Geochemical and isotopic tracers to define the aquifer's vulnerability: the case study of the alluvial multi-aquifer system of the Friulian plain.

The Friuli-Venezia Giulia Region (north of Italy) is characterized by the presence of high-quality freshwater resources which benefit local citizens, animals, environmental habitats, and also agriculture and production activities. Waters from wells, canal, and wastewater selected in the Fiume Veneto area, through a detailed lithological modeling, were sampled and analyzed to characterize them from a geochemical point of view. The chemical and isotopic characterization made it possible to establish provenance, and the average age of water used, making available the estimation of the relationships between recharge capacity and water use in the Fiume Vento area. The focus of this study is to define the average age of the resources based on the time required for the recharge contributions to compensate the losses induced by exploitation. The results made it possible to support the plans for a water balance using the provenance and average age of water sources for the protection of water reserves formed by the multi-aquifer system of the high and medium Friuli plain. The methodology applied has followed the legislation of the water directive considering the overexploitation due to unauthorized withdrawals of the sampling area.

Understanding through drone image analysis the interactions between geomorphology, vegetation and marine debris along a sandy spit.

Marine litter (ML) is recognized as one of the main socio-economic and environmental concerns and monitoring operations have been realized worldwide in order to collect information on the types, quantities and distribution of marine debris. In this study, we used Unmanned Aerial Vehicle (UAV) images to map the presence of ML on a coastal spit in relation to geomorphological aspects and vegetation. Our results show that ML is present everywhere, but concentrates in the beach wrack, dunes, and saltmarshes, highlighting the role of the vegetation in trapping ML. Moreover, ML will most probably remain trapped by the saltmarsh vegetation, since they are not visible and easily accessible to allow cleaning operations. On the contrary, cleaning operations may remove the ML present in the beach wrack. Finally, our results provide useful information to support decision-makers for improving beach cleaning activities in the Po river Delta areas (Italy).

A multi-analytical evaluation of the depositional pattern on open-air rock art panels at "Abrigo del Lince" (Badajoz, Spain).

Microscopic observation correlated with chemical-mineralogical characterization was performed on pigment samples from "Abrigo del Lince" rock art site (V-IV millennium BC), in order to provide contributions to the study of prehistoric schematic art on granite in the province of Badajoz (Spain). The research objectives include the understanding of technological and cultural aspects, as well as of conservation and deterioration issues related to the pictographs. The multi-analytical approach encompasses the integration of microscopic observation, SEM-EDS analysis, micro-Raman spectroscopy, and ATR-FTIR and allowed to achieve a multispectral overview of the samples and to describe their varied composition and the alteration pattern which connects them. The main phases overlying the granitic bedrock and involved in this sequence are as follows: hematite, whewellite, and gypsum. While hematite could be stratigraphically considered the most ancient layer and assigned to the use of red ochre as a pigment, whewellite and gypsum are the main constituent of the alteration layer which forms a patina over the pictographs, due to weathering processes. Finally, the role of biofilms in rock art conservation is discussed, suggesting that, especially for what concern thin and homogenous layers of oxalates, their presence should not be necessarily considered an issue.

Microplastic accumulation in commercial fish from the Adriatic Sea.

We assessed the presence and concentration of microplastics in fishes from the Northern Adriatic Sea on sale for human consumption. Microplastics were extracted from the digestive tract of 180 specimens, belonging to 6 different species (2 pelagic, and 4 demersal). Microplastics were identified through Nile red staining, and selected particles were analyzed by µ-Raman spectroscopy. The 47.8% of examined fish were found to contain microplastics (233 fragments). The mean concentration of microplastics in the 6 species ranged between 4.11 ± 2.85 items/individual in Adriatic soles, and 1.75 ± 0.71 items/individual in pilchards. Microplastics ranged in size between 0.054 mm and 0.765 mm. Polyethylene and polypropylene were the polymer types identified through µ-Raman spectroscopy. Despite our estimates are underestimations, these results are of particular concern, as the fish analyzed are consumed without being eviscerated, and the microplastics they contain are transferred directly to humans.

Plastic ingestion by Atlantic horse mackerel (Trachurus trachurus) from central Mediterranean Sea: A potential cause for endocrine disruption.

