Brunella Raco

O-H-C isotope ratio determination in wine in order to be used as a fingerprint of its regional origin

Stable isotopes have been applied to determine the origin assignment and verify the geographical provenance that is considered important characteristics of wine products both for consumers and the international regulations, of wines. Stable isotope analyses of (18)O/(16)O, D/H and (13)C/(12)C ratio for the detection of origin and of adulteration in wine are discussed in this study. The δ(13)C analysis of ethanol and wines water δ(18)O underlines the importance of the photosynthetic pathway and the environmental conditions of wine. Also we discuss the main factors that are responsible for the differentiation of the oxygen isotope ratios of wine water. Data interpretation demonstrated the efficacy of δ(18)O analysis not only in the wine but also in grape berries, preferably if the determination of the δ(18)O value is employed together with the determination of the δ(2)H isotope content of wine, for the detection of the geographical origin of wine.

A Quick and Reliable Method to Detect and Quantify Contamination from MSW Landfills: a Case Study

Geochemical characterization of two landfills, one closed and the other still active, both located near Komotini (Thrace, Greece), has been carried out. The aim was to provide an integrated and reliable methodology for a rapid assessment of the real impact of a municipal solid waste landfill, in the main environmental matrices (air and water) of the surrounding areas. The chemical (CO2, CH4, CO, H2, N2, and O2 + Ar) and isotopic characterization (δ13C(CO2) and δ13C(CH4)) of landfill gas and chemical (Na+, K+, Ca2+, Mg2+, Cl−, SO42−, HCO3−, NH4+, NO3−, NO2−, B, COD, Fe, Mn, As, Cr, Ni, Cu, Zn, Cd, Pb, and Hg) and isotopic analysis (δD, δ18O, tritium content, and δ13CDIC) of leachate, stream waters and groundwaters, and flux survey on the air–soil interface has been carried out. Combined chemical and isotopic analysis of the fluids collected inside and in the surroundings of the Komotini landfills supply a detailed picture of biogas emission and composition as well as of leachate chemistry and interaction with local waters. The results arising in this case study demonstrate that it is possible to propose a quick and reliable geochemical protocol to get a detailed picture of the state of health of the environment around a landfill.

Geochemical characterization of the ground waters from the former Hg-mining area of Abbadia San Salvatore (Mt. Amiata, central Italy): criticalities and perspectives for the reclamation process

This study was aimed to geochemically characterize the groundwater system of the Abbadia San Salvatore (Mt. Amiata, Siena, central Italy) former Hg-mining area, whose activity closed at the end of the seventies, in order to accomplish the reclamation process after that the former ownership of the mining concession (E.N.I. National Agency for Hydrocarbons, AGIP Division) passed the property to the Munici pality of Abbadia San Salvatore in 2008. The study area covers a surface of about 65 ha and since February 2013 old and new piezometers were used to assess the main chemical features along with the concentrations of As, Hg and Sb. Four sampling campaigns were carried out up to January 2014 and a relatively large spatial and temporal geochemical variability was observed. Apparently, the working activities related to the construction of an artificial channel (commenced in March 2013 and terminated at the end of 2013), which crosscuts the whole mining area to drain the surface waters in order to minimize the interaction between the meteoric waters and the by-products deriving by the production of metallic mercury, did not affect the groundwater system. Slag, roasted material and other by-products deriving from the local and surrounding Hg mining activities were indeed used to fill the terrain where most of the mining structures lie. The dominating geochemical facies was Ca(Mg)-SO4 and, subordinately, Ca(Mg)-HCO3, while Na-HCO3 compositions were rarely found. Dissolution of gypsum/anhydrite and carbonates and hydrolysis of sulfide minerals are likely the main geochemical process that produced the observed geochemical compositions. The contents of As and Sb only sporadically exceeded the maximum allowable concentrations intended for human consumption (98/83 EC Directive 1998), i.e. 10 and 5 mg L-1. Conversely, those of Hg were constantly above the EC directive, e.g. 1 mg L-1, with the exception of those waters located up- and downstream the groundwater flow. This indicates that the exotic filling terrains in the mining area, mainly consisting of roasting products, likely play a pivotal role in regulating the concentrations of Hg, which reached values up 853 mg L-1. The construction of permeable reactive barriers, located downstream the water flow, appears to be the most promising solution for the removal of Hg, although, according to the literature, several materials, tested with laboratory experiments, can be used and, as a consequence, it is necessary to individuate specific piezometers with different Hg concentrations where pilot investigations are to be carried out before undertaking any remediation actions.

