The condensed products of pyrolysis embrace a wide range of compounds, ranging from relatively low molecularweight (MW) hydrocarbons ("light tar") to progressively heavier species, including large PAHs ("heavy tar"),ending up with fine carbonaceous particles (soot) of nanometric and, in some cases, even micrometric size. Whilemost part of "light tar" from either coal or biomass pyrolysis can be effectively detected by conventional gaschromatography/mass spectrometry (GC/MS), a detailed analysis of "heavy tar" and soot turns out to be rathercumbersome and more susceptible of errors, especially when the techniques, originally developed for fossil fuels-derived products, are applied to the oxygen rich biomass products. Size exclusion chromatography (SEC) coupledwith UV-Visible (UV-Vis) absorption detector is applied to both coal and biomass "heavy tar", providing evidenceof high mass components reaching MWs of thousands of u, similar to incipient soot. Carbon particles reach themicrometric scale in some coal pyrolysis products, so that "ad hoc" solvent-based separation procedures havebeen developed in order to distinguish soot from char fines. In biomass pyrolysis products, carbon rich partic-ulate remains confined to the nano-size range. The latter exhibits fluorescence emission in the green wavelengthrange, with a relatively high quantum efficiency, and can therefore be regarded as carbon dots. Recent progressshows that the molecular mass and size of the heaviest species in biomass heavy pyrolysis products can beassessed by SEC with a fluorescence detector. However, the technique still requires refinement due to the lack ofSEC calibration data valid for all tar species. Laser desorption ionization time of flight mass spectrometry (LDITOFMS) turns out to be a valid support to evaluate the molecular range of such ill-defined products.

Biogas is becoming one of the most used and profitable renewable sources. It is obtained through many different processes that frequently involve different green renewable sources. During the different steps of the process, it generates several by-products that could be reused as organic fertilizers. The aim of this work was to study the volatile fraction and determine the volatile fingerprint of 6 different organic samples involved in biogas production by the innovative Small Sensor System (S3) based on Semiconductor Metal Oxide (MOX) gas sensors. Obtained results show the volatile profile of each sample that at the same time support the sensor's device results. S3 result shows a perfect discrimination of the volatile fraction of the different studied matrices based on the different composition of their volatile set. matrix and shows how the sensors are able, in real time, to cluster and discriminate the fingerprint of these renewable sources. In the end, S3 results are very promising to enhance the traceability and the origin of the sources in the biogas industry at each specific stage of production, focusing on the possible release of off-flavors in the environment from different types of organic biomass and the reuse of their by-products supporting circular economy. The aim of this work was to find and identify the VOCs set that characterizes different types of organic renewable sources through the use of the tailor made Small Sensor Systems S3 to distinguish between different odor sources based on their qualitative and quantitative differences in VOCs profile, in order to be able in the future to produce a user friendly fast, economic and with auto learning capabilities to support the aforementioned green industrial processes.

The production of sparkling wine (SW) through the champenoise method involves the "in bottle" secondary fermentation of the base wine commonly carried out using yeast strains belonging to the Saccharomyces cerevisiae species. Nevertheless, the use of few widely used strains can cause a flattening of the sensory profile. To the best of our knowledge, few studies [2, 3] have so far investigated the impact of native starter strains on the volatile and non-volatile profiles of SW. In addition, there are no studies based on the comparison of volatile and chemical profiles of sparkling wines produced from two different Italian indigenous cultivars, i.e. Bombino Bianco and Bombino Nero, using both native and commercial strains. The application of an untargeted metabolomic approach based on HPLC-HRMS and GC-MS techniques has shown that the yeast strain is able to affect the chemical profile of sparkling wines by modifying the quali- quantitative profile of several secondary products of microbial fermentation, including polysaccharides, organic acids, phenolic acids and lipids. Moreover, an HPLC-HRMS/GC-MS correlation analysis was performed, resulting in a map that is a useful tool for monitoring different aroma release patterns. This contribution provides information to modulate the quality of regional sparkling wines from minor indigenous grape varieties using selected microbial resources.

