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  • 1
    Publication Date: 2021-04-14
    Description: In February 2016, 47 ingots were found in the seabed of Contrada Bulala (Gela, CL, Italy) near the site where 40 ingots had previously been recovered. The ingots composition was determined to be a Cu - Zn alloy, dated by the archaeologist to the VI century B.C. This specific alloy was then known as Orichalcum. From an archaeological point of view, the first question raised about the new discovery was whether the ingots of the first and the second excavations belonged to the same shipwreck. Following the previous study, an elemental analysis was performed on the ingots from the second finding by using ICP-OS and ICP-MS techniques. The chemometric treatment of the analytical results obtained on both sets, i.e. ingots from first and second discovery, confirms their similarity. Therefore, the two findings can be considered to belong to the same naval load. The lead isotopic ratios were determined on selected/representative ingots to improve the knowledge about this treasure. Results can provide information about probable location of the lead sources, that could be very useful for the reconstruction of the ancient trade routes in the Mediterranean Sea.
    Description: Published
    Description: 102901
    Description: 2IT. Laboratori analitici e sperimentali
    Description: JCR Journal
    Keywords: Orichalcum ingots ; Lead Isotopic ratio ; ICP-OES ICP-MS ; Chemometric approach ; 05.09. Miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2021-06-07
    Description: Very little is known about the volatile element makeup of the gaseous emissions of Nyamulagira volcano. This paper tries to fill this gap by reporting the first gas composition measurements of Nyamulagira’s volcanic plume since the onset of its lava lake activity at the end of 2014. Two field surveys were carried out on 1 November 2014, and 13–15 October 2015. We applied a broad toolbox of volcanic gas composition measurement techniques in order to geochemically characterize Nyamulagira’s plume. Nyamulagira is a significant emitter of SO2, and our measurements confirm this, as we recorded SO2 emissions of up to ~ 14 kt/d during the studied period. In contrast to neighbouring Nyiragongo volcano, however, Nyamulagira exhibits relatively low CO2/SO2 molar ratios (〈 4) and a highH2O content (〉 92%of total gas emissions). Strong variations in the volatile composition, in particular for the CO2/SO2 ratio, were measured between 2014 and 2015, which appear to reflect the simultaneous variations in volcanic activity.We also determined the molar ratios for Cl/S, F/S and Br/S in the plume gas, finding values of 0.13 and 0.17, 0.06 and 0.11, and 2.3·10−4 and 1·10−4, in 2014 and 2015, respectively. A total gas emission flux of 48 kt/ d was estimated for 2014. The I/S ratio in 2015 was found to be 3.6·10−6. In addition, we were able to distinguish between hydrogen halides and non-hydrogen halides in the volcanic plume. Considerable amounts of bromine (18–35% of total bromine) and iodine (8–18%of total iodine) were found in compounds other than hydrogen halides. However, only a negligible fraction of chlorine was found as compounds other than hydrogen chloride.
    Description: Published
    Description: 90
    Description: 5V. Dinamica dei processi eruttivi e post-eruttivi
    Description: JCR Journal
    Keywords: Nyamulagira ; Plume composition ; Total gas flux ; 04.08. Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 3
    Publication Date: 2021-06-22
    Description: Rare Earth Elements (REE; lanthanides and yttrium) are elements with high economic interest because they are critical elements for modern technologies. This study mainly focuses on the geochemical behavior of REE in hyperacid sulphate brines in volcanic-hydrothermal systems, where the precipitation of sulphate minerals occurs. Kawah Ijen lake, a hyperacid brine hosted in the Ijen caldera (Indonesia), was used as natural laboratory. ∑REE concentration in the lake water is high, ranging from 5.86 to 6.52 mg kg-1. The REE pattern of lake waters normalized to the average local volcanic rock is flat, suggesting isochemical dissolution. Minerals spontaneously precipitated in laboratory at 25 °C from water samples of Kawah Ijen were identified by XRD as gypsum. Microprobe analyses and the chemical composition of major constituents allow to identify possible other minerals precipitated: jarosite, Al-sulphate and Sr, Ba-sulphate. ∑REE concentration in minerals precipitated (mainly gypsum) range from 59.53 to 78.64 mg kg-1. The REE patterns of minerals precipitated normalized to the average local magmatic rock show enrichment in LREE. The REE distribution coefficient (KD), obtained from a ratio of its concentration in the minerals precipitated (mainly gypsum) and the lake water, shows higher values for LREE than HREE. KD-LREE/KD-HREE increases in the studied samples when the concentrations of BaO, MgO, Fe2O3, Al2O3, Na2O and the sum of total oxides (except SO3 and CaO) decrease in the solid phase. The presence of secondary minerals different than gypsum can be the cause of the distribution coefficient variations. High concentrations of REE in Kawah Ijen volcanic lake have to enhance the interest on these environments as possible REE reservoir, stimulating future investigations. The comparison of the KD calculated for REE after mineral precipitation (mainly gypsum) from Kawah Ijen and Poás hyperacid volcanic lakes allow to generalize that the gypsum precipitation removes the LREE from water.
