Toxicological analysis of metals content in agro-food wastes as possible supplement in animal feed.

The agro-food surplus is considered the most abundant renewable resource, interesting for the economic and environmental impact, with a possible employment in different productive fields such as supplement in animal feed. For a safe and effective enhancement of agro-food wastes it is needed a toxicological analysis before of their employment, to avoid potential risks to animals, humans and environment. The purpose of this study was to evaluate the metals content (Cu, Fe, Zn, Mg, Na, K, Ca, Mn, Se, Zn, Co, Ni, V, Sb, Mo, Cr and Pb, Cd, As, Ba), in agro-food wastes through ICP-MS analysis. The results obtained showed the presence of metals analysed with a significant content of essential micro and macro-elements; with regard to toxic metals, only strawberries and fennel samples showed Pb levels above the MRL. These data confirm, from the toxicological point of view, a possible and safe reuse of the most of all agro-food wastes, as raw material at low cost and rich of essential nutrients and particularly as supplement in animal feed.

Effect of Filtration Process on Oxidative Stability and Minor Compounds of the Cold-Pressed Hempseed Oil during Storage.

Cold-pressed hempseed oil (HO) has been increasingly exploited in the human diet for its excellent nutritional and healthy properties. However, it has a high content of polyunsaturated fatty acids (PUFAs) and chlorophylls, which inevitably accelerate its oxidative deterioration, especially in the presence of light. In this scenario, the filtration technology may ameliorate the oxidative stability of the oil, with positive effects on its nutritional quality and shelf life. Therefore, in this study, the oxidative stability and minor compounds of non-filtered and filtered HO (NF-HO and F-HO) were monitored over 12 weeks of storage in transparent glass bottles. F-HO showed a better hydrolytic and oxidative status than NF-HO during storage. As a result, F-HO also displayed better preservation of total MUFAs and PUFAs in the autoxidation process. Filtration consistently reduced chlorophylls, thus causing a variation in the natural color of HO. Accordingly, F-HO not only revealed an increased resistance to photooxidation but it was also suitable for storage in clear bottles within 12 weeks. F-HO predictably showed lower carotenoids, tocopherols, polyphenols, and squalene compared to NF-HO. However, filtration appeared to play a "protective role" toward these antioxidants, which had lower degradation rates in F-HO than NF-HO for 12 weeks. Interestingly, the element profile of HO was not affected by filtration and remained stable during the study period. Overall, this study may be of practical use to both producers and marketers of cold-pressed HO.

Nanoscale chemical analysis of 2D molecular materials using tip-enhanced Raman spectroscopy.

Two-dimensional (2D) molecular materials have attracted immense attention due to their unique properties, promising a wide range of exciting applications. To understand the structure-property relationship of these low-dimensional materials, sensitive analytical tools capable of providing structural and chemical characterisation at the nanoscale are required. However, most conventional analytical techniques fail to meet this challenge, especially in a label-free and non-destructive manner under ambient conditions. In the last two decades, tip-enhanced Raman spectroscopy (TERS) has emerged as a powerful analytical technique for nanoscale chemical characterisation by combining the high spatial resolution of scanning probe microscopy and the chemical sensitivity and specificity of surface-enhanced Raman spectroscopy. In this review article, we provide an overview of the application of TERS for nanoscale chemical analysis of 2D molecular materials, including 2D polymers, biomimetic lipid membranes, biological cell membranes, and 2D reactive systems. The progress in the structural and chemical characterisation of these 2D materials is demonstrated with key examples from our as well as other laboratories. We highlight the unique information that TERS can provide as well as point out the common pitfalls in experimental work and data interpretation and the possible ways of averting them.

Monitoring Cannabinoids and the Safety of the Trace Element Profile of Light Cannabis sativa L. from Different Varieties and Geographical Origin.