Pistacia vera oleoresin is one of the natural products used traditionally for the management of wounds. However, there were no scientific reports documented so far on the wound healing activities to substantiate the claim. This study assesses the potential of the oleoresin of P. vera collected in Italy and Algeria for wound healing efficacy via in vivo circular wound excision model. Italian and Algerian oleoresins were subjected to purification and successive fractionation to obtain three matrices. The fractions have been characterized using GC-FID and GC-MS analyses. Oleoresins mixed with vaseline (5% w/w) were topically applied on wound excision induced on the dorsum of rabbits. Wound healing effects were evaluated by percent of wound contraction. Biopsies performed after healing were histologically assessed. Phytochemical results showed a high content of terpenoids components inducing an efficient wound healing effect determined by an in vivo study. Italian and Algerian oleoresins ointments showed significant wound contraction from day 8 to day 16 as compared to the negative control. The two ointments have not showed statistically difference as compared to Cicatryl, reference drug. These results have also been confirmed by the histological evaluation of the tissues involved. The absence of signs of toxicity on the skin of rabbits indicated the safety of the ointments. The study showed that both oleoresins have a very high effectiveness as wound healing agents and appear to justify their traditional use in wound healing in several countries and offer a scientific support to the treatment of traditional healers.

Nitrogen (N) fertilization is one of the main inputs to increase crop yield and food production. However, crops utilize only 30-40% of N applied; the remainder is leached into the soil, causing environmental and health damage. In this scenario, the improvement of nitrogen-use efficiency (NUE) will be an essential strategy for sustainable agriculture. Here, we compared two pairs of NUE-contrasting eggplant (Solanum melongena L.) genotypes, employing GC-MS and UPLC-qTOF-MS-based technologies to determine the differential profiles of primary and secondary metabolites in root and shoot tissues, under N starvation as well as at short-and long-term N-limiting resupply. Firstly, differences in the primary metabolism pathways of shoots related to alanine, aspartate and glutamate; starch, sucrose and glycine; serine and threonine; and in secondary metabolites biosynthesis were detected. An integrated analysis between differentially accumulated metabolites and expressed transcripts highlighted a key role of glycine accumulation and the related glyA transcript in the N-use-efficient genotypes to cope with N-limiting stress. Interestingly, a correlation between both sucrose synthase (SUS)-and fructokinase (scrK)-transcript abundances, as well as D-glucose and D-fructose accumulation, appeared useful to distinguish the N-use-efficient genotypes. Furthermore, increased levels of L-aspartate and L-asparagine in the N-use-efficient genotypes at short-term low-N exposure were detected. Granule-bound starch synthase (WAXY) and endoglucanase (E3.2.1.4) downregulation at long-term N stress was observed. Therefore, genes and metabolites related to these pathways could be exploited to improve NUE in eggplant.

Among all the emerging contaminants, fragrances are gaining more relevance for their proven allergenic and, in some cases, endocrine-disrupting properties. To date, little information exists on their concentration in the air. This study aims to fill this gap by developing a method for the determination of semivolatile fragrances in the indoor gaseous phase with sampling protocols usually adopted for the collection of atmospheric particulate matter (sampling time 24 h, flow rate 10 L min-1) and instrumental analysis by gas chromatography coupled with mass spectrometry. The method was developed on 66 analytes and tested at three concentration levels: 20 compounds showed analytical recoveries >=72% with percentage standard deviations always better than 20%. For most compounds, negligible sampling breakthroughs were observed. The method was then applied to real samples collected in a coffee bar and in a private house. Considering the fragrances for which the method has shown good effectiveness, the highest concentrations were observed for carvone in the coffee bar (349 ng m-3) and camphor in the house (157 ng m-3). As concerns certain or suspected endocrine disruptors, lilyal and galaxolide were detected at both sites, ?-isomethylionone was the second most concentrated compound in the house (63.2 ng m-3), musk xylene and musk ketone were present at lower concentration (? 1 or 2 ng m-3)