    Description: Published
    Description: 140133
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: 2IT. Laboratori analitici e sperimentali
    Description: JCR Journal
    Keywords: Gypsum precipitation ; Rare Earth Elements ; Hyperacid crater lake ; Kawah Ijen volcano ; Poás volcano ; REE fractionation ; Geochemistry ; 04.08. Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 4
    Publication Date: 2021-06-22
    Description: Major, minor and rare earth elements were analyzed in the acid sulphate - chloride thermal springs associated to Puracé volcano – hydrothermal system. The waters of Puracé were classified in 2 different groups as a function of the physico-chemical parameters and element distributions. Group 1 is characterized by the highest pH (⁓ 3.5), an outlet temperature of ⁓ 81 °C and a strong depletion of Fe, Al, Si and Ba with respect to the isochemical dissolution of the average volcanic local rock. Group 2 waters have lower pH values ⁓ 1.9 and temperature (⁓ 48 °C) compared with Group 1. Moreover, Group 2 is not characterized by a typical pathway representing the congruent dissolution of the rock and shows a distribution of major and minor elements that is more close to the near-congruent dissolution of the average volcanic local rock with respect to Group 1. These geochemical features of major and minor elements allow to propose that the chemical composition of the waters of Group 1 is strongly affected by the precipitation of secondary minerals such as alunite, jarosite, kaolinite, barite and polymorphs of SiO2. The grouping of waters is also supported by the distribution of dissolved REE normalized to the average volcanic local rock. Group 1 shows REE patterns strongly depleted in light rare earth elements (LREE), typical of water that formed alunitic and/or kaolinitic rocks. On the contrary, Group 2 is characterized by flat patterns, in according to the near-congruent dissolution of the rocks. REE dissolved in waters of Puracé were compared with REE in the acidic waters of Nevado del Ruiz and Azufral Colombian volcanoes and with REE in minerals recognized in advanced argillic alteration (alunite, gypsum and kaolinite). Precipitation of secondary minerals is proposed as a common process depleting LREE in acidic sulphate – chlorine waters in volcano – hydrothermal systems. Furthermore, the chemical fractionation of the major and minor elements was interpreted together with the corresponding distributions of REE in order to trace the water – rock interaction processes. Saturation indexes of most common secondary minerals identified in advanced argillic alterations were calculated using PHREEQC software in a range of temperature from 25 to 250 °C. This geochemical approach allows to identify the possible mineral precipitation or dissolution of secondary minerals as well as the temperature at which the water reached equilibrium with a given set of minerals. In Group 1, the precipitation of secondary minerals LREE enriched (alunite minerals and kaolinite) was traced at temperature of precipitation higher than ⁓ 101 °C.
