Geochemical characterization, U–Pb apatite geochronology, and geodynamic significance of olivine minette dykes from the Julian Alps, NE Italy

We investigated olivine minette dykes from the Rio Colan Valley of the Julian Alps (NE Italy) to provide new constraints on the mantle geochemistry underneath this extreme sector of the Italian Southern Alps. Petrographic observations, high Mg#s, high Cr and Ni contents, low Dy/YbCN ratios and flat heavy rare earth element (REE) profiles imply these are primary magmas derived from a depleted peridotite with olivine and garnet as possible residual phases. However, high K2O and incompatible trace element contents, coupled with superchondritic Nb/Ta ratios, suggest that the source was modified into a rutile–phlogopite-bearing carbonated peridotite by multiple metasomatic events such as recycling of crustal material and carbonatitic metasomatism related to an old orogenic event and rutile-rich metasomatism linked to the Pangaea break-up. Laser ablation – multi-collector – inductively coupled plasma – mass spectrometer (LA-MC-ICP-MS) U–Pb geochronology of apatites from two dykes yielded differences between unforced and forced discordia ages up to ∼45 Ma, likely due to the initial 207Pb/206Pb correction adopted. Nonetheless, because forced discordia and 206Pb/238U weighted mean ages are overall similar within the uncertainty, our preferred interpretation is that olivine minettes intruded and crystallized at ∼67 Ma. The age and anorogenic signature of these magmas are consistent with the regional extensional tectonics in the Julian Alps due to the advance of the external Dinaric front following Adria plate eastward subduction. Eventually, we show also that Rio Colan magmas are geochemically hybrid products between lamprophyres and lamproites compared with similar Italian and Western Mediterranean volcanics

Os diques na encosta ocidental da Serra de Ybytyruzú, região centro‑oriental do Paraguai

The Cordillera del Ybytyruzú region of central‑eastern Paraguay is predominantly formed by tholeiitic lava flows from the Early Cretaceous age (130–134 Ma) cut by K‑alkaline dykes and intrusive bodies aged between 125 and 127 Ma. Petrochemical studies focusing on 14 samples of dykes from the region show an apparent affinity to Roman Province Type rocks and total consistency with the overall petrographic association of the Asunción‑Sapucai‑Villarrica (ASV) graben. Two main potassic suites are distinguished: B‑P (basanite‑tephrite‑phonotephrite‑phonolite) and AB‑T (alkali basalt‑trachybasalt‑trachyandesite‑trachyphonolite/trachyte).The occurrence of lamproitic rocks in the area has so far not been confirmed.A Cordilheira do Ybytytyruzú na região centro‑oriental do Paraguai é formada dominantemente de derrames de lavas toleíticas de idade Cretáceo Inferior (130–134 Ma) cortados por diques alcalinos potássicos e corpos intrusivos com idades entre 125 e 127 Ma. Estudos petroquímicos focalizando 14 amostras de diques da região mostram uma aparente afinidade com as rochas da Província do Tipo Romano e total consistência com a associação petrográfica global do gráben Assunção‑Sapucai‑Villarrica (ASV). Duas suítes potássicas principais são distinguidas: B‑P (basanito‑tefrito‑fonotefrito‑fonolito) e AB‑T (álcali basalto‑traquibasalto‑traquiandesito‑traquifonolito/traquito). A ocorrência de rochas lamproíticas na área não foi até então confirmada

Whetstones from Bronze Age hill forts of North Eastern Italy

A group of Bronze Age whetstones from Protohistoric hill forts, locally called Castellieri, of eastern Friuli Venezia Giulia (north eastern Italy) has been studied using different techniques, including non destructive methods such as X-ray computed micro-tomography and portable X-ray fluorescence, in order to characterize the raw material and define its origin. The obtained results suggest that small pebbles of reddish subarkose and quartz arenites collected from the gravel deposits of river Isonzo, perhaps deriving from Val Gardena Formation outcrops, were exploited for the production of the studied artefacts during the Bronze Age. These data complement our knowledge about the lithic raw materials exploitation strategies during the ancient phase of Castellieri culture, almost exclusively based on local rock type