Isotopic analysis for degradation diagnosis of calcite matrix in mortar

Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (δ13C and δ18O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO2 and water during calcite formation and degradation processes. Isotopic change of the initial δ13C and δ18O in carbonate matrix was caused by alteration of the primary source of CO2 and H2O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO2 from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter δ18O and δ13C in lime mortar.

Towards the Concept of Background/baseline Compositions: A Practicable Path?

Water geochemistry is often investigated considering a large number of variables, including major, minor and trace elements. Some of these are usually well associated due to coherent geochemical behaviour, but the effect of anthropic factors tends to increase data variability, sometimes obscuring the natural laws governing their relationships. It may thus be difficult to identify geochemical features linked to natural phenomena, as well as to separate geogenic anomalies from the anthropogenic ones, or to define background or baseline concentrations for single chemical elements. This is particularly true at regional level, where numerous phenomena may interact and mix together, forming a complex pattern not easy to interpret. The identification of background or baseline values is particularly difficult due to the compositional nature of chemical variables, so that under the Compositional Data Analysis (CoDA) theory single background or baseline values lose their meaning. However, they are fundamental references for public institutions and government policies. In this contribution a new approach is proposed, aimed at investigating the regionalised structure of the geochemical data by considering the joint behaviour of several chemical elements. The approach is based on the robust CoDA theory, so that the proportionality features of abundance data are fully taken into account, enhancing their relative multivariate behaviour, as well as the influence of outliers. An application example is presented for the groundwater compositions in Tuscany Region, a surface of about 23,000 km\(^2\), where more than 6000 wells have been sampled and analysed. The mapping of robust Mahalanobis distance was able to indicate (1) in which part of the investigated area the pressure toward anomalous behaviour was higher, (2) where the compositions nearest to the barycentre were and (3) if spatial continuity was present in limited portions of the territory.

GEOBASI: The geochemical Database of Tuscany Region (Italy) Acque Sotterranee

In this study the new Regional Geochemical Database (RGDB), called GEOBASI, is presented and illustrated in the framework of a joint collaboration among the three Tuscan universities (Florence, Pisa and Siena), CNR-IGG (Institute of Geosciences and Earth Resources of Pisa), ARPAT (Regional Agency for the Environmental Protection), LAMMA (Environmental Modelling and Monitoring Laboratory for Sustainable Development) Consortium and S.I.R.A. (Territorial and Environmental Informative System of Tuscany). The database has permitted the construction of a repository where the geochemical information (compositional and isotopic) has been stored in a structured way so that it can be available for different groups of users (e.g. institutional, public and private companies). The information contained in the database can in fact be downloaded freely and queried to correlate geochemistry to other non compositional variables. The first phase of the project was aimed at promoting the use of the geochemical data already available from previous investigations through a powerful Web-GIS interface to implement the exploratory statistics graphical-numerical tools used to: 1) analyse the spatial variability of the investigated context, 2) highlight the geographic location of data pertaining to classes of values or single cases, 3) compare the results of different analytical methodologies applied to the determination of the same element and/or chemical species, 4) extract the geochemical data related to specific monitoring plans and/or geographical areas, and finally 5) recover information about data below the detection limit to understand their impact on the behaviour of the investigated variable. Developments of this project will be focused on the definition of rules and standardized methods in a way that external users could also interactively pursue the RGDB. Furthermore, a detailed investigation of the Scarlino-Follonica plain will permit the improvement and test of statistical and geostatistical methods, using open source software (QGIS and R) to support the process of evaluation of the geochemical baseline.