    Description: Published
    Description: 107106
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: JCR Journal
    Keywords: Puracé volcano Acidic waters Rare Earth elements fractionation Advanced argillic alteration Alunite Kaolinite ; 04.08. Volcanology ; 05. General ; Geochemistry
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 5
    Publication Date: 2021-06-22
    Description: The critical role of rare earth elements (Lanthanides plus Yttrium; hereafter REE) in high-tech technologies and consequently their increasing demand from the industry, in addition to the capability of REE to trace water–rock interaction processes, boosted the study of REE in unconventional extreme environments. This study is focused on the geochemical behaviour of REE in the hyperacid sulphate-rich brine of the crater lake of Poás volcano (Costa Rica), where the precipitation of gypsum occurs. This system can hence be considered as a natural laboratory to evaluate the fractionation of REE between the lake water (mother brine) and the precipitating gypsum mineral. Total REE concentrations dissolved in waters range from 1.14 to 2.18 mg kg−1. Calculated distribution coefficients (KD) for REE between the gypsum and the mother brine indicate a preferential removal of the light REE (LREE) with respect to the heavy REE (HREE), with KD values mainly decreasing from La to Lu. During the observation period (2007–2009), the distributions of REE concentrations dissolved in lake water normalized to the average local volcanic rock show two different trends: i) LREE depleted patterns, and ii) flat patterns. The identification of the LREE depleted pattern is justified by the KD calculated in this study. We demonstrate that the precipitation of gypsum is able to strongly fractionate the REE in hyperacid sulphate-rich brine, inducing changes in REE concentrations and distributions over time. X-ray computed tomography imaging was performed on gypsum crystal (precipitated from the lake waters) to gain insights on crystal-scale processes possibly controlling the REE geochemistry, i.e. surface processes vs. structural substitution. Accordingly, the heavy metals and possibly the REE seem to be mainly located on the crystal surface rather than inside the crystal, suggesting that a surface process could be the major process controlling REE removal from the water to the crystal.
    Description: Published
    Description: 87-96
    Description: 3V. Proprietà dei magmi e dei prodotti vulcanici
    Description: 2IT. Laboratori sperimentali e analitici
    Description: JCR Journal
    Keywords: Poas volcano ; Water–rock interaction ; Hyperacid brine lake ; Rare earth elements ; Gypsum precipitation ; 04.08. Volcanology ; Geochemistry
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 6
    Publication Date: 2021-01-26
    Description: Hydrothermally-altered rocks collected at Solfatara volcano, Campi Flegrei caldera complex, Italy, are comparable to zones of steam-heated alterations found at low sulfidation epithermal deposits, and volcanic gases collected at Solfatara have temperatures and C-O-H isotopic compositions akin to those forming low sulfidation epithermal deposits. By contrast, hydrothermal alterations collected at La Fossa volcano, Vulcano island, Italy, are comparable to zones of residual vuggy silica formed in high sulfidation epithermal deposits, and volcanic gases collected at La Fossa have temperatures and C-O-H isotopic compositions comparable to those forming high sulfidation epithermal deposits. At Solfatara, amorphous and hydrous opal-A is responsible for shifts in δ7Li values, from +2.2‰ in fresher rocks, to −3.6‰ in most altered rocks, with increases in Au and Cu concentrations (up to 3 ppb and 96 ppm). The increase in Au and Cu concentrations in progressively-altered rocks resulted from the transport of Cu-Au in magmatic-hydrothermal fluids and their partitioning into pyrite, Fe oxides, phyllosilicates, sulfates, and/or opal-A. It is proposed that the combination of opal-A, decreases in δ7Li values, and increases in Cu and Au concentrations represent an exploration vector for low sulfidation epithermal veins. At La Fossa, α-cristobalite is responsible for shifts in δ7Li values, ranging from −0.9‰ in least-altered rocks, to +4.7‰ in most altered rocks, with decreases in Au-Cu concentrations. The decrease in Au and Cu concentrations in progressively-altered rocks may have resulted from the metasomatism of pyrite and Fe oxides, the dissolution of clinopyroxene and opal, and the invasion of the samples by α-cristobalite. The combination of α-cristobalite, increases in δ7Li values, and decreases in Cu and Au concentrations are proposed as proxies for potential high sulfidation epithermal disseminations. Alternating phases of high eruptive activity and quiescent degassing at volcanoes generally, and at Solfatara and La Fossa specifically, suggest that the physicochemical conditions of individual subvolcanic hydrothermal systems should also be alternating, between conditions that are characteristic of low- and high sulfidation epithermal ore-forming environments, and that the related zones of silicification should be alternating between low δ7Li and high Cu-Au values dominated by opal-A, and higher δ7Li and lower Cu-Au values dominated by α-cristobalite.