Non-intoxicating Cannabis sativa L. (i.e., hemp) is increasingly used for industrial, cosmetic and food applications. Despite the fact that the EU has not yet established a regulatory framework on hazardous compounds (i.e., toxic inorganic elements), the monitoring of cannabis products is of paramount importance to safeguard consumers, also in view of the species propensity to accumulate toxic metals from the environment. The aim of this work was to assess the compliance with Law n. 242/2016 and the safety of hemp inflorescences from different varieties and Italian regions by monitoring the main cannabinoids and trace elements. All samples complied with the Italian law due to a THC content <0.6% counterbalanced by high CBD levels. However, inflorescences grown in Apulia and Lombardy, and from Finola and Tiborzallasi varieties accumulated higher Cu, Co, Cr, Ni and Pb contents than products from other producing areas (i.e., Sicily and Latium) and varieties (i.e., Antal, Futura75, Kompolti and Carmagnola), being moreover above the limits set by the US Pharmacopeia. A principal component analysis confirmed that trace elements, including toxic metals, were mainly affected by the geographical origin more than the botanical variety. Overall, this study highlights the need to continuously monitor hemp products and establish the earliest related regulatory frameworks.

Probing coke formation during the methanol-to-hydrocarbon reaction on zeolite ZSM-5 catalyst at the nanoscale using tip-enhanced fluorescence microscopy.

The deactivation mechanism of the widely used zeolite ZSM-5 catalysts remains unclear to date due to the lack of analytical techniques with sufficient sensitivity and/or spatial resolution. Herein, a combination of hyperspectral confocal fluorescence microscopy (CFM) and tip-enhanced fluorescence (TEFL) microscopy is used to study the formation of different coke (precursor) species involved in the deactivation of zeolite ZSM-5 during the methanol-to-hydrocarbon (MTH) reaction. CFM submicron-scale imaging shows a preferential formation of graphite-like coke species at the edges of zeolite ZSM-5 crystals within 10 min of the MTH reaction (i.e., working catalyst), whilst the amount of graphite-like coke species uniformly increased over the entire zeolite ZSM-5 surface after 90 min (i.e., deactivated catalyst). Furthermore, TEFL nanoscale imaging with ∼35 nm spatial resolution revealed that formation of coke species on the zeolite ZSM-5 surface is non-uniform and a relatively larger amount of coke is formed at the crystal steps, indicating a higher initial catalytic activity.

Effect of Dietary Enrichment with Flaxseed, Vitamin E and Selenium, and of Market Class on the Broiler Breast Meat-Part 2: Technological and Sensorial Traits.

The influence of diet enrichment with flaxseed, selenium and vitamin E, and market class on breast meat was investigated in terms of technological and sensorial quality of breast meat. A randomized complete block design with an experimental unit of n = 6000 broilers receiving a standard or enriched diet, and slaughtered at 37 (light class), 47 (medium class), or 57 (heavy class) days of life, was developed. Then, enriched and standard breast muscles from every market class were studied for their technological and sensorial traits­both at 24 h post-mortem and after one month of frozen storage­by a statistical multiple linear model. Redness and yellowness of muscles significantly (p < 0.05) increased and decreased with increasing market age. Moreover, the yellowness significantly (p < 0.05) raised after frozen storage. However, obtained data were always indicative of a normal meat color. The water holding capacity improved following fed enrichment and significantly (p < 0.05) worsened after frozen storage. For the sensory analysis, juiciness and chewing rest of meat resulted significantly (p < 0.05) improved with increasing slaughtering age and diet enrichment, as well as their mutual interaction, while they deteriorated after frozen storage. Overall, fresh and enriched muscles from heavy broilers had the best technological and sensorial traits, thus, confirming that market size and diet should be highly considered to obtain breast meat with greater consumer acceptance.

The fiscal response to the Italian COVID-19 crisis: A counterfactual analysis.

The COVID-19 pandemic is an unprecedented worldwide event with a massive impact on the economic system. The first Western country that had to face the COVID-19 crisis was Italy, which therefore represents a natural "case study." By using the microdata and granular policy information available at the Italian Ministry of Economy and Finance, this paper provides a macroeconomic quantitative assessment of the initial emergency fiscal measures introduced in 2020 and an analysis of the impact of the COVID-19 shock during the lockdown. We find that emergency measures avoided an additional fall of GDP of about 4.4% in 2020. The impact of public interventions on the dynamics of investments is particularly significant.

Effect of Dietary Enrichment with Flaxseed, Vitamin E and Selenium, and of Market Class on the Broiler Breast Meat-Part 1: Nutritional and Functional Traits.