A crystal/melt partitioning study for sulfur and halogens: pyroxenes as probes for assessing gas loads in LIP magmas

A link between magmatism from Large Igneous Provinces (LIPs) and mass extinctions has been observed at leastin five occasions in the Phanerozoic. Volatile species such as S, C and halogen compounds severely impactedthe global environment, released both from melts and thermal metamorphism of volatile-rich sediments. It is stillchallenging to obtain quantitative estimates of the degassed volatiles for ancient magmatic systems, particularly inthe absence of melt inclusions. We propose to fill the gap of knowledge on sulfur partitioning between mineralsand melts, at the aim of using phenocrysts as probes of volatile contents in the melts from which they crystallized.Measuring a volatile concentration in natural minerals (chiefly clinopyroxene) and combining it with an experi-mentally determined partition coefficient (KD), the volatile load in basaltic equilibrium melts can be calculated.We measured a clinopyroxene/melt sulfur KD of 0.0009\ub10.0001 for basaltic experiments performed at conditionstypical of LIP basalts (FMQ-2; 800-1000 MPa; 1000 \u30a-1350 \u30aC), through ion microprobe (Nordsim). Basaltic ex-periments were also simultaneously analyzed for Cl and F. For these elements the measured clinopyroxene/meltKDs were more variable, 0.0071\ub10.0052 and 0.1985\ub10.087, respectively. Compatibility of sulfur, chlorine andfluorine in clinopyroxene from basaltic systems is markedly different (F>Cl>S), in agreement with what observedby previous studies, and the partition coefficient is well constrained around 0.001 for S. Application of the newlymeasured sulfur KD to samples from thoroughly-dated lava piles from the Deccan Traps and from the SiberianTraps sills reveal that most of the basalts were at or near sulfide saturation (up to ca. 2000 ppm for low fO2melts)

Late-stage magmatic to deuteric/metasomatic accessory minerals from the Cerro Boggiani agpaitic complex (Alto Paraguay Alkaline Province)

This work describes rare accessory minerals in volcanic and subvolcanic silica-undersaturated peralkaline and agpaitic rocks from the Permo-Triassic Cerro Boggiani complex (Eastern Paraguay) in the Alto Paraguay Alkaline Province. These accessory phases consist of various minerals including Th U oxides/silicates, Nb-oxide, REE-Sr-Ba bearing carbonates-fluorcarbonates-phosphates-silicates and Zr Na rich silicates. They form a late-stage magmatic to deuteric/ metasomatic assemblage in agpaitic nepheline syenites and phonolite dykes/lava flows made of sodalite, analcime, albite fluorite, calcite, ilmenite-pyrophanite, titanite and zircon. It is inferred that carbonatitic fluids rich in F, Na and REE percolated into the subvolcanic system and metasomatically interacted with the Cerro Boggiani peralkaline and agpaitic silicate melts at the thermal boundary layers of the magma chamber, during and shortly after their late-stage magmatic crystallization and hydrothermal deuteric alteratio

Paleomagnetism of the Penatecaua magmatism: The CAMP intrusive rocks in the Amazonas Basin, northern Brazil

The Penatecaua magmatism (~201 Ma) is part of the Central Atlantic Magmatic Province (CAMP) and is represented by voluminous sills in the Amazonas Basin, north Brazil. The sills appear south of the Amazonas River, particularly in the Medicilândia, Placas, and Rurópolis cities. To the north of the river, near Monte Alegre and Alenquer, smaller sills and NNE-SSW dikes prevail. Paleomagnetic data from 28 sampling sites of sills and dikes from all areas gave consistent results of normal polarity. Despite the large area of occurrence, the VGPs show small dispersion, consistent with a very brief emplacement time, as indicated by the radiometric ages. However, some sites, mainly from Alenquer and the southern sills, gave anomalous directions that may represent the record of a transitional geomagnetic field. The calculated paleomagnetic pole includes former data from Guerreiro and Schult (1986) plotting at 260.1°E 77.5°S (N = 30; A95 = 3.8°; k = 48) and agrees with other high-quality CAMP poles for South America