Plastics in the oceans can break up into smaller size and shape resembling prey or particles selected for ingestion by marine organisms. Plastic polymers may contain chemical additives and contaminants, including known endocrine disruptors that may be harmful for the marine organisms, in turn posing potential risks to marine ecosystems, biodiversity and food availability. This study assesses the presence of plastics in the contents of the gastrointestinal tract (GIT) of a commercial fish species, the Atlantic horse mackerel, Trachurus trachurus, sampled from two different fishing areas of central Mediterranean Sea. Adverse effect of plastics occurrence on T. Trachurus health were also assessed quantifying the liver expression of vitellogenin (VTG), a biomarker for endocrine disruption. A total of 92 specimens were collected and morphometric indices were analysed. A subgroup was examined for microplastics (MP < 1 mm) and macroplastics (MaP >1 cm) accumulation in the GIT and for VTG expression. Results indicated that specimens from the two locations are different in size and maturity but the ingestion of plastic is widespread, with microplastics (fragments and filaments) abundantly present in nearly all samples while macroplastics were found in the larger specimens, collected in one of the two locations. Spectroscopic analysis revealed that the most abundant polymers in MP fragments were polystyrene, polyethylene and polypropylene, whereas MP filaments were identified mainly as nylon 6, acrylic and polyester. MaP were composed mainly of weathered polyethylene or polypropylene. The expression of VTG was observed in the liver of 60% of all male specimens from both locations. The results of this study represent a first evidence that the ingestion of plastic pollution may alter endocrine system function in adult fish T. Trachurus and warrants further research.

Examining the dependence of macroplastic fragmentation on coastal processes (Chesapeake Bay, Maryland).

Plastic debris in the coastal environment is subject to complex and poorly characterized weathering processes. To better understand how key environmental factors affect plastic degradation in a coastal zone, we conducted an in situ experiment. We deployed strips of high density polyethylene (HDPE) and polystyrene (PS) in paired coastal areas of contrasting conditions (hydrodynamic activity: erosional or depositional; water depths: subtidal or intertidal). Strips were collected after environmental exposures at 4, 8, and 43 weeks and analyzed for change in mass, algal biofilm growth, and imaged by petrographic and electron microscopy (SEM-EDS). Significant surface erosion was evident on both polymers, and was more rapid and more extensive with PS. Degradation of PS was responsive to intensity of hydrodynamic activity, and was greater at intertidal depths, highlighting the critical role played by photo-oxidation in the coastal zone, and suggesting that algal biofilms may slow degradation by playing a photo-protective role.

Comparative Study of SPA Mud from "Bacino Idrominerario Omogeneo dei Colli Euganei (B.I.O.C.E.)-Italy" and Industrially Optimized Mud for Skin Applications.

The term "Salus per aquam (SPA) therapies" refers to therapeutic pathways that includes mud therapy. The therapeutic efficacy of a peloid depends on its chemical and mineralogical composition, as well as its technological properties. Considering the increasing use of clay-based products, it becomes essential to characterize peloids from a qualitative and quantitative point of view. Therefore, this research project aimed to develop a protocol that allows characterization of the chemical-physical composition of sludges collected from different areas of the Homogeneous Euganean Hills Hydromineral Basin (B.I.O.C.E.). The study established a comparative study both between different matrices and between the same matrices at different maturation times, including also a comparison with an industrialized product, that can be used at home, which maintains the characteristics of a natural mud. This research was developed studying the pH, grain size distribution, and chemical and mineralogical composition. Peloids are characterized by a neutral/basic pH and are divided into two categories from a granulometric point of view: The chemical composition allowed observation of numerous correlations between oxides present in the samples and to quantify the presence of heavy metals. Mineralogical analysis made it possible to identify and compare the composition of each sample, also according to the maturation time. Thanks to the methods adopted, important correlations were achieved.

Adverse effects of plastic ingestion on the Mediterranean small-spotted catshark (Scyliorhinus canicula).

