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  • 1
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    Mobility of REE from a hyperacid brine to secondary minerals precipitated in a volcanic hydrothermal system: Kawah Ijen crater lake (Java, Indonesia) (2020)
    Elsevier
    Details
    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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  • 2
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    Precipitation of secondary minerals in acid sulphate-chloride waters traced by major, minor and rare earth elements in waters: The case of Puracé volcano (Colombia) (2021)
    Elsevier
    Details
    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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  • 3
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    Rare Earth Elements Variations in a Hyperacid Crater Lake and Their Relations With Changes in Phreatic Activity, Physico-Chemical Parameters, and Chemical Composition: The Case of Poás Volcano (Costa Rica) (2022)
    Frontiers Media S.A.
    Details
    Publication Date: 2022-03-07
    Description: Decades of geochemical monitoring at active crater lakes worldwide have confirmed that variations in major elements and physico-chemical parameters are useful to detect changes in volcanic activity. However, it is still arduous to identify precursors of single phreatic eruptions. During the unrest phase of 2009–2016, at least 679 phreatic eruptions occurred at the hyperacid and hypersaline crater lake Laguna Caliente of Poás volcano (Costa Rica). In this study, we investigate the temporal variations of Rare Earth Elements (REE) dissolved in Laguna Caliente in order to 1) scrutinize if they can be used as a new geochemical tool to monitor changes of phreatic activity at hyperacid crater lakes and 2) identify the geochemical processes responsible for the variations of REE concentrations in the lake. The total concentration of REE varies from 950 to 2,773 μg kg−1. (La/Pr)N-local rock ratios range from 0.93 to 1.35, and Light REE over Heavy REE (LREE/HREE)N-local rock ratios vary from 0.71 to 0.95. These same parameters vary in relation to significant changes in phreatic activity; in particular, the (La/Pr)N-local rock ratio increases as phreatic activity increases, while that of (LREE/HREE)N-local rock decreases when phreatic activity increases. REE concentrations and their ratios were compared with the variations of major elements and physico-chemical parameters of the lake. Calcium versus (La/Pr)N-local rock and versus (LREE/HREE)N-local rock ratios show different trends compared to the other major elements (Na, K, Mg, Al, Fe, SO4, and Cl). Moreover, a higher loss of Ca (up to 2,835 ppm) in lake water was found with respect to the loss of Al, K, and Na. This loss of Ca is argued to be due to gypsum precipitation, a process corroborated by the mass balance calculation simulating the precipitation of gypsum and the contemporaneous removal of REE from the lake water. The observed relations between REE, changes in phreatic activity, and the parameters commonly used for the monitoring of hyperacid volcanic lakes encourage investigating more on the temporal and cause-effect relationship between REE dynamics and changes in phreatic activity at crater lake-bearing volcanoes.
    Description: Published
    Description: 716970
    Description: 5V. Processi eruttivi e post-eruttivi
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: 2IT. Laboratori analitici e sperimentali
    Description: JCR Journal
    Keywords: Rare Earth Elements ; Poas Volcano ; phreatic eruptions ; geochemical monitoring ; hyperacid volcanic lakes ; Geochemistry
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 4
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    Fluid-mineral dynamics at the Rincón de la Vieja volcano—hydrothermal system (Costa Rica) inferred by the study of major, minor and rare earth elements in the hyperacid crater lake (2024)
    Frontiers S.A.
    Details
    Publication Date: 2024-03-20
    Description: Volcanic lakes are complex natural systems and their chemical composition is related to a myriad of processes. The chemical composition of major, minor, Rare Earth Elements (REE) and physico-chemical parameters at the hyperacid crater lake of Rincón de la Vieja volcano (Costa Rica) are here investigated during February 2013–August 2014. The study of the lake chemical composition allows to identify the main geochemical processes occurring in the lake and to track the changes in the volcanic activity, both important for active volcanoes monitoring. The total REE concentration ( REE) dissolved in the crater lake varies from 2.7 to 3.6 mg kg−1 during the period of observation. REE in the water lake samples normalized to the average volcanic local rock (REEN-local rock) are depleted in light REE (LREE). On the contrary REEN-local rock in the solids precipitated (mainly gypsum/anhydrite), from lake water samples in laboratory at 22°C, are enriched in LREE. The low variability of (La/Pr)N-local rock and (LREE/ HREE)N-local rock ratios (0.92–1.07 and 0.66–0.81, respectively) in crater lake waters is consistent with the low phreatic activity (less than 10 phreatic eruptions in 2 years) observed during the period of observation. This period of low activity precedes the unrest started in 2015, thus, it could be considered as a pre-unrest, characterized by infrequent phreatic eruptions. No clear changes in the REE chemistry are associated with the phreatic eruption occurred at mid- 2013. The results obtained investigating water-rock interaction processes at theRincón de la Vieja crater lake show that rock dissolution and mineral precipitation/ dissolution are the main processes that control the variability of cations composition over time. In particular, precipitation and dissolution of gypsum and alunite are responsible for the variations of REE in the waters. Despite the low variations of (La/Pr)N-local rock and (LREE/HREE)N-local rock ratios, this study allows to suggest that REE can be used, together with major elements, as practical tracers of water-rock interaction processes and mineral precipitation/ dissolution at active hyperacid crater lakes over time, also during periods of quiescence and low phreatic activity.
    Description: Published
    Description: 1197568
    Description: OSV3: Sviluppo di nuovi sistemi osservazionali e di analisi ad alta sensibilità
    Description: JCR Journal
    Keywords: Rare earth elements ; hyperacid crater lake ; geochemical monitoring ; sulfate minerals ; water-rock interaction
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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