Eleonora Braschi

High-precision 87Sr/86Sr analyses in wines and their use as a geological fingerprint for tracing geographic provenance.

The radiogenic isotopic compositions of inorganic heavy elements such as Sr, Nd, and Pb of the food chain may constitute a reliable geographic fingerprint, their isotopic ratios being inherited by the geological substratum of the territory of production. The Sr isotope composition of geomaterials (i.e., rocks and soils) is largely variable, and it depends upon the age of the rocks and their nature (e.g., genesis, composition). In this study we developed a high-precision analytical procedure for determining Sr isotopes in wines at comparable uncertainty levels of geological data. With the aim of verifying the possibility of using Sr isotope in wine as a reliable tracer for geographic provenance, we performed Sr isotope analyses of 45 bottled wines from four different geographical localities of the Italian peninsula. Their Sr isotope composition has been compared with that of rocks from the substrata (i.e., rocks) of their vineyards. In addition wines from the same winemaker but different vintage years have been analyzed to verify the constancy with time of the (87)Sr/(86)Sr. Sr isotope compositions have been determined by solid source thermal ionization mass spectrometry following purification of Sr in a clean laboratory. (87)Sr/(86)Sr of the analyzed wines is correlated with the isotopic values of the geological substratum of the vineyards, showing little or no variation within the same vineyard and among different vintages. Large (87)Sr/(86)Sr variation is observed among wines from the different geographical areas, reinforcing the link with the geological substratum of the production territory. This makes Sr isotopes a robust geochemical tool for tracing the geographic authenticity and provenance of wine.

Geochemistry and Sr-Nd-Pb isotopes of Monte Amiata Volcano, Central Italy: evidence for magma mixing between high-K calc-alkaline and leucititic mantle-derived magmas

Monte Amiata is a small volcano composed by trachytic to olivine latitic lava flows and domes emplaced in a very short time between 305 and 231 ka. The main petrographic features are represented by the occurrence of i) abundant rounded magmatic enclaves increasing in dimension and quantity passing from early to late erupted Monte Amiata volcanic rocks, ii) large sanidine megacrysts, mainly confined in the second stage of activity characterised by the emplacement of exogenous domes and massive lava flows, and iii) mafic olivine latitic lava flows, with intermediate compositions between the early silica-rich volcanic rocks and the most mafic rounded magmatic enclaves hosted by the Monte Amiata volcanic rocks. The occurrence of rounded magmatic enclaves testifies fresh magma injection and stirring within a differentiated magma reservoir. This triggered the pouring out of the viscous trachydacitic resident magma. A reverse differentiation pathway is observed with time of magma emplacement, which is accompanied by the decrease of silica contents and increase of MgO and compatible elements passing from early trachydacites to final olivine-latites. The same timely reverse differentiation pathway is observed among magmatic enclaves, with the most mafic terms hosted by final olivine-latitic lava flows. Fine-grained rounded magmatic enclaves, indeed, range in composition from potassic trachybasalt (absarokite) to olivine-latite. The overall geochemical and isotopic features agree with a mixing process between a highly differentiated (i.e., high silica), and partially crystallised, high-K calc-alkaline end- member and a mafic ultrapotassic magma possibly leucite-bearing. Absence of leucite in the Amiata rocks and enclaves is due to high-silica activity of derived magmas caused by the high-silica end-member of the mixing process.

New 40Ar-39Ar dating and revision of the geochronology of the Monte Amiata Volcano, Central Italy

The duration of the Mt. Amiata volcanic activity is still a matter of debate, in spite of the presence of several geochronological data in the literature. We performed new 40Ar-39Ar dating on the sanidinegroundmass pairs of the upper stratigraphic units: Dome and massive Lava flows Complex (DLC) and Olivine Latitic final Lavas (OLF). The aim was twofold: to check the reliability of sanidine ages as geochronometer in these products, questioned in the literature, and to better define the chronology of the late activity of this volcano. Ages obtained on coexisting sanidine and groundmass of the Dome and massive Lava flows Complex (DLC) samples overlap within errors, demonstrating that sanidine crystals recorded reliable emplacement ages in these rocks. The Olivine Latite final lavas (OLF) display a different scenario, where the groundmass has an age younger than that of the sanidine, which is xenocrystic and, evidently, retains inherited Ar. Preferred ages for analysed DLC samples are comprised between 301 and 294 ka, an interval of time too short to resolve the ages of the four dome samples taken into account. The Ermeta lava is about 60 ka younger. We propose that the majority of Mt. Amiata volcanic rocks were emplaced in a narrow interval of time, whilst a temporal gap, which needs more detailed constraints, exists with at least one of the Olivine Latite final lavas (OLF).