Groundwater Contamination Studies by Environmental Isotopes: A review

Water demand for urban, industrial, and agricultural purposes is a major concern in developed and third world countries. A careful evaluation for an appropriate and sustainable use of water resources is a priority. Geochemical processes can lead to measurable variations of the aquatic environment, which can be studied through the analysis of the dissolved solutes. Even if this review is not meant to be exhaustive, it is intended to give a view on the importance of environmental isotopes in the context of groundwater quality assessments. This is done by briefly recalling some basic notions for each described system, followed by relevant applications and reports about some significant case studies. This review includes well-established isotopic systematics, such as those of O and H in water, C in dissolved inorganic carbon (DIC), S and O in sulfates, and N and O in nitrates and those of boron and Sr, which in the last lustrums have found large application in the field of water geochemistry. This chapter ends with some examples related to nontraditional isotopes, i.e., Fe, Cr, and Cu, in order to highlight the potential of the environmental isotopes to trace sources, fate, and behavior of different solutes and metals in surface water and groundwater.

Dal modello concettuale al modello numerico: il caso di studio del sistema acquifero di Follonica (GR, Toscana meridionale)

The groundwater body hosted in the Follonica coastal plain (Grosseto, Italy) is the Italian aquifer system that was chosen for the experimentation of the FREEWAT Platform, a collection of free andopen source software tools for water resource management and quantitative and qualitative modeling developed within the EU project Horizon 2020. In consideration of the studies carried out by the Institute of Geosciences and Earth Resources of the Italian National Research Council from 2006 to 2015 for the geological, hydrogeological and geochemical characterization of the 66 regional groundwater bodies (CIS), the Tuscany Region, partner of the project, has entrusted CNRIGG for the implementation of the numerical model.A conceptual model of the aquifer system was developed by processing and combining all the geological, hydrogeological and geochemical-isotopic data. The supposed hydrostructure was tested and validated through its 3D solid construction, defining the geometry and the physical limits of the multi-layered aquifer system and ensuring its coherence and consistency with respect to the other geographical databases. Hydrogeological and geochemical data processing ledto identify the aquifer system feeding components, the relationships between surface hydrography and groundwater and the main physical and chemical processes taking place (ion exchange, seawater ingress, etc). On this basis, the development and implementation of the flow model has started, based on the Modflow code.A focus group was organized as part of the project and stakeholders were involved with their active participation to the elaboration of the conceptual model by sharing data and other useful information.This paper describes the methodology used and the results obtained so far.

The GEOBASI (Geochemical Database of Tuscany) open source tools

13 The tools implemented for the new Regional Geochemical Database, called GEOBASI, are hereafter 14 presented. The database has permitted the construction of a repository where the geochemical 15 information (compositional and isotopic) has been stored in a structured way so that it can be available 16 for different groups of users (e.g. institutional, public and private companies). The information 17 contained in the database can in fact be downloaded freely and queried to correlate geochemistry to 18 other non compositional variables. 19 The repository has been aimed at promoting the use of the geochemical data already available from 20 previous investigations through a powerful Web-GIS interface. The resulting graphical-numerical 21 tools in such a complex database have been developed to: 1) analyse the spatial variability of the 22 investigated context, 2) highlight the geographic location of data pertaining to classes of values or 23 single cases, 3) compare the results of different analytical methodologies applied to the determination 24 of the same element and/or chemical species, 4) extract the geochemical data related to specific 25 monitoring plans and/or geographical areas, and finally 5) recover information about data below the 26 detection limit to understand their impact on the behaviour of the investigated variable. 27

Isotope Geochemistry Survey in Ierissos Gulf Basin, North Greece

Major element chemistry of water samples in Ierissos gulf basin is dominated by Ca2+, Mg2+ and HCO3 - ions. Water rock interaction is an important mechanism in the mineralization of waters. A link between Skouries and Gomati samples (Mg-HCO3) was detected reflecting the well documented M. Panagia-Gomati fault. In Neochori and M. Panagia samples were identified fluids with different origin. Regarding surface waters, extended bicarbonates action of meteoric waters and reductive conditions, probably control As concentration in surface water. Generally, surface waters in Kokkinolakas basin exceed the WHO limits for As, Sb, Cr, Ni, Cd, Pb, Mn, Fe in great rates as natural immobilization mechanisms are suspended.