Plastics are widely diffused in the oceans and their ingestion by marine organisms is raising concern for potentially adverse effects. The risk of harmful interactions with marine plastic pollution depends on the biology of the species as well as the distribution and abundance of the different plastic types. The aim of this study was to assess the occurrence of plastic ingestion by the small-spotted catshark (Scyliorhinus canicula), one of the most abundant elasmobranchs in the Mediterranean Sea. The expression levels of genes indicative of total immune system function were analyzed to gather preliminary data for further investigation of any potential correlations between plastic presence and immune activation. One hundred catsharks were collected during the Spring 2018 in two geographic locations in the southern region of the central Mediterranean Sea: 1) near Mazara del Vallo, SW Sicily and 2) near Lampedusa island, Italy's southernmost. Standard measurements were recorded for each specimen and its organs and sex was determined. The gastrointestinal tract (GIT) was preserved for plastic detection and identification. Where present, plastics (macro- and micro-) were characterized in terms of size, shape and polymer typology through microscopy and µ-Raman spectroscopy. Spleen from a subset of thirty samples was preserved for RNA extraction, then used to quantify by real time PCR the transcripts of T cell receptor beta (TCRB), T cell receptor delta (TCRD) and IgM genes. The results indicated that ingestion of plastic is widespread, with microplastics (MP, from 1 µm to <1 mm) abundantly present in nearly all samples and macroplasticplastic (MaP, > 1 cm) in approximately 18% of the specimens collected. A significant increase in the expression of TCRB, TCRD and IgM was observed in the spleen of MaP + specimens from Mazara del Vallo waters, in parallel with 67% increase in liver weight. While the presence of MP alone is not enough to induce a strong activation of the immunity, some type of plastics falling into the MaP category may be more toxic than others and crucial in the activation of the immune response. The results of this study represent a first evidence that plastic pollution represents an emerging threat to S. canicula, the Mediterranean food web and human consumers.

Geographical origin of Vitis vinifera cv. Cannonau established by the index of bioaccumulation and translocation coefficients.

Geochemical fingerprints in grape require an identification of major and trace elements that show correlations between concentrations in soil and in plant tissues: these correlations are relevant to discriminate grapes according to geographical origin. The Vitis vinifera cultivar Cannonau is used to produce the renowned Italian controlled designation of origin (DOC) wine "Cannonau" from Sardinia. Two Cannonau vineyards located in Sardinia Region were studied to establish the relationship between geochemical features of vineyard soil and chemical composition of leaves and grape berries. Major and trace elements were determined by X-ray fluorescence and inductively coupled plasma-mass spectrometry in soil, leaf, and grape berry samples. The index of bioaccumulation and the translocation coefficients were also calculated for all elements. Data from the two study areas were compared by a non-parametric test and multivariate statistics (principal component analysis). The results showed a specific assimilation of these elements in leaf and grape berry from vine in two different soils. Moreover, geochemical characterization and statistical analysis enabled to discriminate the cultivar "Cannonau" according to geographical origin. The results showed that the elements that could establish a reliable correlation between the soil vineyard and leaves and grape berries from the two study areas were B, Sr, and Zr. These elements may therefore be used as geochemical fingerprints to identify the geographic origin of V. vinifera cv. Cannonau in the two study areas.

Discrimination of geographical origin of hop (Humulus lupulus L.) using geochemical elements combined with statistical analysis.

Beer is a popular alcoholic beverage worldwide, traditionally made from water, barley and hop (Humulus lupulus L.) strobili. The strobili contain lupulin glands whose components (mostly bitter acids and polyphenols) confer unique and locally different flavours to beer types. It is therefore relevant for brewers and consumers to precisely know the geographical origin of hop plants used for high-quality beer. Hop plants belonging to the variety Hallertau Perle, grown in two locations, Cavalese and Imèr, of the Trentino Region (Italy) were analysed to establish a direct relationship between the chemical elements detected in soil and in plant parts. Chemical elements were determined by X-ray fluorescence and inductively coupled plasma mass spectrometry in soil, leaf and strobili samples from Cavalese and Imèr. The data from the two areas were compared by a nonparametric test (Mann-Whitney) and multivariate statistics (principal component analysis and partial least squares discriminant analysis). The geochemical characterization and the statistical analyses showed different concentrations of major and trace elements in soil and plant parts from the two areas. A reliable correlation could be established between some elements in soil and strobili samples, that is Nb, Fe, Rb and Zr for Cavalese and Mg, Ni, Zn and Zr for Imèr. These elements could therefore be used as geochemical fingerprints to identify the geographical origin of strobili from the two study areas, an approach useful to verify the origin of hop plants for the production of high-quality beer.

Geochemical caper fingerprints as a tool for geographical origin identification.