Pre-eruptive magmatic processes re-timed using a non-isothermal approach to magma chamber dynamics

Constraining the timescales of pre-eruptive magmatic processes in active volcanic systems is paramount to understand magma chamber dynamics and the triggers for volcanic eruptions. Temporal information of magmatic processes is locked within the chemical zoning profiles of crystals but can be accessed by means of elemental diffusion chronometry. Mineral compositional zoning testifies to the occurrence of substantial temperature differences within magma chambers, which often bias the estimated timescales in the case of multi-stage zoned minerals. Here we propose a new Non-Isothermal Diffusion Incremental Step model to take into account the non-isothermal nature of pre-eruptive processes, deconstructing the main core-rim diffusion profiles of multi-zoned crystals into different isothermal steps. The Non-Isothermal Diffusion Incremental Step model represents a significant improvement in the reconstruction of crystal lifetime histories. Unravelling stepwise timescales at contrasting temperatures provides a novel approach to constraining pre-eruptive magmatic processes and greatly increases our understanding of magma chamber dynamics.

Strontium Isotopes in Biological Material: A Key Tool for the Geographic Traceability of Foods and Humans Beings

This chapter discusses the application in geology of the isotope ratio 87Sr/86Sr, where 87Sr is the long-lived radiogenic daughter of 87Rb (t1/2 = 48.8 billion years), and its use as geologic fingerprint for geographic traceability in food, forensic, and archaeological sciences. The 87Sr/86Sr ratio of any geological material (i.e. minerals and rocks) on Earth depends on its time integrated 87Rb/86Sr ratio and thus it is related to three main parameters: (1) the initial radiogenic isotopic abundance, (2) the age of the rock/mineral, and (3) the parent/daughter isotope ratio. Being a ratio between two nuclides of the same element 87Sr/86Sr is not modified during the uptake of the plant and it is transferred unchanged to all living beings of the food chain, thus remaining identical to that of the substratum from which the original plant or vegetable grew.

High-Precision In Situ 87Sr/86Sr Analyses through Microsampling on Solid Samples: Applications to Earth and Life Sciences

An analytical protocol for high-precision, in situ microscale isotopic investigations is presented here, which combines the use of a high-performing mechanical microsampling device and high-precision TIMS measurements on micro-Sr samples, allowing for excellent results both in accuracy and precision. The present paper is a detailed methodological description of the whole analytical procedure from sampling to elemental purification and Sr-isotope measurements. The method offers the potential to attain isotope data at the microscale on a wide range of solid materials with the use of minimally invasive sampling. In addition, we present three significant case studies for geological and life sciences, as examples of the various applications of microscale 87Sr/86Sr isotope ratios, concerning (i) the pre-eruptive mechanisms triggering recent eruptions at Nisyros volcano (Greece), (ii) the dynamics involved with the initial magma ascent during Eyjafjallajökull volcanos (Iceland) 2010 eruption, which are usually related to the precursory signals of the eruption, and (iii) the environmental context of a MIS 3 cave bear, Ursus spelaeus. The studied cases show the robustness of the methods, which can be also be applied in other areas, such as cultural heritage, archaeology, petrology, and forensic sciences.

High-Nb hawaiite–mugearite and high-Mg calc-alkaline lavas from northeastern Iran: Oligo-Miocene melts from modified mantle wedge

ABSTRACT Tertiary volcanic rocks in northwestern Firoozeh, Iran (the Meshkan triangular structural unit), constitute vast outcrops (up to 250 km2) of high-Mg basaltic andesites to dacites that are associated with high-Nb hawaiites and mugearites. Whole-rock 40Ar/39Ar ages show a restricted range of 24.1 ± 0.4–22.9 ± 0.5 Ma for the volcanic rocks. The initial ratios of 87Sr/86Sr and 143Nd/144Nd vary from 0.703800 to 0.704256 and 0.512681 to 0.512877, respectively, in the high-Mg basaltic andesites–dacites. High-Th contents (up to 11 ppm) and Sr/Y values (27–100) and the isotopic composition of the subalkaline high-Mg basaltic andesites–dacites indicate derivation from a mantle modified by slab and sediment partial melts. Evidence such as reverse zoning and resorbed textures and high Ni and Cr contents in the evolved samples indicate that magma mixing with mafic melts and concurrent fractional crystallization lead to the compositional evolution of this series. The high-Nb hawaiites and mugearites, by contrast, have a sodic alkaline affinity and are silica undersaturated; they are also enriched in Nb (up to 47 ppm) and a wide range of incompatible trace elements, including LILE, LREE, and HFSE. Geochemistry and Sr–Nd isotopic compositions of the high-Nb hawaiites and mugearites suggest derivation from a mantle source affected by lower degrees of slab melts. Post-orogenic slab break-off is suggested to have prompted the asthenospheric upwelling that triggered partial melting in mantle metasomatized by slab-derived melts.