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Funding Information: This work was supported by the NoAW project (‘‘Innovative approaches to turn agricultural waste into ecological and economic assets”), founded by the European Union Horizon 2020 research and innovation program under the grant agreement No 688338. This research was carried out within the Agritech National Research Center and received funding from the European Union Next-GenerationEU (PIANO NAZIONALE DI RIPRESA E RESILIENZA (PNRR)–MISSIONE 4 COMPONENTE 2, INVESTIMENTO 1.4–D.D. 1032 17/06/2022, CN00000022), Italy. This study was also funded by national funding by FCT, Foundation for Science and Technology, MCTES, and by ESF (European Social Fund) through NORTE 2020 (Programa Operacional Região Norte), Portugal, through the individual PhD research grant (SFRH/BD/146080/2019) of V.L. This work was also supported by the MEtRICs unit which is funded by national funds from FCT/MCTES (UIDB/04077/2020 and UIDP/04077/2020) and by the Associate Laboratory for Green Chemistry–LAQV which is financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020). Publisher Copyright: © 2023 by the authors. In the last 20 years, an increased interest has been shown in the application of different types and combinations of enzymes to obtain phenolic extracts from grape pomace in order to maximize its valorization. Within this framework, the present study aims at improving the recovery of phenolic compounds from Merlot and Garganega pomace and at contributing to the scientific background of enzyme-assisted extraction. Five commercial cellulolytic enzymes were tested in different conditions. Phenolic compound extraction yields were analyzed via a Design of Experiments (DoE) methodology and a second extraction step with acetone was sequentially added. According to DoE, 2% w/w enzyme/substrate ratio was more effective than 1%, allowing a higher total phenol recovery, while the effect of incubation time (2 or 4 h) variation was more enzyme-dependent. Extracts were characterized via spectrophotometric and HPLC-DAD analyses. The results proved that enzymatic and acetone Merlot and Garganega pomace extracts were complex mixtures of compounds. The use of different cellulolytic enzymes led to different extract compositions, as demonstrated using PCA models. The enzyme effects were observed both in water enzymatic and in the subsequent acetone extracts, probably due to their specific grape cell wall degradation and leading to the recovery of different molecule arrays. publishersversion published

Uso del QPCS con matricole universitarie (PLS–Chimica Unibo) dall’a.a. 2018-19, con ipotesi di partenza: lo sviluppo dell’autodirezione nell’apprendimento favorisce la continuità negli studi. Il percorso è in tre fasi: a) somministrazione del QPCS a matricole chimiche (N=436); b) restituzione in presenza dei risultati; c) tutorato a 44 studenti. Riflessioni: modalità di restituzione, uso dei risultati QPCS, reazioni degli studenti. Obiettivo: costruire un quadro concettuale per futura ricerca., Dirigere se stessi nello studio e nel lavoro. Competenzestrategiche.it: strumenti e applicazioni