The effect of dietary enrichment with flaxseed, selenium and vitamin E, and market class on the nutritional and functional value of breast meat was evaluated. A completely randomized block design was set up, where the experimental unit (n = 6000 birds) received conventional or enriched diet and was slaughtered at 37 (light class), 47 (medium class), or 57 (heavy class) days of life. Hence, functional and standard Pectoralis major muscles from every market class were analyzed for FA composition, inorganic elements and vitamin E. Lipid metabolism indices and health lipid indicators were assessed along with the nutritional value. A multiple linear model revealed that in breasts, the dietary treatment significantly influenced (p < 0.05) the FA profile, lipid metabolism and health lipid indices, while the slaughtering weight was related (p < 0.05) to most of elements (e.g., Na, Mg, K, Mn, and Se) and vitamin E. The interdependence of the two factors had strong relations (p < 0.05) with total PUFAs, including linolenic acid, desaturase activities, health lipid indices, trace essential elements and vitamin E. Consequently, enriched meat from heavy chickens showed the best functional and nutritional traits. Overall, the study pointed out that both market class and dietary manipulation are two relevant factors to consider for producing breast meat with higher nutritional and functional value.

Aptapaper─An Aptamer-Functionalized Glass Fiber Paper Platform for Rapid Upconcentration and Detection of Small Molecules.

We tested a paper-based platform ("Aptapaper") for the upconcentration and analysis of small molecules from complex matrices for two well-characterized aptamers, quinine and serotonin binding aptamers (QBA and SBA, respectively). After incubating the aptapaper under conditions that ensure correct aptamer folding, the aptapaper was used to upconcentrate target analytes from complex matrices. Aptapaper was rinsed, dried, and the target analyte was detected immediately or up to 4 days later by paper spray ionization coupled to high-resolution mass spectrometry (PS-MS). The minimum concentrations detectable were 81 pg/mL and 1.8 ng/mL for quinine and serotonin, respectively, from 100 mM AmAc or water. Complementary characterization of the QBA aptapaper system was performed using an orthogonal fluorescence microscopy method. Random adsorption was analyte-specific and observed for quinine, but not serotonin. This aptapaper approach is a semiquantitative (10-20% RSD) platform for upconcentration of small metabolites by mass spectrometry.

Comprehensive Chemical Characterization of Chia (Salvia hispanica L.) Seed Oil with a Focus on Minor Lipid Components.

A comprehensive chemical characterization of different lipid components, namely fatty acid composition after derivatization in fatty acid methyl esters (FAMEs), triacylglycerols (TAGs), phospholipids (PLs), free fatty acids (FFAs), sterols, carotenoids, tocopherols, and polyphenols in Chia seed oil, obtained by Soxhlet extraction, was reported. Reversed phase liquid chromatography (RP-LC) coupled to UV and mass spectrometry (MS) detectors was employed for carotenoids, polyphenols, and TAGs determination; normal phase-LC in combination with fluorescence detector (FLD) was used for tocopherols analysis; PL and FFA fractions were investigated after a rapid solid phase extraction followed by RP-LC-MS and NanoLC coupled to electron ionization (EI) MS, respectively. Furthermore, gas chromatography (GC)-flame ionization (FID) and MS detectors were used for FAMEs and sterols analysis. Results demonstrated a significant content of bioactive compounds, such as the antioxidant tocopherols (22.88 µg mL-1), and a very high content of essential fatty acids (81.39%), namely α-linolenic (62.16%) and linoleic (19.23%) acids. In addition, for the best of authors knowledge, FFA profile, as well as some carotenoid classes has been elucidated for the first time. The importance of free fatty acids in vegetable matrices is related to the fact that they can be readily involved in metabolic processes or biosynthetic pathways of the plant itself. For a fast and reliable determination of this chemical class, a very innovative and sensitive NanoLC-EI-MS analytical determination was applied.

Mineral content and physico-chemical parameters of honey from North regions of Algeria.

