lower extent of oxidation in fried peanuts compared to food samples packaged in control films, suggesting the potential of ML/LDPE_CAR films as sustainable and antioxidant food packaging systems to offer protection against lipid oxidation in foods. Sensory evaluation confirmed that ML/LDPE_CAR films provided the peanut samples with an extra aroma due to the volatile degradation products of ß-carotene (such as ß-cyclocitral or 6-methyl-5-hepten-2-ol).

Optimization of Volatile Compounds Extraction from Industrial Celery (Apium graveolens) By-Products by Using Response Surface Methodology and Study of Their Potential as Antioxidant Sources.

In this study, the potential of industrial celery by-products (the stalk and root) serving as sources of aromatics and antioxidants was investigated. A headspace solid phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) procedure was optimized to isolate volatile compounds from celery by-products. A Box-Behnken experimental design was proposed to optimize the procedure through a response surface methodology. The optimal extraction conditions were found to be 1.6 g of homogenized fresh by-product at 30 °C for 60 min. Under these conditions, 26 volatile compounds in stalk and root samples were identified, monoterpenes and sesquiterpenes being the main components. The content of limonene and γ-terpinene found in the stalk was significantly higher in comparison with root samples. Total phenolic content and antioxidant activity (ABTS and FRAP) results underlined the celery wastes studied as good sources of free radical scavengers. This work suggests the potential application of these by-products in the food industry and opens new pathways to valorize celery residues, contributing to the circular economy.

Potential of Industrial Pineapple (Ananas comosus (L.) Merrill) By-Products as Aromatic and Antioxidant Sources.

Pineapple is meanly commercially processed. However, it is a fruit that generates a high proportion of nonedible wastes, which are rich in antioxidant compounds and have a varied aromatic profile. These characteristics turn these by-products into potential agri-food waste that can be revalued and applied in different fields such as medical, pharmaceutical, or food applications. The aim of the present work was the characterization and extraction of the volatile compounds present in two pineapple by-products (peel and core) and the subsequent evaluation of their antioxidant capacity. For this purpose, the analysis of the aromatic profile of both by-products has been carried out using the headspace solid-phase microextraction technique coupled to gas chromatography with a mass spectrometry detector (HS-SPME-GC-MS). The optimization of the extraction conditions of the volatile compounds has been validated using a Box-Behnken experimental design. In addition, a quantitative analysis was carried out to determine the contents of two important volatiles in pineapple wastes, isopentyl, and ethyl acetate. Moreover, the estimation of the antioxidant capacity of the subproducts extracts was carried out using different methods All the antioxidant assays demonstrated that pineapple subproducts are rich in easily extractable antioxidants with possible applications in the food industry.

Volatile Profile of Nuts, Key Odorants and Analytical Methods for Quantification.

The presence of nuts in diets has notably increased due to their composition, and the presence of antioxidants and their unsaturated fatty acid profile has led to a considerable increase in their consumption. The volatile profile of nuts is important from different points of view. It affects consumer's selection, influences raw material selection for the production of composite foods, dictates variety selection in breeding programs, and, from a quality perspective, its changes can indicate food degradation or alteration. A review of the published bibliography concerning the determination of volatiles in nuts has been carried out. The information retrieved has been divided into four main sections. First, a discussion on the main volatiles present in nuts is performed; next, a revision of the methods used to determine the volatiles is presented; and, finally, two sections describing how harvesting conditions, healthy state and the thermal treatment of nuts modifies their volatile profile are added. Analysis of the published bibliography denoted the complexity of volatile determination and the different variables that can modify the compounds present in the volatile fraction of nuts.

New Trends in the Use of Volatile Compounds in Food Packaging.

In the last years, many of the research studies in the packaging industry have been focused on food active packaging in order to develop new materials capable of retaining the active agent in the polymeric matrix and controlling its release into food, which is not easy in many cases due to the high volatility of the chemical compounds, as well as their ease of diffusion within polymeric matrices. This review presents a complete revision of the studies that have been carried out on the incorporation of volatile compounds to food packaging applications. We provide an overview of the type of volatile compounds used in active food packaging and the most recent trends in the strategies used to incorporate them into different polymeric matrices. Moreover, a thorough discussion regarding the main factors affecting the retention capacity and controlled release of volatile compounds from active food packaging is presented.

Double-Function Oxygen Scavenger and Aromatic Food Packaging Films Based on LDPE/Polybutadiene and Peanut Aroma.