The identification of geographical origin of food products is important for both consumers and producers to ensure quality and avoid label falsifications. The caper plant (Capparis spinosa L., Brassicales Capparidaceae), a xerophytic shrub common in the Mediterranean area, produces buds and fruits that are commercialized in brine at high price. Those grown in Italy in the Aeolian Islands are renowned for their high quality. This study is aimed to establish a correlation between the geological and geochemical features of soil and the chemical composition of caper buds grown in two Aeolian Islands, Lipari and Salina. Major and trace elements were investigated by X-ray fluorescence and inductively coupled plasma-mass spectrometry in soil and caper samples from three localities in Lipari and Salina, and data from the three sites were compared by a nonparametric test, a correlation test and multivariate statistics (principal component analysis). The results allowed to discriminate soils according to geolithological characteristics of each area and detect a statistically significant correspondence between soil and caper samples for the elements Co, Fe, Mg and Rb, identifying thus possible geochemical caper fingerprints of origin. These results may also be useful to protect the high quality of Aeolian caper products by a suitable "Made in Italy" trademark and avoid falsifications and frauds.

Chemical elements as fingerprints of geographical origin in cultivars of Vitis vinifera L. raised on the same SO4 rootstock.

The uptake of major and trace elements in grapevine (Vitis vinifera L.) can be influenced by soil, climate, geographic origin, and rootstock type. Rootstocks were mainly selected to resist phylloxera and for specific tolerance to lime, mineral uptake, drought, and salinity. The relationship among concentrations of major, trace, and rare earth elements was studied in soil and leaves from two Italian grapevine cultivars, "Cabernet Sauvignon" and "Corvina," employed to produce renowned controlled designation of origin (DOC) wines. The cultivars were raised on the same rootstock SO4 in two different areas of the Veneto Region (Northern Italy). The elements were studied by X-ray fluorescence and inductively coupled plasma mass spectrometry, and data were elaborated by non-parametric tests and multivariate linear discrimination analysis. The related index of bioaccumulation was calculated to define the specific assimilation of the elements from soil to leaves. A statistically significant correspondence between soil and leaf samples was observed for Mg, Sm, V, and Zr. The results allowed to discriminate soil and leaf samples of the two cultivars according to geographical provenance, possibly providing geochemical markers (fingerprints) useful against fraudulent use of DOC wine labels.

Geochemical fingerprints of "Prosecco" wine based on major and trace elements.

The terroir can be defined as interactive ecosystem that includes climate, geology, soil and grapevine, and it is used to explain the hierarchy of high quality of wine. In order to understand the terroir functions, it is necessary to analyse the interactions among the geology, soil and wine. To define a geochemical fingerprint, the relationship between geochemistry of vineyard soil and chemical composition of wine from Veneto Italian Region was studied. The vineyards tested belonged to four distinct wineries located in the Veneto alluvial plain, included in the Controlled Designation of Origin (DOC) area of Prosecco. We investigated the relationship between major and trace elements in soil and their concentrations in Prosecco wine according to geographical origin. The detection of chemical composition in soil and wine were analysed by inductively coupled plasma mass spectrometry, and data were elaborated by nonparametric test and multivariate statistics Linear Discrimination Analysis. The geochemical and statistical analyses allowed to discriminate the vineyard soils according to geo-lithological characteristics of each area and to identify the geochemical "Prosecco" fingerprints, useful against fraudulent use of DOC wine labels.

Saharan dust particles in snow samples of Alps and Apennines during an exceptional event of transboundary air pollution.

Southern European countries are often affected in summer by transboundary air pollution from Saharan dust. However, very few studies deal with Saharan dust pollution at high altitudes in winter. In Italy, the exceptional event occurred on February 19, 2014, colored in red the entire mountain range (Alps and Apennines) and allowed to characterize the particulate matter deposited on snow from a morphological and chemical point of view. Snow samples were collected after this event in four areas in the Alps and one in the Apennines. The particulate matter of the melted snow samples was analyzed by scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS) and by inductively coupled plasma mass spectrometry (ICP-MS). These analyses confirmed the presence of Saharan dust particle components in all areas with similar percentages, supported also by the positive correlations between Mg-Ca, Al-Ca, Al-Mg, and Al-K in all samples.

Rare earth elements distribution in grapevine varieties grown on volcanic soils: an example from Mount Etna (Sicily, Italy).