The Champenoise method for the production of sparkling wines consists of an "in bottle" re-fermentation induced by a low number of commercial Saccharomyces cerevisiae strains. However, the limited use of these strains can induce a flattening of the sensorial properties of the produced wine. Indeed, the volatile compounds produced by the yeasts during the fermentative process, play an essential role in the constitution of the Bouchet of sparkling wines prepared using indigenous grape varieties and, in particular, deriving from Apulia (Southern Italy), whose economic significance is constantly increasing . To the best of our knowledge, only two investigations assessed the influence of the autochthonous starter strains on the volatiles profile of sparkling wine. Moreover, no information exists on the oenological potential, for the production of typical sparkling wine, of the indigenous grape cv Maresco. This investigation evaluated the impact of the selected autochthonous yeast strains on the chemical properties of Maresco sparkling wines applying a non-targeted metabolomics approach by the application of HPLC-HRMS and GC-MS techniques. Saccharomyces cerevisiae DV10 (Lallemand, USA) was used as control. The obtained findings indicated that native yeast strains, previously selected, influenced the amount of several fermentative compounds, i.e. polysaccharides, organic acids, phenolic acids, and lipids. In order to reveal any grouping of the wines based on the composition of volatile compounds and chemical data, as well as to identify the main components contained within each group, the data were subjected to principal component analysis (PCA). Also, the correlation matrix on HPLC-HRMS/GC-MS data was performed and permitted to obtain a map, which is a useful tool to monitor the different patterns of aroma release. This contribution supplies information that will support the modulation of the sensorial properties of regional sparkling wines obtained from typical autochthonous grape varieties by using selected autochthonous microbial resources. Acknowledgments: This work was partially supported by the Apulia Region projects: "Innovazione nella tradizione: tecnologie innovative per esaltare le qualità dei vini autoctoni spumante della murgia barese-INVISPUBA" (P.S.R. Puglia 2014/2020 -Misura 16.2).

In this review, we examined the European legislative context on water protection concerning pesticide residues monitoring and the relevant National Action Plans and strategies that were undertaken in European countries to better identify and manage the problem in water bodies. Furthermore, we illustrated the development of analytical methodologies and criticalities connected to determine pesticide residues in water matrices, including sampling, sample preparation approaches, instrumental techniques and specific applications emphasising those works published after 2015. Details about sampling strategies, analytical feasibility, official methods, degradation products and behaviour in the environment for a subset of 160 pesticides are also provided.

This paper presents a multi-analytical investigation performed for the study of the ecclesiastical vestment, with insignia, of Pope Pius VII, painted from the end of the 18th up to the beginning of the 19th century, made of five clothing elements: chasuble, stole, maniple, chalice veil and purse. The aim of this research was to assess the conservation state of the silk and painted backgrounds; to define the manufacturing technique of the work; to localize, if present, the underdrawing and any retouching; to identify the pigments and, where possible, the binders used. A diagnostic protocol was developed based on preliminary investigations through multiband imaging techniques known as MBI (visible, ultraviolet-induced visible luminescence (UVL), near-infrared reflected (NIR) and infrared reflected false color (IRRFC) photography). The images acquired with MBI techniques ensured a more specific choice of spots to be analyzed directly in situ by non-invasive techniques. In particular, portable digital optical microscopy and X-ray fluorescence (XRF) were performed. Two fragments detached from the chasuble were also analyzed by microFT-IR, microRaman, scanning electron microscopy (SEM-EDS) and gas chromatography/mass spectrometry (GC-MS). Application of the multi-analytical protocol enabled the materials used to be characterized and helped to define the peculiar execution technique used. The presence of an underdrawing made with a carbon pencil was highlighted by MBI. Red lakes, iron-based pigments and copper-based pigments have been identified on the painting palette, applied with arabic gum as a binder.

Tea is the second most consumed beverage, and its aroma, determined by volatile compounds (VOCs) present in leaves or developed during the processing stages, has a great influence on the final quality. The goal of this study is to determine the volatilome of different types of tea to provide a competitive tool in terms of time and costs to recognize and enhance the quality of the product in the food chain. Analyzed samples are representative of the three major types of tea: black, green, and white. VOCs were studied in parallel with different technologies and methods: gas chromatography coupled with mass spectrometer and solid phase microextraction (SPME-GC-MS) and a device called small sensor system, (S3). S3 is made up of tailor-made metal oxide gas sensors, whose operating principle is based on the variation of sensor resistance based on volatiloma exposure. The data obtained were processed through multivariate statistics, showing the full file of the pre-established aim. From the results obtained, it is understood how supportive an innovative technology can be, remotely controllable supported by machine learning (IoF), aimed in the future at increasing food safety along the entire production chain, as an early warning system for possible microbiological or chemical contamination.