The aim of this study was to develop a double function active packaging material for nuts. The packaging solution, on the one hand, integrated polybutadiene (PB) as an oxygen scavenger and, on the other hand, it incorporated peanut aroma (PA) to improve customer's sensorial experience. Different formulations based on low density polyethylene (LDPE), commercial PA (5 wt %) and PB at two levels (5 wt % and 13 wt %) were obtained by cast film extrusion. The obtained films were compared in terms of their mechanical, structural, optical and thermal properties confirming a plasticizing effect of PA and PB resulting in an increase in the ductility of the polymer and in a slight decrease in the thermal properties, maintaining their transparency. Regarding the oxygen capacity of the films, values of 4.4 mL and 2.7 mL O2 g-1 film were obtained for PE/PA/PB13 and PE/PA/PB5, respectively, after 6 days proving the suitability of the UV irradiation treatment in improving the oxygen absorption capacity of PB without the need of a metal catalyst. The aroma retention capacity into the polymer matrix was also evaluated in the developed formulations. The incorporation of PB in 13 wt % into a LDPE matrix improved the PA retention. This behavior was attributed to the ability of PB in enhancing cross-linking of LDPE as the concentration of PB increases. The results suggested the potential of PE/PB/PB13 films as oxygen scavenger and aromatic food packaging system to offer protection against lipid oxidation in nuts.

Effect of Frying and Roasting Processes on the Oxidative Stability of Sunflower Seeds (Helianthus annuus) under Normal and Accelerated Storage Conditions.

The effect of different cooking processes such as frying and roasting on the oxidative stability of sunflower seeds was evaluated under accelerated oxidation and normal storage conditions. The fatty acid composition by GC-MS showed a higher amount of linoleic acid in fried samples due to the replacement of the seed moisture by the frying oil. On the other hand, roasted samples presented a higher oleic acid content. DSC and TGA results showed some decrease in the thermal stability of sunflower seed samples, whereas PV and AV showed the formation of primary and secondary products, with increasing oxidation time. Roasted sunflower seeds showed seven main volatile compounds characteristic of the roasting process by HS-SPME-GC-MS: 2-pentylfuran, 2,3-dimethyl-pyrazine, methyl-pyrazine, 2-octanone, 2-ethyl-6-methylpyrazine, trimethyl-pyrazine, and trans,cis-2,4-decadienal, whereas fried samples showed six volatile characteristic compounds of the frying process: butanal, 2-methyl-butanal, 3-methyl-butanal, heptanal, 1-hexanol, and trans,trans-2,4-decadienal. The generation of hydroperoxides, their degradation, and the formation of secondary oxidation products were also investigated by ATR-FTIR analysis. The proposed methodologies in this work could be suitable for monitoring the quality and shelf-life of commercial processed sunflower seeds with storage time.

Variability of Chemical Profile in Almonds (Prunus dulcis) of Different Cultivars and Origins.

Almonds show a great variability in their chemical composition. This variability is a result of the existence of a diverse range of almond cultivars, the self-incompatibility of most almond cultivars, and the heterogeneous harvesting conditions found around the different locations where almons are grown. In the last years, the discrimination among almond cultivars has been the focal point of some research studies to avoid fraud in protected geographical indications in almond products and also for selecting the best cultivars for a specific food application or the most interesting ones from a nutritional point of view. In this work, a revision of the recent research works related to the chemical characterization and classification of almond cultivars from different geographical origins has been carried out. The content of macronutrients, tocopherols, phytosterols, polyphenols, minerals, amino acids, and volatile compounds together with DNA fingerprint have been reported as possible cultivar and origin markers. The analysis of the results showed that no individual almond compound could be considered a universal biomarker to find differences among different almond cultivars. Hence, an adequate selection of variables or the employment of metabolomics and the application of multivariate statistical techniques is necessary when classification studies are carried out to obtain valuable results. Meanwhile, DNA fingerprinting is the perfect tool for compared cultivars based on their genetic origin.

The effect of sewage sludge containing microplastics on growth and fruit development of tomato plants.

Microplastics (MPs) are becoming an environmental growing concern, being the sewage sludge applied to agriculture fields one of the most important inputs to the environment. To date, there is no standardized protocol for their extraction and changes in vegetative growth and fruit maturation on cultivated plants induced by sludge containing MPs have not been studied yet. Sewage sludge from three different wastewater treatment plants located in Murcia, Spain, were studied. First, the microplastic concentration was estimated and, then, the effects of the sewage sludge in the development of tomato plants and fruit production was analyzed. The measured parameters in tomato plants were both, biomass and length, for shoot and root part, as well as, stem diameter and tomato production. The present work has developed and validated a protocol for the extraction and quantification of MPs comprising several shapes, materials and sizes from samples of sewage sludges, which offers a good compromise for the extraction of different types of microplastic. The protocol used for MPs extraction had a recovery efficiency of 80 ± 3% (mean ± SE) and used bicarbonate, to maximize MPs extraction. The mean abundance of MPs in the studied sewage sludge samples was 30,940 ± 8589 particles kg-1 dry weight. Soils with sludge containing MPs fostered the growth of tomato plants, while delaying and diminished fruit production. However, other factors or their interactions with MPs could have influenced the outcomes. Further studies are necessary to corroborate these findings and explain the mechanisms of possible effects of MPs on plants.