A geochemical and statistical approach has allowed identifying in rare earth elements (REEs) absorption a good fingerprinting mark for determining the territoriality and the provenance of Vitis vinifera L. in the district of Mount Etna (southern Italy). Our aim is to define the REEs distribution in different parts of the plants which grow in the same volcanic soil and under the same climate conditions, and therefore to assess whether REEs distribution may reflect the composition of the provenance soil or if plants can selectively absorb REEs in order to recognize the fingerprint in the Etna Volcano soils as well as the REEs pattern characteristic of each cultivar of V. vinifera L. The characteristic pattern of REEs has been determined by ICP-MS analyses in the soils and in the selected grapevine varieties for all the following parts: leaves, seeds, juice, skin, and berries. These geochemical criteria, together with the multivariate statistical analysis of the principal component analysis (PCA) and of the linear discriminant analysis (LDA) that can be summarized with the box plot, suggest that leaves mostly absorb REEs than the other parts of the plant. This work investigates the various parts of the plant in order to verify if each grape variety presents a characteristic geochemical pattern in the absorption of REEs in relationship with the geochemical features of the soil so to highlight the individual compositional fingerprint. Based on REE patterns, our study is a useful tool that allows characterizing the differences among the grape varieties and lays the foundation for the use of REEs in the geographic origin of the Mount Etna wine district.

Fungal spores and pollen in particulate matter collected during agricultural activities in the Po Valley (Italy).

Airborne particulate matter (PM) containing fungal spores and pollen grains was sampled within a monitoring campaign of wheat threshing, plowing and sowing agricultural operations. Fungal spores and pollen grains were detected and identified on morphological basis. No studies were previously available about fungal spore and pollen content in agricultural PM in the Po Valley. Sampling was conducted in a Po Valley farmland in Mezzano (Ferrara, Italy). The organic particles collected were examined by scanning electron microscopy with energy dispersive X-ray spectrometer. Fungal spores and pollen grains were identified when possible at the level of species. The most frequent components of the organic particles sampled were spores of Aspergillus sp., which could represent a risk of developing allergies and aspergillosis for crop farmers.

Distribution of rare earth elements in soil and grape berries of Vitis vinifera cv. "Glera".

The renowned Vitis vinifera L. cultivar "Glera" (Magnoliopsida Vitaceae) has been grown for hundreds of years in the Italian regions of Veneto and Friuli to produce the sparkling Prosecco wine, with controlled designation of origin (DOC). We evaluated the relationship among the concentrations of rare earth elements (REE) in soil and in "Glera" grape berries in vineyards belonging to five different localities in the Veneto alluvial plain, all included in the DOC area of Prosecco. The concentration of REE in samples of soil and juice or solid residues of grape berries was determined by inductively coupled plasma mass spectrometry (ICP-MS), and the index of bioaccumulation was calculated to define the specific assimilation of these elements from soil to grape berries. The concentration of REE in soil samples allowed an identification of each locality examined, and REE were mostly detected in solid grape berry residues in comparison to juice. These data may be useful to associate REE distribution in soil and grape berries to a specific geographical origin, in order to prevent fraudulent use of wine denomination labels.

Geochemical characterization of elements in Vitis vinifera cv. Negroamaro grape berries grown under different soil managements.

The present geochemical study concerns the impact of viticultural practices in the chemical composition of the grape cultivar "Negroamaro" in Apulia, a southern Italian region renowned for its quality wine. Three types of soil management (SM), two cover cropping with different mixtures, and a soil tillage were considered. For each SM, the vines were irrigated according to two irrigation levels. Chemical composition of soil and of berries of Vitis vinifera cultivar "Negroamaro" were analyzed by X-ray fluorescence, inductively coupled plasma-mass spectrometry and multivariate statistics (linear discrimination analysis). In detail, we investigated major and trace elements behavior in the soil according to irrigation levels, the related index of bioaccumulation (BA) and the relationship between trace element concentration and soil management in "Negroamaro" grapes. The results indicate that soil management affects the mobility of major and trace elements. A specific assimilation of these elements in grapes from vines grown under different soil management was confirmed by BA. Multivariate statistics allowed to associate the vines to the type of soil management. This geochemical characterization of elements could be useful to develop fingerprints of vines of the cultivar "Negroamaro" according to soil management and geographical origin.