    Description: Published
    Description: 103934
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Keywords: Active ore-forming processes ; Opalization and cristobalization ; Lithium isotopes ; High and low sulfidation epithermal Au-Cu ore deposits ; La Fossa, Vulcano, Italy ; Solfatara, Campi Flegrei, Italy ; 04.08. Volcanology ; 05.04. Instrumentation and techniques of general interest ; Geochemistry
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 7
    Publication Date: 2021-06-14
    Description: The eruption of Mt. Etna which occurred on December 24th 2018 was characterized by strombolian activity and fire fountains, emitted by the New South-East Crater and along a fissure that propagated towards the SE. The influence of volcanic emissions on atmospheric deposition was clearly detectable at several kilometres from the source. Wet and dry (bulk) deposition samples were collected each month, through a network of eleven collectors, in the areas of Milazzo, and Priolo between June 2018 and June 2019. They were analysed for major ions and trace elements concentrations. The pH values range from 3.9 to 8.3, while the EC values range from 7 to 396 μS cm-1. An extensive neutralization of the acidity has been recognised mainly due to the suspended alkaline dust particles, which have a buffering role in rainwater. A high load of Na+ and Cl- was observed at all sites, related to the closeness of the study areas to the coast, showing a high positive correlation (R2 = 0.989) along the line of Na+/Cl- ratio in seawater. During the eruption, the volcanic plume was carried by the winds for long distance (more than 300 km) affecting the area of Priolo but not that of Milazzo, which was upwind with respect to Mt. Etna. The impact of volcanic HF was clearly recognised in the samples collected after the eruption. Volcanic SO2 and HCl had a lower impact due to the overwhelming input of anthropogenic sulfate and marine chloride. On the contrary, the signature of the Mt. Etna eruption can be well recognised in the high concentrations of certain trace elements in the samples collected immediately after the eruption. The strongest contrast between affected and non-affected samples was recognised in Al, Cd, and especially in the volatile elements Tl and Te, which are typically enriched in volcanic emissions. The results showed that volcanic eruptions might have a relevant effect on the atmospheric chemistry and on the composition of rainwater up to distances of 80 km from the emission vents.
    Description: Published
    Description: 341-358
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: JCR Journal
    Keywords: rainwater ; fluoride ; trace elements ; volcanic emissions ; 01. Atmosphere ; 03. Hydrosphere ; 04.08. Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 8
    Publication Date: 2024-05-09
    Description: Nisyros Island (Greece) is an active volcano hosting a high-enthalpy geothermal system. During June 2013, an extensive survey on Hg concentrations in different matrices (fumarolic fluids, atmosphere, soils and plants) was carried out at Lakki Plain, an intra-caldera area affected by widespread soil and fumarolic degassing. Concentrations of gaseous elemental mercury (GEM), H2S and CO2, were simultaneously measured in both the fumarolic emissions and the atmosphere around them. At the same time, 130 samples of top soils and 31 samples of plants (Cistus Creticus and Salvifolius and Erica Arborea and Manipuliflora) were collected for Hg analysis. Mercury concentrations in fumarolic gases ranged from 10,500 to 46,300 ng/m3, while Hg concentrations in the air ranged from high background values in the Lakki Plain caldera (10-36 ng/m3) up to 7100 ng/m3 in the fumarolic areas. Outside the caldera, the concentrations were relatively low (2-5 ng/m3). The positive correlation with both CO2 and H2S in air highlighted the importance of hydrothermal gases as carrier for GEM. On the other hand, soil Hg concentrations (0.023-13.7 µg/g) showed no significant correlations with CO2 and H2S in the soil gases, whereas it showed a positive correlation with total S content and an inverse one with the soil-pH, evidencing the complexity of the processes involving Hg carried by hydrothermal gases while passing through the soil. Total Hg concentrations in plant leaves (0.010-0.112 μg/g) had no direct correlation with soil Hg, with Cistus leaves containing higher values of Hg respect to Erica. Even though GEM concentrations in air within the caldera are sometimes orders of magnitude above the global background, they should not be considered dangerous to human health. Values exceeding the WHO guideline value of 1000 ng/m3 are very rare (〈0.1%) and only found very close to the main fumarolic vents, where the access to tourists is prohibited.
    Description: Published
    Description: ID 4783514
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: JCR Journal
    Keywords: Fumarolic mercury ; Atmospheric mercury ; Soil mercury ; Plant mercury ; Mercury output ; 05.09. Miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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