COVID-19 is a highly transmissible respiratory illness that has rapidly spread all over the world causing more than 115 million cases and 2.5 million deaths. Most epidemiological projections estimate that the Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) virus causing the infection will circulate in the next few years and raise enormous economic and social issues. COVID-19 has a dramatic impact on health care systems and patient management, and is delaying or stopping breath research activities due to the risk of infection to the operators following contact with patients, potentially infected samples or contaminated equipment. In this scenario, we investigated whether virus inactivation procedures, based on a thermal treatment (60 C for 1 h) or storage of tubes at room temperature for 72 h, could be used to allow the routine breath analysis workflow to carry on with an optimal level of safety during the pandemic. Tests were carried out using dry and humid gaseous samples containing about 100 representative chemicals found in exhaled breath and ambient air. Samples were collected in commercially available sorbent tubes, i.e. Tenax GR and a combination of Tenax TA, Carbograph 1TD and Carboxen 1003. Our results showed that all compounds were stable at room temperature up to 72 h and that sample humidity was the key factor affecting the stability of the compounds upon thermal treatment. Tenax GR-based sorbent tubes were less impacted by the thermal treatment, showing variations in the range 20%-30% for most target analytes. A significant loss of aldehydes and sulphur compounds was observed using carbon molecular sieve-based tubes. In this case, a dry purge step before inactivation at 60 C significantly reduced the loss of the target analytes, whose variations were comparable to the method variability. Finally, a breath analysis workflow including a SARS-CoV-2 inactivation treatment is proposed.

Background: Colorectal cancer represents one of the prominent causes of mortality worldwide in men and women. The objective of this study was to search for new potential anticancer compounds, both in prevention and treatment of colorectal cancer. The anticancer potential of marine bacterial extracts against Human colorectal carcinoma cell line (HCT116) was evaluated as well as the partial identification of bioactive metabolites.Methods: All bacterial extracts were tested for their cytotoxicity against HCT116 cell line by means of MTT assay. The highly cytotoxic dichloromethane extracts of marine sponge-associated bacteria Vibrio sp. and Bacillus sp. were analyzed by GC-MS.Results: Two fractions, Vib3 and Bac3, exhibited a very interesting cytotoxicity against human colorectal carcinoma (HCT116) cell line, with a percentage of cytotoxicity of 96.04 % and 29.48 %, respectively.Discussion: The GC-MS analysis revealed the presence of two major fatty acids, palmitic and oleic acids, in Vib3 fraction and fatty acid esters and phenolic compounds in Bac3 fraction.Conclusion: Based on previous literature, it may be hypothesized that the anticancer activity of bacterial extracts could be, at least partially, to the fatty acids fraction.

This work aims to investigate the correlation between the painting materials used by Picasso to create four artworks in Barcelona in 1917 and their actual conditions. Specifically, a range of crack types and patterns was observed in the painted layers. The paintings, kept together in Picasso's family house until they were donated to the Museu Picasso in 1970, had significant differences in their condition, even though they present several similarities in the choice of materials, technique and in their conservation history. A multi-analytical approach was adopted to characterise the painted layers by X-ray fluorescence spectroscopy, fibre optic reflectance spectroscopy in the 350-2200 nm range, gas chromatographymass spectrometry, and Fourier transform infrared spectroscopy. The obtained results have been combined with those from a previous analytical campaign focused on the study of grounds and canvases of these four paintings and with visual examination of the cracks to establish hypotheses about the differences in degradation. This combined overview of non-invasive documentation techniques, chemical analysis and observations of the mechanical damage has provided an insight into the possible contribution each layer could have played in the damage observed in the four canvas paintings.

This work has been aimed at studying the effect of red thyme oil (RTO, Thymus vulgaris L.) on the shelf-life and Penicillium decay of oranges during cold storage. RTO vapours significantly reduced (P <= 0.05) the percentage of infected wounds, the external growth area and the production of spores in inoculated orange fruit stored for 12 days at 7 °C in a polypropylene film selected for its appropriate permeability. Among the RTO compounds, p-cymene and thymol were the most abundant in packed boxes at the end of cold storage. The RTO vapours did not affect the main quality parameters of the oranges, or the taste and odour of the juice. The results have shown that an active packaging, using RTO vapours, could be employed, by the citrus industry, to extend the shelf-life of oranges for fresh market use and juice processing.

Food poisoning is still the first cause of hospitalization worldwide and the most common microbial agent, Campylobacter jejuni, is the most commonly reported gastrointestinal disease in humans in the EU (European Union) as is reported by the European Union One Health 2018 Zoonoses Report styled by the EFSA (European Food Safety Authority) and ECDC (European Center for Disease Prevention and Control). One of the vehicles of transmission of this disease is milk. Nanostructured MOS (Metal Oxide Semiconductor) sensors have extensively demonstrated their ability to reveal the presence and follow the development of microbial species. The main objective of this work was to find a set up for the detection and development follow up of C. jejuni in milk samples. The work was structured in two different studies, the first one was a feasibility survey and the second one was to follow up the development of the bacteria inside milk samples. The obtained results of the first study demonstrate the ability of the sensor array to differentiate the contaminated samples from the control ones. Thanks to the second study, it has been possible to find the limit of microbial safety of the contaminated milk samples.