Honey is accepted as food and medicine by all generations both ancient and modern. In this study the concentrations of K, Mg, Na, Zn, Fe, Mn, Cu, Cr, Ni, Se, As, Pb, Cd, Sb, Ti, V, Co, Hg and the determination of some physico-chemical parameters in 29 multifloral honeys collected from different North regions of Algeria: Algiers, Bouria, Ghardaïa, Laghouat, M'sila, Naâma, Tlemcen and El Bayadth during year 2018 were carried out. All minerals were determined by ICP-OES/MS and Hg by DMA-80. The most abundant minerals decreased in the following order: K, Na, Mg, Fe, Zn. Lead content exceeded the Codex Alimentarius and the European Union in all honey samples analysed, Cd and As levels were lower than the limits fixed by the European legislation and the regulations of the Codex Alimentarius. The Recommended Dietary Allowance values and benchmark levels were employed to assess the honey quality and safety.

Molecular Perturbation Effects in AFM-Based Tip-Enhanced Raman Spectroscopy: Contact versus Tapping Mode.

Tip-enhanced Raman spectroscopy (TERS) is a powerful tool for nondestructive and label-free surface chemical characterization at nanometer length scales. However, despite being considered nondestructive, the interaction of the TERS probe used in the analysis can alter the molecular organization of the sample. In this study, we investigate the role of the atomic force microscopy (AFM) feedback (contact mode and tapping mode) on molecular perturbation in TERS analysis of soft samples using a self-assembled monolayer (SAM) of 2-chloro-4-nitrobenzene-1-thiol (Cl-NBT) as a test sample. Surprisingly, the tapping mode shows a consistently higher TERS signal resulting from a minimal perturbation of the Cl-NBT SAM compared to the contact mode. This study provides novel insights into the choice of the correct AFM-TERS operation mode for nanoscale chemical analysis of soft and delicate samples and is expected to expedite the growing application of TERS in this area.

Physicochemical, Nutritional, Microbiological, and Sensory Qualities of Chicken Burgers Reformulated with Mediterranean Plant Ingredients and Health-Promoting Compounds.

The quality of chicken burgers reformulated by the partial replacement of meat by Mediterranean plant ingredients and enriched with peculiar amounts of n-3 PUFAs, Mg, Fe, Se, and folic acid, was evaluated in comparison to conventional chicken burgers. Specifically, two types of burger were developed, namely the "Sicilian burger"-based on cherry tomato and rosemary-and the "Mediterranean burger"-with basil leaves and thyme essential oil-every recipe being differentially functionalized according to the nutritional requirements of consumers, such as children, pregnant women and elderly. Mediterranean ingredients were responsible for different pH, color, and cooking loss between conventional and functional burgers. Except for n-3 PUFAs resulting poorly fortified, the functionalization with Mg, Fe, Se, and vitamin B9 was successful in all products. Considering the target consumer categories, the daily consumption of the functional burger may assure an intake of Mg, Fe, and Se equal, respectively, to 37.31-59.90%, 17.76-46.81%, and 27.20-50.05%, and a cover of vitamin B9 of 31.98-48.31% of the relative population reference intakes. Fortified products kept a good microbiological quality during 5 days of refrigerated storage, and, according to the sensorial descriptive analysis and the hedonic test, they showed a higher acceptability than conventional burgers.

Organic pollutants in marine samples from Tunisian coast: Occurrence and associated human health risks.

140 contaminants belonging to various classes (organochlorine and organophosphorus pesticides, pyrethroid insecticides, carbamates, fungicides, acaricides, herbicides, synergists, insect growth regulators, polychlorobiphenyls, polycyclic aromatic hydrocarbons) were simultaneously analysed by GC-MS/MS in marine sediments, aquatic plant leaves and fish tissues samples. A total of 260 samples from five stations along the coast of Tunisia were evaluated. The results highlight that only 28 residues (12 polychlorobiphenyls, 8 organochlorine pesticides, 7 polycyclic aromatic hydrocarbons and triphenyl phosphate) were detected at levels higher than relative LOQ values. The amounts in sediment samples were compared with Sediment Quality Guidelines (SQGs) showing that the values are acceptable and no toxic effect is expected on aquatic organisms. A little variation of contaminant residues in sediment samples among coastal stations was recorded. Namely, with respect to almost all polychlorobiphenyls and organochlorine pesticides, higher values were recorder in summer. With respect to almost all polycyclic aromatic hydrocarbons, higher values were recorder in autumn. Aquatic plant leaves showed a residue accumulation higher than that of other compartments of marine system. The data about fish samples (Sparus aurata and Sarpa salpa, the two most frequently caught fish species at five sites on the central coast of Tunisia) do not pose direct hazard to human health because values were lower than protection limits.