Sulfur and fluorine degassing from Deccan Traps lavas inferred from pyroxene chemistry: potential for end-Cretaceous volcanic winters

The Cretaceous-Paleogene (K-Pg) mass extinction was a pivotal event in Earth's history and is attributed to the interplay of two major events—the Deccan Traps volcanism and the Chicxulub asteroid impact. We contribute to refine of our understanding of the volcanic stressor for this extinction by investigating the sulfur and fluorine budgets of Deccan lavas from the Western Ghats (India), spanning the K-Pg boundary. Sulfur and fluorine concentrations were analyzed in clinopyroxene phenocrysts from Deccan Traps lavas, by Synchrotron-light X-ray fluorescence (beamline I18, Diamond Light Source, U.K.), and ion probe (CAMECA IMS 1280 at Nordsim Laboratory, Swedish Museum of Natural History, Stockholm, SE), respectively. The results were divided by experimentally determined partition coefficients to calculate melt concentrations. Our analyses reveal variable magmatic volcanic fluorine concentrations ranging from 400 to 3000 parts per million, suggesting the potential for regional environmental impact. The highest sulfur concentrations, reaching up to 1800 parts per million, are observed in Deccan lavas emplaced just prior to the extinction interval, within a timeframe of 0.1 million years. In contrast, later basalts generally exhibit lower sulfur concentrations, only up to 750 parts per million. Independent evidence supports that eruption of the Deccan flood basalts occurred in multiple voluminous eruptive pulses each lasting on the order of centuries, as typical of continental flood basalts. Our findings propose that the volcanic sulfur degassing associated with such activity may have led to repeated, short-lived global temperature drops, too short to be recorded by global paleotemperature record, albeit coupled with a global cooling trend. Sulfur-induced cold snaps likely imposed stress on ecosystems long before the decisive impact of the Chicxulub bolide at the end of the Cretaceous

Sulfur and chlorine in nakhlite clinopyroxenes: Source region concentrations and magmatic evolution

The volatile concentrations of the martian mantle and martian magmas remain important questions due to their role in petrogenesis and planetary habitability. The sulfur and chlorine concentrations, and their spatial distribution, in clinopyroxenes from nakhlites MIL 03346, Nakhla, and NWA 998 were measured to provide insight into these volatiles in the parental melts and source regions of nakhlites, and to constrain the evolution of the nakhlite melts. Sulfur and chlorine in four clinopyroxene crystals from MIL 03346, four from Nakhla, and five from NWA 998 were measured in crystal cores and rims by synchrotron X-ray fluorescence using beamline I18 at the Diamond Light Source. Portions of two crystals from MIL 03346 and one from Nakhla were mapped for S and Cl; a few reconnaissance analyses of Cl and F in MIL 03346 and Nakhla were made by ion microprobe. Clinopyroxene cores in Nakhla and NWA 998 contain ~ 10 ppm S, ~ 10 ppm Cl and ~ 74 ppm F (only Nakhla analyzed), whereas the cores of MIL 03346 contain ~ 10 ppm S, ~ 5 ppm Cl and ~ 53 ppm F. Using the volatile concentrations in the cores combined with previously determined partition coefficients we calculate that these clinopyroxenes crystallized from evolved basaltic melts containing ~ 500 ppm S, ~ 500 to 1900 ppm Cl, and 160 to 420 ppm F. These evolved melts can be used to calculate primitive melts in equilibrium with martian peridotite and the concentrations of S, Cl and F in the mantle source region of the nakhlite melts. Depending upon the extent of melting (5 to 30 %) necessary to produce the primary melts associated with nakhlites, our calculations indicate that the nakhlite source region has a S concentration between 20 (5 % melting) to 120 ppm (30 % melting), Cl between 16 to 97 ppm, and F between 14 to 48 ppm. These concentrations in the nakhlite magma source region are similar to previous estimates for the martian mantle; our calculated source region concentrations of F and Cl agree best with previous estimates if the martian mantle undergoes 10 to 20% melting to produce primary magmas that evolve to be parental to nakhlites. However, our maximum estimated sulfur concentration of the source (calculated for 30 % melting) is near previous minimum estimates for the martian mantle, suggesting the possibility that the nakhlite source region is depleted in sulfur relative to much of Mars’ mantle. Mapping the spatial distribution of volatiles in three clinopyroxene crystals demonstrates that S and Cl concentrations of the evolving melts changed significantly from the core to the rim, particularly those in MIL 03346. Increasing S and Cl concentrations between the core and rim of MIL 03346 crystals are attributed to incorporation of additional volatiles through assimilation, but the Nakhla crystal shows no such evidence. However, concentrations of Cl and S at some outer crystal rims of one MIL 03346 crystal decrease, most probably due to volatile degassing during the final stages of clinopyroxene growth