Biodegradable plastics can alter carbon and nitrogen cycles to a greater extent than conventional plastics in marine sediment.

The seabed constitutes a global sink for plastic debris, where they can remain for centuries. Biodegradable plastics offer the advantage of having less persistence in the environment than conventional ones. The seabed is responsible for key ecosystem functions related to the cycling of elements by decomposing the labile fraction of organic matter and fueling primary production, while storing the most recalcitrant part of this organic matter and limiting CO2 emissions. Although plastics are expected to affect these processes, knowledge on this matter is scarce. In controlled microcosms, we show that biodegradable plastics can stimulate the decomposition of marine-buried carbon and reduce the release of inorganic nitrogen. We found that conventional and biodegradable plastics promoted anaerobic sediment metabolic pathways. Biodegradable plastics produced a two-fold CO2 release to the water column, which suggests the decomposition of not only plastics, but also of buried organic carbon. The stimulation of sediment metabolism could be due to excessive carbon consumption by bacteria that derives from a rise in the carbon:nitrogen ratio. Accordingly, the NH4+ flux to the water column lowered. As NOx fluxes also lowered, biodegradable plastics might promote nitrification-denitrification coupling. If biodegradable plastics become a major component of marine pollution, then sediment biogeochemical cycles might be strongly influenced, which could affect the carbon sequestration of coastal ecosystems and compromise their mitigation capacity against climate change.

Authentication of "Adelita" Raspberry Cultivar Based on Physical Properties, Antioxidant Activity and Volatile Profile.

Agricultural selection programmes are, today, working hard to obtain novel raspberry cultivars with higher nutritional and commercial quality. One of those cultivars is "Adelita". This study aims to provide novel tools for raspberry cultivar identification-more specifically, the differentiation of "Adelita" from other raspberry cultivars. To perform this study, five "Adelita" samples were analysed-four cultivated in Spain and one, in Morocco-and they were compared to seven samples from six raspberry cultivars ("P04", "Lupita", "Enrosadira", "P10", "Quanza" and "Versalles"). The physical parameters (mass, length, equatorial diameter and firmness) combined with the Total Phenolic Content (TPC); the antioxidant capacity according to the antioxidant activity tested with the 2,2-diphenyl-1-picrylhydrazyl (DPPH), ferric-reducing antioxidant power (FRAP) and 2,2-azinobis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) methods; and the main target volatile compounds were used as independent variables. Principal component and cluster analysis showed that the target volatiles and physical parameters together with the TPC and DPPH values could be useful to classify Adelita cultivars separately from the rest of the cultivars included in the work. Those results proved that the developed methodology could be proposed as a reliable approach for the identification of cultivar fraud in the supply chain.

Novel Antioxidant Packaging Films Based on Poly(ε-Caprolactone) and Almond Skin Extract: Development and Effect on the Oxidative Stability of Fried Almonds.

Antioxidant films based on poly(ε-caprolactone) (PCL) containing almond skin extract (ASE) were developed for food packaging applications. The effect of ASE incorporation on the morphological, structural, colour, mechanical, thermal, barrier and antioxidant properties of the prepared films were evaluated. The structural, tensile and thermal properties of the films were not altered due to ASE addition. Although no significant differences were observed for the oxygen permeability of samples, some increase in water absorption and water vapour permeability was observed for active films due to the hydrophilic character of ASE phenolic compounds, suggesting the suitability of this novel packaging for fatty foods conservation. ASE conferred antioxidant properties to PCL films as determined by the DPPH radical scavenging activity. The efficiency of the developed films was evaluated by the real packaging application of fried almonds at different ASE contents (0, 3, 6 wt.%) up to 56 days at 40 °C. The evolution of peroxide and p-anisidine values, hexanal content, fatty acid profile and characteristic spectroscopy bands showed that active films improved fried almonds stability. The results suggested the potential of PCL/ASE films as sustainable and antioxidant food packaging systems to offer protection against lipid oxidation in foods.

Monitoring polymer degradation under different conditions in the marine environment.