Properties of a New Food Supplement Containing Actinia equina Extract.

Marine species represent a great source of biologically active substances; Actinia equina (AE), an Anthozoa Cnidaria belonging to the Actinidiae family, have been proposed as original food and have already been included in several cooking recipes in local Mediterranean shores, and endowed with excellent nutraceutical potential. The aim of this study was to investigate some unexplored features of AE, through analytical screening and an in-vitro and in-vivo model. An in-vitro study, made on RAW 264.7 stimulated with H2O2, showed that the pre-treatment with AE exerted an antioxidant action, reducing lipid peroxidation and up-regulating antioxidant enzymes. On the other hand, the in-vivo study over murine model demonstrated that the administration of AE extracts is able to reduce the carrageenan (CAR)-induced paw edema. Furthermore, the histological damage due to the neutrophil infiltration is prevented, and this highlights precious anti-inflammatory features of the interesting food-stuff. Moreover, it was assessed that AE extract modulated nuclear factor kappa-light-chain-enhancer of activated B cells (NF-kB) and The nuclear factor erythroid 2-related factor 2 (Nrf-2) pathways. In conclusion, our data demonstrated that thanks to the antioxidant and anti-inflammatory properties, AE extract could be used as a new food supplement for inflammatory pathology prevention.

Carotenoids, Fatty Acids, and Volatile Compounds in Apricot Cultivars from Romania-A Chemometric Approach.

Lipophilic constituents are important for the color and aroma of apricots, but also for their health benefits. In the present study, carotenoids, fatty acids, and volatiles were analyzed in 11 apricot cultivars, from which nine were obtained in Romania. High performance liquid chromatography coupled to a diode array detector with atmospheric pressure chemical ionization and mass spectrometry (HPLC-DAD-APCI-MS methodology applied on unsaponified carotenoid extracts allowed the identification and quantification of 19 compounds. The predominant carotenoids in all cultivars were all-trans-ß-carotene and its cis isomers. Lutein was present exclusively in non-esterified form, while ß-cryptoxanthin was predominantly esterified, mainly with oleic, palmitic, lauric, and stearic acid. Moreover, ß-cryptoxanthin linoleate, linolenate, and stearate were detected for the first time in Harogem cultivar. Variation in carotenoid content and composition was observed, with the highest carotenoid content being recorded in Tudor, Harogem, and Mamaia cultivars. The predominant fatty acids determined by gas chromatography-mass spectrometry (GC-MS) were linoleic (up to 47%), palmitic (up to 32.7%), and linolenic (up to 17.16%), with small variations among cultivars. In-tube extraction technique (ITEX)/GC-MS was applied for profiling the volatiles in apricot fruits and 120 compounds were identified, with terpenoids and esters as the most abundant classes. Principal component analysis (PCA) revealed that the carotenoids and the fatty acids profile can be used for variety authentication and discrimination in apricots.

Assessment and Monitoring of Fish Quality from a Coastal Ecosystem under High Anthropic Pressure: A Case Study in Southern Italy.

Fish is a nutrient-rich food but, at the same time, consumption of fish is a possible source of exposure to heavy metals. Since many coastal Mediterranean areas suffer from great anthropomorphic pressure, the aim of this study was to assess the level of potentially toxic inorganic elements in different fish samples from the coastal zone of Southern Italy (Gela) where there is a high mortality rate linked to cancer disease and congenital malformations. The presence of mercury, cadmium, lead, nickel, arsenic, vanadium, and chromium was measured by inductively coupled plasma-mass spectrometry (ICP-MS). The risk assessment was evaluated in terms of estimated daily intake by calculating the amount of potentially toxic elements that an average individual adult weighing 60 kg would ingest. Moreover the non-carcinogenic risk was estimated by target hazard quotient (THQ). The study evidenced significant contamination by inorganic elements, especially cadmium, which can be linked to industrial pollution. The THQ indexes, as indicators of human health, suggest that the consumption of fish from the study area is not free of risk.