Time-related variation of volatile contents of Western Ghats volcanic formations, Deccan, India

Deccan volcanism in India covered more than 1 million square km and reached a maximum thickness of about 3 km, as presently preserved in the Western Ghats volcanic lava piles. Volcanic activity started at about 66.4 Ma (Jawhar formation) and ended at about 65.5 Ma (Mahabaleshwar unit; Renne et al., 2015). Deccan volcanism straddled the Cretaceous-Paleogene boundary (ca. 66.0 Ma) and possibly contributed to the end-Cretaceous mass extinction event through emission of gases such as SO2, CO2, Cl, F that may have triggered global climate changes. Severe pollution by volcanic gases is supported by the high S and Cl contents (up to 1400 and up to 900 ppm, respectively; Self et al., 2008) measured in a few olivine- and plagioclase-hosted melt inclusions from the Jawhar, Neral, and Thakurvadi Formations (early lava flows, ca. 66.3-66.4 \ub1 0.1 Ma; Renne et al., 2015) and by magmatic S contents (up to 1800 ppm; Callegaro et al., 2014) calculated from S measurements in clinopyroxenes from the Mahabaleshwar unit (ca. 65.5 \ub1 0.1; Schoene et al., 2015). Here, we present new analyses of S, Cl, and F, obtained by ion-probe and synchrotron light micro-fluorescence analyses on clinopyroxenes and plagioclase phenocrysts from ?al? lava flow units of the Western Ghats. The volatile contents of the host magmas have been calculated from recently published clinopyroxene/basalt partition coefficients. These new data will describe the time-related variation of volatile elements hosted and eventually emitted by Deccan lavas and shed light on their environmental impact. References: Callegaro S. et al. (2014). Geology 42, 895-898. Renne P.R. et al. (2015). Science 350, 76-78. Schoene B. et al. (2015). Science 347, 192-184. Self S. et al. (2008). Science 319, 1654-1657

Prehistoric Stone Disks from Entrances and Cemeteries of North-Eastern Adriatic Hillforts

The paper presents a group of four, approximately 0.5m large, stone disks from entrances or cemeteries of two protohistoric hillforts of north-eastern Adriatic. The disks, having a sparse chronology with the exception of one dated to the Middle Bronze Age, show flat and plain surfaces or covered with sub-circular depressions. One disk shows two larger cup-marks at the centre of both faces. They are interpreted as ritual artefacts based on the association with sacred settlement locations and comparisons with similar coeval stones found mainly close to citadel entrances, burials and thresholds in the Aegean area and Anatolia