The perdurability of plastics in the environment is one of the major concerns of plastic pollution and, as a consequence, oceans are accumulating large amounts of plastic. The degradation of conventional and biobased materials was evaluated through a laboratory experiment for a year simulating four different conditions in the marine environment. The water column environmental compartment was simulated under euphotic and aphotic (with and without light availability) conditions. The seafloor environmental compartment was simulated with sediment under non-polluted and polluted conditions. By combining weight loss (%), spectroscopic and thermal analyses, the degradation patterns regarding the polymer structure were assessed. The studied biobased materials were polylactic acid (PLA) based materials and showed higher degradability than conventional ones. The weight loss of conventional materials was not influenced by the water column or sediment, while in PLA-based materials, the degradation rates were ca. 5 times greater in the sediment than in the water column. The absorbance (Abs) value at 3400 cm-1 for polyethylene terephthalate (PET), and carbonyl (CO) index for PET and PLA could be useful to detect early signs of degradation. The crystallization index could be a useful parameter to discriminate degradation stages. The obtained results highlight the different degradability rates of materials depending on the specific environmental marine conditions.

Plastic debris accumulation in the seabed derived from coastal fish farming.

In this study, we assessed plastic accumulation in marine sediments due to finfish aquaculture using floating net-pens. We studied plastic concentrations around three fish farms located at the Mediterranean coastline of Spain. The macroplastic categories and abundances were determined by video monitoring, detecting the majority of elements (78%), including ropes, nets and fibres, a basket trap and a cable tie, close to the facilities, which were not exclusively linked to fish farming but also to fishing activities. Concentrations of microplastics (<5 mm) ranged from 0 to 213 particles/kg dry weight sediment with higher values in sites directly under the influence of the fish farms. Most particles (27.8%) were within the size fraction from 1.1 to 2.0 mm and fibre was the most common shape with 62.2%. The Infrared spectroscopy analysis showed that PE and PP were the predominant types of polymers analysed. In addition, changes in the enthalpy of melting (ΔHm (J/g)) and the degree of crystallinity indicate degradation of the microplastics analysed. This study shows that, in the studied fish farms, levels of microplastic pollution can be one order of magnitude lower compared to other areas suffering other anthropogenic pressures from the same or similar regions. Nevertheless, more research effort is needed to get concluding results.

Influence of Cooking and Ingredients on the Antioxidant Activity, Phenolic Content and Volatile Profile of Different Variants of the Mediterranean Typical Tomato Sofrito.

In this study, six different sofrito formulations were compared with the raw recipe for total phenolic content (TPC), antioxidant activity tested by 2,2-diphenyl-1-picrylhydrazyl (DPPH), ferric-reducing antioxidant power (FRAP) and 2,2-azinobis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) methods. The volatile profile was also obtained by the headspace solid-phase microextraction-gas chromatography mass spectrometry (HS-SPME-GC-MS) procedure. The cooking process and the addition of herbs, and garlic improved the final content of antioxidant compounds compared to the basic recipe and the raw ingredients. The total volatile content was higher in the samples that contained rosemary and thymus. Some of the volatiles had proven antioxidant properties and for that reason the sofrito with rosemary with the higher volatile content was also the one with the higher antioxidant capacity and TPC. In conclusion, as well as the processing technique, the addition of selected typical Mediterranean herbs apart from given flavour can contribute to improving the nutritional antioxidant profile of dishes and be used as a natural method to increase the shelf-life of preparation.

Characterization and classification of almond cultivars by using spectroscopic and thermal techniques.

UNLABELLED: Three different almond cultivars (Spanish Guara, Marcona, and Butte from U.S.A.) were characterized by using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and thermal analysis techniques (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). All samples were directly analyzed without the need of a previous oil extraction. Similar FTIR bands were observed for all studied cultivars corresponding to specific functional groups characteristics of almond ingredients (water, fat, protein, and carbohydrates). Significant differences were observed between cultivars according to absorbance and maximum wave number values of specific bands observed by FTIR and melting and crystallization parameters obtained by DSC. TGA showed that samples were stable up to around 220 °C. Different stages of degradation were observed with increasing temperature corresponding to the degradation of the complex matrix of the samples. Successful discrimination was obtained for all samples by applying multivariate stepwise linear discriminant analysis (LDA) separately to data obtained from FTIR and DSC. A satisfactory multidisciplinary approach was also performed by inserting together all parameters obtained from the 3 techniques as predictors ensuring higher reliability of the obtained model. The obtained results proved the suitability of the studied analytical techniques combined with LDA for an easy and fast discrimination among different almond cultivars in food processing. PRACTICAL APPLICATION: The study of spectroscopic and thermal parameters could be used as a control tool for the direct and fast assessment of almond samples in food processing, particularly for protected designation of origin products.