The analysis of VOCs emanating from biological samples appears as one of the most promising approaches in metabolomics for the study of diseases. The presence of volatile markers has been explored in exhaled breath, urine, blood, saliva, feces, human semen and cell cultures. Detection and quantification of VOCs are carried out by gas chromatograph-mass spectrometer system (GC-MS) and/or gas sensors.

Inquinamento indoor: contaminanti vecchi e nuovi in forma particolata: natura e metodi di campionamento e analisi chimica strumentale

The paper explores changes in reactivity and chemico-physical characteristics of char and tar produced by severe heat treatment of lignite in both inert atmospheres and CO2 rich atmospheres. The role of mineral matter, in particular metal oxides, in catalysing chemical and physical transformations is also addressed. A Rhenish Lignite from the Garzweiler mine was studied and compared with: a) mineral-free synthetic carbon (HTC), obtained from cellulose; b) a synthetic carbon doped with iron oxide (Fe2O3). A heated strip reactor (HSR) was employed at temperatures of 1300 and 1800 degrees C in N-2 and CO2 atmospheres. Liquid and solid products (tar and char) were analysed and compared. Tar composition was evaluated by extraction and gas chromatography-mass spectrometry, whereas the solid carbonaceous material produced by pyrolysis, mainly composed of char, was characterized regarding its thermal behaviour by thermogravimetric analysis and its structure by Raman spectroscopy and scanning electron microscopy. Results show that iron oxide exerts a catalytic influence on both pyrolysis and char oxidation. Upon severe heat treatment, it reduces char reactivity promoting graphitization and structural ordering. The overall effect on char reactivity is therefore not easy to predict.

Chemical communication in bacteria relies on the production, release, and detection of small molecules called autoinducers (AIs) that regulate gene expression in a cell-density-dependent manner (quorum sensing, QS). QS not only serve as intraspecies but also in interspecies communication. Furthermore, the clinical significance of interkingdom crosstalk between bacteria and human host is becoming more and more evident. Typically, signal molecules are produced at a very low concentration and their detection requires highly sensitive techniques. Biosensors have allowed fast screening of microorganisms for AI production; however, for their specific identification, the gold choice are mass spectrometry-based methodologies, coupled with either gas or liquid chromatography. Sample extraction, cleanup, and preconcentration greatly improve autoinducer identification from complex matrices allowing reliable quantification. The present chapter provides an overview on the most recent and advanced analytical approaches to identify and quantify these bacterial chemical messages with a special focus on N-acyl-L-homoserine lactones (AHLs/Acyl-HSLs).

Introduction The evaluation of volatile organic compounds(VOCs) emitted by human body offers a unique tool to set up new non-invasive devices for early diagnosis and long-lasting monitoring of most human diseases. However, their cellular origin and metabolic fate have not been completely elucidated yet, thus limiting their clinical application. Endothelium acts as an interface between blood and surrounding tissues. As such, it adapts its physiology in response to different environmental modifications thus playing a role in the pathogenesis of many metabolic and inflammatory diseases. Objectives Since endothelium specifically reshapes its physiologic functions upon environmental changes the objective of this study was to evaluate if and how pro-inflammatory stimuli affect VOC metabolism in endothelial cell in culture. Methods Gas chromatography with mass spectrometric detection was applied to profile VOCs in the headspace of cultured endothelial cells (EC) in the absence or presence of the pro-inflammatory stimulus lipopolysaccharide (LPS). Results We observed that, under resting conditions, EC affected the amount of 58 VOCs belonging to aldehyde, alkane and ketone families. Among these, LPS significantly altered the amount of 15 VOCs. ROC curves show a perfect performance (AUC = 1) for 10 metabolites including 1-butanol, 3-methyl-1-butanol and 2-ethyl-1-hexanol. Discussion The emission and uptake of the aforementioned VOCs disclose potential unexplored metabolic pathways for EC that deserve to be investigated. Overall, we identified new candidate VOC potentially exploitable, upon experimental confirm in in vivo model of disease, as potential biomarkers of sepsis and pro-inflammatory clinical settings.