Summary/Riassunto The aim of this work is to clarify some aspects that should allow an interpretation of the analytical data unique, shared and accepted by the community as obtained through statisticalmathematical tools (chemometric) essential in the expression and interpretation of any measurements. There is objectively a difficulty of communication between scientists and jurists when applying regulations involving the use of statistical and mathematical tools: literature is filled by several lawsuits resulting from this difficulty; it being understood the right of defense that a party has, however, you need to put a fundamental point on certain aspects (numeric, and therefore objective) that should not be matter for discussion anymore. Regarding the breathalyzer, it is already accepted the conversion constant between the concentration of ethanol in exhaled air and blood concentration: for such constant, regardless of how it can be scientifically shareable its interpretation, during a judicial procedure no objection is admissible. But, about the verification of exceeding the legal limits, are still needed to establish an indisputable method, which must take into account all the law prescriptions: both the established limits, both the measurement uncertainties associated with the breathalyzer. This paper aims to highlight how, once the analytical result expressed in the correct form (significant digits, uncertainty, etc.), you can beyond any reasonable doubt compare the limit values to express an objective and unequivocal judgment of compliance to the norm. Lo scopo della presente riflessione è chiarire alcuni aspetti che dovrebbero permettere un'interpretazione del dato analitico unica, condivisa e da tutti accettata in quanto ottenuta attraverso strumenti statistico-matematici (chemiometrici) essenziali nell'espressione ed interpretazione di qualsiasi misurazione tecnica. Esiste obiettivamente una difficoltà di comunicazione tra Scienziati e Giuristi quando si applicano normative che comportano l’uso di strumenti statistici e matematici: numerose cause derivanti da tale difficoltà riempiono la letteratura giudiziaria; fermo restando il diritto di difesa che una controparte ha, è necessario però porre un punto fermo su certi aspetti (numerici, e quindi oggettivi) che non dovrebbero più essere motivo di discussione. Nel caso dell’etilometro, si è già posto un punto fermo nell’utilizzo della costante di conversione tra concentrazione di etanolo nell’aria espirata e concentrazione nel sangue: per tale costante, indipendentemente da quanto possa essere scientificamente condivisibile una sua interpretazione, in sede dibattimentale non viene più ammessa alcuna contestazione. Ma per quanto riguarda la verifica del superamento dei limiti di legge c’è ancora bisogno di stabilire un metodo incontestabile, che deve tenere conto di tutte le indicazioni della legge: sia i limiti stabiliti, sia le incertezze di misura associate alle misure effettuate su persone soggette a controlli mediante etilometro. Nel presente lavoro si vuole mettere in luce come, una volta espresso il risultato analitico nella forma corretta (cifre significative, incertezza, etc.), si può oltre ogni ragionevole dubbio confrontarlo con i valori-limite per esprimere un oggettivo ed inequivocabile giudizio di conformità o meno alla norma.

Cosmetics are widely used even for daily usage. Raw materials and industrial machines used for their preparation are inevitably affected by contamination from metals, because these species are ubiquitous in the world. For instance, nickel, lead and cadmium are frequently unintentionally added to cosmetics as impurities during manufacturing. In fact, some metals are very dangerous for human health. This is true over safe limits of concentration even in the case of metals which are essential for human metabolism. Moreover, heavy metals may accumulate in the body over time and repetitive product applications, leading to significant exposure levels. International regulation about metals in cosmetics is very heterogeneous from Country to Country. Moreover, in many Countries the regulation is incomplete or absent. In some cases, regulations provide safe limits, but the analytical techniques useful to check for those limits are not indicated. In other cases, the safe limits are below the limit of detection of available analytical methodologies, hence the development of new methods is necessary. For these reasons, a deep knowledge of metals content in personal care products and cosmetics is necessary using reliable, and high-throughput, sensitive and selective analytical assays are needed. The present review proposes an exhaustive focus onwhat arethemetalsof interest, and what is the state of the art about analytical methodologies suitable to detectthesetoxic metals in cosmetics and personal care products (PCPs). This review would also be a stimulus to solicit International Organizations to fill the gap of the lack of strict and comprehensive laws regulating the maximum allowable concentrations for an increasing number of contaminants in these matrices, especially considering their enormous daily use.

Recently, pollution linked to airborne particulate matter has drawn attention. The issue is due to a drastic increase of anthropic activities: industrial activities, in all their different typologies, and more and more increasing vehicular traffic. As a consequence, the totality of the pollutants associated with the various types of particulate are everywhere strictly dependent on the type of source of the same particulate. Moreover, the particle size evidently has a particular importance, since the decrease of the aerodynamic diameter of particulate corresponds to greater ease of penetration of the same particulate in the deeper levels of the respiratory system. This obviously is a serious problem for human and animal health, implying high costs in health care. Due to multiple simultaneous sources in areas at high anthropic impact, there are many pollutants associated with airborne particulate matter, both of inorganic and organic kind, and even simultaneously present on the same particulate samples. In any case, the pollutant determination in airborne particulate matter certainly must be accurate, reproducible and it must be especially characterized by very low limits of detection. In particular, the present work reports and discusses the different analytical procedures for the voltammetric and spectroscopic determination of heavy metals and metalloids (copper, lead, cadmium, zinc, mercury, tellurium, arsenic, selenium, tin, antimony, vanadium, nickel, chromium) in airborne particulate matter sampled in two sites, differently influenced by anthropic pollution. An additional sampling, carried out in a zone at very low anthropic impact, was chosen for eventual comparisons. The chosen particulate-matter size was PM2.5 (aerodynamic diameter < 2.5 µm) even if the proposed methodologies evidently can be also applied to all other particle sizes of interest. A separate section will be dedicated to the analytical procedure for the determination in airborne particulate matter of new emerging anthropic polluting traffic-related pollutants, i.e. the platinum group metals (PGMs) — platinum, palladium, rhodium, osmium, ruthenium and iridium — that, in the last decade, have aroused much interest from scientific community.