Tip Recycling for Atomic Force Microscopy-Based Tip-Enhanced Raman Spectroscopy.

Tip-enhanced Raman spectroscopy (TERS) is a powerful tool for the characterization of surfaces and two-dimensional materials, delivering both topographical and chemical information with nanometer-scale spatial resolution. Atomic force microscopy (AFM)-TERS combines AFM with a Raman spectrometer and is a very versatile technique, capable of working in vacuum, air, and liquid, and on a variety of different samples. A metalized AFM tip is necessary in order to take advantage of the plasmonic enhancement. The most commonly used metal is Ag, thanks to its high plasmonic activity in the visible range. Unfortunately, though, the tip metallization process is still challenging and not fully reliable, yielding inconsistent enhancement factors even within the same batch of tips; as a consequence, many tips are usually prepared at once (for a single experiment), to ensure that at least one of them is sufficiently active. As the lifetime of an unprotected, Ag-coated plasmonic probe is only a few hours, the procedure is inefficient and results in a substantial waste of materials and money. In this work, we establish a cleaning routine to effectively re-use Ag-coated AFM-TERS probes, drastically reducing costs without compromising the quality of the experimental results.

Grape water: reclaim and valorization of a by-product from the industrial cryoconcentration of grape (Vitis vinifera) must.

BACKGROUND: The term 'grape (Vitis vinifera) water' refers to a by-product from the cryoconcentration of must that, if not reclaimed, would be considered as wastewater. In this study, the nutraceutical potential of waters reclaimed from the cryoconcentration of Grillo and Moscato musts was evaluated. RESULTS: Both waters showed physicochemical parameters in agreement with Italian regulation for drinking water, and interesting levels of F- (3.02-8.02 mg L-1 ) and SO4 - (52.85-49.34 mg L-1 ). Inorganic elements, including Mg (5.54-7.78 mg L-1 ), K (47.12-59.87 mg L-1 ), Fe (219.09-205.32 µg L-1 ), and Zn (189.65-127.30 µg L-1 ), and phenolic contents <35 mg GAE L-1 contributed to determine moderate antioxidant activities. Considering fatty acid composition, oleic and linoleic acids predominated, being higher in Moscato than Grillo samples (64.42% versus 58.22%, and 5.42% versus 6.07%). Grape waters displayed also rich aroma profiles, including mainly esters, alcohols and terpenoids. The latter components (i.e. linalool and α-terpineol) were more abundant in Moscato than in Grillo (13% versus 8%). Interestingly, some minor volatiles, characterized the vine of provenance (e.g. benzaldehyde and 3-methylbutylacetate in Moscato). All grape waters showed also a considerable fraction of ethyl lactate, six-carbon compounds and acetates, reflecting the proximity of samples to the grapes of origin. CONCLUSION: In a growing scenario of environmental decay and resource depletion, results from this study support an innovative and profitable waste recycling strategy for the wine industry. © 2020 Society of Chemical Industry.

Accumulation of PCBs, PAHs, plasticizers and inorganic elements in Hexanchus griseus from the strait of Messina (Central Mediterranean sea).

This study investigates the inorganic elements and the persistent organic pollutants (POPs) accumulated in liver of a sexually mature Hexanchus griseus living in the Mediterranean Sea. The casual finding of a specimen in the Strait of Messina (April 2018) allowed us to carefully analyse its liver which can be considered a very important biological indicator. The determination of inorganic elements was carried out by ICP-MS technique. Quantitative determination of polycyclic aromatic hydrocarbons (PAH) and poly-chloro-biphenyl compounds (PCB), distinguished in dioxine-like (DL) and not-dioxine-like (NDL) derivates, has been carried out by HRGC/MS and HRGC-MS/MS respectively. Worrying levels of PCB-DL (TEQ = Σ(PCB-DL)*TEF = 5.96 ng g-1), PCB-NDL (Σ(PCB-NDL) = 1390.4 ng g-1) together with the presence of pesticides and plasticizers were found in the shark liver oil. The levels of heavy metals were below the legal limits.