In the environmental field and in the last decade, the scientific attention has been addressed to platinum group metals (PGMs) owing to their increasing concentration in all the environmental matrices. This is due to the increasing use of these metals in several fields as for example production of industrial catalysts, anticancer drugs, jewels, even if in any case the cause of their growing concentrations in the environment is consequence of the compelling employment of autocatalytic converters. In fact the incorrect use “stop and go” of these converters, with consequent deterioration and abrasion, certainly implies a considerable release in the environment of airborne particulate matter at high PGMs concentration, which results to be the greatest, if not the only, source of contamination of the various environmental matrices, i.e. superficial water, soils, sediments, vegetables and so on. Really, after the first massive use of platinum, palladium and rhodium in the production of autocatalytic converters, there has been a gradual reduction of these PGMs with consequent growing use of iridium, ruthenium and, especially, osmium. Indeed, in the last decade, and more and more frequently, osmium together with iridium has been employed as alloying with platinum, palladium and rhodium in the manufacturing of autocatalytic converters in order to withstand high temperature and high wear. In fact, osmium in particular is rarely used in its pure state, and it is instead considered an important alloying agent especially in high-wear applications, owing to its strong corrosion resistance even at very high temperatures. Thus, this work intends to propose voltammetric methods for the osmium determination at ultra-trace level concentration in environmental samples: airborne particulate matter, superficial waters, soils/sediments, vegetables, mussels, clams and algae. To better validate the proposed analytical procedures, a critical comparison with spectroscopic measurements — electro-thermal atomic absorption spectroscopy (ET–AAS) because of its well established and tested robustness — has been also carried out and discussed here, taking into account all the parameters of interest to set-up an analytical method, such as precision and trueness (that together give accuracy), limit of detection and quantification, selectivity and, especially, sensitivity.

A rapid diffusion of heavy metals as environmental contaminants has called the attention to their determination. Indeed, heavy metals, together with pesticides, are very dangerous pollutants owing to their bioaccumulation and toxicity. It is therefore necessary to determine these metals at trace and ultra-trace level especially in aquatic ecosystems to establish reasonable water quality criteria. Moreover, toxic metals accumulate in certain marine species and thus enter the aquatic food chain. In particular mussels and clams, but also oysters, shrimps, fish and algae, sequestrate and concentrate several metals from their aqueous environment, possibly becoming dangerous to human health in consequence of their consumption. In particular mussels, clams and oysters, being filtering organisms - an adult organism is able to filter also up to 4-5 L h-1, depending on its weight - they require particular attention and inspections before being sold on the market. In addition to this important and fundamental aspect of public health, the determination of heavy metals in mussels and clams, that are not only filtering organisms but also sessile species, can be usefully employed for bio-monitoring campaigns, that evaluate the long-term trend of the pollution load of an aquatic ecosystem, information that evidently cannot be provided by punctual determinations. For completely mapping environmental pollution, the sampling duration and cadence are very important. In our opinion, the use of bio-monitors (mussels and clams in the present case), just proposed by several authors, but certainly not scientifically supported, is possible only in the case of a long sampling plan. In any case, the metal determination in mussels and clams evidently must be accurate, reproducible and especially it must show very low limits of detection. The present work reports and discusses the different analytical methodologies for the voltammetric and spectroscopic determination of heavy metals (copper, lead, cadmium, zinc, mercury, arsenic, selenium, tin and antimony) in oysters, mussels and clams. A separate section will be dedicated to the analytical procedure for the determination in such organisms of new emerging anthropic polluting traffic-related pollutants, i.e., the platinum group metals (platinum, palladium, rhodium, osmium, ruthenium and iridium).